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Sample records for aragonite

  1. Enrichment of lanthanides in aragonite

    Institute of Scientific and Technical Information of China (English)

    瞿成利; 路波; 刘刚

    2009-01-01

    Using the constant addition technique,the coprecipitation of lanthanum,gadolinium,and lutetium with aragonite in seawater was experimentally investigated at 25 ℃.Their concentrations in aragonite overgrowths were determined by inductive coupled plasma mass spectrometer.All these lanthanides were strongly enriched in aragonite overgrowths.The amount of lanthanum,gadolinium,and lutetium incorporated into aragonite accounted for 57%-99%,50%-89%,and 40%-91% of their initial total amount,respectively.With the in...

  2. Aragonite twinning in gastropod nacre

    Science.gov (United States)

    Mukai, Hiroki; Saruwatari, Kazuko; Nagasawa, Hiromichi; Kogure, Toshihiro

    2010-10-01

    Aragonite twinning in gastropod nacre has been investigated using scanning electron microscopy (SEM), electron back-scattered diffraction (EBSD), and transmission electron microscopy (TEM) with the focused ion beam (FIB) sample preparation technique. At the growth front of nacre, Haliotis discus hannai and Omphalius rusticus form a "stack-of-coins" structures, which consist of pseudo-hexagonal and elliptical aragonite tablets, respectively. SEM, EBSD, and TEM analyses revealed that these tablets are monolithic single crystal and almost free of the {1 1 0} twins that are common in aragonite of biotic or abiotic origin. The longest diagonal of the hexagon and the longer axis of the ellipse are parallel to the a-axis of aragonite. The crystal orientation of each tablet in a stack, measured by TEM-Kikuchi pattern analysis, is almost the same but there is occasionally {1 1 0} twin-like relationship between adjacent tablets along the stacking. On the other hand, the fibrous aragonite layer formed prior to the nacreous structure is composed of polycrystalline aragonite with high density of {1 1 0} twins. TEM observation suggests that the interlamellar organic sheet prevents the inheritance of the twins, by selecting only single domain of the twins, through the mineral bridge.

  3. Determination of aragonite trace element distribution coefficients from speleothem calcite-aragonite transitions

    Science.gov (United States)

    Wassenburg, J. A.; Scholz, D.; Jochum, K. P.; Cheng, H.; Oster, J.; Immenhauser, A.; Richter, D. K.; Häger, T.; Jamieson, R. A.; Baldini, J. U. L.; Hoffmann, D.; Breitenbach, S. F. M.

    2016-10-01

    The processes that govern the incorporation of (trace) elements into speleothems can often be linked to environmental changes. Although element incorporation into speleothem calcite is now reasonably well understood, current knowledge regarding trace element variability in speleothem aragonite is very limited. Of particular interest is whether trace element distribution coefficients are above or below one in order to assess the extent to which prior aragonite precipitation has affected speleothem aragonite trace element records. This study uses nine calcite-to-aragonite transitions in seven speleothems from diverse environmental settings to derive the first quantitative estimates of the distribution coefficients for several elements in speleothem aragonite: DMg(Ar) = 9.7E-5 ± 9.01E-5, DBa(Ar) = 0.91 ± 0.88, DSr(Ar) = 1.38 ± 0.53, and DU(Ar) = 6.26 ± 4.54 (1σ SD). For one speleothem from western Germany, the distribution coefficients are generally higher, which is potentially related to the very low growth rates (negative correlation with growth rate when growth rate is below 20 μm/year. In summary, our results demonstrate that speleothem aragonite DMg(Ar) is below one, DU(Ar) is considerably above one, and DSr(Ar) is above one or close to unity. For DBa(Ar), reaching a similar conclusion is difficult due to the relatively high uncertainty. Enhanced prior aragonite precipitation will thus result in lower U and higher Mg concentrations in speleothem aragonite, although in many cases Mg in speleothem aragonite is most likely dominated by other processes. This result suggests that U concentrations in aragonitic stalagmites could serve as a very effective proxy for palaeo-rainfall.

  4. Crystal growth of aragonite in the presence of phosphate

    Science.gov (United States)

    Tadier, Solène; Rokidi, Stamatia; Rey, Christian; Combes, Christèle; Koutsoukos, Petros G.

    2017-01-01

    The crystal growth of aragonite was investigated at pH 7.8, 37 °C and constant solution supersaturation from aragonite-seeded supersaturated solutions. The effect of the presence of orthophosphate ions in the supersaturated solution on the kinetics of crystallization of aragonite was investigated over the range of orthophosphate concentrations of 0.25 μM-1 mM. In the presence of orthophosphate in the range of 0.25 μM-8 μM, the crystal growth rate of aragonite decreased with increasing phosphate concentration. At orthophosphate concentration levels exceeding 2 μM, induction times were measured and were found to increase with orthophosphate concentration. At orthophosphate concentration levels >8 μM, the crystal growth of aragonite was inhibited, suggesting the blockage of the active growth sites by the adsorption of orthophosphate ions. Adsorption was confirmed by the investigation of orthophosphate uptake on aragonite, which was: i) found to depend on the equilibrium concentration of orthophosphate in aqueous solutions saturated with respect to aragonite; ii) not influenced by the ionic strength of the electrolyte up to 0.15 M NaCl, showing that electrostatic interactions between orthophosphate and CaCO3 did not play a significant role in this concentration range. Adsorption data of orthophosphate on the aragonite crystals gave satisfactory fit to the Langmuir adsorption model and was confirmed by XPS analysis.

  5. Synthesis and characterization of lamellar aragonite with hydrophobic property

    Energy Technology Data Exchange (ETDEWEB)

    Wang Chengyu, E-mail: wangcy@nefu.edu.cn [College of Materials Science and Engineering, Northeast Forestry University, 150040 (China); Xu Yang [China Nation Center for Quality Supervision and Test of Woodworking Machinery, Northeast Forestry University, 150040 (China); Liu Yalan; Li Jian [College of Materials Science and Engineering, Northeast Forestry University, 150040 (China)

    2009-04-30

    A novel and simple synthetic method for the preparation of hydrophobic lamellar aragonite has been developed. The crystallization of aragonite was conducted by the reaction of sodium carbonate with calcium chloride in the presence of sodium stearate. The resulting products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and the contact angle. The results revealed that sodium stearate plays an important role in determining the structure and morphology of the sample. Besides, we have succeeded in surface modification of particles in situ at the same time. The contact angle of the modified aragonite reached 108.59 deg.

  6. Processes of multibathyal aragonite undersaturation in the Arctic Ocean

    Science.gov (United States)

    Wynn, J.G.; Robbins, L.L.; Anderson, L.G.

    2016-01-01

    During 3 years of study (2010–2012), the western Arctic Ocean was found to have unique aragonite saturation profiles with up to three distinct aragonite undersaturation zones. This complexity is produced as inflow of Atlantic-derived and Pacific-derived water masses mix with Arctic-derived waters, which are further modified by physiochemical and biological processes. The shallowest aragonite undersaturation zone, from the surface to ∼30 m depth is characterized by relatively low alkalinity and other dissolved ions. Besides local influence of biological processes on aragonite undersaturation of shallow coastal waters, the nature of this zone is consistent with dilution by sea-ice melt and invasion of anthropogenic CO2 from the atmosphere. A second undersaturated zone at ∼90–220 m depth (salinity ∼31.8–35.4) occurs within the Arctic Halocline and is characterized by elevated pCO2 and nutrients. The nature of this horizon is consistent with remineralization of organic matter on shallow continental shelves bordering the Canada Basin and the input of the nutrients and CO2 entrained by currents from the Pacific Inlet. Finally, the deepest aragonite undersaturation zone is at greater than 2000 m depth and is controlled by similar processes as deep aragonite saturation horizons in the Atlantic and Pacific Oceans. The comparatively shallow depth of this deepest aragonite saturation horizon in the Arctic is maintained by relatively low temperatures, and stable chemical composition. Understanding the mechanisms controlling the distribution of these aragonite undersaturation zones, and the time scales over which they operate will be crucial to refine predictive models.

  7. Processes of multibathyal aragonite undersaturation in the Arctic Ocean

    Science.gov (United States)

    Wynn, J. G.; Robbins, L. L.; Anderson, L. G.

    2016-11-01

    During 3 years of study (2010-2012), the western Arctic Ocean was found to have unique aragonite saturation profiles with up to three distinct aragonite undersaturation zones. This complexity is produced as inflow of Atlantic-derived and Pacific-derived water masses mix with Arctic-derived waters, which are further modified by physiochemical and biological processes. The shallowest aragonite undersaturation zone, from the surface to ˜30 m depth is characterized by relatively low alkalinity and other dissolved ions. Besides local influence of biological processes on aragonite undersaturation of shallow coastal waters, the nature of this zone is consistent with dilution by sea-ice melt and invasion of anthropogenic CO2 from the atmosphere. A second undersaturated zone at ˜90-220 m depth (salinity ˜31.8-35.4) occurs within the Arctic Halocline and is characterized by elevated pCO2 and nutrients. The nature of this horizon is consistent with remineralization of organic matter on shallow continental shelves bordering the Canada Basin and the input of the nutrients and CO2 entrained by currents from the Pacific Inlet. Finally, the deepest aragonite undersaturation zone is at greater than 2000 m depth and is controlled by similar processes as deep aragonite saturation horizons in the Atlantic and Pacific Oceans. The comparatively shallow depth of this deepest aragonite saturation horizon in the Arctic is maintained by relatively low temperatures, and stable chemical composition. Understanding the mechanisms controlling the distribution of these aragonite undersaturation zones, and the time scales over which they operate will be crucial to refine predictive models.

  8. Aragonite coating solutions (ACS) based on artificial seawater

    Energy Technology Data Exchange (ETDEWEB)

    Tas, A. Cuneyt, E-mail: c_tas@hotmail.com

    2015-03-01

    Graphical abstract: - Highlights: • Developed completely inorganic solutions for the deposition of monolayers of aragonite spherules (or ooids). • Solutions mimicked the artificial seawater. • Biomimetic crystallization was performed at the tropical sea surface temperature of 30 °C. - Abstract: Aragonite (CaCO{sub 3}, calcium carbonate) is an abundant biomaterial of marine life. It is the dominant inorganic phase of coral reefs, mollusc bivalve shells and the stalactites or stalagmites of geological sediments. Inorganic and initially precipitate-free aragonite coating solutions (ACS) of pH 7.4 were developed in this study to deposit monolayers of aragonite spherules or ooids on biomaterial (e.g., UHMWPE, ultrahigh molecular weight polyethylene) surfaces soaked in ACS at 30 °C. The ACS solutions of this study have been developed for the surface engineering of synthetic biomaterials. The abiotic ACS solutions, enriched with calcium and bicarbonate ions at different concentrations, essentially mimicked the artificial seawater composition and started to deposit aragonite after a long (4 h) incubation period at the tropical sea surface temperature of 30 °C. While numerous techniques for the solution deposition of calcium hydroxyapatite (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}), of low thermodynamic solubility, on synthetic biomaterials have been demonstrated, procedures related to the solution-based surface deposition of high solubility aragonite remained uncommon. Monolayers of aragonite ooids deposited at 30 °C on UHMWPE substrates soaked in organic-free ACS solutions were found to possess nano-structures similar to the mortar-and-brick-type botryoids observed in biogenic marine shells. Samples were characterized using SEM, XRD, FTIR, ICP-AES and contact angle goniometry.

  9. Aragonite precipitation by "proto-polyps" in coral cell cultures.

    Directory of Open Access Journals (Sweden)

    Tali Mass

    Full Text Available The mechanisms of coral calcification at the molecular, cellular and tissue levels are poorly understood. In this study, we examine calcium carbonate precipitation using novel coral tissue cultures that aggregate to form "proto-polyps". Our goal is to establish an experimental system in which calcification is facilitated at the cellular level, while simultaneously allowing in vitro manipulations of the calcifying fluid. This novel coral culturing technique enables us to study the mechanisms of biomineralization and their implications for geochemical proxies. Viable cell cultures of the hermatypic, zooxanthellate coral, Stylophora pistillata, have been maintained for 6 to 8 weeks. Using an enriched seawater medium with aragonite saturation state similar to open ocean surface waters (Ω(arag~4, the primary cell cultures assemble into "proto-polyps" which form an extracellular organic matrix (ECM and precipitate aragonite crystals. These extracellular aragonite crystals, about 10 µm in length, are formed on the external face of the proto-polyps and are identified by their distinctive elongated crystallography and X-ray diffraction pattern. The precipitation of aragonite is independent of photosynthesis by the zooxanthellae, and does not occur in control experiments lacking coral cells or when the coral cells are poisoned with sodium azide. Our results demonstrate that proto-polyps, aggregated from primary coral tissue culture, function (from a biomineralization perspective similarly to whole corals. This approach provides a novel tool for investigating the biophysical mechanism of calcification in these organisms.

  10. Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

    Science.gov (United States)

    Rossi, Carlos; Lozano, Rafael P.

    2016-11-01

    Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32- concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1 mol/mol. Within the analyzed ranges of pH (8.2-8.6), CO32- concentration (1-6 mg/L), supersaturation (SIaragonite: 0.08-1.08; SIcalcite: 0.23-1.24), drip rate (0.2-81 drops/min) and dissolved Zn (6-90 μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11 °C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is

  11. Nucleation of metastable aragonite CaCO3 in seawater.

    Science.gov (United States)

    Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

    2015-03-17

    Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

  12. Aragonite-calcite transformation in fossil snail shells of loess sequences in Loess Plateau, Central China

    Institute of Scientific and Technical Information of China (English)

    SHENG Xuefen; CHEN Jun; CAI Yuanfeng; CHEN Yang; JI Junfeng

    2005-01-01

    The methods of X-ray diffraction (XRD) and ICP-AES are applied to analyzing the mineral composition of modern and fossil snail shells in Luochuan section and Xifeng section. The results show that the mineral phase of calcium carbonate in modern snail shells is aragonite, but for some fossil snail shells in certain layers of loess sequences, a part of aragonite is transformed into calcite. In Luochuan and Xifeng sections, the stratigraphic borderline of aragonite-calcite transformation appearing obviously is between L5 and L6. Under the earth surface condition, the aragonite-calcite transformation is influenced by the factor of temperature only in a long time scale. It seems that the pressure is not the factor influencing the aragonite-calcite transformation. The results also show that existing age of snail shells is possibly the dominant and principal factor for the aragonite-calcite transformation. To a certain extent, the degree of aragonite-calcite transformation in snail shell is controlled by the content of trace element, such as Mg2+. The trace element can improve the stability of snail shell aragonite and impede the process of aragonite transforming into calcite.

  13. Intra- and inter-annual uranium concentration variability in a Belizean stalagmite controlled by prior aragonite precipitation: A new tool for reconstructing hydro-climate using aragonitic speleothems

    Science.gov (United States)

    Jamieson, Robert A.; Baldini, James U. L.; Brett, Marianne J.; Taylor, Jessica; Ridley, Harriet E.; Ottley, Chris J.; Prufer, Keith M.; Wassenburg, Jasper A.; Scholz, Denis; Breitenbach, Sebastian F. M.

    2016-10-01

    Aragonitic speleothems are increasingly utilised as palaeoclimate archives due to their amenability to high precision U-Th dating. Proxy records from fast-growing aragonitic stalagmites, precisely dated to annual timescales, can allow investigation of climatic events occurring on annual or even sub-annual timescales with minimal chronological uncertainty. However, the behaviour of many trace elements, such as uranium, in aragonitic speleothems has not thus far been as well constrained as in calcitic speleothems. Here, we use uranium concentration shifts measured across primary calcite-to-aragonite mineralogical transitions in speleothems to calculate the distribution coefficient of uranium in aragonitic speleothems (derived DU = 3.74 ± 1.13). Because our calculated DU is considerably above 1 increased prior aragonite precipitation due to increased karst water residence time should strongly control stalagmite aragonite U/Ca values. Consequently, uranium concentrations in aragonitic speleothems should act as excellent proxies for effective rainfall. We test this using a high-resolution ICP-MS derived trace element dataset from a Belizean stalagmite. YOK-G is an aragonitic stalagmite from Yok Balum cave in Belize with an extremely robust monthly-resolved chronology built using annual δ13C cycles. We interpret seasonal U/Ca variations in YOK-G as reflecting changes in the amount and seasonality of prior aragonite precipitation driven by variable rainfall amounts. The U/Ca record strongly suggests that modern drying has occurred in Belize, and that this drying was primarily caused by a reduction in wet season rainfall. This is consistent with published stable isotope data from YOK-G also very strongly suggesting modern rainfall reductions, previously interpreted as the result of southward ITCZ displacement. Our results strongly suggest that U/Ca values in aragonitic speleothems are excellent proxies for rainfall variability. This new tool, combined with the

  14. Visualization of newt aragonitic otoconial matrices using transmission electron microscopy

    Science.gov (United States)

    Steyger, P. S.; Wiederhold, M. L.

    1995-01-01

    Otoconia are calcified protein matrices within the gravity-sensing organs of the vertebrate vestibular system. These protein matrices are thought to originate from the supporting or hair cells in the macula during development. Previous studies of mammalian calcitic, barrel-shaped otoconia revealed an organized protein matrix consisting of a thin peripheral layer, a well-defined organic core and a flocculent matrix inbetween. No studies have reported the microscopic organization of the aragonitic otoconial matrix, despite its protein characterization. Pote et al. (1993b) used densitometric methods and inferred that prismatic (aragonitic) otoconia have a peripheral protein distribution, compared to that described for the barrel-shaped, calcitic otoconia of birds, mammals, and the amphibian utricle. By using tannic acid as a negative stain, we observed three kinds of organic matrices in preparations of fixed, decalcified saccular otoconia from the adult newt: (1) fusiform shapes with a homogenous electron-dense matrix; (2) singular and multiple strands of matrix; and (3) more significantly, prismatic shapes outlined by a peripheral organic matrix. These prismatic shapes remain following removal of the gelatinous matrix, revealing an internal array of organic matter. We conclude that prismatic otoconia have a largely peripheral otoconial matrix, as inferred by densitometry.

  15. Towards an Understanding of the Role of Aragonite in the Mechanical Properties of Nacre

    Energy Technology Data Exchange (ETDEWEB)

    2010-08-25

    Nacre, also known as mother-of-pearl, is a biocomposite material that exhibits higher strength and fracture toughness than its component materials. It derives its strength from the brick-and-mortar layering of aragonite (CaCO{sub 3}) platelets and organic binder. It is believed that the protein binder helps redistribute the stress throughout all tablets for optimal mechanical performance. In this study, we attempt to measure the mechanical properties of aragonite within nacre and compare them to bulk aragonite and bulk nacre and understand the redistribution of stresses. Here we show that x-ray diffraction techniques are useful for isolating and measuring strain of crystallites within a composite material. Our results show that the apparent stiffness of aragonite varies with crystallographic directions and is higher than the stiffness of bulk nacre in all cases, meaning that aragonite tablets are exposed to less than the average bulk stress. The average force applied to the bulk sample is partitioned between the aragonite and the binder, so that the protein layer bears as much as 27.2% of the total applied force. Different crystallographic directions exhibit behaviors different than bulk aragonite or bulk nacre. These are related to texture of aragonite platelets (i.e. preferred orientations within nacre). By examining nacre, we can obtain a better understanding of the mechanical relationship between the ceramic and polymer in composite materials. We expect that x-ray diffraction will become the standard method for probing the mechanical properties of composite materials.

  16. Uranium isotope fractionation during coprecipitation with aragonite and calcite

    Science.gov (United States)

    Chen, Xinming; Romaniello, Stephen J.; Herrmann, Achim D.; Wasylenki, Laura E.; Anbar, Ariel D.

    2016-09-01

    Natural variations in 238U/235U of marine calcium carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ∼7.5 and ∼8.5 to study possible U isotope fractionation during incorporation into these minerals. Small but significant U isotope fractionation was observed in aragonite experiments at pH ∼8.5, with heavier U isotopes preferentially enriched in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007 + 0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ∼7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3(aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism. These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2 , Ca2+, or Mg2+ concentrations. In general, these effects are likely to be small (<0.13‰), but are nevertheless potentially significant because of the small natural range of

  17. Unusual micrometric calcite-aragonite interface in the abalone shell Haliotis (Mollusca, Gastropoda).

    Science.gov (United States)

    Dauphin, Yannicke; Cuif, Jean-Pierre; Castillo-Michel, Hiram; Chevallard, Corinne; Farre, Bastien; Meibom, Anders

    2014-02-01

    Species of Haliotis (abalone) show high variety in structure and mineralogy of the shell. One of the European species (Haliotis tuberculata) in particular has an unusual shell structure in which calcite and aragonite coexist at a microscale with small patches of aragonite embedded in larger calcitic zones. A detailed examination of the boundary between calcite and aragonite using analytical microscopies shows that the organic contents of calcite and aragonite differ. Moreover, changes in the chemical composition of the two minerals seem to be gradual and define a micrometric zone of transition between the two main layers. A similar transition zone has been observed between the layers in more classical and regularly structured mollusk shells. The imbrication of microscopic patches of aragonite within a calcitic zone suggests the occurrence of very fast physiological changes in these taxa.

  18. The calcite → aragonite transformation in low-Mg marble: Equilibrium relations, transformations mechanisms, and rates

    Science.gov (United States)

    Hacker, Bradley R.; Rubie, David C.; Kirby, Stephen H.; Bohlen, Steven R.

    2005-01-01

    Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

  19. Ultrasonic Observation of the Calcite-Aragonite Transition

    Science.gov (United States)

    Ahrens, T. J.; Katz, S.

    1963-01-01

    Elastic-wave velocities were measured as a function of pressure by ultrasonic pulse Interferometry in Solenhofen and Manilus limestone specimens to pressures of 27 and 38 kb. Longitudinal velocities decrease sharply from 5.3 km/sec at a mean pressure of 4 kb to a minimum of 4.8 km/sec at 8 kb. Transverse velocities decrease from 3.1 to 2.9 km/sec. At the minimum bulk and rigidity moduli are 25 and 20 per cent below their 4-kb values. A density increase of 1.7 per cent is associated with this minimum. The observed effects are attributed to the calcite-aragonite transition, and they may be due to an inherent property of the material, a component of which undergoes a polymorphic transition, the low- and high-pressure phases coexisting over a considerable pressure range. This may be an additional mechanism to account for low-velocity zones in the earth?s interior.

  20. Aragonite saturation state dynamics in a coastal upwelling zone

    Science.gov (United States)

    Harris, Katherine E.; Degrandpre, Michael D.; Hales, Burke

    2013-06-01

    upwelling zones may be at enhanced risk from ocean acidification as upwelling brings low aragonite saturation state (ΩAr) waters to the surface that are further suppressed by anthropogenic CO2. ΩAr was calculated with pH, pCO2, and salinity-derived alkalinity time series data from autonomous pH and pCO2 instruments moored on the Oregon shelf and shelf break during different seasons from 2007 to 2011. Surface ΩAr values ranged between 0.66 ± 0.04 and 3.9 ± 0.04 compared to an estimated pre-industrial range of 1.0 ± 0.1 to 4.7 ± 0.1. Upwelling of high-CO2 water and subsequent removal of CO2 by phytoplankton imparts a dynamic range to ΩAr from ~1.0 to ~4.0 between spring and autumn. Freshwater input also suppresses saturation states during the spring. Winter ΩAr is less variable than during other seasons and is controlled primarily by mixing of the water column.

  1. Study of Binding Interaction between Pif80 Protein Fragment and Aragonite

    Science.gov (United States)

    Du, Yuan-Peng; Chang, Hsun-Hui; Yang, Sheng-Yu; Huang, Shing-Jong; Tsai, Yu-Ju; Huang, Joseph Jen-Tse; Chan, Jerry Chun Chung

    2016-08-01

    Pif is a crucial protein for the formation of the nacreous layer in Pinctada fucata. Three non-acidic peptide fragments of the aragonite-binding domain (Pif80) are selected, which contain multiple copies of the repeat sequence DDRK, to study the interaction between non-acidic peptides and aragonite. The polypeptides DDRKDDRKGGK (Pif80-11) and DDRKDDRKGGKDDRKDDRKGGK (Pif80-22) have similar binding affinity to aragonite. Solid-state NMR data indicate that the backbones of Pif80-11 and Pif80-22 peptides bound on aragonite adopt a random-coil conformation. Pif80-11 is a lot more effective than Pif80-22 in promoting the nucleation of aragonite on the substrate of β-chitin. Our results suggest that the structural arrangement at a protein-mineral interface depends on the surface structure of the mineral substrate and the protein sequence. The side chains of the basic residues, which function as anchors to the aragonite surface, have uniform structures. The role of basic residues as anchors in protein-mineral interaction may play an important role in biomineralization.

  2. 88Sr/86Sr fractionation in inorganic aragonite and in corals

    Science.gov (United States)

    Fruchter, Noa; Eisenhauer, Anton; Dietzel, Martin; Fietzke, Jan; Böhm, Florian; Montagna, Paolo; Stein, Moti; Lazar, Boaz; Rodolfo-Metalpa, Riccardo; Erez, Jonathan

    2016-04-01

    Conflicting results have been reported for the stable Sr isotope fractionation, specifically with respect to the influence of temperature. In an experimental study we have investigated the stable Sr isotope systematics for inorganically precipitated and biogenic (coral) aragonite (natural and laboratory-cultured). Inorganic aragonite precipitation experiments were performed from natural seawater using the CO2 diffusion technique. The experiments were performed at different temperatures and different carbonate ion concentrations. 88Sr/86Sr of the inorganic aragonite precipitated in the experiments are 0.2‰ lighter than seawater, but showed no correlation to the water temperature or to CO32- concentration. Similar observations are made in different coral species (Cladocora caespitosa, Porites sp. and Acropora sp.), with identical fractionation from the bulk solution and no correlation to temperature or CO32- concentration. The lack of 88Sr/86Sr variability in corals at different environmental parameters and the similarity to the 88Sr/86Sr fractionation in inorganic aragonite may indicate a similar Sr incorporation mechanism in corals skeleton and inorganic aragonite, and therefore the previously proposed Rayleigh-based multi element model (Gaetani et al., 2011) cannot explain the process of Sr incorporation in the coral skeletal material. It is proposed that the relatively constant 88Sr/86Sr fractionation in aragonite can be used for paleo reconstruction of seawater 88Sr/86Sr composition. The seawater 88Sr/86Sr ratio reconstruction can be further used in calcite samples to reconstruct paleo precipitation rates.

  3. Climatological distribution of aragonite saturation state in the global oceans

    Science.gov (United States)

    Jiang, Li-Qing; Feely, Richard A.; Carter, Brendan R.; Greeley, Dana J.; Gledhill, Dwight K.; Arzayus, Krisa M.

    2015-10-01

    Aragonite saturation state (Ωarag) in surface and subsurface waters of the global oceans was calculated from up-to-date (through the year of 2012) ocean station dissolved inorganic carbon (DIC) and total alkalinity (TA) data. Surface Ωarag in the open ocean was always supersaturated (Ω > 1), ranging between 1.1 and 4.2. It was above 2.0 (2.0-4.2) between 40°N and 40°S but decreased toward higher latitude to below 1.5 in polar areas. The influences of water temperature on the TA/DIC ratio, combined with the temperature effects on inorganic carbon equilibrium and apparent solubility product (K'sp), explain the latitudinal differences in surface Ωarag. Vertically, Ωarag was highest in the surface mixed layer. Higher hydrostatic pressure, lower water temperature, and more CO2 buildup from biological activity in the absence of air-sea gas exchange helped maintain lower Ωarag in the deep ocean. Below the thermocline, aerobic decomposition of organic matter along the pathway of global thermohaline circulation played an important role in controlling Ωarag distributions. Seasonally, surface Ωarag above 30° latitudes was about 0.06 to 0.55 higher during warmer months than during colder months in the open-ocean waters of both hemispheres. Decadal changes of Ωarag in the Atlantic and Pacific Oceans showed that Ωarag in waters shallower than 100 m depth decreased by 0.10 ± 0.09 (-0.40 ± 0.37% yr-1) on average from the decade spanning 1989-1998 to the decade spanning 1998-2010.

  4. Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral

    Science.gov (United States)

    Domínguez-Villar, David; Krklec, Kristina; Pelicon, Primož; Fairchild, Ian J.; Cheng, Hai; Edwards, Lawrence R.

    2017-03-01

    Formerly aragonite speleothems recrystallized to calcite result from solutions subsaturated in aragonite and supersaturated in calcite that infiltrate into the speleothem through the interconnected porosity. In most cases, the crystal replacement takes place through a thin solution film. This diagenetic process can occur under open or semi-closed geochemical conditions. Thus, secondary calcite crystals record the composition of the fluid at the time of diagenesis affected by calcite partition coefficients and fractionation factors (open system) or partly inherit the composition of the primary aragonite (semi-closed system). So, whether or not recrystallized aragonite speleothems can record reliable geochemical signals from the time of speleothem primary deposition still is an open debate. We studied a stalagmite from Eagle Cave (Spain) predominantly composed of secondary calcite that replaced aragonite, although a core of primary aragonite extending 45 mm along the growth direction was preserved at the base of the sample. We obtained Mg and Sr compositional maps, paired U-Th dating and δ18O and δ13C profiles across the diagenetic front. Additionally, two parallel isotope records were obtained along the speleothem growth direction in the aragonite and calcite sectors. Our results support that recrystallization of this speleothem took place in open system conditions for δ18O, δ13C, Mg and Sr, but in semi-closed system conditions for U and Th. The recrystallization of this sample took place during one or several events, likely after the Younger Dryas as a result of climate change influencing drip water composition. Based on compositional zoned patterns, we suggest that the advance of diagenetic fronts in this speleothem had an average rate of 50 ± 45 μm/yr. Such recrystallization rate can transform any aragonite speleothem into calcite within a few centuries. We suggest that the volume of water interacting with the speleothem at the time of recrystallization is

  5. Biotic control of skeletal growth by scleractinian corals in aragonite-calcite seas.

    Directory of Open Access Journals (Sweden)

    Tomihiko Higuchi

    Full Text Available Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas.

  6. Aragonite crystallization in primary cell cultures of multicellular isolates from a hard coral, Pocillopora damicornis.

    Science.gov (United States)

    Domart-Coulon, I J; Elbert, D C; Scully, E P; Calimlim, P S; Ostrander, G K

    2001-10-09

    The foundation of marine coral reef ecosystems is calcium carbonate accumulated primarily by the action of hard corals (Coelenterata: Anthozoa: Scleractinia). Colonial hard coral polyps cover the surface of the reef and deposit calcium carbonate as the aragonite polymorph, stabilized into a continuous calcareous skeleton. Scleractinian coral skeleton composition and architecture are well documented; however, the cellular mechanisms of calcification are poorly understood. There is little information on the nature of the coral cell types involved or their cooperation in biocalcification. We report aragonite crystallization in primary cell cultures of a hard coral, Pocillopora damicornis. Cells of apical coral colony fragments were isolated by spontaneous in vitro dissociation. Single dissociated cell types were separated by density in a discontinuous Percoll gradient. Primary cell cultures displayed a transient increase in alkaline phosphatase (ALP) activity, to the level observed in intact corals. In adherent multicellular isolate cultures, enzyme activation was followed by precipitation of aragonite. Modification of the ionic formulation of the medium prolonged maintenance of isolates, delayed ALP activation, and delayed aragonite precipitation. These results demonstrate that in vitro crystallization of aragonite in coral cell cultures is possible, and provides an innovative approach to investigate reef-building coral calcification at the cellular level.

  7. Abrupt onset and prolongation of aragonite undersaturation events in the Southern Ocean

    Science.gov (United States)

    Hauri, Claudine; Friedrich, Tobias; Timmermann, Axel

    2016-02-01

    Ocean acidification may lead to seasonal aragonite undersaturation in surface waters of the Southern Ocean as early as 2030 (ref. ). These conditions are harmful to key organisms such as pteropods, which contribute significantly to the pelagic foodweb and carbon export fluxes in this region. Although the severity of ocean acidification impacts is mainly determined by the duration, intensity and spatial extent of aragonite undersaturation events, little is known about the nature of these events, their evolving attributes and the timing of their onset in the Southern Ocean. Using an ensemble of ten Earth system models, we show that starting around 2030, aragonite undersaturation events will spread rapidly, affecting ~30% of Southern Ocean surface waters by 2060 and >70% by 2100, including the Patagonian Shelf. On their onset, the duration of these events will increase abruptly from 1 month to 6 months per year in less than 20 years in >75% of the area affected by end-of-century aragonite undersaturation. This is likely to decrease the ability of organisms to adapt to a quickly evolving environment. The rapid equatorward progression of surface aragonite undersaturation can be explained by the uptake of anthropogenic CO2, whereas climate-driven physical or biological changes will play a minor role.

  8. Aragonite observed in the prismatic layer of seawater-cultured pearls

    Institute of Scientific and Technical Information of China (English)

    MA Hongyan; ZHANG Beili; LEE I-S; QIN Zuolu; TONG Zhangfa; QIU Shuheng

    2007-01-01

    The prismatic layer is obviously different from the parallel layer in seawater-cultured pearls.X-ray diffraction (XRD),optical microscopy(OM)and micro-infrared(IR)spectroscopy have been applied to characterize the crystallized layers of high-and low-quality seawater-cultured pearls produced in South China.The result shows that the prismatic layer is not only composed of calcite as reported in previous researches.Three types of prisms were found in seawater-cultured pearls:calcite prism,aragonite prism and calcite and aragonite prism.Therefore,we have a new understanding of the biomineralization of the prismatic layer in seawater-cultured pearls.The result makes us review the traditional viewpoint that the increased content of aragonite improves the quality of pearls.We discovered that some seawater prismatic pearls almost completely composed of aragonite have the worst quality.We thought that the thickness and the spatial distribution of prisms are the main factors that can affect the quality of seawater-cultured pearls.

  9. Aragonite saturation states and nutrient fluxes in coral reef sediments in Biscayne National Park, FL, USA

    Science.gov (United States)

    Lisle, John T.; Reich, Christopher D.; Halley, Robert B.

    2014-01-01

    Some coral reefs, such as patch reefs along the Florida Keys reef tract, are not showing significant reductions in calcification rates in response to ocean acidification. It has been hypothesized that this recalcitrance is due to local buffering effects from biogeochemical processes driven by seagrasses. We investigated the influence that pore water nutrients, dissolved inorganic carbon (DIC) and total alkalinity (TA) have on aragonite saturation states (Ωaragonite) in the sediments and waters overlying the sediment surfaces of sand halos and seagrass beds that encircle Alinas and Anniversary reefs in Biscayne National Park. Throughout the sampling period, sediment pore waters from both bottom types had lower oxidation/reduction potentials (ORP), with lower pH relative to the sediment surface waters. The majority (86.5%) of flux rates (n = 96) for ΣNOx–, PO43–, NH4+, SiO2, DIC and TA were positive, sometimes contributing significant concentrations of the respective constituents to the sediment surface waters. The Ωaragonite values in the pore waters (range: 0.18 to 4.78) were always lower than those in the overlying waters (2.40 to 4.46), and 52% (n = 48) of the values were aragonite in 75% (n = 16) of the samples, but increased it in the remainder. The elevated fluxes of nutrients, DIC and TA into the sediment–water interface layer negatively alters the suitability of this zone for the settlement and development of calcifying larvae, while enhancing the establishment of algal communities.

  10. Limpets counteract ocean acidification induced shell corrosion by thickening of aragonitic shell layers

    Directory of Open Access Journals (Sweden)

    G. Langer

    2014-08-01

    Full Text Available Specimens of the patellogastropod limpet Patella caerulea were collected within (pHlow-shells and outside (pHn-shells a CO2 vent site at Ischia, Italy. Four pHlow-shells and four pHn-shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. The pHlow-shells displayed a twofold increase in aragonite area fraction and size normalised aragonite area. Size normalised calcite area was halved in pHlow-shells. Taken together with the increased apical and the decreased flank size normalised thickness of the pHlow-shells, these data led us to conclude that low pH exposed P. caerulea specimens counteract shell dissolution by enhanced shell production. The latter is different from normal elongation growth and proceeds through addition of aragonitic layers only, while the production of calcitic layers is confined to elongation growth. Therefore aragonite cannot be regarded as a per se disadvantageous polymorph under ocean acidification conditions.

  11. Limpets counteract ocean acidification induced shell corrosion by thickening of aragonitic shell layers

    Science.gov (United States)

    Langer, G.; Nehrke, G.; Baggini, C.; Rodolfo-Metalpa, R.; Hall-Spencer, J. M.; Bijma, J.

    2014-12-01

    Specimens of the patellogastropod limpet Patella caerulea were collected within (pHlow-shells) and outside (pHn-shells) a CO2 vent site at Ischia, Italy. Four pHlow-shells and four pHn-shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. The pHlow-shells displayed a twofold increase in aragonite area fraction and size-normalised aragonite area. Size-normalised calcite area was halved in pHlow-shells. Taken together with the increased apical and the decreased flank size-normalised thickness of the pHlow-shells, these data led us to conclude that low-pH-exposed P. caerulea specimens counteract shell dissolution by enhanced shell production. This is different from normal elongation growth and proceeds through addition of aragonitic parts only, while the production of calcitic parts is confined to elongation growth. Therefore, aragonite cannot be regarded as a disadvantageous polymorph per se under ocean acidification conditions.

  12. Dissolution dominating calcification process in polar pteropods close to the point of aragonite undersaturation.

    Science.gov (United States)

    Bednaršek, Nina; Tarling, Geraint A; Bakker, Dorothee C E; Fielding, Sophie; Feely, Richard A

    2014-01-01

    Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Ω(ar)). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Ω(ar) ∼ 0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Ω(ar) levels slightly above 1 and lower at Ω(ar) levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Ω(ar) derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Ω(ar) levels close to 1, with net shell growth ceasing at an Ω(ar) of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean.

  13. Nacre and false nacre (foliated aragonite) in extant monoplacophorans (=Tryblidiida: Mollusca)

    Science.gov (United States)

    Checa, Antonio G.; Ramírez-Rico, Joaquín; González-Segura, Alicia; Sánchez-Navas, Antonio

    2009-01-01

    Extant monoplacophorans (Tryblidiida, Mollusca) have traditionally been reported as having an internal nacreous layer, thus representing the ancestral molluscan condition. The examination of this layer in three species of Neopilinidae ( Rokopella euglypta, Veleropilina zografi, and Micropilina arntzi) reveals that only V. zografi secretes an internal layer of true nacre, which occupies only part of the internal shell surface. The rest of the internal surface of V. zografi and the whole internal surfaces of the other two species examined are covered by a material consisting of lath-like, instead of brick-like, crystals, which are arranged into lamellae. In all cases examined, the crystallographic c-axis in this lamellar material is perpendicular to the surface of laths and the a-axis is parallel to their long dimension. The differences between taxa relate to the frequency of twins, which is much higher in Micropilina. In general, the material is well ordered, particularly towards the margin, where lamellae pile up at a small step size, which is most likely due to processes of crystal competition. Given its morphological resemblance to the foliated calcite of bivalves, we propose the name foliated aragonite for this previously undescribed biomaterial secreted by monoplacophorans. We conclude that the foliated aragonite probably lacks preformed interlamellar membranes and is therefore not a variant of nacre. A review of the existing literature reveals that previous reports of nacre in the group were instead of the aragonitic foliated layer and that our report of nacre in V. zografi is the first undisputed evidence of nacre in monoplacophorans. From the evolutionary viewpoint, the foliated aragonite could easily have been derived from nacre. Assuming that nacre represents the ancestral condition, as in other molluscan classes, it has been replaced by foliated aragonite along the tryblidiidan lineage, although the fossil record does not presently provide evidence as to

  14. Comparison of Dissolution and Surface Reactions Between Calcite and Aragonite in L-Glutamic and L-Aspartic Acid Solutions

    Directory of Open Access Journals (Sweden)

    Kwangsuk You

    2010-01-01

    Full Text Available We have investigated dissolution and surface reaction of calcite and aragonite in amino acid solutions of L-glutamic (L-glu and L-aspartic acid (L-asp at weak acidity of above pH 3. The surface reactions of calcite and aragonite were related with the dissolution. Calcite was dissolved in both solutions but the dissolution was limited by an adsorption of Ca-carboxylate salt. Aragonite was neither dissolved nor reacted in amino acid solutions because the crystal surface consisted of a hard to dissolve structure.

  15. Aragonite undersaturation in the Arctic Ocean: effects of ocean acidification and sea ice melt.

    Science.gov (United States)

    Yamamoto-Kawai, Michiyo; McLaughlin, Fiona A; Carmack, Eddy C; Nishino, Shigeto; Shimada, Koji

    2009-11-20

    The increase in anthropogenic carbon dioxide emissions and attendant increase in ocean acidification and sea ice melt act together to decrease the saturation state of calcium carbonate in the Canada Basin of the Arctic Ocean. In 2008, surface waters were undersaturated with respect to aragonite, a relatively soluble form of calcium carbonate found in plankton and invertebrates. Undersaturation was found to be a direct consequence of the recent extensive melting of sea ice in the Canada Basin. In addition, the retreat of the ice edge well past the shelf-break has produced conditions favorable to enhanced upwelling of subsurface, aragonite-undersaturated water onto the Arctic continental shelf. Undersaturation will affect both planktonic and benthic calcifying biota and therefore the composition of the Arctic ecosystem.

  16. Synthesis and Characterisation of Calcium Carbonate Aragonite Nanocrystals from Cockle Shell Powder (Anadara granosa

    Directory of Open Access Journals (Sweden)

    Abdullahi Shafiu Kamba

    2013-01-01

    Full Text Available The synthesis of pure calcium carbonate nanocrystals using a high pressure homogeniser (HPH via a microemulsion system produced uniform nanosized particles, which were characterised using transmission electron microscopy (TEM, field-emission scanning electron microscopy (FESEM, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR, and thermogravimetric analysis (TGA. The identified particles were aragonite polymorphs with a rod shape and were approximately 50 nm in size. The aragonite polymorph of calcium carbonate was prepared from biogenic materials, cockle shells, and exhibited unique characteristics (i.e., a higher density than that of calcite, which makes it biocompatible and potentially suitable for applications in the medical, pharmaceutical, cosmetic, and paint industries. The methods adopted and the nonionic surfactant used in the synthesis of calcium carbonate nanocrystalline aragonite polymorphs were environmentally friendly and can be scaled up for industrial production. The sources are naturally available materials that are by-products of the seafood industry, which offers an opportunity for exploitation in numerous industrial applications.

  17. Element substitution by living organisms: the case of manganese in mollusc shell aragonite

    Science.gov (United States)

    Soldati, Analia L.; Jacob, Dorrit E.; Glatzel, Pieter; Swarbrick, Janine C.; Geck, Jochen

    2016-03-01

    Determining the manganese concentration in shells of freshwater bivalves provides a unique way to obtain information about climate and environmental changes during time-intervals that pre-date instrumental data records. This approach, however, relies on a thorough understanding of how manganese is incorporated into the shell material -a point that remained controversial so far. Here we clarify this issue, using state-of-the-art X-ray absorption and X-ray emission spectroscopy in combination with band structure calculations. We verify that in the shells of all studied species manganese is incorporated as high-spin Mn2+, i.e. manganese always has the same valence as calcium. More importantly, the unique chemical sensitivity of valence-to-core X-ray emission enables us to show that manganese is always coordinated by a CO3-octahedron. This, firstly, provides firm experimental evidence for manganese being primarily located in the inorganic carbonate. Secondly, it indicates that the structure of the aragonitic host is locally altered such that manganese attains an octahedral, calcitic coordination. This modification at the atomic level enables the bivalve to accommodate many orders of magnitude more manganese in its aragonitic shell than found in any non-biogenic aragonite. This outstanding feature is most likely facilitated through the non-classical crystallization pathway of bivalve shells.

  18. Formation of single-crystalline aragonite tablets/films via an amorphous precursor.

    Science.gov (United States)

    Amos, Fairland F; Sharbaugh, Denise M; Talham, Daniel R; Gower, Laurie B; Fricke, Marc; Volkmer, Dirk

    2007-02-13

    Thin tablets and films of calcium carbonate have been grown at the air-water interface via an amorphous precursor route using soluble process-directing agents and a Langmuir monolayer based on resorcarene. By using appropriate concentrations of poly(acrylic acid-sodium salt) in combination with Mg2+ ion, an initially amorphous film is deposited on the monolayer template, which subsequently crystallizes into a mosaic film composed of a mixture of single-crystalline and spherulitic patches of calcite and aragonite. Of particular importance is the synthesis of single-crystalline "tablets" of aragonite (approximately 600 nm thick), because this phase generally forms needle-like polycrystalline aggregates when grown in vitro. To our knowledge, a tabular single-crystalline morphology of aragonite has only been observed in the nacreous layer of mollusk shells. Therefore, this in vitro system may serve as a useful model for examining mechanistic issues pertinent to biomineralization, such as the influence of organic templates on nucleation from an amorphous phase.

  19. 4.6 billion year old aragonite and its implications for understanding the geological record of Ca-carbonate

    OpenAIRE

    Lee, Martin R.; Lindgren, Paula

    2015-01-01

    Owing to its diagenetic instability, aragonite is rare in the geological record and almost entirely absent from pre-carboniferous sedimentary rocks. The former presence of this mineral in older deposits has to be inferred from petrographic, chemical or isotopic proxies. Crystals of aragonite that formed around 4563 million years ago occur in carbonaceous chondrite meteorites, showing that under certain conditions, the orthorhombic polymorph of Ca-carbonate can survive essentially indefinitely...

  20. Influences of organic matter and calcification rate on trace elements in aragonitic estuarine bivalve shells

    Science.gov (United States)

    Takesue, R.K.; Bacon, C.R.; Thompson, J.K.

    2008-01-01

    A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction and shell calcification rates. The average organic content of whole C. amurensis shells is 19%. After treating whole powdered shells with an oxidative cleaning procedure to remove organic matter, shells contained on average 33% less total Mg and 78% less total Mn. Within our analytical uncertainty, Sr and Ba contents were unchanged by the removal of organic matter. These results show that aragonitic C. amurensis shells have a large component of non-lattice-bound Mg and Mn that probably contribute to the dissimilarity of [M]/Ca profiles among five same-sized shells. Non-lattice-bound trace elements could complicate the development and application of geochemical proxy relationships in bivalve shells. Because B, Ba and Sr occur exclusively in shell aragonite, they are good candidates for external proxy relationships. [M]/Ca ratios were significantly different in prismatic and nacreous aragonite and in two valves of the same shell that had different crystal growth rates. Some part of these differences can be attributed to non-lattice-bound trace elements associated with the organic fraction. The differences in [M]/Ca ratios were also consistent with the calcification rate-dependent ion transport model developed by Carr?? et al. [Carr?? M., Bentaleb I

  1. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Science.gov (United States)

    Kimball, Justine; Eagle, Robert; Dunbar, Robert

    2016-12-01

    Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near-constant temperature, salinity, and pH and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate-related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and high-Mg calcitic gorgonian (Isididae and Coralliidae) deep-sea corals and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures, and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than high-Mg calcitic gorgonian corals and the two groups of coral produce statistically different relationships between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate clumped isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset

  2. Structural distortion of biogenic aragonite in strongly textured mollusc shell layers

    Energy Technology Data Exchange (ETDEWEB)

    Chateigner, D., E-mail: daniel.chateigner@ensicaen.f [CRISMAT-ENSICAEN, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Ouhenia, S. [CRISMAT-ENSICAEN, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Lab. De Physique, Faculte des Sciences Exactes, Bejaia 06000 (Algeria); Krauss, C. [CRISMAT-ENSICAEN, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Belkhir, M. [Lab. De Physique, Faculte des Sciences Exactes, Bejaia 06000 (Algeria); Morales, M. [CIMAP-ENSICAEN, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France)

    2010-02-15

    The stabilisation of strong textures in mollusc shells has for long been a strong drawback towards precise structural determinations of these natural biocomposites. We demonstrate here on several crossed lamellar and nacre layers from two gastropods (Charonia lampas lampas and Haliotis tuberculata tuberculata) and one bivalve (Pinctada maxima), that on real specimens (without grinding or specific preparation), the textural information can be used efficiently for precise structural determination of the biogenic aragonite. This is done through the combination of orientation distribution function and cyclic Rietveld refinements on several hundreds to thousands of diffractions diagrams.

  3. Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

    Energy Technology Data Exchange (ETDEWEB)

    Du Yang; Lian Fei [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Zhu Lingyan, E-mail: zhuly@nankai.edu.cn [Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, Tianjin Key Laboratory of Urban Ecology Environmental Remediation and Pollution Control, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

    2011-07-15

    The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb{sup 2+}, Cd{sup 2+} and Zn{sup 2+} from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbent's dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent. - Highlights: > Mollusk shells display high removal efficiency to heavy metals in contaminated water. > Surface precipitation leading to crystal growth takes place during the sorption. > Crystal structure similarity between precipitates and substrates affects the sorption. > pH, sorbent dosage and grain size of adsorbent affects the removal efficiency. > Organic matter in mollusk shells affects the removal efficiency to a less extent. - Mollusk shells display high sorption ability to heavy metals and crystal structure similarity between precipitates and substrates affects the sorption.

  4. The role of aragonite matrix surface chemistry on the chondrogenic differentiation of mesenchymal stem cells.

    Science.gov (United States)

    Gross-Aviv, Talia; Vago, Razi

    2009-02-01

    In the present research we study the effects of surface chemistry of an aragonite crystalline biomatrix on the chondrogenesis of mesenchymal stem cells (MSCs). An aragonite matrix obtained from the coral Porites lutea and a gold-coated P. lutea matrix were seeded with MSCs, with and without the addition of growth factors (GFs). Scanning electron microscopy, histochemical staining, immunofluorescence, biochemical analyses and quantitative polymerase chain reaction showed that the chemistry of the matrix influenced the differentiation process of the MSCs. The calcium carbonate composition of the coral promoted osteogenesis, while impeding cell-material contact (by gold coating) altered the differentiation lineage of MSCs towards chondrogenic fate. Supplementation of the culture medium with GFs intensified the influence of the surface composition on the differentiation of MSCs, and the synergistic effect of the biomatrix surface composition and the GFs induced chondrogenesis and facilitated maintenance of the chondrocyte phenotype. Therefore, we suggest that scaffolding material candidates for tissue engineering should be examined for their effects on the MSCs differentiation process and their effect on signal transduction events in the cells.

  5. From colloidal nanoparticles to a single crystal: new insights into the formation of nacre's aragonite tablets.

    Science.gov (United States)

    Zhang, Gangsheng; Xu, Jun

    2013-04-01

    Nacre has long served as a model for understanding the biomineralization mechanism and designing bio-inspired materials. However, its basic building blocks, the aragonite tablets, are still under debate in terms of their fine structure at the nanoscale and corresponding formation mechanism. Here, using a field emission scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM), and X-ray diffractometer, we comparatively investigate the immature and mature tablet from the green mussel's nacre. We find that: (1) the early immature tablet consists of closely-packed colloidal nanoparticles, which contain nanocrystals surrounded by the amorphous calcium carbonate (ACC) phase. Moreover, these nanocrystals are generally different in shape, size, and orientation; (2) the immature tablet can grow via oriented attachment besides via transformation of the ACC phase; and (3) with growth, the colloidal nanoparticles gradually increase in crystallinity and size until fully crystallized and fused together, leading to a mature tablet that is a monolithic single crystal of aragonite. Based on these findings, we propose a new model showing how the mature tablet evolves from the primary colloidal ACC nanoparticles. We expect this work will provide new insights into the formation of single crystal biominerals via the amorphous precursor route.

  6. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    Directory of Open Access Journals (Sweden)

    J. Kimball

    2015-12-01

    Full Text Available Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near constant temperature, salinity and pH, and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly-substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp. and calcitic gorgonian (Isididae and Coralliidae deep-sea corals, and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than calcitic gorgonian corals and the two groups of coral produce statistically different relationship between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate "clumped" isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset

  7. CaCO{sub 3}/Ca-P biphasic materials prepared by microwave processing of natural aragonite and calcite

    Energy Technology Data Exchange (ETDEWEB)

    Pena, J.; LeGeros, R.Z.; Rohanizadeh, R.; LeGeros, J.P. [New York Univ., NY (United States). Coll. of Dentistry

    2001-07-01

    The purpose of this study was to prepare CaCO{sub 3}/Ca-P biphasic or composite materials using microwave technology. Particles of coral (natural aragonite) and a porous limestone (natural calcite) were suspended in phosphate solutions of different pH and concentrations and heated for different periods (up to 5 hrs) using a domestic microwave. Parallel experiments were carried out using hydrolysis method. Higher extents of transformation were observed with microwave processed materials. Depending on the reaction pH and reaction period, partial transformation of aragonite (coral) or calcite (limestone) to acidic calcium (monetite) or basic (carbonatehydroxyapatite, CHA) calcium phosphates was achieved (orig.)

  8. Li/Mg in biogenic aragonite as a potential paleotemperature proxy

    Science.gov (United States)

    Marchitto, T.; Bryan, S.; Montagna, P.; McCulloch, M.

    2008-12-01

    Although planktic foraminiferal Mg/Ca has been widely applied as a paleotemperature proxy, benthic foraminiferal Mg/Ca has seen much more limited application. Recent benthic calibrations have shown that seawater saturation with respect to CaCO3 (ΔCO32-) is likely an important factor influencing the incorporation of Mg, thereby limiting the utility of Mg/Ca as a simple paleotemperature tool. We have shown (Bryan and Marchitto, Paleoceanography, 2008) that in the Florida Straits, benthic foraminiferal Mg/Li is better correlated to temperature than Mg/Ca is. We suggested that Mg and Li are influenced similarly by ΔCO32-, such that dividing Mg by Li largely corrects for this effect and isolates the temperature influence. The promise of this approach is most dramatic for the aragonitic foraminifer Hoeglundina elegans, in which the variance explained by temperature is only 49% for Mg/Ca but 90% for Mg/Li . Recent work on coral Mg and Li at fine-scale resolution (Montagna et al., Goldschmidt Conference, 2008) appears to tell a similar story. Li/Ca is inversely correlated to temperature in both the high-latitude zooxanthellate coral Cladocora caespitosa and the deep-water coral Lophelia pertusa, but each taxon exhibits a unique relationship. However the Li/Mg (or Mg/Li) relationship to temperature is indistinguishable between the two taxa, with a combined r2 of 0.96. The slope of this relationship is identical within one standard error of the H. elegans Li/Mg relationship, and the intercept is similar. We further explore the promise of this method by (1) measuring H. elegans Li/Mg in additional core tops from around the world ocean; (2) measuring H. elegans Li/Mg in Last Glacial Maximum sediments from the Florida Straits, where Mg-rich overgrowths appear to be a problem for calcitic benthic foraminifera; and (3) measuring Li/Mg in various aragonitic gastropods from Florida Straits core tops, to see if the temperature relationship can be generalized to other biogenic

  9. Climate and cave control on Pleistocene/Holocene calcite-to-aragonite transitions in speleothems from Morocco: Elemental and isotopic evidence

    Science.gov (United States)

    Wassenburg, Jasper A.; Immenhauser, Adrian; Richter, Detlev K.; Jochum, Klaus Peter; Fietzke, Jan; Deininger, Michael; Goos, Manuela; Scholz, Denis; Sabaoui, Abdellah

    2012-09-01

    The occurrence of aragonite in speleothems has commonly been related to high dripwater Mg/Ca ratios, because Mg is known to be a growth inhibitor for calcite. Laboratory aragonite precipitation experiments, however, suggested a more complex array of controlling factors. Here, we present data from Pleistocene to Holocene speleothems collected from both a dolostone and a limestone cave in northern Morocco. These stalagmites exhibit both lateral and stratigraphic calcite-to-aragonite transitions. Aragonite fabrics are well-preserved and represent primary features. In order to shed light on the factors that control alternating calcite and aragonite precipitation, elemental (Mg, Sr, Ba, U, P, Y, Pb, Al, Ti and Th) abundances were measured using LA-ICP-MS, and analysed with Principal Component Analysis. Samples were analyzed at 100-200 μm resolution across stratigraphic and lateral transitions. Carbon and oxygen isotope ratios were analysed at 100 μm resolution covering stratigraphic calcite-to-aragonite transitions. Results show that the precipitation of aragonite was driven by a decrease in effective rainfall, which enhanced prior calcite precipitation. Different geochemical patterns are observed between calcite and aragonite when comparing data from the Grotte de Piste and Grotte Prison de Chien. This may be explained by the increased dripwater Mg/Ca ratio and enhanced prior aragonite precipitation in the dolostone cave versus lower dripwater Mg/Ca ratio and prior calcite precipitation in the limestone cave. A full understanding for the presence of lateral calcite-to-aragonite transitions is not reached. Trace elemental analysis, however, does suggest that different crystallographic parameters (ionic radius, amount of crystal defect sites, adsorption potential) may have a direct effect on the incorporation of Sr, Mg, Ba, Al, Ti, Th and possibly Y and P.

  10. Synthesis, characterization, and cytocompatibility of potential cockle shell aragonite nanocrystals for osteoporosis therapy and hormonal delivery

    Directory of Open Access Journals (Sweden)

    Jaji AZ

    2017-01-01

    Full Text Available Alhaji Zubair Jaji,1,2 Md Zuki Bin Abu Bakar,1,3 Rozi Mahmud,4 Mohamad Yusof Loqman,5 Mohamad Noor Mohamad Hezmee,1 Tijani Isa,3 Fu Wenliang,3 Nahidah Ibrahim Hammadi1 1Department of Veterinary Pre-Clinical Science, Universiti Putra Malaysia, Serdang, Selangor, Malaysia; 2Department of Veterinary Anatomy, Faculty of Veterinary Medicine, University of Ilorin, Ilorin, Kwara, Nigeria; 3Molecular Biomedicine Laboratory, Institute of Bioscience, Universiti Putra Malaysia, Serdang, Selangor, Malaysia; 4Department of Imaging, Faculty of Medicine and Health Science, Universiti Putra Malaysia, Serdang, Selangor, Malaysia; 5Department of Companion Animal Medicine and Surgery, Universiti Putra Malaysia, Serdang, Selangor, Malaysia Abstract: Calcium carbonate is a porous inorganic nanomaterial with huge potential in biomedical applications and controlled drug delivery. This study aimed at evaluating the physicochemical properties and in vitro efficacy and safety of cockle shell aragonite calcium carbonate nanocrystals (ANC as a potential therapeutic and hormonal delivery vehicle for osteoporosis management. Free and human recombinant parathyroid hormone 1-34 (PTH 1-34-loaded cockle shell aragonite calcium carbonate nanocrystals (PTH-ANC were synthesized and evaluated using standard procedures. Transmission electron microscopy and field emission scanning electron microscopy results demonstrated highly homogenized spherical-shaped aragonite nanocrystals of 30±5 nm diameter. PTH-ANC had a zeta potential of −27.6 ± 8.9 mV. The encapsulation efficiency of the formulation was found to be directly proportional to the concentrations of the drug fed. The X-ray diffraction patterns revealed strong crystallizations with no positional change of peaks before and after PTH-ANC synthesis. Fourier transform infrared spectroscopy demonstrated no detectable interactions between micron-sized aragonite and surfactant at molecular level. PTH-ANC formulation was stabilized

  11. Heterogeneous growth of calcite at aragonite {001}- and vaterite {001}-melt interfaces: A molecular dynamics simulation study

    Science.gov (United States)

    Nada, Hiroki; Nishimura, Tatsuya; Sakamoto, Takeshi; Kato, Takashi

    2016-09-01

    Crystal growth at the interface between a calcium carbonate (CaCO3) crystal and its melt at a high temperature of 1500 K is investigated by means of a molecular dynamics simulation. The simulation is performed for the interfaces of a calcite {104} plane, aragonite {001}, {100}, and {010} planes, and vaterite {001}, {110}, and {100} planes. The growth from a pure melt and that from a melt containing Mg2+ are examined. Calcite growth occurs on the calcite {104} plane, aragonite growth occurs on the aragonite {100}, and {010} planes, and vaterite growth occurs on the vaterite {110} and {100} planes. However, the heterogeneous growth of calcite occurs on the {001} plane of aragonite and vaterite, irrespective of the presence of Mg2+. The results advance our understanding of geological processes that occur at high temperature, such as the formation of CaCO3 crystals from carbonatite magma and the formation of marble. Moreover, the results provide useful information for the control of CaCO3 crystal formation in material design.

  12. Relationship between Late Pleistocene sea-level variations, carbonate platform morphology and aragonite production (Maldives, Indian Ocean)

    DEFF Research Database (Denmark)

    Paul, A.; Reijmer, J.J.G.; Fürstenau, J.

    2012-01-01

    of the atolls of the Maldives carbonate platform. Platform flooding events were characterized by strongly increased deposition of aragonite and mud within the Inner Sea of the Maldives. Exposure events, in contrast, can be recognized by rapid decreases in the values of both proxy records. The results show...

  13. Altervalent substitution of sodium for calcium in biogenic calcite and aragonite

    Science.gov (United States)

    Yoshimura, Toshihiro; Tamenori, Yusuke; Suzuki, Atsushi; Kawahata, Hodaka; Iwasaki, Nozomu; Hasegawa, Hiroshi; Nguyen, Luan T.; Kuroyanagi, Azumi; Yamazaki, Toshitsugu; Kuroda, Junichiro; Ohkouchi, Naohiko

    2017-04-01

    Sodium concentrations in biogenic CaCO3 are several thousands of parts per million, and, on a molar basis, Na is among the most abundant constituent minor element in these carbonates. Nevertheless, the chemical form of Na in CaCO3 is not well constrained. We used synchrotron X-ray spectroscopy to identify the dominant molecular host sites for Na in biogenic calcite and aragonite precipitated by corals, bivalves, and foraminifera. We also used the K-edge X-ray absorption near-edge structure to investigate the chemical environment of Na in biogenic calcium carbonates and identify the altervalent substitution of Na into Ca sites in the lattice structures of calcite and aragonite. Minor cation and anion concentrations in biogenic CaCO3 suggest that the principal substitution mechanism involves charge compensation through the creation of CO32- vacancies. The mostly homogeneous Na concentrations in the skeletal microstructures of the various biota we examined indicate that environmental and biological controls, such as temperature, skeletal microstructure, and calcification rates, have only minor influences on skeletal Na concentrations. A decrease of Na:Ca ratios with increasing age of foraminiferal shells picked from a Quaternary sediment core, indicates progressive release of Na, which suggests that structurally-substituted Na in biogenic CaCO3 is readily leached during burial diagenesis. Whereas the sediment that undergo diagenesis release some Na back to the water column, sodium co-precipitation in biogenic CaCO3 serves as a potential sink of Na for the ocean.

  14. First-principles study of boron speciation in calcite and aragonite

    Science.gov (United States)

    Balan, Etienne; Pietrucci, Fabio; Gervais, Christel; Blanchard, Marc; Schott, Jacques; Gaillardet, Jérome

    2016-11-01

    Despite the importance of boron as a proxy of past ocean pH, the crystal-chemical factors controlling its incorporation in the structure of calcium carbonates are still poorly understood. This is partly linked to an imperfect knowledge of the coordination, protonation state and local environment of boron species in these minerals. In the present study, we use first-principles quantum mechanical tools to model selected trigonal and tetragonal boron species in calcite and aragonite. The stable geometry of the models is obtained from standard energy minimization schemes or using a more advanced metadynamics exploration of their configurational space. The computation of 11B NMR chemical shifts and quadrupolar coupling parameters enables a straightforward comparison of the models to existing experimental NMR data. The results show that B in calcium carbonates does occur as structural species substituted for CO32- anions. The B speciation depends on the polymorph considered. In calcite, structural boron is present as partially deprotonated trigonal BO2(OH)2- species coexisting with a fraction of substituted B(OH)4- groups. In aragonite, the B(OH)4- substitution for CO32- anions is dominant. Different species, including entrapped B(OH)3 molecules and substituted BO33- groups also occur in biogenic samples. The diversity of B speciation reflects a diversity of B incorporation mechanisms and sheds light on previous studies confronting B isotopic composition determination with NMR observations. The mechanisms of boron incorporation in calcium carbonates are probably more complex than usually assumed in the literature using boron isotopes as a proxy of paleo-atmospheric CO2 reconstructions. Although not invalidating the empirical paleo-pH proxy, these results call for a better understanding of the fundamental mechanisms of boron incorporation in carbonates.

  15. Development of nanoantibiotic delivery system using cockle shell-derived aragonite nanoparticles for treatment of osteomyelitis

    Directory of Open Access Journals (Sweden)

    Saidykhan L

    2016-02-01

    Full Text Available Lamin Saidykhan,1 Md Zuki Bin Abu Bakar,2 Yaya Rukayadi,1,3 Aminu Umar Kura,4 Saiful Yazan Latifah5 1Microbiology Unit, Laboratory of Natural Products, Institute of Bioscience, 2Laboratory of Anatomy and Histology, Department of Veterinary Preclinical Sciences, Faculty of Veterinary Medicine, 3Department of Food Science, Faculty of Food Science and Technology, 4Vaccine and Immunotherapeutics Laboratory Unit, Institute of Bioscience, 5Department of Biomedical Science, Faculty of Medicine and Health Sciences, Universiti Putra Malaysia, Serdang, Selangor Darul Ehsan, Malaysia Abstract: A local antibiotic delivery system (LADS with biodegradable drug vehicles is recognized as the most effective therapeutic approach for the treatment of osteomyelitis. However, the design of a biodegradable LADS with high therapeutic efficacy is too costly and demanding. In this research, a low-cost, facile method was used to design vancomycin-loaded aragonite nanoparticles (VANPs with the aim of understanding its potency in developing a nanoantibiotic bone implant for the treatment of osteomyelitis. The aragonite nanoparticles (ANPs were synthesized from cockle shells by a hydrothermal approach using a zwitterionic surfactant. VANPs were prepared using antibiotic ratios of several nanoparticles, and the formulation (1:4 with the highest drug-loading efficiency (54.05% was used for physicochemical, in vitro drug release, and biological evaluation. Physiochemical characterization of VANP was performed by using transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction, and Zetasizer. No significant differences were observed between VANP and ANP in terms of size and morphology as both samples were cubic shaped with sizes of approximately 35 nm. The Fourier transform infrared spectroscopy of VANP indicated a weak noncovalent interaction between ANP and vancomycin, while the zeta potential values were slightly increased from -19

  16. Large-Scale Growth of Tubular Aragonite Whiskers through a MgCl2-Assisted Hydrothermal Process

    Directory of Open Access Journals (Sweden)

    Changyin Dong

    2011-08-01

    Full Text Available In this paper, we have developed a facile MgCl2-assissted hydrothermal synthesis route to grow tubular aragonite whiskers on a large scale. The products have been characterized by powder X-ray diffraction (XRD, optical microscopy, and scanning electronic microscopy (SEM. The results show the as-grown product is pure tubular aragonite crystalline whiskers with a diameter of 5–10 mm and a length of 100–200 mm, respectively. The concentration of Mg2+ plays an important role in determining the quality and purity of the products. Furthermore, the method can be extended to fabricate CaSO4 fibers. The high quality of the product and the mild conditions used mean that the present route has good prospects for the growth of inorganic crystalline whiskers.

  17. Aragonite, breunnerite, calcite and dolomite in the CM carbonaceous chondrites: High fidelity recorders of progressive parent body aqueous alteration

    OpenAIRE

    Lee, Martin R.; Lindgren, Paula; Sofe, Mahmood R.

    2014-01-01

    Carbonate minerals in CM carbonaceous chondrite meteorites, along with the silicates and sulphides with which they are intergrown, provide a detailed record of the nature and evolution of parent body porosity and permeability, and the chemical composition, temperature and longevity of aqueous solutions. Fourteen meteorites were studied that range in petrologic subtype from mildly aqueously altered CM2.5 to completely hydrated CM2.0. All of them contain calcite, whereas aragonite occurs only i...

  18. Baseline monitoring of the western Arctic Ocean estimates 20% of Canadian basin surface waters are undersaturated with respect to aragonite.

    Directory of Open Access Journals (Sweden)

    Lisa L Robbins

    Full Text Available Marine surface waters are being acidified due to uptake of anthropogenic carbon dioxide, resulting in surface ocean areas of undersaturation with respect to carbonate minerals, including aragonite. In the Arctic Ocean, acidification is expected to occur at an accelerated rate with respect to the global oceans, but a paucity of baseline data has limited our understanding of the extent of Arctic undersaturation and of regional variations in rates and causes. The lack of data has also hindered refinement of models aimed at projecting future trends of ocean acidification. Here, based on more than 34,000 data records collected in 2010 and 2011, we establish a baseline of inorganic carbon data (pH, total alkalinity, dissolved inorganic carbon, partial pressure of carbon dioxide, and aragonite saturation index for the western Arctic Ocean. This data set documents aragonite undersaturation in ≈ 20% of the surface waters of the combined Canada and Makarov basins, an area characterized by recent acceleration of sea ice loss. Conservative tracer studies using stable oxygen isotopic data from 307 sites show that while the entire surface of this area receives abundant freshwater from meteoric sources, freshwater from sea ice melt is most closely linked to the areas of carbonate mineral undersaturation. These data link the Arctic Ocean's largest area of aragonite undersaturation to sea ice melt and atmospheric CO2 absorption in areas of low buffering capacity. Some relatively supersaturated areas can be linked to localized biological activity. Collectively, these observations can be used to project trends of ocean acidification in higher latitude marine surface waters where inorganic carbon chemistry is largely influenced by sea ice meltwater.

  19. Baseline monitoring of the western Arctic Ocean estimates 20% of Canadian basin surface waters are undersaturated with respect to aragonite.

    Science.gov (United States)

    Robbins, Lisa L; Wynn, Jonathan G; Lisle, John T; Yates, Kimberly K; Knorr, Paul O; Byrne, Robert H; Liu, Xuewu; Patsavas, Mark C; Azetsu-Scott, Kumiko; Takahashi, Taro

    2013-01-01

    Marine surface waters are being acidified due to uptake of anthropogenic carbon dioxide, resulting in surface ocean areas of undersaturation with respect to carbonate minerals, including aragonite. In the Arctic Ocean, acidification is expected to occur at an accelerated rate with respect to the global oceans, but a paucity of baseline data has limited our understanding of the extent of Arctic undersaturation and of regional variations in rates and causes. The lack of data has also hindered refinement of models aimed at projecting future trends of ocean acidification. Here, based on more than 34,000 data records collected in 2010 and 2011, we establish a baseline of inorganic carbon data (pH, total alkalinity, dissolved inorganic carbon, partial pressure of carbon dioxide, and aragonite saturation index) for the western Arctic Ocean. This data set documents aragonite undersaturation in ≈ 20% of the surface waters of the combined Canada and Makarov basins, an area characterized by recent acceleration of sea ice loss. Conservative tracer studies using stable oxygen isotopic data from 307 sites show that while the entire surface of this area receives abundant freshwater from meteoric sources, freshwater from sea ice melt is most closely linked to the areas of carbonate mineral undersaturation. These data link the Arctic Ocean's largest area of aragonite undersaturation to sea ice melt and atmospheric CO2 absorption in areas of low buffering capacity. Some relatively supersaturated areas can be linked to localized biological activity. Collectively, these observations can be used to project trends of ocean acidification in higher latitude marine surface waters where inorganic carbon chemistry is largely influenced by sea ice meltwater.

  20. Proteomic and profile analysis of the proteins laced with aragonite and vaterite in the freshwater mussel Hyriopsis cumingii shell biominerals.

    Science.gov (United States)

    Berland, Sophie; Ma, Yufei; Marie, Arul; Andrieu, Jean-Pierre; Bedouet, Laurent; Feng, Qingling

    2013-10-01

    Hyriopsis cumingii (Lea, Unionidae), a freshwater bivalve species widely distributed in China and commercially exploited for freshwater pearl production, was chosen as the reference model to investigate the protein signature in the organic scaffold matching calcium carbonate crystallization mode. This study takes advantage of different calcium carbonate habits production by the organism: aragonite in shell and pearl and vaterite in alternative pearl formation. Amino acid global composition and proteomics analysis have been undertaken to study the amino acid imbalance with respect to biominerals and microstructures. Forty peptides sequences were obtained by proteomics, of which ten are shared by all the different samples, nine are laced with aragonite; another nine with vaterite and twelve are related to pearls. Bioinformatics analysis allowed the peptides to be matched to the deduced protein sequences from EST databases and allowed functional assignment (e.g. scaffolding, strain strength, chitin binding or carbonic anhydrase function) to the proteins found in the different materials. Such panel of motifs tailored in vaterite and aragonite habits produced in a freshwater mollusk gives food for thought about organic control of the biomineralization processes.

  1. The Raman spectrum of CaCO{sub 3} polymorphs calcite and aragonite: A combined experimental and computational study

    Energy Technology Data Exchange (ETDEWEB)

    De La Pierre, Marco, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; Maschio, Lorenzo; Orlando, Roberto; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS (Nanostructured Interfaces and Surfaces) Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Carteret, Cédric, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; André, Erwan [Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME), UMR 7564, Université de Lorraine-CNRS, 405 rue de Vandoeuvre, 54601 Villers-lès-Nancy (France)

    2014-04-28

    Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm{sup −1} for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to {sup 18}O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra.

  2. A novel acidic matrix protein, PfN44, stabilizes magnesium calcite to inhibit the crystallization of aragonite.

    Science.gov (United States)

    Pan, Cong; Fang, Dong; Xu, Guangrui; Liang, Jian; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2014-01-31

    Magnesium is widely used to control calcium carbonate deposition in the shell of pearl oysters. Matrix proteins in the shell are responsible for nucleation and growth of calcium carbonate crystals. However, there is no direct evidence supporting a connection between matrix proteins and magnesium. Here, we identified a novel acidic matrix protein named PfN44 that affected aragonite formation in the shell of the pearl oyster Pinctada fucata. Using immunogold labeling assays, we found PfN44 in both the nacreous and prismatic layers. In shell repair, PfN44 was repressed, whereas other matrix proteins were up-regulated. Disturbing the function of PfN44 by RNAi led to the deposition of porous nacreous tablets with overgrowth of crystals in the nacreous layer. By in vitro circular dichroism spectra and fluorescence quenching, we found that PfN44 bound to both calcium and magnesium with a stronger affinity for magnesium. During in vitro calcium carbonate crystallization and calcification of amorphous calcium carbonate, PfN44 regulated the magnesium content of crystalline carbonate polymorphs and stabilized magnesium calcite to inhibit aragonite deposition. Taken together, our results suggested that by stabilizing magnesium calcite to inhibit aragonite deposition, PfN44 participated in P. fucata shell formation. These observations extend our understanding of the connections between matrix proteins and magnesium.

  3. Aragonite infill in overgrown conceptacles of coralline Lithothamnion spp. (Hapalidiaceae, Hapalidiales, Rhodophyta): new insights in biomineralization and phylomineralogy.

    Science.gov (United States)

    Krayesky-Self, Sherry; Richards, Joseph L; Rahmatian, Mansour; Fredericq, Suzanne

    2016-04-01

    New empirical and quantitative data in the study of calcium carbonate biomineralization and an expanded coralline psbA framework for phylomineralogy are provided for crustose coralline red algae. Scanning electron microscopy (SEM) and energy dispersive spectrometry (SEM-EDS) pinpointed the exact location of calcium carbonate crystals within overgrown reproductive conceptacles in rhodolith-forming Lithothamnion species from the Gulf of Mexico and Pacific Panama. SEM-EDS and X-ray diffraction (XRD) analysis confirmed the elemental composition of these calcium carbonate crystals to be aragonite. After spore release, reproductive conceptacles apparently became overgrown by new vegetative growth, a strategy that may aid in sealing the empty conceptacle chamber, hence influencing the chemistry of the microenvironment and in turn promoting aragonite crystal growth. The possible relevance of various types of calcium carbonate polymorphs present in the complex internal structure and skeleton of crustose corallines is discussed. This is the first study to link SEM, SEM-EDS, XRD, Microtomography and X-ray microscopy data of aragonite infill in coralline algae with phylomineralogy. The study contributes to the growing body of literature characterizing and speculating about how the relative abundances of carbonate biominerals in corallines may vary in response to changes in atmospheric pCO2 , ocean acidification, and global warming.

  4. Variations in Cenozoic seawater uranium reconstructed from well preserved aragonitic fossil corals

    Science.gov (United States)

    Gothmann, A. O.; Higgins, J. A.; Bender, M. L.; Stolarski, J.; Adkins, J. F.; McKeon, R. E.; Farley, K. A.; Wang, X.; Planavsky, N.

    2015-12-01

    U/Ca ratios were measured in a subset (n ≈ 30) of well preserved scleractinian fossil corals previously described by Gothmann et al. (2015) in order to investigate Cenozoic changes in seawater [U]. He/U dating studies and measurements of 234U/238U and δ238/235U provide constraints on fossil coral U preservation. He/U ages also demonstrate the ability of well preserved coral aragonite to retain most of its radiogenic He over million year timescales. We find that fossil coral U/Ca has increased by a factor of ~4 between the Early Cenozoic and today. This number is calculated from the change in seawater [Ca2+] implied by brine inclusions and other proxies, and the assumption that the U/Ca in shallow water corals equals the seawater ratio. The change cannot be attributed to a dependence of coral U uptake on seawater pH or [CO32-] (e.g., Inoue et al., 2011), which would lead to a decrease in U/Ca going forward in time. Instead, we suggest that seawater [U] has increased since the Early Cenozoic. Possible explanations for the inferred change include: (1) a small decrease in uranium uptake in suboxic and anoxic sediments over the Cenozoic, (2) a decrease in the rate of low-temperature hydrothermal alteration, and associated U uptake, over the Cenozoic, and (3) a decrease in U removal from seawater resulting from an increase in UO2-CO3 complexation, as originally suggested by Broecker (1971). References: Broecker, W. S. (1971) A Kinetic Model for the Chemical Composition of Sea Water. Quaternary Research, 1, 188-207. Gothmann, A.M., Stolarski, J., Adkins, J.F., Dennis, K.J., Schrag, D.P., Schoene, B., Bender, M.L. (2015) Fossil corals as an archive of secular variations in seawater chemistry. Geochimica et Cosmochimica Acta, 160, 188-208. Inoue, M., Suwa, R., Suzuki, A., Sakai, K., and Kawahata, H., (2011) Effects of seawater pH on growth and skeletal U/Ca ratios of Acropora digitifera coral polyps. Geophysical Research Letters 38, 12801-12804.

  5. Sr/Ca Sensitivity to Aragonite Saturation in Cultured Coral Measured by NanoSIMS (Invited)

    Science.gov (United States)

    Gagnon, A. C.; Adkins, J. F.; Erez, J.

    2010-12-01

    NanoSIMS was used to identify and com¬positionally characterize the micron scale region of skeletal growth resulting from a short coral culture experiment. Using this technique we quantify the sensitivity of Sr/Ca, a proxy for temperature, to aragonite saturation (Ω), a parameter that varied in the past ocean and is predicted to change with continued ocean acidification. Five adult branches of the surface coral Stylophora sp. were all grown at 25 °C but at different and near constant carbonate ion concentrations, from 180 to 400 µM (pH of 7.9 to 8.5), yielding a two-fold range in calcification rate. Despite the range of Ωs and calcification rates, the average Sr/Ca of nanoSIMS spot measurements corresponding to each condition are within 1.2% (2σ std. dev. of the 5 means). Furthermore, the average Sr/Ca measured in this study agrees with two previous coral culture experiments conducted at the same temperature but where Ω was not controlled. These results suggest carbonate ion concentration is not a complicating factor to Sr/Ca paleothermometry over this range of Ω. Within the framework of a closed system (Rayleigh) model for biomineralization, similar Sr/Ca ratios suggest similar amounts of Rayleigh fractionation. Combined with existing data for low Ω conditions, the extent of Rayleigh fractionation is used to test alternative biomineralization models governing the acid-base chemistry of the calcifying fluid. Assuming that coral use alkalinity pumping to increase local calcifying fluid carbonate ion concentration, we try to understand what controls this pumping. Under most conditions, Sr/Ca ratios are consistent with a scenario where calcifying fluid alkalinity increases until reaching a target pH. However, under conditions of very low seawater Ω, coral cannot pump enough alkalinity to reach the target pH. Below this threshold value, between approximately 1<Ω<2.4, coral pump a maximal and finite amount of alkalinity. The interaction between these rules

  6. Application of aragonite shells for the removal of aqueous metals in polluted soils and wastewaters.

    Science.gov (United States)

    Bucca, M.; Köhler, S. J.; Dietzel, M.

    2009-04-01

    In the present study the use of coupled precipitation/dissolution processes for metal (Me) removal from polluted soils and waters by biogenic carbonate (CaCO3) shell surfaces is proposed, according to the following overall reaction: CaCO3 + Me2+ = MeCO3 + Ca2+ This reaction has been investigated at fixed experimental conditions using synthetic model systems consisting in columns, batch, and reactors (e.g. lead, zinc, and cadmium artificial solutions mixed with aragonite shells) that allowed quantifying the kinetics of the process of metal carbonate formation. The above mentioned process has the potential of being used in three different areas of water treatment: a) use of shells as a cheap and effective geologic barrier for contaminated ground or surface waters, b) use as a material in filter beds or fluidized bed for selective cleaning of waste water with the potential of partial metal recovery and c) use as seed crystals during the elimination of metals through precipitation with soda (Na2CO3). Acidic wastewaters containing several pollutants, including heavy and trace metals, are created during production of pesticides, paper, lubricating oil, batteries, acid/alkali, or in ship repair manufacturing, mines drainage systems, metalworking and metal plating industries. Biogenic shells are a waste product in many coastal countries and may thus be more favorable than other solid phases such as clays or zeolithes from an economic viewpoint. Our metal elimination study aims at setting up a low-cost effective elimination system for various types of metal rich waste waters. A number of experimental techniques such as batch, column and flow through reactors were used to optimize the metal removal efficiency in both synthetic and waste waters from the metal finishing industry. Solid liquid ratio, initial and final pH, metal concentration and combination of metals have been varied. Measurements of pH, metal concentration, conductivity and alkalinity were recorded over the

  7. Elemental and Isotopic Incorporation into the Aragonitic Shells of Arctica Islandica: Insights from Temperature Controlled Experiments

    Science.gov (United States)

    Wanamaker, A. D.; Gillikin, D. P.

    2014-12-01

    The long-lived ocean quahog, Arctica islandica, is a fairly well developed and tested marine proxy archive, however, the utility of elemental ratios in A. islandica shell material as environmental proxies remains questionable. To further evaluate the influence of seawater temperature on elemental and isotopic incorporation during biomineralization, A. islandica shells were grown at constant temperatures under two regimes during a 16-week period from March 27 to July 21, 2011. Seawater from the Darling Marine Center in Walpole, Maine was pumped into temperature and flow controlled tanks that were exposed to ambient food and salinity conditions. A total of 20 individual juvenile clams with an average shell height of 36 mm were stained with calcein (a commonly used biomarker) and cultured at 10.3 ± 0.3 °C for six weeks. After this, shell heights were measured and the clams were again stained with calcein and cultured at 15.0 ± 0.4 °C for an additional 9.5 weeks. The average shell growth during the first phase of the experiment was 2.4 mm with a linear extension rate of 0.40 mm/week. The average shell growth during the second phase of the experiment was 3.2 mm with an extension rate of 0.34 mm/week. Average salinity values were 30.2 ± 0.7 and 30.7 ±0.7 in the first and second phases of the experiment, respectively. Oxygen isotopes from the cultured seawater were collected throughout the experiment and provide the basis for establishing if shells grew in oxygen isotopic equilibrium. Elemental ratios (primarily Ba/Ca, Mg/Ca, Sr/Ca) in the aragonitic shells were determined via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), while stable oxygen and carbon isotope ratios were measured using continuous flow isotope ratio mass spectrometry. Continuous sampling within and across the temperature conditions (from 10 °C to 15 °C) coupled with the calcein markings provides the ability to place each sample into a precise temporal framework. The

  8. Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

    Science.gov (United States)

    Plummer, L. N.; Busenberg, E.

    1987-06-01

    Dissolution of synthetic strontianite-aragonite solid solutions was followed analytically to stoichiometric saturation using large solid to solution ratios in CO 2-H 2O solution at 25 and 76°C. The compositional dependence of the equilibrium constant was calculated from the composition of saturated (stoichiometric) solutions and used to calculate the activities and activity coefficients of CaCO 3 and SrCO 3 in the solid Ca (1- x) Sr xCO 3 at 25 and 76°C. The results show that the solid-solution is not regular but unsymmetrical. The excess free energy of mixing is closely modeled for all compositions by the relation G E = x(1-x)[A 0 + A 1(2x-1)] where A0 is 8.49 ± 0.30 and 7.71 ± 0.20 KJ/mole and A1 is -4.51 ± 0.20 and -3.36 ± 0.40 KJ/mole at 25 and 76°C, respectively. The equilibrium constant is denned as a function of the SrCO 3 mole fraction, x, by the relation ln K (x) = x(1-x)/RT[A 0 + A 1(2x - 1)] + (2 - x) ln (K A(1 - x)) + x ln (K sx) where R is the gas constant, T is in Kelvins and KA and KS are the aragonite and strontianite equilibrium constants. The experimental results indicate the Henry's law coefficients of SrCO 3 in aragonites containing 0 to 6 mole percent SrCO 3 are approximately 91± 8 and 23 ± 1 at 25 and 76°C, respectively and for strontianites the Henry's law coefficients and applicable compositional ranges are approximately 7.3 ± 0.3 (0.84 ≤ x ≤ 1.00) and 3.3 ± 0.5 (0.50 ≤ x ≤ 1.00) at 25 and 76°C, respectively. Substitution of small amounts of Sr in aragonite and Ca in strontianite initially increases the stability of the solid. The most stable aragonites and strontianites contain 0.58 ± 0.03 and 12.5 ± 1.1 mole percent SrCO 3 and CaCO 3 at 25°C and 3.1 ± 0.3 and 17.2 ± 1.1 mole percent SrCO 3 and CaCO 3 at 76°C, respectively. The spinode occurs over the regions 0.065 ± 0.001 ≤ x ≤ 0.620 ± 0.014 at 25°C and 0.103 ± 0.007 ≤ x ≤ 0.585 ± 0.019 at 76°C where all compositions are unstable. A miscibility gap

  9. Aragonite crystals grown on bones by reaction of CO2 with nanostructured Ca(OH)2 in the presence of collagen. Implications in archaeology and paleontology.

    Science.gov (United States)

    Natali, Irene; Tempesti, Paolo; Carretti, Emiliano; Potenza, Mariangela; Sansoni, Stefania; Baglioni, Piero; Dei, Luigi

    2014-01-21

    The loss of mechanical properties affecting archeological or paleontological bones is often caused by demineralization processes that are similar to those driving the mechanisms leading to osteoporosis. One simple way to harden and to strengthen demineralized bone remains could be the in situ growth of CaCO3 crystals in the aragonite polymorph - metastable at atmospheric pressure -which is known to have very strong mechanical strength in comparison with the stable calcite. In the present study the controlled growth of aragonite crystals was achieved by reaction between atmospheric CO2 and calcium hydroxide nanoparticles in the presence of collagen within the deteriorated bones. In a few days the carbonation of Ca(OH)2 particles led to a mixture of calcite and aragonite, increasing the strength of the mineral network of the bone. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS) and Fourier transform infrared (FT-IR) spectrometry showed that aragonite crystallization was achieved. The effect of the aragonite crystal formation on the mechanical properties of the deteriorated bones was investigated by means of X-rays microtomography, helium porosimetry, atomic force microscopy (AFM), and Vickers microhardness techniques. All these data enabled to conclude that the strength of the bones increased of a factor of 50-70% with respect to the untreated bone. These results could have immediate impact for preserving archeological and paleontological bone remains.

  10. Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C

    Science.gov (United States)

    Plummer, L.N.; Busenberg, E.

    1987-01-01

    Dissolution of synthetic strontianite-aragonite solid solutions was followed analytically to stoichiometric saturation using large solid to solution ratios in CO2-H2O solution at 25 and 76°C. The compositional dependence of the equilibrium constant was calculated from the composition of saturated (stoichiometric) solutions and used to calculate the activities and activity coefficients of CaCO3 and SrCO3 in the solid Ca(1−x)SrxCO3 at 25 and 76°C. The results show that the solid-solution is not regular but unsymmetrical. The excess free energy of mixing is closely modeled for all compositions by the relation where A0 is 8.49 ± 0.30 and 7.71 ± 0.20 KJ/mole and A1 is −4.51 ± 0.20 and −3.36 ± 0.40 KJ/mole at 25 and 76°C, respectively. The equilibrium constant is denned as a function of the SrCO3 mole fraction, x, by the relation where R is the gas constant, T is in Kelvins and KA and KS are the aragonite and strontianite equilibrium constants.

  11. Early and late lithification of aragonitic bivalve beds in the Purbeck Formation (upper jurassic-lower cretaceous) of Southern England

    Science.gov (United States)

    El-Shahat, Adam; West, Ian

    1983-05-01

    Beds of euryhaline bivalves alternating with shales constitute much of the middle Purbeck Formation. They originated on "tidal" flats at the western margin of an extensive brackish lagoon. When these shell beds are thin and enclosed in shale they are often still preserved as aragonite and are associated with "beef", fibrous calcite formed during compaction. In most cases, however, the shell debris has been converted by diagenesis into calcitic biosparrudite limestones. A compacted type has been lithified at a late stage, after deep burial. In this, pyrite is abundant and most of the shell aragonite has been replaced neomorphically by ferroan pseudopleochroic calcite. A contrasting uncompacted type of biosparrudite is characterised by bivalve fragments with micrite envelopes. Shells and former pores are occupied by non-ferroan sparry calcite cement, and there is little pyrite. These limestones frequently contain dinosaur footprints and originated in "supratidal" environments where they were cemented early, mainly in meteoric water. Once lithified they were unaffected by compaction. This uncompacted type indicates phases of mild uplift or halts in subsidence. These shell-bed lithologies, and also intermediate types described here, will probably be recognised in other lagoonal formations.

  12. Characteristics of the Aragonitic Layer in Adult Oyster Shells, Crassostrea gigas: Structural Study of Myostracum including the Adductor Muscle Scar

    Directory of Open Access Journals (Sweden)

    Seung-Woo Lee

    2011-01-01

    Full Text Available Myostracum, which is connected from the umbo to the edge of a scar, is not a single layer composed of prismatic layers, but a hierarchically complex multilayered shape composed of minerals and an organic matrix. Through the analysis of the secondary structure, the results revealed that a β-antiparallel structure was predominant in the mineral phase interface between the myostracum (aragonite and bottom folia (calcite. After the complete decalcification and deproteinization, the membrane obtained from the interface between the myostracum buried in upper folia, and the bottom folia was identified as chitin. The transitional zone in the interface between the adductor muscle scar and folia are verified. The myostracum disappeared at the edge of the scar of the posterior side. From this study, the entire structure of the myostracum from the adult oyster shell of Crassostrea gigas could be proposed.

  13. The extent of ocean acidification on aragonite saturation state along the Washington-Oregon continental shelf margin in late summer 2012

    Science.gov (United States)

    Feely, R. A.; Alin, S. R.; Hales, B. R.; Juranek, L.; Greeley, D.

    2012-12-01

    The Washington-Oregon continental shelf region is exposed to conditions of low aragonite saturation state during the late spring/early summer upwelling season. However, the extent of its evolution in late summer/early fall has been largely unknown. Along this continental margin, ocean acidification, upwelling, biological productivity, and respiration processes in subsurface waters are major contributors to the variability in dissolved inorganic carbon (DIC), pH and aragonite saturation state. The persistence of water with aragonite saturation state Washington and Oregon has been previously identified and could have profound ecological consequences for benthic and pelagic calcifying organisms such as mussels, oysters, abalone, echinoderms, and pteropods. In the late summer of 2012 we studied the extent of acidification conditions employing shipboard cruises and profiling gliders. We conducted several large-scale chemical and hydrographic surveys of the region in order to better understand the interrelationships between these natural and human-induced processes and their effects on aragonite saturation. We will compare the results of these new surveys with our previous work in 2011 and 2007.

  14. Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates - Relation between textural control on effective element fluxes and resulting carbonate phase

    Science.gov (United States)

    Jonas, Laura; Müller, Thomas; Dohmen, Ralf; Immenhauser, Adrian; Putlitz, Benita

    2017-01-01

    Dolomitization, i.e., the secondary replacement of calcite or aragonite (CaCO3) by dolomite (CaMg[CO3]2), is one of the most volumetrically important carbonate diagenetic processes. It occurs under near surface and shallow burial conditions and can significantly modify rock properties through changes in porosity and permeability. Dolomitization fronts are directly coupled to fluid pathways, which may be related to the initial porosity/permeability of the precursor limestone, an existing fault network or secondary porosity/permeability created through the replacement reaction. In this study, the textural control on the replacement of biogenic and abiogenic aragonite by Mg-carbonates, that are typical precursor phases in the dolomitization process, was experimentally studied under hydrothermal conditions. Aragonite samples with different textural and microstructural properties exhibiting a compact (inorganic aragonite single crystal), an intermediate (bivalve shell of Arctica islandica) and open porous structure (skeleton of coral Porites sp.) were reacted with a solution of 0.9 M MgCl2 and 0.015 M SrCl2 at 200 °C. The replacement of aragonite by a Ca-bearing magnesite and a Mg-Ca carbonate of non-stoichiometric dolomitic composition takes place via a dissolution-precipitation process and leads to the formation of a porous reaction front that progressively replaces the aragonite precursor. The reaction leads to the development of porosity within the reaction front and distinctive microstructures such as gaps and cavities at the reaction interface. The newly formed reaction rim consists of chemically distinct phases separated by sharp boundaries. It was found that the number of phases and their chemical variation decreases with increasing initial porosity and reactive surface area. This observation is explained by variations in effective element fluxes that result in differential chemical gradients in the fluid within the pore space of the reaction rim. Observed

  15. Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

    Science.gov (United States)

    Jones, Brian; Peng, Xiaotong

    2016-11-01

    Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

  16. P-V-T equation of state of CaCO3 aragonite to 29 GPa and 1673 K: In situ X-ray diffraction study

    Science.gov (United States)

    Litasov, Konstantin D.; Shatskiy, Anton; Gavryushkin, Pavel N.; Bekhtenova, Altyna E.; Dorogokupets, Peter I.; Danilov, Boris S.; Higo, Yuji; Akilbekov, Abdirash T.; Inerbaev, Talgat M.

    2017-04-01

    Pressure-volume-temperature relations have been measured to 29 GPa and 1673 K for CaCO3 aragonite using synchrotron X-ray diffraction with a multianvil apparatus at the 'SPring-8' facility. A least-squares fit of the room-temperature compression data to the Vinet-Rydberg equation of state (EOS) yielded KT0 = 65.7 ± 0.8 GPa and KT' = 5.1 ± 0.1, with fixed V0 = 227.11 Å3. Further analysis of the high-temperature compression data led to the temperature derivative of the bulk modulus (∂KT/∂T)P = -0.016 ± 0.001 GPa/K and zero-pressure thermal expansion α = a0 + a1T with a0 = 4.98 (22) × 10-5 K-1 and a1 = 2.81(38) × 10-8 K-2. The Mie-Gruneisen-Debye approach revealed the Gruneisen parameter γ0 = 1.39 at a fixed Debye temperature θ0 = 516 K and the parameter q = 1. Analysis of axial compressibility and thermal expansion indicates that the c-axis is two times more compressible than the b-axis and four times more compressible than the a-axis, whereas zero-pressure thermal expansion of the a-axis (a0a = 2.6 × 10-5 K-1 and a1a = 2.3 × 10-8 K-2) is weaker than that of the b-axis axis (a0b = 6.3 × 10-5 K-1 and a1b = 0.1 × 10-8 K-2) and c-axis axis (a0c = 5.2 × 10-5 K-1 and a1c = 9.5 × 10-8 K-2). A full set of thermodynamic parameters (including heat capacity, enthalpy and free energy) for aragonite and updated equations of state for magnesite and siderite was obtained using the Kunc-Einstein approach. The new EOS parameters were used for thermodynamic calculations for aragonite decarbonation reactions. The present thermal EOS provides accurate calculations of aragonite density to deep mantle. Decarbonation of subducting oceanic crust containing 2 wt% aragonite would result in a 0.5% density reduction at 30 GPa and 1273 K. Aragonite becomes denser than magnesite at pressures about 16 GPa along the 1500 K isotherm and at 9 GPa along the 298 K isotherm.

  17. Uranium concentrations from an aragonite speleothem as a proxy for Mesoamerican Monsoon Variability over the last 2,250 years

    Science.gov (United States)

    Crotty, C.; Lachniet, M. S.; Asmerom, Y.; Polyak, V. J.; Bernal, J. P.

    2015-12-01

    Trace element concentrations (Mg and U) were measured in an aragonite stalagmite (JX-6) from Juxtlahuaca Cave ("JX Cave"), in southwestern Mexico, using an inductively coupled plasma mass spectrometer (ICP-MS). These trace element concentrations were compared to previously analyzed δ18O and δ13C values from JX-6, and to the results of previous studies comparing U concentrations in speleothems to paleoclimate. U concentrations of JX-6 correlate well with δ13C and δ18O values, and we interpret them to be a proxy for soil moisture above Juxtlahuaca Cave. This study concludes that U concentrations in JX-6 may be controlled by changes in the pCO2 of overlying soils in relation to plant respiration possibly linked to the consistency of wet season (May - November) rainfall and temperature between 240 BCE to 1800 CE. Comparison to previous studies suggests that speleothem U concentrations are controlled by local cave conditions and are best used with the support of additional trace element and stable isotope data. Anomalous spikes in trace element concentrations were also observed in JX-6 at ~1862, 1871, 1904, and 1933 CE. These spikes were interpreted to be caused by increased U mobilization in overlying soils related to multiple deforestation events in association with the clearing of land above Juxtlahuaca Cave for agricultural use.

  18. Self-Assembly of Nano Hydroxyapatite or Aragonite Induced by Molecular Recognition to Soy Globulin 7S or 11S.

    Science.gov (United States)

    Liu, Dagang; Tian, Huafeng; Kumar, Rakesh; Zhang, Lina

    2009-09-01

    Molecular self-assembly is emerging as a viable 'bottom-up' approach to build stable organic/inorganic nanometer-scale blocks. Herein, under the conditions of appropriate pH and ionic strength, soy globulin 7S or 11S were coprecipitated with hydroxyapatite (HAp) or aragonite (Arag), respectively, to fabricate two organic/inorganic hybrids: 7S/HAp and 11S/Arag. Results from high-resolution transmission electron microscopy show that the hybrids exhibit a nanosized core-shell structure with globulin monomer 7S or 11S as core and HAp or Arag as shells. 7S/HAp and 11S/Arag present a disk and hexagon shape, respectively. After calcinations, monodispersed HAp without support from globulins existed as nanospheres. It was revealed that the globulin as host induces the self-assembly and growth layer by layer of HAp or Arag nanocrystals. The factors of molecular recognition and surface potential definitely affected the size and shape of the hierarchical blocks. This work provided a novel pathway to controllably synthesize a wide variety of precise plant protein/biomineral hybrid biomaterials.

  19. Application of a fluidized bed reactor charged with aragonite for control of alkalinity, pH and carbon dioxide in marine recirculating aquaculture systems

    Science.gov (United States)

    Paul S Wills, PhD; Pfeiffer, Timothy; Baptiste, Richard; Watten, Barnaby J.

    2016-01-01

    Control of alkalinity, dissolved carbon dioxide (dCO2), and pH are critical in marine recirculating aquaculture systems (RAS) in order to maintain health and maximize growth. A small-scale prototype aragonite sand filled fluidized bed reactor was tested under varying conditions of alkalinity and dCO2 to develop and model the response of dCO2 across the reactor. A large-scale reactor was then incorporated into an operating marine recirculating aquaculture system to observe the reactor as the system moved toward equilibrium. The relationship between alkalinity dCO2, and pH across the reactor are described by multiple regression equations. The change in dCO2 across the small-scale reactor indicated a strong likelihood that an equilibrium alkalinity would be maintained by using a fluidized bed aragonite reactor. The large-scale reactor verified this observation and established equilibrium at an alkalinity of approximately 135 mg/L as CaCO3, dCO2 of 9 mg/L, and a pH of 7.0 within 4 days that was stable during a 14 day test period. The fluidized bed aragonite reactor has the potential to simplify alkalinity and pH control, and aid in dCO2 control in RAS design and operation. Aragonite sand, purchased in bulk, is less expensive than sodium bicarbonate and could reduce overall operating production costs.

  20. Baseline monitoring of the western Arctic Ocean estimates 20% of the Canadian Basin surface waters are undersaturated with respect to aragonite

    Science.gov (United States)

    Robbins, Lisa L.; Wynn, Jonathan G.; Lisle, John T.; Yates, Kimberly K.; Knorr, Paul O.; Byrne, Robert H.; Liu, Xuewu; Patsavas, Mark C.; Azetsu-Scott, Kumiko; Takahashi, Taro

    2013-01-01

    Marine surface waters are being acidified due to uptake of anthropogenic carbon dioxide, resulting in surface ocean areas of undersaturation with respect to carbonate minerals, including aragonite. In the Arctic Ocean, acidification is expected to occur at an accelerated rate with respect to the global oceans, but a paucity of baseline data has limited our understanding of the extent of Arctic undersaturation and of regional variations in rates and causes. The lack of data has also hindered refinement of models aimed at projecting future trends of ocean acidification. Here, based on more than 34,000 data records collected in 2010 and 2011, we establish a baseline of inorganic carbon data (pH, total alkalinity, dissolved inorganic carbon, partial pressure of carbon dioxide, and aragonite saturation index) for the western Arctic Ocean. This data set documents aragonite undersaturation in ~20% of the surface waters of the combined Canada and Makarov basins, an area characterized by recent acceleration of sea ice loss. Conservative tracer studies using stable oxygen isotopic data from 307 sites show that while the entire surface of this area receives abundant freshwater from meteoric sources, freshwater from sea ice melt is most closely linked to the areas of carbonate mineral undersaturation. These data link the Arctic Ocean’s largest area of aragonite undersaturation to sea ice melt and atmospheric CO2 absorption in areas of low buffering capacity. Some relatively supersaturated areas can be linked to localized biological activity. Collectively, these observations can be used to project trends of ocean acidification in higher latitude marine surface waters where inorganic carbon chemistry is largely influenced by sea ice meltwater.

  1. Aragonite saturation state gridded to 1x1 degree latitude and longitude at depth levels of 0, 50, 100, 200, 500, 1000, 2000, 3000, and 4000 meters in the global oceans (NCEI Accession 0139360)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This archival package contains gridded data of aragonite saturation state across the global oceans (spatial distributions with a resolution of 1x1 degree latitude...

  2. Review: geological and experimental evidence for secular variation in seawater Mg/Ca (calcite-aragonite seas) and its effects on marine biological calcification

    Science.gov (United States)

    Ries, J. B.

    2010-09-01

    Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO3 precipitates (ooids, marine cements) throughout Phanerozoic time are believed to have been caused by tectonically induced variations in the Mg/Ca ratio of seawater (molar Mg/Ca>2="aragonite seas", experimental seawaters formulated with seawater Mg/Ca ratios that favor their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary production increased along with calcification within the bryopsidalean and coccolithophorid algae in mineralogically favorable seawater is consistent with the hypothesis that calcification promotes photosynthesis within some species of these algae through the liberation of CO2. The experiments also revealed that aragonite-secreting bryopsidalean algae and scleractinian corals, and bacterial biofilms that secrete a mixture of aragonite and high Mg calcite, began secreting an increased proportion of their calcium carbonate as the calcite polymorph in the lower-Mg/Ca experimental seawaters. Furthermore, the Mg/Ca ratio of calcite secreted by the coccolithophores, coralline red algae, reef-dwelling animals (crustacea, urchins, calcareous tube worms), bacterial biofilms, scleractinian corals, and bryopsidalean algae declined with reductions in seawater Mg/Ca. Notably, Mg fractionation in autotrophic organisms was more strongly influenced by changes in seawater Mg/Ca than in heterotrophic organisms, a probable consequence of autotrophic organisms inducing a less controlled mode of calcification simply through the removal of CO2 via photosynthesis. These results indicate that biomineralogical control can be partially overridden by ambient seawater Mg/Ca and suggest that modern aragonite

  3. Review: geological and experimental evidence for secular variation in seawater Mg/Ca (calcite-aragonite seas and its effects on marine biological calcification

    Directory of Open Access Journals (Sweden)

    J. B. Ries

    2010-09-01

    Full Text Available Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO3 precipitates (ooids, marine cements throughout Phanerozoic time are believed to have been caused by tectonically induced variations in the Mg/Ca ratio of seawater (molar Mg/Ca>2="aragonite seas", <2="calcite seas". Here, I assess the geological evidence in support of secular variation in seawater Mg/Ca and its effects on marine calcifiers, and review a series of recent experiments that investigate the effects of seawater Mg/Ca (1.0–5.2 on extant representatives of calcifying taxa that have experienced variations in this ionic ratio of seawater throughout the geologic past.

    Secular variation in seawater Mg/Ca is supported by synchronized secular variations in (1 the ionic composition of fluid inclusions in primary marine halite, (2 the mineralogies of late stage marine evaporites, abiogenic carbonates, and reef- and sediment-forming marine calcifiers, (3 the Mg/Ca ratios of fossil echinoderms, molluscs, rugose corals, and abiogenic carbonates, (4 global rates of tectonism that drive the exchange of Mg2+ and Ca2+ along zones of ocean crust production, and (5 additional proxies of seawater Mg/Ca including Sr/Mg ratios of abiogenic carbonates, Sr/Ca ratios of biogenic carbonates, and Br concentrations in marine halite.

    Laboratory experiments have revealed that aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibit higher rates of calcification and growth in experimental seawaters formulated with seawater Mg/Ca ratios that favor their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary

  4. Aragonite saturation states and pH in western Norwegian fjords: seasonal cycles and controlling factors, 2005-2009

    Science.gov (United States)

    Omar, Abdirahman M.; Skjelvan, Ingunn; Rune Erga, Svein; Olsen, Are

    2016-07-01

    The uptake of anthropogenic carbon dioxide (CO2) by the ocean leads to a process known as ocean acidification (OA), which lowers the aragonite saturation state (ΩAr) and pH, and this is poorly documented in coastal environments including fjords due to lack of appropriate observations.Here we use weekly underway data from the Voluntary Observing Ships (VOS) program covering the period 2005-2009 combined with data from research cruises to estimate ΩAr and pH values in several adjacent western Norwegian fjords, and to evaluate how seawater CO2 chemistry drives their variations in response to physical and biological factors.The OA parameters in the surface waters of the fjords are subject to strong seasonal and spatially coherent variations. These changes are governed by the seasonal changes in temperature, salinity, formation and decay of organic matter, and vertical mixing with deeper, carbon-rich coastal water. Annual mean pH and ΩAr values were 8.13 and 2.21, respectively. The former varies from minimum values ( ≈ 8.05) in late December - early January to maximum values of around 8.2 during early spring (March-April) as a consequence of the phytoplankton spring bloom, which reduces dissolved inorganic carbon (DIC). In the following months, pH decreases in response to warming. This thermodynamic decrease in pH is reinforced by the deepening of the mixed layer, which enables carbon-rich coastal water to reach the surface, and this trend continues until the low winter values of pH are reached again. ΩAr, on the other hand, reaches its seasonal maximum (> 2.5) in mid- to late summer (July-September), when the spring bloom is over and pH is decreasing. The lowest ΩAr values ( ≈ 1.3-1.6) occur during winter (January-March), when both pH and sea surface temperature (SST) are low and DIC is its highest. Consequently, seasonal ΩAr variations align with those of SST and salinity normalized DIC (nDIC).We demonstrate that underway measurements of fugacity of CO2 in

  5. Marine biogeochemistries of Be and Al: A study based on cosmogenic 10Be, Be and Al in marine calcite, aragonite, and opal

    Indian Academy of Sciences (India)

    Weiquan Dong; Devendra Lal; Barbara Ransom; Wolfgang Berger; Marc W Caffee

    2001-06-01

    The geochemical behaviors of Be and Al in ocean waters have been successfully studied in recent years using natural, cosmogenic, radioactive 10Be and 26Al as tracers. The present day dissolved concentrations and distribution of the stable and radioactive isotopes of Be and Al in ocean waters have revealed their short residence times and appreciable effects of exchange uxes at the coastal and ocean-sediment interfaces. It follows that concentrations of these particle-active elements must have varied in the past with temporal changes in climate, biological productivity and aeolian ux of continental detritus to the oceans. We therefore investigated the feasibility of extending the measurements of Be and Al isotope concentrations in marine systems to the 103-106 BP time scale. We report here the discovery of significant amounts of intrinsic Be and Al in marine foraminiferal calcite and coral aragonite, and of Al in opal (radiolarians) and aragonite (coral), which makes it possible to determine 10Be/Be and 26Al/Al in oceans in the past. We also report measured 10Be/9Be in foraminiferal calcite in Pacific Ocean cores, which reveal that the concentrations and ratios of the stable and cosmogenic isotopes of Be and Al have varied significantly in the past 30 ky. The implications of these results are discussed.

  6. Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

    Science.gov (United States)

    Plummer, L.N.; Busenberg, E.; Glynn, P.D.; Blum, A.E.

    1992-01-01

    Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25

  7. Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

    Science.gov (United States)

    Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

    2014-01-01

    To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

  8. Antibacterial Activity of Ciprofloxacin-Encapsulated Cockle Shells Calcium Carbonate (Aragonite Nanoparticles and Its Biocompatability in Macrophage J774A.1

    Directory of Open Access Journals (Sweden)

    Tijani Isa

    2016-05-01

    Full Text Available The use of nanoparticle delivery systems to enhance intracellular penetration of antibiotics and their retention time is becoming popular. The challenge, however, is that the interaction of nanoparticles with biological systems at the cellular level must be established prior to biomedical applications. Ciprofloxacin–cockle shells-derived calcium carbonate (aragonite nanoparticles (C-CSCCAN were developed and characterized. Antibacterial activity was determined using a modified disc diffusion protocol on Salmonella Typhimurium (S. Typhimurium. Biocompatibilittes with macrophage were evaluated using the 3-(4,5-Dimethylthiazol-2-yl-2,5-diphenyltetrazolium bromide (MTT and 5-Bromo-2′-deoxyuridine (BrdU assays. Transcriptional regulation of interleukin 1 beta (IL-1β was determined using reverse transcriptase-polymerase chain reaction (RT-PCR. C-CSCCAN were spherical in shape, with particle sizes ranging from 11.93 to 22.12 nm. Encapsulation efficiency (EE and loading content (LC were 99.5% and 5.9%, respectively, with negative ζ potential. X-ray diffraction patterns revealed strong crystallizations and purity in the formulations. The mean diameter of inhibition zone was 18.6 ± 0.5 mm, which was better than ciprofloxacin alone (11.7 ± 0.9 mm. Study of biocompatability established the cytocompatability of the delivery system without upregulation of IL-1β. The results indicated that ciprofloxacin–nanoparticles enhanced the antibacterial efficacy of the antibiotic, and could act as a suitable delivery system against intracellular infections.

  9. Antibacterial Activity of Ciprofloxacin-Encapsulated Cockle Shells Calcium Carbonate (Aragonite) Nanoparticles and Its Biocompatability in Macrophage J774A.1.

    Science.gov (United States)

    Isa, Tijani; Zakaria, Zuki Abu Bakar; Rukayadi, Yaya; Mohd Hezmee, Mohd Noor; Jaji, Alhaji Zubair; Imam, Mustapha Umar; Hammadi, Nahidah Ibrahim; Mahmood, Saffanah Khuder

    2016-05-19

    The use of nanoparticle delivery systems to enhance intracellular penetration of antibiotics and their retention time is becoming popular. The challenge, however, is that the interaction of nanoparticles with biological systems at the cellular level must be established prior to biomedical applications. Ciprofloxacin-cockle shells-derived calcium carbonate (aragonite) nanoparticles (C-CSCCAN) were developed and characterized. Antibacterial activity was determined using a modified disc diffusion protocol on Salmonella Typhimurium (S. Typhimurium). Biocompatibilittes with macrophage were evaluated using the 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and 5-Bromo-2'-deoxyuridine (BrdU) assays. Transcriptional regulation of interleukin 1 beta (IL-1β) was determined using reverse transcriptase-polymerase chain reaction (RT-PCR). C-CSCCAN were spherical in shape, with particle sizes ranging from 11.93 to 22.12 nm. Encapsulation efficiency (EE) and loading content (LC) were 99.5% and 5.9%, respectively, with negative ζ potential. X-ray diffraction patterns revealed strong crystallizations and purity in the formulations. The mean diameter of inhibition zone was 18.6 ± 0.5 mm, which was better than ciprofloxacin alone (11.7 ± 0.9 mm). Study of biocompatability established the cytocompatability of the delivery system without upregulation of IL-1β. The results indicated that ciprofloxacin-nanoparticles enhanced the antibacterial efficacy of the antibiotic, and could act as a suitable delivery system against intracellular infections.

  10. Total individual ion activity coefficients of calcium and carbonate in seawater at 25°C and 35%. salinity, and implications to the agreement between apparent and thermodynamic constants of calcite and aragonite

    Science.gov (United States)

    Plummer, L. Neil; Sundquist, Eric T.

    1982-01-01

    We have calculated the total individual ion activity coefficients of carbonate and calcium,  and , in seawater. Using the ratios of stoichiometric and thermodynamic constants of carbonic acid dissociation and total mean activity coefficient data measured in seawater, we have obtained values which differ significantly from those widely accepted in the literature. In seawater at 25°C and 35%. salinity the (molal) values of  and  are 0.038 ± 0.002 and 0.173 ± 0.010, respectively. These values of  and  are independent of liquid junction errors and internally consistent with the value . By defining  and  on a common scale (), the product  is independent of the assigned value of  and may be determined directly from thermodynamic measurements in seawater. Using the value  and new thermodynamic equilibrium constants for calcite and aragonite, we show that the apparent constants of calcite and aragonite are consistent with the thermodynamic equilibrium constants at 25°C and 35%. salinity. The demonstrated consistency between thermodynamic and apparent constants of calcite and aragonite does not support a hypothesis of stable Mg-calcite coatings on calcite or aragonite surfaces in seawater, and suggests that the calcite critical carbonate ion curve of Broecker and Takahashi (1978,Deep-Sea Research25, 65–95) defines the calcite equilibrium boundary in the oceans, within the uncertainty of the data.

  11. The solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

    Science.gov (United States)

    Plummer, L. Niel; Busenberg, Eurybiades

    1982-01-01

    Calculations based on approximately 350 new measurements (CaT-PCO2) of the solubilities of calcite, aragonite and vaterite in CO2-H2O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants KC, KA, and KV respectively, for the reaction CaCO3(s) = Ca2+ + CO2−3: 

  12. Rare earth elements in the aragonitic shell of freshwater mussel Corbicula fluminea and the bioavailability of anthropogenic lanthanum, samarium and gadolinium in river water.

    Science.gov (United States)

    Merschel, Gila; Bau, Michael

    2015-11-15

    High-technology metals - such as the rare earth elements (REE) - have become emerging contaminants in the hydrosphere, yet little is known about their bioavailability. The Rhine River and the Weser River in Germany are two prime examples of rivers that are subjected to anthropogenic REE input. While both rivers carry significant loads of anthropogenic Gd, originating from contrast agents used for magnetic resonance imaging, the Rhine River also carries large amounts of anthropogenic La and lately Sm which are discharged into the river from an industrial point source. Here, we assess the bioavailability of these anthropogenic microcontaminants in these rivers by analyzing the aragonitic shells of the freshwater bivalve Corbicula fluminea. Concentrations of purely geogenic REE in shells of comparable size cover a wide range of about one order of magnitude between different sampling sites. At a given sampling site, geogenic REE concentrations depend on shell size, i.e. mussel age. Although both rivers show large positive Gd anomalies in their dissolved loads, no anomalous enrichment of Gd relative to the geogenic REE can be observed in any of the analyzed shells. This indicates that the speciations of geogenic and anthropogenic Gd in the river water differ from each other and that the geogenic, but not the anthropogenic Gd is incorporated into the shells. In contrast, all shells sampled at sites downstream of the industrial point source of anthropogenic La and Sm in the Rhine River show positive La and Sm anomalies, revealing that these anthropogenic REE are bioavailable. Only little is known about the effects of long-term exposure to dissolved REE and their general ecotoxicity, but considering that anthropogenic Gd and even La have already been identified in German tap water and that anthropogenic La and Sm are bioavailable, this should be monitored and investigated further.

  13. Rare earth elements in the aragonitic shell of freshwater mussel Corbicula fluminea and the bioavailability of anthropogenic lanthanum, samarium and gadolinium in river water

    Energy Technology Data Exchange (ETDEWEB)

    Merschel, Gila, E-mail: g.merschel@jacobs-university.de; Bau, Michael

    2015-11-15

    High-technology metals — such as the rare earth elements (REE) — have become emerging contaminants in the hydrosphere, yet little is known about their bioavailability. The Rhine River and the Weser River in Germany are two prime examples of rivers that are subjected to anthropogenic REE input. While both rivers carry significant loads of anthropogenic Gd, originating from contrast agents used for magnetic resonance imaging, the Rhine River also carries large amounts of anthropogenic La and lately Sm which are discharged into the river from an industrial point source. Here, we assess the bioavailability of these anthropogenic microcontaminants in these rivers by analyzing the aragonitic shells of the freshwater bivalve Corbicula fluminea. Concentrations of purely geogenic REE in shells of comparable size cover a wide range of about one order of magnitude between different sampling sites. At a given sampling site, geogenic REE concentrations depend on shell size, i.e. mussel age. Although both rivers show large positive Gd anomalies in their dissolved loads, no anomalous enrichment of Gd relative to the geogenic REE can be observed in any of the analyzed shells. This indicates that the speciations of geogenic and anthropogenic Gd in the river water differ from each other and that the geogenic, but not the anthropogenic Gd is incorporated into the shells. In contrast, all shells sampled at sites downstream of the industrial point source of anthropogenic La and Sm in the Rhine River show positive La and Sm anomalies, revealing that these anthropogenic REE are bioavailable. Only little is known about the effects of long-term exposure to dissolved REE and their general ecotoxicity, but considering that anthropogenic Gd and even La have already been identified in German tap water and that anthropogenic La and Sm are bioavailable, this should be monitored and investigated further. - Highlights: • Corbicula fluminea shells are bioarchives of dissolved geogenic REE in

  14. Precipitation rates and kinetics of calcite and aragonite in seawater near equilibrium%近平衡状态海水中方解石和文石沉淀速率及动力学研究

    Institute of Scientific and Technical Information of China (English)

    陶小晚; 蒲晓强

    2011-01-01

    The influence of carbon doxide partial pressure (p(CO2)) in seawater on the precipitation rates and kinetics of calcite and aragonite was studied using "freedrift" open reaction system at constant temperature (25.0℃±0.2 ℃) and p(CO2). The precipitation rates were measured under different p(CO2). We found that: (1) the precipitation rate of aragonite was higher than that of calcite, and the lower the p(CO2)was, the higher the precipitation rate was at the same saturation state (Ω) and constant p(CO2); (2) as for calcite, the reaction order was 2.4 when p(CO2) was fluctuating between 3 050× 10-6~3 200× 10-6 and 1.5<Ω<3.1, and was 2.6 when p(CO2)≈130× 10-6 and 1.2<Ω<3.0; as for aragonite, the reaction order was 3.2 when p(CO2)≈2 300× 10-6 and 1.1<Ω< 2.0, and was 2.0 when p(CO2)≈320× 10-6 and 1.1 <Ω<1.9. Results of this study have deepened the understanding of the precipitation mechanisms of calcite and aragonite under different sedimentary conditions. In addition, the different precipitation rates of calcite and aragonite under different calcite saturation (Ωc) provide an explanation of why aragonite dominates the carbonate sediments in modern shallow sea while the main authigenic carbonate mineral in marine sediments is calcite.%利用"freedrift"开放反应系统,研究人工海水中近沉淀平衡状态时二氧化碳分压(p(CO2))的变化对方解石、文石沉淀速率及其动力学方程的影响.反应在恒定的温度(25.0℃±0.2℃)、p(CO2)环境下进行,通过实验得到了不同p(CO2)环境下,方解石和丈石的沉淀速率及动力学方程.研究发现:(1)晶体类型和碳酸盐碱度相同时,p(CO2)越低沉淀速率越大;饱和度(Ω)和p(CO2)相同时,方解石沉淀速率低于文石,且p(CO2)越高,沉淀速率越低.(2)对于方解石,当p(CO2)介于3 050×10-6和3 200×10-6之间,1.5<Ω<3.1时,反应级数n=2.4;当p(CO2)≈130×10-6,1.2<Ω<3.0时,n=2.6;对于丈石,当p(CO2)≈ 2300×10

  15. 洞穴文石石笋古气候环境变化研究进展、存在问题及研究方向%Aragonite stalagmite use in paleoclimate and environmental change research:Progress,disadvantages and further research directions

    Institute of Scientific and Technical Information of China (English)

    殷建军; 林玉石; 唐伟

    2014-01-01

    Due to global warming,extreme climate events have increased in frequency and intensity.Thus,it is important to use the geologic record to reconstruct climate change during the past 2 000 years,including the warm period (Medieval Warm Period),cold period (Little Ice Age)and the human-activity-influenced Current Warm Period,to better understand the mechanisms of climate change and extreme climate events. This paper focuses on aragonite stalagmites with high levels of uranium,allowing for high precision dating. The high precision dating enables study of the relationship between climate and cultural changes (such as the development and disintegration of the Mayan political systems),differences in regional climate (such as dry-wet conditions in the Asian monsoon area),and reconstruction of extreme climate events (such as the mech-anism of drought events in the Asian monsoon area). When aragonite stalagmites are used in paleoclimate reconstruction,it is very important to know both the aragonite formation conditions and the aragonite-to-calcite transition conditions.To address these issues, the following techniques may be used,First,87 Sr/86 Sr,δ26 Mg,δ18 O andδ13 C should be integrated into anal-ysis of the stalagmite provenance,to determine if the stalagmite Mg comes from bedrock dolomite or is due to the hydrologic process.Second,synthetically analyze the aragonite formation environment and the hydro-logic process using Mg/Ca,Sr/Ca,δ13 C and △47 to determine if changes in temperature or hydrologic process may have caused PCP (Prior Calcite Precipitation)or PAP (Prior Aragonite Precipitation).Third, use crystallography and physical chemistry in aragonite-to-calcite transition analysis.The aragonite-to-calcite transition is not progressive in some aragonite stalagmites,and this may be due to pore water between crys-tals and infiltration water from the surface of the stalagmite.This is very important for crystallography and physical chemistry research in the

  16. THE ORIENTATION OF CaCO3 ARAGONITE CRYSTALS FROM SEVERAL ORGANISMS%几种生物CaCO3霰石结晶的取向性

    Institute of Scientific and Technical Information of China (English)

    蒋新农; 李敬之; 徐学红

    2001-01-01

    The CaCO3 crystals are widely distributed in organisms. Thecalcite, aragonite and vaterite are the main crystal polymorphisms of CaCO3. In this paper, CaCO3 crystals were obtained from the nacreous layers of Hyriopsis cumingii Lea and Pinctada martensii Dunker, the internal shell of a cuttlefish and the otolith of Pseudosciaena crocea. X-ray diffraction measurement was used to analyze the crystal orientation of CaCO3 crystals: The results showed that each kind of natural CaCO3 crystal has an orientation on specific plane. In detail, the crystal orientations of the nacreous layers are higher than the internal shell, and the orientation of the otolith is the lowest. Except the nacreous layers of Pinctada martensii, whose highest peak is on the crystal plane (312), all the other three natural samples have the highest peak on the crystal plane (012). As to ground CaCO3 crystals, the differences between their corresponding d values are very small, so each ground sample has the CaCO3 aragonite structure characterized by the JCPDS card (5-0453).%CaCO3结晶广泛分布于生物界,其主要结晶形式为方解石、霰石及球霰石。用X-射线衍射法对三角帆蚌及合浦珍珠母贝的珍珠层、墨鱼骨和大黄鱼耳石的CaCO3结晶进行测定,发现各样品均有一定取向性,以三角帆蚌和合浦珍珠母贝珍珠层的取向性为最强,墨鱼骨的取向性次之,大黄鱼耳石的取向性最小,以上材料粉末样的衍射分析表明,各样品对应d值间差异极小,均为X射线衍射卡(5-0453)所表征的CaCO3霰石结构。

  17. Subsurface low pH and carbonate saturation state of aragonite on China side of the North Yellow Sea: combined effects of global atmospheric CO2 increase, regional environmental changes, and local biogeochemical processes

    Directory of Open Access Journals (Sweden)

    J.-Y. Wang

    2013-02-01

    Full Text Available Based upon seven field surveys conducted between May 2011 and January 2012, we investigated pH, carbonate saturation state of aragonite (Ωarag, and ancillary parameters on the Chinese side of the North Yellow Sea, a western North Pacific continental margin of major economic importance. Subsurface waters were nearly in equilibrium with air in May and June. From July to October, the fugacity of CO2 (fCO2 of bottom water gradually increased to 697 ± 103 μatm and pH decreased to 7.83 ± 0.07 due to respiration/remineralization processes of primary production induced biogenic particles. In November and January, bottom water fCO2 decreased and pH gradually returned to an air-equilibrated level due to cooling enhanced vertical mixing. The corresponding bottom water Ωarag was 1.74 ± 0.17 (May, 1.77 ± 0.26 (June, 1.70 ± 0.26 (July, 1.72 ± 0.33 (August, 1.32 ± 0.31 (October, 1.50 ± 0.28 (November, and 1.41 ± 0.12 (January. Critically low Ωarag values of 1.0 to 1.2 were mainly observed in subsurface waters in a salinity range of 31.5–32.5 psu in October and November, accounting for ~ 10% of the North Yellow Sea area. Water mass derived from the adjacent Bohai Sea had a typical water salinity of 30.5–31.5 psu, and bottom water Ωarag values ranged mostly between 1.6 and 2.4. This study showed that the carbonate system in the North Yellow Sea was substantially influenced by global atmospheric CO2 increase. The community respiration/remineralization rates in typical North Yellow Sea bottom water mass were estimated at 0.55–1.0 μmol O2 kg−1 d−1 in warm seasons, leading to seasonal drops in subsurface pH and Ωarag. Outflow of the Bohai Sea water mass counteracted the subsurface Ωarag reduction in the North Yellow Sea.

  18. In vivo transformation of a calcium carbonate (aragonite) based implant's biomaterial to bone. A histological, chemical and FT-IR study

    OpenAIRE

    Ramón González; Nelson Merino(Instituto de Física, Pontificia Universidad Católica de Valparaíso, Casilla 4059, Valparaíso, Chile); Pedro Rodríguez; Victor M. Rodríguez

    2004-01-01

    Se estudió la respuesta del tejido óseo a implantes de carbonato de calcio aragonito (CCA). Se utilizaron implantes de Hidroxiapatita Coralina (HA) en la misma forma y proceder quirúrgico como biomaterial de control comparativo. Se investigó el efecto de la composición química sobre la capacidad de curación y la velocidad de reabsorción de ambos biomateriales implantados en el fémur de ratas. Los animales fueron sacrificados a los 3, 7, 15, 21 y 60 d y los implantes fueron recuperados para lo...

  19. The use of external micro-PIXE to investigate the factors determining the Sr:Ca ratio in the shells of fossil aragonitic molluscs

    Energy Technology Data Exchange (ETDEWEB)

    Purton-Hildebrand, Louise M.A.; Grime, Geoff W. E-mail: geoff.grime@materials.ox.ac.uk; Shields, Graham A.; Brasier, Martin D

    2001-07-01

    The ratio of strontium to calcium in the shells of fossil marine molluscs has been proposed as an indicator of seawater temperature in past epochs, since this is less affected by other environmental conditions (such as variation of salinity) than the more conventional seawater palaeotemperature proxy {delta}{sup 18}O. However, in this paper, we demonstrate that the Sr:Ca ratio is influenced by several factors including temperature and growth rate. Two fossil molluscs, a large spiral gastropod, Clavilithes macrospira, and a large bivalve, Venericarda planicosta, from the Eocene-aged deposits of Southern England were selected for study. The variation of the Sr:Ca ratio as a function of distance along the growth direction was measured using PIXE in the Oxford external microbeam facility and the {delta}{sup 18}O was measured using small samples removed by drilling at points along the same direction. The Sr:Ca profiles show a significant increase of Sr with age, as well as seasonal, possibly temperature-related variations. Comparison of the Sr:Ca profiles with those for {delta}{sup 18}O and the spacing of the dark annual growth bands suggests that Sr incorporation is controlled primarily by metabolic activity, which in turn is influenced by factors such as temperature, salinity, age and growth rate.

  20. 利用原位沉积生成的文石型碳酸钙改善旧报纸脱墨浆性能%Improving Recycled Fiber by Applying In-situ Aragonite Calcium Carbonate Formation Process

    Institute of Scientific and Technical Information of China (English)

    陈军伟

    2015-01-01

    在旧报纸(ONP)脱墨浆中通过碳酸化法进行了原位沉积生成针状的文石型沉淀碳酸钙(PCC)的实验。结果表明,与未处理的ONP脱墨浆相比,经文石型PCC原位沉积生成工艺处理ONP脱墨浆所抄造手抄片的白度提高了20.4%(从56.8%增至68.4%),ERIC降低55.4%(从292.1 mg/kg降至130.4 mg/kg)。原位沉积生成文石型PCC不仅可改善成纸光学性能,同时还可保留手抄片的强度性能,这归因于文石型PCC的针状形态。

  1. Review on Researches of Aragonite Saturation State in the Arctic Ocean: A Key Parameter of Arctic Ocean Acidification%北冰洋酸化指标——海水文石饱和度变异的研究进展

    Institute of Scientific and Technical Information of China (English)

    祁第; 陈立奇

    2014-01-01

    文石饱和度(Ω文石)是评估海洋酸化及对海洋钙质生物影响的重要指标之一.海洋吸收CO2引起海洋酸化,导致Ω文石显著下降.模式研究预测表明北冰洋表层海水将成为最先出现Ω文石<1的世界大洋.通过对北冰洋Ω文石有关研究进行归纳总结,重点阐述了北冰洋Ω文石的分布特征,讨论海—气CO2交换过程、融冰过程以及生物过程等因素对北冰洋Ω文石分布的影响,展望未来的变化趋势并提出一些关键的科学问题.

  2. Meteoric diagenesis, marine diagenesis, and microporosity in Pleistocene and Oligocene limestones, Enewetak Atoll, Marshall Islands

    Science.gov (United States)

    Saller, Arthur H.; Moore, Clyde H.

    1989-07-01

    Microporosity occurs in Pleistocene and Oligocene limestones cored on Enewetak Atoll. In cores of Pleistocene limestone (10-80 m deep), mi microporosity is present in aragonitic skeletal grains that underwent partial intrafabric dissolution (chalkification) leaving a porous meshwork of aragonite needles. Microporous aragonite is most abundant in 5-10 m thick intervals below zones of intense diagenesis associated with paleo-freshwater lenses. Extensive microporosity was apparently generated by slow intrafabric dissolution of aragonite in mixing zones below freshwater lenses. Microporous aragonite is an intermediate step in the calcitization or dissolution of aragonite. Most calcitized aragonite (neomorphic calcite) formed by precipitation of sparry calcite in (over) microporous aragonite. Aragonitic fossils were not converted to microporous, microcrystalline calcite. Therefore, data from the Pleistocene of Enewetak suggest that widespread, microporous, microcrystalline calcite does not form directly from pure aragonite, at least not in open meteoric systems or mixing zones. Microporous micrite occurs in Oligocene wackestones 930 m deep deposited in a slope environment. The microporous micrite is characterized by equant and prismatic crystals of low-magnesium calcite (LMC). Equant crystals are anhedral to euhedral and 2-10 μm in diameter. Prismatic calcite crystals are subhedral, 5-10 μm wide, and 20-50 μm long. Stable isotopic and trace element geochemistry suggest that microporous micrite formed by diagenetic alteration of high-magnesium calcite (HMC) micrite in deep seawater undersaturated with respect to HMC but supersaturated with respect to LMC (probably near the sediment-water interface). Mineralogy and crystal morphology of the microporous aragonite is very different from microporous shelf limestones in the Thamama Group (Cretaceous, Persian Gulf; see Moshier, 1989). Equant microcrystals of calcite in the Oligocene micrites are similar to those in

  3. Calcium carbonate precipitation in the Cueva di Watapana on Bonaire, Netherlands Antilles

    NARCIS (Netherlands)

    Meer Mohr, van der C.G.

    1978-01-01

    Calcium carbonate precipitates as low Mg-calcite and aragonite in slightly brackish water in a cave in the Pleistocene Middle Terrace of southern Bonaire. The calcium carbonate precipitates at the atmosphere-water interface forming floating calcite scales (calcite ice). Aragonite crystals frequently

  4. Lime muds and their genesis off-Northwestern India during the late Quaternary

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, V.P.; AnilKumar, A.; Naqvi, S.W.A.; Chivas, A.R.; Sekar, B.; Kessarkar, P.M.

    and Wilber R J 1993 Great Bahama Bank aragonitic muds: mostly inorgani- cally precipitated, mostly exported; J. Sedim. Petrol. 63 589–595. Mitterer R M 1972 Biogeochemistry of aragonite mud and ooids; Geochim Cosmochim Acta 36 1407–1422. Morse J W...

  5. Submarine terrace limestones from the continental slope off Saurashtra-Bombay: Evidence of Late Quaternary neotectonic activity

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, V.P.; Veerayya, M.

    m depth terrace. Some of these limestones consist of thin micrite layer on the top and a sandy layer below and others are similar to calcarenites. They contain greater than 95% aragonite and minor high and low-magnesium calcite. Acicular aragonite...

  6. Authigenic carbonates in the sediments of Goa offshore basin, western continental margin of India

    Digital Repository Service at National Institute of Oceanography (India)

    Kocherla, M.

    authigenic minerals while high-Mg calcite, dolomite and siderite occur in minor amounts. Morphological evidences such as euhedral carbonate crystals and slender radiating aragonite crystals suggest that they are formed authigenically in the sediment column...

  7. Crystal nucleation and near-epitaxial growth in nacre

    CERN Document Server

    Olson, Ian C; Tamura, Nobumichi; Kunz, Martin; Gilbert, Pupa U P A

    2013-01-01

    Nacre, the iridescent inner lining of many mollusk shells, interests materials scientists because of its unique brick-and-mortar periodic structure at the sub-micron scale and its remarkable resistance to fracture. However, it remains unclear how nacre forms. Here we present 20-nm, 2{\\deg}-resolution Polarization-dependent Imaging Contrast (PIC) images of shells from 15 species, mapping nacre tablets and their orientation patterns, showing where crystals nucleate and how they grow in nacre. In all shells we found stacks of co-oriented aragonite (CaCO3) tablets arranged into vertical columns or staggered diagonally. Only near the nacre-prismatic boundary are disordered crystals nucleated, as spherulitic aragonite. Overgrowing nacre tablet crystals are most frequently co-oriented with the underlying spherulitic aragonite or with another tablet, connected by mineral bridges. Therefore aragonite crystal growth in nacre is epitaxial or near-epitaxial, with abrupt or gradual changes in orientation, with c-axes with...

  8. Studies on structure and organization of calcium carbonate deposits in algae

    Digital Repository Service at National Institute of Oceanography (India)

    Kerkar, V.; Untawale, A.G.

    The structure and organization of calcium carbonate deposits is studied in species of Halimeda, Udotea, Neomeris (Chlorophyta) and Padina (Phaeophyta). It was found that in Halimeda aragonite deposition takes place outside the cell wall...

  9. Coral Cores for selected locations in the Pacific Ocean obtained to determine calcification and extension rates of Porites spp. corals

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Laboratory experiments reveal calcification and extension rates of corals are strongly correlated to seawater aragonite saturation state. Predictions of reduced...

  10. Calcification Rates of Crustose Coralline Algae derived from Calcification Accretion Units (CAUs) deployed across U.S. Pacific Reefs since 2010 (NCEI Accession 0137093)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Laboratory experiments reveal calcification rates of crustose coralline algae are strongly correlated to seawater aragonite saturation state. Predictions of reduced...

  11. Improved Understanding of In Situ Chemical Oxidation. Technical Objective 2: Soil Reactivity

    Science.gov (United States)

    2009-05-01

    Chemosphere, 49, 413-420. Huang, K., Zhao, Z., Hoag, G.E., Dahmani, A., and Block, P.A., 2005. Degradation of volatile organic compounds with thermally ...plagioclase feldspar calcite calcite calcite - calcite (plagioclase) aragonite aragonite dolomite - trace magnetite & ilmenite trace feldspars trace feldspars...structures that makes up the AOM. In the presence of oxygen, the most labile compounds are consumed at high rates while the degradation of the

  12. Endolithic algae and micrite envelope formation in Bahamian oolites as revealed by scanning electron microscopy.

    Science.gov (United States)

    Margolis, S.; Rex, R. W.

    1971-01-01

    Examination of Holocene Bahamian ooelites by scanning electron and light microscopy has revealed the morphology and orientation of aragonite crystals in the lamellar ooelitic envelope, and their modification by the boring activities of endolithic algae. The voids produced by these algae are found in progressive stages of being lined and filled with precipitated microcrystalline aragonite, which is similar to the process of micrite envelope formation in molluscan and other skeletal carbonate grains.

  13. Skeletal growth phases of the cold-water coral Lophelia pertusa shown by scanning electron microscope and electron backscatter diffraction

    Science.gov (United States)

    Mouchi, Vincent; Vonlanthen, Pierre; Verrecchia, Eric P.; Crowley, Quentin G.

    2016-04-01

    Lophelia pertusa is a cold-water coral, which may form reefs by the association of multiple coralites within which a polyp lives. Each individual polyp builds an aragonite skeleton by an initial phase of early mineralization (traditionally referred to as centres of calcification) from which aragonite fibres grow in thickening deposits. The skeleton wall features successive optically opaque and translucent bands previously attributed to different regimes of growth as either uniform in crystal orientation (translucent bands) or with a chaotic organization (opaque bands). The processes involved in any organizational changes are still unknown. Microlayers in the coral wall, which represent separate periods of skeletal growth, have been recently identified and described. These growth patterns are readily visible under scanning electron microscope (SEM) after etching in dilute formic acid, but they do not necessarily form continuously visible structures. Here we present high quality SEM images and electron backscatter diffraction (EBSD) maps to study aragonite fibre orientation across the wall of L. pertusa. Both microlayers and opaque and translucent bands are compared to the crystallographic orientation of the aragonite fibres. EBSD maps and SEM images indicate that aragonite fibres do not exhibit a chaotic orientation, even in opaque bands. The absence of continuity of microlayers is partially explained by an association of multiple crystallographic preferred orientations of aragonite fibres. In the case of L. pertusa, careful textural characterisation is necessary prior to elemental or isotope analysis in order to select a skeletal transect representing a linear and continuous time period.

  14. Impact of rapid sea-ice reduction in the Arctic Ocean on the rate of ocean acidification

    Directory of Open Access Journals (Sweden)

    A. Yamamoto

    2011-10-01

    Full Text Available The largest pH decline and widespread undersaturation with respect to aragonite in this century due to uptake of anthropogenic carbon dioxide in the Arctic Ocean have been projected. The reductions in pH and aragonite saturation state have been caused primarily by an increase in the concentration of atmospheric carbon dioxide. However, in a previous study, simulations with and without warming showed that these reductions in the Arctic Ocean also advances due to the melting of sea ice caused by global warming. Therefore, future projections of pH and aragonite saturation in the Arctic Ocean will be affected by how rapidly the reduction in sea ice occurs. In this study, the impact of sea-ice reduction rate on projected pH and aragonite saturation state in the Arctic surface waters was investigated. Reductions in pH and aragonite saturation were calculated from the outputs of two versions of an earth system model (ESM with different sea-ice reduction rates under similar CO2 emission scenarios. The newer model version projects that Arctic summer ice-free condition will be achieved by the year 2040, and the older version predicts ice-free condition by 2090. The Arctic surface water was projected to be undersaturated with respect to aragonite in the annual mean when atmospheric CO2 concentration reached 480 (550 ppm in year 2040 (2048 in new (old version. At an atmospheric CO2 concentration of 520 ppm, the maximum differences in pH and aragonite saturation state between the two versions were 0.08 and 0.15, respectively. The analysis showed that the decreases in pH and aragonite saturation state due to rapid sea-ice reduction were caused by increases in both CO2 uptake and freshwater input. Thus, the reductions in pH and aragonite saturation state in the Arctic surface waters are significantly affected by the difference in future projections for sea-ice reduction rate. The critical CO2 concentration

  15. The nacre protein perlucin nucleates growth of calcium carbonate crystals.

    Science.gov (United States)

    Blank, S; Arnoldi, M; Khoshnavaz, S; Treccani, L; Kuntz, M; Mann, K; Grathwohl, G; Fritz, M

    2003-12-01

    Atomic force microscopy (AFM) in aqueous solution was used to investigate native nacre of the marine snail Haliotis laevigata on the microscopic scale and the interaction of purified nacre proteins with calcium carbonate crystals on the nanoscopic scale. These investigations were controlled by scanning electron microscopy (SEM), light microscopy (LM) and biochemical methods. For investigations with AFM and SEM, nacre was cleaved parallel to the aragonite tablets in this biogenic polymer/mineral composite. Multilamellar organic sheets consisting of a core of chitin with layers of proteins attached on both sides lay between the aragonite layers consisting of confluent aragonite tablets. Cleavage appeared to occur between the aragonite tablet layer and the protein layer. AFM images revealed a honeycomb-like structure to the organic material with a diameter of the 'honeycombs' equalling that of the aragonite tablets. The walls of the structures consisted of filaments, which were suggested to be collagen. The flat regions of the honeycomb-like structures exhibited a hole with a diameter of more than 100 nm. When incubated in saturated calcium carbonate solution, aragonite needles with perfect vertical orientation grew on the proteinacous surface. After treatment with proteinase K, no growth of orientated aragonite needles was detected. Direct AFM measurements on dissolving and growing calcite crystals revealed a surface structure with straight steps the number of which decreased with crystal growth. When the purified nacre protein perlucin was added to the growth solution (a super-saturated calcium carbonate solution) new layers were nucleated and the number of steps increased. Anion exchange chromatography of the water-soluble proteins revealed a mixture of about 10 different proteins. When this mixture was dialysed against saturated calcium carbonate solution and sodium chloride, calcium carbonate crystals precipitated together with perlucin leaving the other proteins

  16. The structure-function relationship of MSI7, a matrix protein from pearl oyster Pinctada fucata

    Institute of Scientific and Technical Information of China (English)

    Qiaoli Feng; Zi Fang; Zhenguang Yan; Rui Xing; Liping Xie; Rongqing Zhang

    2009-01-01

    We previously identified a matrix protein, MSI7, from pearl oyster Pinctada fucata. According to the struc-tural analysis, the DGD site in the N-terminal of MSI7 is crucial for its role in the shell formation. In this study, we expressed a series of recombinant MSI7 pro-teins, including the wild-type and several mutants directed at the DGD site, using an Escherichia coli expression system to reveal the structure-function relationship of MSI7. Furthermore, in vitro crystalliza-tion, crystallization speed assay, and circular dichroism spectrometry were carried out. Results indicated that wild-type MSI7 could induce the nucleation of arago-nite and inhibit the crystallization of calcite. However, none of the mutants could induce the nucleation of ara-gonite, but all of them could inhibit the crystallization of calcite to some extent. And all the proteins acceler-ated the crystallization process. Taken together, the results indicated that MSI7 could contribute to arago-nite crystallization by inducing the nucleation of arago-nite and inhibiting the crystallization of calcite, which agrees with our prediction about its role in the nacr-eous layer formation of the shell. The DGD site was critical for the induction of the nucleation of aragonite.

  17. New robertinid foraminifers from the Early Jurassic of Adnet, Austria and their evolutionary importance

    Directory of Open Access Journals (Sweden)

    Sylvain Rigaud

    2016-12-01

    Full Text Available New benthic multichambered foraminifers have been discovered in the Hettangian–Sinemurian of the Northern Calcareous Alps (Adnet, Salzburg, Austria. Originally aragonitic, these forms are completely recrystallized but the early impregnation of their tests by Fe-Mn solutions has, to some extent, allowed an indirect preservation of their primary structure. The most remarkably preserved specimens are found in close vicinity to the marmorea crust, a heavily mineralized multiphased hardground. We describe two new genera, Velleditsiella gen. nov., a microgastropod look-alike foraminifer, which includes the species V. felicitaszae gen. et sp. nov. and V. spinaferra gen. et sp. nov., and Rossanella gen. nov., the first known representative of the superfamily Conorboidoidea, which includes the species R. martinii gen. et sp. nov. Considering their structural and morphological characteristics, Velleditsiella and Rossanella phylogenetically derive from two distinct Triassic lineages, respectively the families Trochosiphoniidae and Variostomatidae. The discovery of diverse aragonitic assemblages in earliest Jurassic strata dismisses the long believed hypothesis that all Jurassic aragonitic multichambered foraminifers originated from a single Oberhauserellidae ancestor. It also supports a lower impact of the Triassic/Jurassic biotic crisis on the evolution of aragonitic foraminifers. Hypotheses for the short term and long term evolution of aragonitic multichambered foraminifers are discussed and new phyletic trees are proposed.

  18. Seasonal variation of CaCO3 saturation state in bottom water of a biological hotspot in the Chukchi Sea, Arctic Ocean

    Science.gov (United States)

    Yamamoto-Kawai, Michiyo; Mifune, Takahisa; Kikuchi, Takashi; Nishino, Shigeto

    2016-11-01

    Distribution of calcium carbonate saturation state (Ω) was observed in the Chukchi Sea in autumn 2012 and early summer 2013. Ω in bottom water ranged from 0.3 to 2.0 for aragonite and from 0.5 to 3.2 for calcite in 2012. In 2013, Ω in bottom water was 1.1-2.8 for aragonite and 1.7-4.4 for calcite. Aragonite and calcite undersaturation was found in high productivity regions in autumn 2012 but not in early summer 2013. Comparison with other parameters has indicated that biological processes - respiration and photosynthesis - are major factors controlling the regional and temporal variability of Ω. From these ship-based observations, we have obtained empirical equations to reconstruct Ω from temperature, salinity and apparent oxygen utilization. Using 2-year-round mooring data and these equations, we have reconstructed seasonal variation of Ω in bottom water in Hope Valley, a biological hotspot in the southern Chukchi Sea. Estimated Ω was high in spring and early summer, decreased in later summer, and remained relatively low in winter. Calculations indicated a possibility that bottom water could have been undersaturated for aragonite on an intermittent basis even in the pre-industrial period, and that anthropogenic CO2 has extended the period of aragonite undersaturation to more than 2-fold longer by now.

  19. Crystallographic Orientation of Cuttlebone Shield Determined by Electron Backscatter Diffraction

    Science.gov (United States)

    Cusack, Maggie; Chung, Peter

    2014-01-01

    In common with many cephalopod mollusks, cuttlefish produce an internal biomineral buoyancy device. This cuttlebone is analogous to a surf board in shape and structure, providing rigidity and a means of controlling buoyancy. The cuttlebone is composed of calcium carbonate in the form of aragonite and comprises an upper dorsal shield and a lower lamellar matrix. The lamellar matrix comprises layers of chambers with highly corrugated walls. The dorsal shield comprises bundles of aragonite needles stacked on top of each other. Electron backscatter diffraction analyses of the dorsal shield reveal that the c-axis of aragonite is parallel with the long axis of the needles in the bundles such that any spread in crystallographic orientation is consistent with the spread in orientation of the fibers as they radiate to form the overall structure of the dorsal shield. This arrangement of c-axis coincident with the long axis of the biomineral structure is similar to the arrangement in corals and in contrast to the situation in the molluskan aragonite nacre of brachiopod calcite where the c-axis is perpendicular to the aragonite tablet or calcite fiber, respectively.

  20. Miniaturized biosignature analysis reveals implications for the formation of cold seep carbonates at Hydrate Ridge (off Oregon, USA

    Directory of Open Access Journals (Sweden)

    T. Leefmann

    2008-05-01

    Full Text Available Methane-related carbonates from Hydrate Ridge typically show several macroscopically distinguishable mineral phases, namely whitish aragonite, lucent aragonite, and gray micrite. The relationship of these phases to particular microorganisms or biogeochemical processes is as yet unclear. We used a miniaturized biomarker technique on mg samples, combined with factor analysis and subsequent electron microprobe analysis, to study lipid biomarkers and chemical compositions of the individual phases. This allows us to identify particular mechanisms involved in the formation of the different carbonate precipitates. Our combined analysis of biomarkers and petrographic traits shows that most of the lipids related to the anaerobic oxidation of methane (>90% by weight are concentrated within only a minor compartment (~20% by volume of the Hydrate Ridge carbonates, the whitish aragonite. The patterns indicate that the whitish aragonite represents fossilized biofilms of methanotrophic consortia containing mainly archaea of the ANME-2 group and sulfate reducing bacteria, whereas the precipitation of the lucent aragonite may have lacked the immediate proximity of microorganisms during formation. By contrast, the gray micrite formed by incorporation of allochthonous organic and inorganic matter during carbonate precipitation induced by the anaerobic oxidation of methane involving ANME-1 archaea.

  1. Isotopic characteristics of shells Mytilus galloprovincialis from eastern coastal area of Adriatic Sea

    Directory of Open Access Journals (Sweden)

    Tjaša Kanduč

    2006-06-01

    Full Text Available Samples of Mytilus galloprovincialis were collected from entire Eastern Adriatic coast to determine δ18O and δ13C performed on calcite and aragonite shell layers. The aim of this work was to check whether shells of M. galloprovincialis are good environmental indicators (water temperature, salinity. Based on measured isotopic composition of oxygen in shell layers and assumed isotopic composition in water temperatures of calcite and aragonite of shell layers were calculated. The calculated temperatures for M. galloprovincialis shell growth of calcite and aragonite shell layer are in good agreement with measured temperatures of sea water. According to our results of δ18O and δ13C in shell layers we canseparate the locations of the investigated area into three groups: those with more influence of fresh water, those with less influence of fresh water and those of marine environments.

  2. Disparate acidification and calcium carbonate desaturation of deep and shallow waters of the Arctic Ocean

    Science.gov (United States)

    Luo, Yiming; Boudreau, Bernard P.; Mucci, Alfonso

    2016-09-01

    The Arctic Ocean is acidifying from absorption of man-made CO2. Current predictive models of that acidification focus on surface waters, and their results argue that deep waters will acidify by downward penetration from the surface. Here we show, with an alternative model, the rapid, near simultaneous, acidification of both surface and deep waters, a prediction supported by current, but limited, saturation data. Whereas Arctic surface water responds directly by atmospheric CO2 uptake, deeper waters will be influenced strongly by intrusion of mid-depth, pre-acidified, Atlantic Ocean water. With unabated CO2 emissions, surface waters will become undersaturated with respect to aragonite by 2105 AD and could remain so for ~600 years. In deep waters, the aragonite saturation horizon will rise, reaching the base of the surface mixed layer by 2140 AD and likely remaining there for over a millennium. The survival of aragonite-secreting organisms is consequently threatened on long timescales.

  3. Molecular approaches to understand biomineralization of shell nacreous layer.

    Science.gov (United States)

    Xie, Li-Ping; Zhu, Fang-Jie; Zhou, Yu-Juan; Yang, Chao; Zhang, Rong-Qing

    2011-01-01

    The nacreous layer of molluskan shells, which consists of highly oriented aragonitic crystals and an organic matrix (including chitin and proteins), is a product of biomineralization. This paper briefly introduces the recent research advances on nacre biomineralization of shells from bivalves and gastropods, which mainly focus on analysis of the micro- and nano-structure and components of shell nacreous layers, and investigations of the characteristics and functions of matrix proteins from nacre. Matrix proteins not only participate in construction of the organic nacre framework, but also control the nucleation and growth of aragonitic crystals, as well as determine the polymorph specificity of calcium carbonate in nacre. Moreover, the inorganic aragonite phase also plays an active role in organizing nacre microstructure. Based on these studies, several models to illustrate the formation mechanism related to lamellar nacre in bivalves, and columnar nacre in gastropods are introduced.

  4. Microstructure, chemistry, and electronic structure of natural hybrid composites in abalone shell.

    Science.gov (United States)

    Srot, Vesna; Wegst, Ulrike G K; Salzberger, Ute; Koch, Christoph T; Hahn, Kersten; Kopold, Peter; van Aken, Peter A

    2013-05-01

    The crystal structure and chemical composition at the inorganic/inorganic and inorganic/organic interfaces in abalone shell (genus Haliotis) were investigated using advanced analytical transmission electron microscopy (TEM) methods. Electron energy-loss near-edge structures (ELNES) of Ca-M2,3, C-K, Ca-L2,3, O-K and low-loss EEL spectra acquired from aragonite and calcite are distinctly different. When comparing biogenic with inorganic material for aragonite, only minor differences in C-K fine structures could be detected. The crystal structure of the mineral bridges was confirmed by ELNES experiments. ELNES and energy-filtered TEM (EFTEM) experiments of regular and self-healed interfaces between nacreous aragonite and prismatic calcite reveal relatively rough transitions. In this work, the importance of TEM specimen preparation and specimen damage on structural features is discussed.

  5. Disparate acidification and calcium carbonate desaturation of deep and shallow waters of the Arctic Ocean

    Science.gov (United States)

    Luo, Yiming; Boudreau, Bernard P.; Mucci, Alfonso

    2016-01-01

    The Arctic Ocean is acidifying from absorption of man-made CO2. Current predictive models of that acidification focus on surface waters, and their results argue that deep waters will acidify by downward penetration from the surface. Here we show, with an alternative model, the rapid, near simultaneous, acidification of both surface and deep waters, a prediction supported by current, but limited, saturation data. Whereas Arctic surface water responds directly by atmospheric CO2 uptake, deeper waters will be influenced strongly by intrusion of mid-depth, pre-acidified, Atlantic Ocean water. With unabated CO2 emissions, surface waters will become undersaturated with respect to aragonite by 2105 AD and could remain so for ∼600 years. In deep waters, the aragonite saturation horizon will rise, reaching the base of the surface mixed layer by 2140 AD and likely remaining there for over a millennium. The survival of aragonite-secreting organisms is consequently threatened on long timescales. PMID:27659188

  6. Direct contribution of the seagrass Thalassia testudinum to lime mud production.

    Science.gov (United States)

    Enríquez, Susana; Schubert, Nadine

    2014-05-22

    Seagrass beds contribute to oceanic carbonate lime mud production by providing a habitat for a wide variety of calcifying organisms and acting as efficient sediment traps. Here we provide evidence for the direct implication of Thalassia testudinum in the precipitation of aragonite needles. The crystals are located internally in the cell walls, and as external deposits on the blade, and are similar in size and shape to the aragonite needles reported for modern tropical carbonate factories. Seagrass calcification is a biological, light-enhanced process controlled by the leaf, and estimates of seagrass annual carbonate production in a Caribbean reef lagoon are as significant as values reported for Halimeda incrassata. Thus, we conclude that seagrass calcification is another biological source for the aragonite lime mud deposits found in tropical banks, and that tropical seagrass habitats may play a more important role in the oceanic carbon cycle than previously considered.

  7. Summertime calcium carbonate undersaturation in shelf waters of the western Arctic Ocean – how biological processes exacerbate the impact of ocean acidification

    Directory of Open Access Journals (Sweden)

    N. R. Bates

    2013-08-01

    Full Text Available The Arctic Ocean accounts for only 4% of the global ocean area, but it contributes significantly to the global carbon cycle. Recent observations of seawater CO2-carbonate chemistry in shelf waters of the western Arctic Ocean, primarily in the Chukchi Sea, from 2009 to 2011 indicate that bottom waters are seasonally undersaturated with respect to calcium carbonate (CaCO3 minerals, particularly aragonite. Nearly 40% of sampled bottom waters on the shelf have saturation states less than one for aragonite (i.e., Ωaragonite 3-secreting organisms, while 80% of bottom waters present had Ωaragonite values less than 1.5. Our observations indicate seasonal reduction of saturation states (Ω for calcite (Ωcalcite and aragonitearagonite in the subsurface in the western Arctic by as much as 0.8 and 0.5, respectively. Such data indicate that bottom waters of the western Arctic shelves were already potentially corrosive for biogenic and sedimentary CaCO3 for several months each year. Seasonal changes in Ω are imparted by a variety of factors such as phytoplankton photosynthesis, respiration/remineralization of organic matter and air–sea gas exchange of CO2. Combined, these processes either increase or enhance in surface and subsurface waters, respectively. These seasonal physical and biological processes also act to mitigate or enhance the impact of Anthropocene ocean acidification (OA on Ω in surface and subsurface waters, respectively. Future monitoring of the western Arctic shelves is warranted to assess the present and future impact of ocean acidification and seasonal physico-biogeochemical processes on Ω values and Arctic marine ecosystems.

  8. Voyaging around nacre with the X-ray shuttle: From bio-mineralisation to prosthetics via mollusc phylogeny

    Energy Technology Data Exchange (ETDEWEB)

    Chateigner, D., E-mail: daniel.chateigner@ensicaen.fr [CRISMAT-ENSICAEN, IUT-Caen, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Ouhenia, S. [CRISMAT-ENSICAEN, IUT-Caen, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Lab. De Physique, Faculte des Sciences Exactes, Bejaia 06000 (Algeria); Krauss, C.; Hedegaard, C. [CRISMAT-ENSICAEN, IUT-Caen, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Gil, O. [ERPCB, IUT-Caen, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Morales, M. [CIMAP-ENSICAEN, Universite de Caen Basse-Normandie, 6 Bd. M. Juin, 14050 Caen (France); Lutterotti, L. [Department of Materials Engineering, Engineering Faculty, University of Trento, via Mesiano, 77 - 38123 Trento (Italy); Rousseau, M. [UMR 7561 CNRS, Nancy University, BP184, 54505 Vandoeuvre les Nancy,France (France); Lopez, E. [UMR7208 BOREA, CNRS/Museum National d' Histoire Naturelle, 43, rue Cuvier 75231, Paris Cedex 05 (France)

    2010-11-25

    Research highlights: {yields} Nacre could be a non ancestral form of calcium carbonate in molluscs. {yields} Texture terms as useful links to ancestors in classification. {yields} X-ray diffraction useful for biomineralisation, phylogeny, cladistic and implantology. {yields} Farming conditions do not influence much shell growth. {yields} Electrodeposition of aragonite as future technique for implant coating. - Abstract: Strong textures of mollusc shell layers are utilised to provide phylogenetic information. Aragonitic and calcitic layers are the targets here, inside which nacre layers, but not only, play a specific role. At the light of the texture patterns and a parcimonious approach, nacre appears not as an ancestral form of calcium carbonate in mollusc layers. Also, from texture terms we can propose some links to ancestral fossilised species. The aragonite unit-cell distortions due to macromolecule complex insertions in the microstructures are measured on raw specimens for several aragonite layers of gastropods and bivalves. The textural information is used to provide precise structural determination of the biogenic aragonite. Such information might provide useful lights on the biomineralisation processes in the future, in cladistic approaches. Farming conditions are shown not to influence much shell textures of Helix aspersa aspersa. Closely related species exhibit globally close textures, among which three are good candidates for bone neogeneration and which textures are identical. Electrodeposition of aragonite, with inclusion of molecular extract from shell species, results in nacre-like layers exhibiting structural distortions similar to known inductive layers. X-ray diffraction experiments are shown to provide invaluable insights in testing biomineralisation and phylogenetic hypotheses.

  9. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    Science.gov (United States)

    Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  10. Calcite formation in soft coral sclerites is determined by a single reactive extracellular protein.

    Science.gov (United States)

    Rahman, M Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-09-09

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature.

  11. Modern carbonate microbialites from an asbestos open pit pond, Yukon, Canada.

    Science.gov (United States)

    Power, I M; Wilson, S A; Dipple, G M; Southam, G

    2011-03-01

    Microbialites were discovered in an open pit pond at an abandoned asbestos mine near Clinton Creek, Yukon, Canada. These microbialites are extremely young and presumably began forming soon after the mine closed in 1978. Detailed characterization of the periphyton and microbialites using light and scanning electron microscopy was coupled with mineralogical and isotopic analyses to investigate the mechanisms by which these microbialites formed. The microbialites are columnar in form (cm scale), have an internal spherulitic fabric (mm scale), and are mostly made of aragonite, which is supersaturated in the subsaline pond water. Initial precipitation is seen as acicular aragonite crystals nucleating onto microbial biomass and detrital particles. Continued precipitation entombs benthic diatoms (e.g. Brachysira vitrea), filamentous algae (e.g. Oedogonium sp.), dinoflagellates, and cyanobacteria. The presence of phototrophs at spherulite centers strongly suggests that these microbes play an important initial role in aragonite precipitation. Substantial growth of individual spherulites occurs abiotically through periodic precipitation of aragonite that forms concentric laminations around spherulite centers while pauses in spherulite growth allow for colonization by microbes. Aragonite associated with biomass (δ(13)C = -4.6‰ VPDB) showed a (13)C-enrichment of 0.8‰ relative to aragonite exhibiting no biomass (δ(13)C = -5.4‰ VPDB), which suggests a modest removal of isotopically light dissolved inorganic carbon by phototrophs. The combination of a low sedimentation rate, high calcification rate, and low microbial growth rate appears to result in the formation of these microbialites. The formation of microbialites at an historic mine site demonstrates that an anthropogenically constructed environment can foster microbial carbonate formation.

  12. Historical reconstruction of ocean acidification in the Australian region

    Directory of Open Access Journals (Sweden)

    A. Lenton

    2015-06-01

    Full Text Available The increase in atmospheric greenhouse gases over the last 200 years has caused an increase in ocean acidity levels. Documenting how the ocean has changed is critical for assessing how these changes could impact marine ecosystems and for the management of marine resources. We use present day ocean carbon observations from shelf and offshore waters around Australia, combined with neural network mapping of CO2, to estimate the current seasonal and regional distributions of carbonate chemistry (pH and aragonite saturation state. These predicted changes in carbonate chemistry are combined with atmospheric CO2 concentration changes since to reconstruct pH and aragonite saturation state changes over the last 140 years (1870–2013. The comparison with data collected at Integrated Marine Observing System National Reference Station sites located on the shelf around Australia shows both the mean state and seasonality for the present day is well represented by our reconstruction, with the exception of sites such as the Great Barrier Reef. Our reconstruction predicts that since 1870 an average decrease in aragonite saturation state of 0.48 and of 0.09 in pH has occurred in response to increasing oceanic uptake of atmospheric CO2. Our reconstruction shows that seasonality is the dominant mode of variability, with only small interannual variability present. Large seasonal variability in pH and aragonite saturation state occur in Southwestern Australia driven by ocean dynamics (mixing and in the Tasman Sea by seasonal warming (in the case of aragonite saturation state. The seasonal and historical changes in aragonite saturation state and pH have different spatial patterns and suggest that the biological responses to ocean acidification are likely to be non-uniform depending on the relative sensitivity of organisms to shifts in pH and saturation state. This new historical reconstruction provides an important to link to biological observations to help elucidate

  13. Historical reconstruction of ocean acidification in the Australian region

    Science.gov (United States)

    Lenton, Andrew; Tilbrook, Bronte; Matear, Richard J.; Sasse, Tristan P.; Nojiri, Yukihiro

    2016-03-01

    The ocean has become more acidic over the last 200 years in response increasing atmospheric carbon dioxide (CO2) levels. Documenting how the ocean has changed is critical for assessing how these changes impact marine ecosystems and for the management of marine resources. Here we use present-day ocean carbon observations, from shelf and offshore waters around Australia, combined with neural network mapping of CO2, sea surface temperature, and salinity to estimate the current seasonal and regional distributions of carbonate chemistry (pH and aragonite saturation state). The observed changes in atmospheric CO2 and sea surface temperature (SST) and climatological salinity are then used to reconstruct pH and aragonite saturation state changes over the last 140 years (1870-2013). The comparison with data collected at Integrated Marine Observing System National Reference Station sites located on the shelf around Australia shows that both the mean state and seasonality in the present day are well represented, with the exception of sites such as the Great Barrier Reef. Our reconstruction predicts that since 1870 decrease in aragonite saturation state of 0.48 and of 0.09 in pH has occurred in response to increasing oceanic uptake of atmospheric CO2. Large seasonal variability in pH and aragonite saturation state occur in southwestern Australia driven by ocean dynamics (mixing) and in the Tasman Sea by seasonal warming (in the case of the aragonite saturation state). The seasonal and historical changes in aragonite saturation state and pH have different spatial patterns and suggest that the biological responses to ocean acidification are likely to be non-uniform depending on the relative sensitivity of organisms to shifts in pH and saturation state. This new historical reconstruction provides an important link to biological observations that will help to elucidate the consequences of ocean acidification.

  14. A qualitative description of preferred orientation in porous carbonate matrices of marine origin

    Energy Technology Data Exchange (ETDEWEB)

    Golan, Yuval; Dahan, David; Vago, Razi

    2003-10-15

    Porous aragonite matrices of marine origin exhibit a prominent preferred orientation in which the (221) crystal planes are aligned perpendicular to the principal growth direction of the organism. Since the aragonite crystallites that compose the matrix appear to be organized perpendicular to the spherical pore surfaces, these apparently conflicting findings can be explained by a bimodal distribution of the crystallites into pore and bulk crystallite populations. Analysis of X-ray diffraction data obtained from matrices taken from eight different organisms was carried out. The validity of the bimodal distribution model was confirmed by correlation with porosity data.

  15. Mechanism of unusual polymorph transformations in calcium carbonate: Dissolution-recrystallization vs additive-mediated nucleation

    Indian Academy of Sciences (India)

    Arpita Sarkar; Samiran Mahapatra

    2012-11-01

    Unusual transformation of one CaCO3 phase to another has been reported by the process of dissolution-recrystallization and under the influence of additive. In one case, while metastable vaterite transforms to another metastable phase aragonite by simple refluxing in distilled water, it instead transforms thermodynamically stable phase calcite upon refluxing in its `mother-liquor’. This is explained by the process of dissolution-recrystallization. In another case, aragonite is preferentially synthesized over calcite in the presence of molten lauric acid as an additive.

  16. Distribution of Calcium and Chitin in the Tardigrade Feeding Apparatus in Relation to its Function and Morphology.

    Science.gov (United States)

    Guidetti, Roberto; Bonifacio, Alois; Altiero, Tiziana; Bertolani, Roberto; Rebecchi, Lorena

    2015-08-01

    The cuticular portion of the tardigrade feeding apparatus is a complex structure that can be schematically divided into four parts: a buccal ring, a buccal tube, a stylet system (formed by two piercing stylets, each within a stylet coat, and two stylet supports), and the lining of a myoepithelial sucking pharynx. To better understand the function and evolution of the feeding apparatus, the morpho-functional traits and chemical composition of the structures forming the feeding apparatuses of eight different species of tardigrades were analyzed. These eight species are representative of almost all main phylogenetic lineages of the phylum. The calcium and chitin in the feeding apparatus were examined by light microscopy, scanning electron microscopy, confocal laser scanning microscopy, energy dispersive X-ray spectroscopy, and Raman microspectroscopy (Raman). In all species, the feeding apparatus had been subjected to biomineralization due to CaCO3 encrustations organized in the crystalline form of aragonite. Aragonite and chitin are present in different concentrations in the feeding apparatus according to the structures and species considered. Generally, where the structures are rigid there is more aragonite than chitin, and vice versa. The buccal tube and piercing stylets are rich in calcium, with the piercing stylets apparently composed exclusively of aragonite. In eutardigrades, chitin is in higher concentration in the structures subject to higher mechanical stresses, such as the crests of the buccal crown and the condyles of the stylet furca.

  17. High-Magnesian Calcite Mesocrystals : A Coordination Chemistry Approach

    NARCIS (Netherlands)

    Lenders, Jos J. M.; Dey, Archan; Bomans, Paul H. H.; Spielmann, Jan; Hendrix, Marco M. R. M.; de With, Gijsbertus; Meldrum, Fiona C.; Harder, Sjoerd; Sommerdijk, Nico A. J. M.

    2012-01-01

    While biogenic calcites frequently contain appreciable levels of magnesium, the pathways leading to such high concentrations remain unclear. The production of high-magnesian calcites in vitro is highly challenging, because Mg-free aragonite, rather than calcite, is the favored product in the presenc

  18. Unhatched and Hatched Eggshells of the Chinese CobraNaja atra

    Institute of Scientific and Technical Information of China (English)

    Zheng WANG; Longhui LIN; Xiang JI

    2014-01-01

    Changes in structure and composition of the eggshell resulting from embryonic mobilization of minerals from the eggshell are found in all oviparous reptiles studied thus far. In this study, we measured samples of unhatched and hatched eggshells of the Chinese cobraNaja atrato determine the percentage of ash and the phase composition of calcium carbonate. The mean percentage of ash was signiifcantly higher in unhatched eggshells (24.6%) than in hatched eggshells (22.3%). The dominant phase in unhatched eggshells was the calcite form of calcium carbonate. In addition to the peaks of calcite, a few small peaks were found to be caused by the aragonite and vaterite phases of calcium carbonate, implying that there are small amounts of aragonite and vaterite in the eggshell. The concentration of the various phases calculated from the intensity of the X-ray diffraction spectra allowed the estimation that percentages of calcite, aragonite and vaterite were about 92%, 4% and 4%, respectively. Hatched eggshells produced similar spectral characteristics as unhatched eggshells, with one exception. The dominant phase composition in the hatched eggshell was also calcite, but the amount of the aragonite phase had a marked increase. Our study adds evidence that embryonic mobilization of minerals from the eggshell may result in changes in structure of the eggshell.

  19. Electron Spin Resonance Studies of Mn2+ in Freshwater Snail Shells: Pomacea Canaliculata Lamarck and Fossilized Snail Shell

    Institute of Scientific and Technical Information of China (English)

    N. Udomkan; S. Meejoo; P. Limsuwan; P. Winotai; Y. Chaimanee

    2005-01-01

    @@ We study paramagnetic Mn2+ ions present in the nowadays shells of univalve freshwater snails of Pomacea canaliculata lamarck (PCL) and the fossilized freshwater snail (FFS), Viviparus. All these shells are abundant in Thailand. The PCL shells were ground into fine powder. A set of seven samples were then separately annealed for 2 h in air atmosphere at different annealing temperatures while the FFS powder was characterized as-received.The PCL shells mainly consist of aragonite and a fraction of calcite. The heat treatments of the PCL powder samples at temperature higher than 450 ℃ resulted in an irreversible phase transformation from aragonite to calcite. However, it is found that the FFS shell is mainly made of calcite, with a minor fraction of aragonite. The crystal structure of the high-temperature-annealed PCL samples are quite similar to that of FFS, which indicates that the metamorphosis (aragonite → calcite) in the FFS shell had occurred but was not yet completed, although it had remained under the pressure and temperature of the Earth's crusts over millions of years. Our detailed ESR spectral analyses of PCL and FFS show that Mn2+ ions enter the Ca2+ sites during a biomineralization process. Simulated ESR parameters of PCL-500 of Mn2+ at a uniaxial site of calcite are reported. It is surprising to find that the ratio of Mn2+ concentration present in FFS to those in PCL shells evaluated from ESR spectra is as much as 10:1.

  20. 78 FR 10601 - Endangered and Threatened Wildlife; 90-Day Finding on a Petition to List 44 Species of Corals as...

    Science.gov (United States)

    2013-02-14

    ... produce either calcium carbonate (argonite or calcite) secretions resulting in a continuous skeleton or as... composed of aragonite, calcite, high-magnesium calcite, amorphous carbonate hydroxylapatite and there is... exclusively of high-magnesium calcite (Stone et al., in preparation). The single pennatulacean listed in...

  1. Authigenic carbonate mounds from active methane seeps on the southern Aquitaine Shelf (Bay of Biscay, France): Evidence for anaerobic oxidation of biogenic methane and submarine groundwater discharge during formation

    Science.gov (United States)

    Pierre, Catherine; Demange, Jérome; Blanc-Valleron, Marie-Madeleine; Dupré, Stéphanie

    2017-02-01

    The widespread methane emissions that were discovered in 2013 on the Aquitaine Shelf at water depth between 140 and 220 m are associated with authigenic carbonate crusts that cover meter-high subcircular reliefs of 10-100 m in diameter. These authigenic carbonates are primarily aragonite plus calcite and dolomite, which cement the fine- to medium-grained sandy sediment. The carbonate cement is often pierced by numerous circular cavities of 5-10 μm in diameter that are considered to be moulds of gas bubbles. Conversely, micron-sized cavities in the aragonite crystals are attributed to dissolution features, in relation to the production of CO2 during the aerobic oxidation of methane. The oxygen isotopic compositions of bulk carbonate (+1.7 to +3.7‰) and aragonite cements obtained from microsampling (-0.1 to +1.4‰) indicate that these carbonates were precipitated in mixtures of seawater and freshwater, i.e., in the context of submarine groundwater discharge at the seafloor. The carbon isotopic compositions of authigenic carbonates (-51.9 to -38.1‰) and of aragonite cements (-49.9 to -29.3‰) show that the dissolved inorganic carbon of pore fluids was mostly produced by the anaerobic oxidation of biogenic methane and also partly from the groundwater system.

  2. Metapopulation Dynamics of the Softshell Clam, Mya arenaria

    Science.gov (United States)

    2008-06-01

    aragonitic tmaritte bivalve shells. Geochetn. Geophys. Geosyst. 6. Q05009. Solow and S. Thorrold were helpful with data interpretation. We Hatmer, P.A... Roberts . D.. Schnitker, D., Baldauf, J., Desprairies, A., Hoinrighausen, R., Huddlestun, P., Keene, J., Kaltenback, A., Krumsick, K., Morton, A

  3. Isotopic fractionation between seawater and the shell of

    NARCIS (Netherlands)

    Santos, S.; Cardoso, J.F.M.F.; Borges, V.; Luttikhuizen, P.C.; van der Veer, H.W.

    2012-01-01

    This study analyzed the isotopic profiles of four aragonitic shells of Scrobicularia plana in conjunction with measured seawater temperatures and salinities. Comparison of delta O-18(SHELL) with expected values revealed fractionation of delta O-18 in near equilibrium with the ambient environment. Gr

  4. Methane seepage intensities traced by biomarker patterns in authigenic carbonates from the South China Sea

    Science.gov (United States)

    Guan, H.; Feng, D.

    2015-12-01

    Authigenic carbonate rocks from an active seep (Site F) at 1120 m water depth of the South China Sea (SCS) were studied using mineralogical and lipid biomarker analyses. Carbonate mineral compositions, in specific samples, were predominantly aragonite, high-Mg calcite (HMC), or a mixture of both. Abundant 13C-depleted lipid biomarkers (various isoprenoids) diagnostic for archaea provide evidence that anaerobic oxidation of methane (AOM) mediated by anaerobic methane oxidizing archaea (ANME) and their bacterial partners is the major process leading to formation of the carbonates. Nearly a pure suite of AOM biomarkers was preserved in aragonitic carbonate in which predominant consortia were most likely ANME-2/Desulfosarcina & Desulfococcus (DSS) assemblages and a mixture of ANME-2/DSS and ANME-1/DSS consortia in the mixed mineral sample, the predominant consortia are in good accordance with the point that the relative higher methane seepage intensity favors the precipitation of aragonite over HMC. In contrast, the completely different biomarker patterns in HMC sample were mainly composed terrestrial organic matter and marine Thaumarchaea, which most likely originally within sediments accompanied with high organic matter input and low methane supply. This environment is known to be favored for archaea of ANME-1 and precipitation of HMC. High concentrations of 13C-depleted hopanoids, including diplopterol, hopanoic acids and hopanols were observed in the aragonite sample that may be sourced by the intermittent presence of oxic conditions in an overall anoxic condition, which was possibly induced by changing seepage intensities.

  5. Petrosraphic and geochemical characterization of seep carbonate from Alaminos Canyon, Gulf of Mexico

    Institute of Scientific and Technical Information of China (English)

    FENG Dong; CHEN DuoFu; QI Liang; Harry H.ROBERTS

    2008-01-01

    Seep carbonates were collected from the Alaminos Canyon lease area, Gulf of Mexico. The carbonates are present as slabs and blocks. Bivalve shell and foraminifer are the dominant bioclasts in carbonate. Pores are common and usually filled with acicular aragonite crystals. XRD investigation shows that aragonite is the dominate mineral (98%). Peloids, clotted microfabirc and botryoidal aragonite are developed in carbonate and suggest a genesis linked with bacterial degradation of the hydrocarbons. The δ13C value of bioclasts in carbonate is from -4.9‰ to -0.6‰, indicating that the carbon source is mainly from sea water as well as the small portion incorporation of the seep hydrocarbon. The microcrystalline and sparite aragonite shows the δ13C value from -31.3‰, to -23.4‰, suggesting that their carbon is derived mainly from microbial degradation of crude oil. 14C analyses give the radiocarbon age of about 10 ka. Rare earth elements (REE) analyses of the 5% HNO3-treated solution of the carbonates show that the total REE content of the carbonates is low, that is from 0.752 to 12.725 ug·g-1. The shale-normalized REE patterns show significantly negative Ce anomalies. This suggests that cold seep carbonate is most likely formed in a relatively aerobic environment.

  6. Physical and chemical constraints limit the habitat window for an endangered mussel

    Science.gov (United States)

    Campbell, Cara; Prestegaard, Karen L.

    2016-01-01

    Development of effective conservation and restoration strategies for freshwater pearly mussels requires identification of environmental constraints on the distributions of individual mussel species. We examined whether the spatial distribution of the endangered Alasmidonta heterodon in Flat Brook, a tributary of the upper Delaware River, was constrained by water chemistry (i.e., calcium availability), bed mobility, or both. Alasmidonta heterodon populations were bracketed between upstream reaches that were under-saturated with respect to aragonite and downstream reaches that were saturated for aragonite during summer baseflow but had steep channels with high bed mobility. Variability in bed mobility and water chemistry along the length of Flat Brook create a “habitat window” for A. heterodon defined by bed stability (mobility index ≤1) and aragonite saturation (saturation index ≥1). We suggest the species may exist in a narrow biogeochemical window that is seasonally near saturation. Alasmidonta heterodon populations may be susceptible to climate change or anthropogenic disturbances that increase discharge, decrease groundwater inflow or chemistry, and thus affect either bed mobility or aragonite saturation. Identifying the biogeochemical microhabitats and requirements of individual mussel species and incorporating this knowledge into management decisions should enhance the conservation and restoration of endangered mussel species.

  7. Initial formation stage and succedent biomineralization of pearls

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Fen [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Tian, Liangguang [Shandong Institute of Supervision and Inspection on Product Quality, Jinan 250100 (China); Xu, Xiangang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China); Hu, Xiaobo, E-mail: xbhu@sdu.edu.cn [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100 (China)

    2014-04-01

    The initial formation stage and succedent biomineralization of pearls were studied using scanning electron microscopy, Raman spectroscopy, transmission electron microscopy and atomic force microscopy. A new initial formation phase with needle-like structure which is found to be nanocrystallites of aragonite was discovered. As a result, two possible formation modes are proposed to describe the initial formation stage of pearls. As for the succedent mineralization of “brick and mortar” structure, nanostripes were first discovered inside the “brick” (aragonite platelet), compared with the foregoing finding of nanograins. The various nanostructures of aragonite platelet allow us to reconsider the role of the inter- and intracrystalline organic material surrounding CaCO{sub 3}, and a possible biomineralization mechanism was proposed. - Highlights: • A new initial formation mineral phase was discovered in pearl. • Nanograins and nanostripes inside aragonite platelets were found in pearl. • Two possible initial formation stages were proposed for pearl. • A possible biomineralization mechanism of nacre in pearl was proposed.

  8. Mineralogical analyses in Peştera Polovragi (Olteţului Gorges and Peştera Muierii (Galbenului Gorges, Gorj County

    Directory of Open Access Journals (Sweden)

    Ştefan Marincea

    2008-01-01

    Full Text Available Following a series of cave mineralogy researches in Peştera Polovragi and Peştera Muierii, Gorj county, we evidence an association made up of hydroxylapatite, taranakite, calcite and secondarily of quartz and illite and respectively, of hydroxylapatite, brushite, calcite and aragonite, and secondarily of α-quartz and illite.

  9. Tectonic forcing of early to middle jurassic seawater Sr/Ca

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz; Hesselbo, Stephen P.; Korte, Christoph

    2013-01-01

    The Jurassic Period (ca. 201–145 Ma) is marked by fundamental reorganizations of paleogeography, paleoceanography, ecosystems, and the progressive shift from aragonite to calcite as the favored marine biogenic carbonate polymorph. Sr/Ca ratios of well-preserved Jurassic oysters and belemnites from...

  10. Composition and origin of authigenic carbonates in the Krishna-Godavari and Mahanadi Basins, eastern continental margin of India

    Digital Repository Service at National Institute of Oceanography (India)

    Teichert, B.M.A; Johnson, J.E.; Solomon, E.A; Giosan, L.; Rose, K; Kocherla, M.; Connolly, E.C.; Torres, M.E.

    Basin) and 19 (Mahanadi Basin). These methane-derived carbonates display typical paragenetic carbonate mineralogies (aragonite, high-Mg calcite with >15 Mol% MgCO3, Ca-rich dolomite). Two separate horizons of methane derived-carbonates are correlated...

  11. Macroalgae contribute to nested mosaics of pH variability in a subarctic fjord

    NARCIS (Netherlands)

    Krause-Jensen, D.; Duarte, C.M.; Hendriks, I.E.; Meire, L.; Blicher, M.E.; Marba, N.; Sejr, M.K.

    2015-01-01

    The Arctic Ocean is considered the most vulnerable ecosystem to ocean acidification, and large-scale assessments of pH and the saturation state for aragonite (Oarag) have led to the notion that the Arctic Ocean is already close to a corrosive state. In high-latitude coastal waters the reg

  12. Threshold of carbonate saturation state determined by CO2 control experiment

    Directory of Open Access Journals (Sweden)

    A. Negishi

    2012-04-01

    Full Text Available Acidification of the oceans by increasing anthropogenic CO2 emissions will cause a decrease in biogenic calcification and an increase in carbonate dissolution. Previous studies have suggested that carbonate dissolution will occur in polar regions and in the deep sea where saturation state with respect to carbonate minerals (Ω will be a (aragonite saturation state value of >1. This is probably related to the dissolution of reef carbonate (Mg-calcite, which is more soluble than aragonite. However, the threshold of Ω for the dissolution of natural sediments has not been clearly determined. We designed an experimental dissolution system with conditions mimicking those of a natural coral reef, and measured the dissolution rates of aragonite in corals, and of Mg-calcite excreted by other marine organisms, under conditions of Ωa > 1, with controlled seawater pCO2. The experimental data show that dissolution of bulk carbonate sediments sampled from a coral reef occurs at Ωa values of 3.7 to 3.8. Mg-calcite derived from foraminifera and coralline algae dissolves at Ωa values between 3.0 and 3.2, and coralline aragonite starts to dissolve when Ωa = 1.0. We show that nocturnal carbonate dissolution of coral reefs occurs mainly by the dissolution of foraminiferans and coralline algae in reef sediments.

  13. ESEM-BSE coupled with rapid nano-scratching for micro-physicochemical analysis of marine exposed concrete

    NARCIS (Netherlands)

    Palin, D.; Thijssen, A.; Wiktor, V.; Jonkers, H.M.; Schlangen, H.E.J.G.

    2015-01-01

    Ordinary Portland cement (OPC) mortar specimens submerged in sea-water were analysed through environmental scanning electron microscopy (ESEM) in back scattered electron (BSE) mode and nano-scratching. Results from both sets of analysis show the presence of distinct phases associated with aragonite,

  14. Polymorphism of CaCO{sub 3} and microstructure of the shell of a Brazilian invasive Mollusc (Limnoperna fortunei)

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura Filho, Arnaldo; Almeida, Arthur Correa de; Riera, Hernan Espinoza; Cardoso, Antonio Valadao, E-mail: nakamuraaf@gmail.com [Rede Tematica em Engenharia de Materiais (REDEMAT), Ouro Preto, MG (Brazil); Araujo, Joao Locke Ferreira de [Centro de Bioengenharia de Especies Invasoras de Hidreletricas(CBEIH), Belo Horizonte, MG (Brazil); Gouveia, Vitor Jose Pinto [Fundacao Centro Tecnologico de Minas Gerais (CETEC), Belo Horizonte, MG (Brazil); Carvalho, Marcela David de [Companhia Energetica de Minas Gerais (CEMIG), Belo Horizonte, MG (Brazil)

    2014-08-15

    Applying the theories of Materials Science and Engineering to describe the composition and hierarchy of microstructures that comprise biological systems could help the search for new materials and results in a deeper insight into evolutionary processes. The layered microstructure that makes up the freshwater bivalve Limnoperna fortunei shell, an invasive specie in Brazil, was investigated utilizing SEM and AFM for the determination of the morphology and organization of the layers; and XRD was used to determine the crystalline phases of the calcium carbonate (CaCO{sub 3}) present in the shell. The presence of the polymorphs calcite and aragonite were confirmed and the calcite is present only on the external side of the shell. The shell of L. fortunei is composed of two layers of aragonite with distinct microstructures (the aragonite prismatic layer and the aragonite sheet nacreous layer) and the periostracum (a protein layer that covers and protects the ceramic part of the shell). A new morphology of the calcite layer was found, below the periostracum, without defined form, albeit crystal (author)

  15. Endolith microborings and their preservation in Holocene-Pleistocene (Bahama-Florida) ooids

    Science.gov (United States)

    Harris, Paul M.; Halley, Robert B.; Lukas, Karen J.

    1979-01-01

    Holocene ooids from Joulters Ooid Shoal (Bahamas) are bored in various ways by blue-green algae that groove along the grain surface, reside just beneath the grain surface, and tunnel extensively a few tens of microns within the grain. The microborings, morphologically distinctive, are documented with scanning electron micrographs of open borings and resin casts. Gentle dissolution of ooid aragonite permits identification of several algal genera by light microscopy and enables comparison with the microboring casts. Pleistocene ooids from the Miami Limestone (Florida) contain natural casts of microborings, some of which are similar in form to Holocene examples. Significantly, these aragonite casts are more resistant to solution than surrounding ooid aragonite. They remain after most of the ooid is leached away and survive replacement of the ooid by low-Mg calcite. Dissolution or precipitation may occur along the walls of microborings, causing morphological alteration during their preservation. This points out a difficulty in the specific identification of endoliths on the basis of fossilized microborings in ancient rocks composed of original aragonite grains.

  16. Transport of Optically Active Particles from the Surface Mixed Layer

    Science.gov (United States)

    2005-09-30

    aragonite in the form of abundant coccoliths and coccospheres, and occasional forams, pteropods and larval gastropods . The δ18O signature of the 2003... APPLICATIONS These experiments were designed to identify the major loss terms of optically-active particles. This indeed was accomplished. Such

  17. Biominerals at the nanoscale: transmission electron microscopy methods for studying the special properties of biominerals

    DEFF Research Database (Denmark)

    Posfai, Mihaly; Kasama, Takeshi; Dunin-Borkowski, Rafal E.

    2013-01-01

    Biominerals have important functions in living organisms: apatite crystals are responsible for the strength of our bones and the hardness of our teeth, calcite and aragonite are used by many organisms for making shells, and magnetite and greigite help bacteria and birds to navigate in magnetic...

  18. Study of the crystallographic architecture of corals at the nanoscale by scanning transmission X-ray microscopy and transmission electron microscopy.

    Science.gov (United States)

    Benzerara, Karim; Menguy, Nicolas; Obst, Martin; Stolarski, Jarosław; Mazur, Maciej; Tylisczak, Tolek; Brown, Gordon E; Meibom, Anders

    2011-07-01

    We have investigated the nanotexture and crystallographic orientation of aragonite in a coral skeleton using synchrotron-based scanning transmission X-ray microscopy (STXM) and transmission electron microscopy (TEM). Polarization-dependent STXM imaging at 40-nm spatial resolution was used to obtain an orientation map of the c-axis of aragonite on a focused ion beam milled ultrathin section of a Porites coral. This imaging showed that one of the basic units of coral skeletons, referred to as the center of calcification (COC), consists of a cluster of 100-nm aragonite globules crystallographically aligned over several micrometers with a fan-like distribution and with the properties of single crystals at the mesoscale. The remainder of the skeleton consists of aragonite single-crystal fibers in crystallographic continuity with the nanoglobules comprising the COC. Our observation provides information on the nm-scale processes that led to biomineral formation in this sample. Importantly, the present study illustrates how the methodology described here, which combines HRTEM and polarization-dependent synchrotron-based STXM imaging, offers an interesting new approach for investigating biomineralizing systems at the nm-scale.

  19. A transient fault-valve mechanism operating in upper crustal level, Sierras Pampeanas, Argentina

    Science.gov (United States)

    Japas, María Silvia; Urbina, Nilda Esther; Sruoga, Patricia; Garro, José Matías; Ibañes, Oscar

    2016-11-01

    Located in the Sierras Pampeanas (the broken-foreland of the Pampean flat slab segment in the southern Central Andes), the Cerro Tiporco volcanic field shows Neogene hydrothermal activity linked to migration of arc-magmatism into the foreland. Late Neogene deposits comprise epithermal vein systems emplaced in Precambrian-Early Palaeozoic igneous-metamorphic basement, Late Miocene sedimentary rocks and Early Pliocene volcaniclastic rocks. Mineralization consists of calcareous onyx, aragonite and calcite veins as well as travertine deposits. Onyx and aragonite occur as fill of low-displacement nearly vertical reverse-sinistral faults striking NW, and nearly horizontal dilatant fractures. The latter consist of load-removal induced fractures affecting the igneous-metamorphic rocks, as well as bedding planes in the Late Miocene sediments. The presence of veins recording multiple fracture episodes and crack-and-seal growth of veins suggests relatively low differential stress and supralithostatic fluid pressure, as well as cyclic changes in pore pressure and high mineral-deposition/fracture-opening ratio. These conditions support a mechanism of fault-valve behaviour during onyx and aragonite vein emplacement. The fault-valve mechanism involves fractures associated with impermeable barriers between environments with different fluid pressure. Faulting generated an appreciable directional permeability triggering fluid migration from the highest to the lowest pressure region, with subsequent deposition and sealing that started a new pressurization-faulting-sealing cycle. Late aragonite and calcite veins suggest a change in kinematics indicating the onset of tectonic-load conditions.

  20. Ocean acidification reduces the crystallographic control in juvenile mussel shells.

    Science.gov (United States)

    Fitzer, Susan C; Cusack, Maggie; Phoenix, Vernon R; Kamenos, Nicholas A

    2014-10-01

    Global climate change threatens the oceans as anthropogenic carbon dioxide causes ocean acidification and reduced carbonate saturation. Future projections indicate under saturation of aragonite, and potentially calcite, in the oceans by 2100. Calcifying organisms are those most at risk from such ocean acidification, as carbonate is vital in the biomineralisation of their calcium carbonate protective shells. This study highlights the importance of multi-generational studies to investigate how marine organisms can potentially adapt to future projected global climate change. Mytilus edulis is an economically important marine calcifier vulnerable to decreasing carbonate saturation as their shells comprise two calcium carbonate polymorphs: aragonite and calcite. M. edulis specimens were cultured under current and projected pCO2 (380, 550, 750 and 1000μatm), following 6months of experimental culture, adults produced second generation juvenile mussels. Juvenile mussel shells were examined for structural and crystallographic orientation of aragonite and calcite. At 1000μatm pCO2, juvenile mussels spawned and grown under this high pCO2 do not produce aragonite which is more vulnerable to carbonate under-saturation than calcite. Calcite and aragonite were produced at 380, 550 and 750μatm pCO2. Electron back scatter diffraction analyses reveal less constraint in crystallographic orientation with increased pCO2. Shell formation is maintained, although the nacre crystals appear corroded and crystals are not so closely layered together. The differences in ultrastructure and crystallography in shells formed by juveniles spawned from adults in high pCO2 conditions may prove instrumental in their ability to survive ocean acidification.

  1. Identification of genes directly involved in shell formation and their functions in pearl oyster, Pinctada fucata.

    Directory of Open Access Journals (Sweden)

    Dong Fang

    Full Text Available Mollusk shell formation is a fascinating aspect of biomineralization research. Shell matrix proteins play crucial roles in the control of calcium carbonate crystallization during shell formation in the pearl oyster, Pinctada fucata. Characterization of biomineralization-related genes during larval development could enhance our understanding of shell formation. Genes involved in shell biomineralization were isolated by constructing three suppression subtractive hybridization (SSH libraries that represented genes expressed at key points during larval shell formation. A total of 2,923 ESTs from these libraries were sequenced and gave 990 unigenes. Unigenes coding for secreted proteins and proteins with tandem-arranged repeat units were screened in the three SSH libraries. A set of sequences coding for genes involved in shell formation was obtained. RT-PCR and in situ hybridization assays were carried out on five genes to investigate their spatial expression in several tissues, especially the mantle tissue. They all showed a different expression pattern from known biomineralization-related genes. Inhibition of the five genes by RNA interference resulted in different defects of the nacreous layer, indicating that they all were involved in aragonite crystallization. Intriguingly, one gene (UD_Cluster94.seq.Singlet1 was restricted to the 'aragonitic line'. The current data has yielded for the first time, to our knowledge, a suite of biomineralization-related genes active during the developmental stages of P. fucata, five of which were responsible for nacreous layer formation. This provides a useful starting point for isolating new genes involved in shell formation. The effects of genes on the formation of the 'aragonitic line', and other areas of the nacreous layer, suggests a different control mechanism for aragonite crystallization initiation from that of mature aragonite growth.

  2. Sr/Ca Ratios of Vaceletia: Implication for Biocalcification Mechanisms of Sclerosponges

    Science.gov (United States)

    Haase-Schramm, A.; Boehm, F.; Eisenhauer, A.; Garbe-Schoenberg, D.; Reitner, J.; Woerheide, G.

    2005-12-01

    Sclerosponges have been established as reliable proxy recorders for several environmental parameters like the radiocarbon and stable carbon isotopic composition, lead concentration, temperature and salinity of ambient water. Specifically, Sr/Ca ratios in skeletons of the Caribbean species Ceratoporella nicholsoni have been shown to record water temperatures with a very high precision. In order to study the variability of strontium incorporation and its temperature dependence in the skeletons of different sclerosponge species, we investigated the Sr/Ca ratios of various specimens of Vaceletia crypta and Vaceletia sp. from different sites and water depths in the Pacific. We determined Sr/Ca ratios and their temperature dependence in Vaceletia skeletons and compared them with published data of Ceratoporella and Astrosclera, inorganic aragonite and ooids. The Sr/Ca-temperature relation in Vaceletia and Ceratoporella is identical within errors (-0.1mmol/mol/K) and stronger than in inorganic aragonites and corals. The distribution coefficient of Sr/Ca in aragonite relative to sea water is similar in Ceratoporella and inorganic aragonite, however it is higher in Vaceletia, Astrosclera and ooids. The sclerosponges Ceratoporella, Vaceletia and Astrosclera precipitate the bulk of skeletal aragonite extracellularly as synvivo-diagenetic, epitactic overgrowth, in carbon and oxygen isotopic equilibrium with ambient sea water. Thus sea water derived carbonate ions are incorporated into the skeleton without biologic modifications. In contrast, the observed interspecific differences of skeletal cation ratios indicate an incorporation process, which involves the biologically controlled modification of the sea water ion composition. I. e. sclerosponges use a calcification mechanism that does not affect carbonate anions, but selectively incorporates certain cations.

  3. CO(2-driven ocean acidification alters and weakens integrity of the calcareous tubes produced by the serpulid tubeworm, Hydroides elegans.

    Directory of Open Access Journals (Sweden)

    Vera Bin San Chan

    Full Text Available As a consequence of anthropogenic CO(2-driven ocean acidification (OA, coastal waters are becoming increasingly challenging for calcifiers due to reductions in saturation states of calcium carbonate (CaCO(3 minerals. The response of calcification rate is one of the most frequently investigated symptoms of OA. However, OA may also result in poor quality calcareous products through impaired calcification processes despite there being no observed change in calcification rate. The mineralogy and ultrastructure of the calcareous products under OA conditions may be altered, resulting in changes to the mechanical properties of calcified structures. Here, the warm water biofouling tubeworm, Hydroides elegans, was reared from larva to early juvenile stage at the aragonite saturation state (Ω(A for the current pCO(2 level (ambient and those predicted for the years 2050, 2100 and 2300. Composition, ultrastructure and mechanical strength of the calcareous tubes produced by those early juvenile tubeworms were examined using X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, scanning electron microscopy (SEM and nanoindentation. Juvenile tubes were composed primarily of the highly soluble CaCO(3 mineral form, aragonite. Tubes produced in seawater with aragonite saturation states near or below one had significantly higher proportions of the crystalline precursor, amorphous calcium carbonate (ACC and the calcite/aragonite ratio dramatically increased. These alterations in tube mineralogy resulted in a holistic deterioration of the tube hardness and elasticity. Thus, in conditions where Ω(A is near or below one, the aragonite-producing juvenile tubeworms may no longer be able to maintain the integrity of their calcification products, and may result in reduced survivorship due to the weakened tube protection.

  4. Shell condition and survival of Puget Sound pteropods are impaired by ocean acidification conditions.

    Directory of Open Access Journals (Sweden)

    D Shallin Busch

    Full Text Available We tested whether the thecosome pteropod Limacina helicina from Puget Sound, an urbanized estuary in the northwest continental US, experiences shell dissolution and altered mortality rates when exposed to the high CO2, low aragonite saturation state (Ωa conditions that occur in Puget Sound and the northeast Pacific Ocean. Five, week-long experiments were conducted in which we incubated pteropods collected from Puget Sound in four carbon chemistry conditions: current summer surface (∼460-500 µatm CO2, Ωa≈1.59, current deep water or surface conditions during upwelling (∼760 and ∼1600-1700 µatm CO2, Ωa≈1.17 and 0.56, and future deep water or surface conditions during upwelling (∼2800-3400 µatm CO2, Ωa≈0.28. We measured shell condition using a scoring regime of five shell characteristics that capture different aspects of shell dissolution. We characterized carbon chemistry conditions in statistical analyses with Ωa, and conducted analyses considering Ωa both as a continuous dataset and as discrete treatments. Shell dissolution increased linearly as aragonite saturation state decreased. Discrete treatment comparisons indicate that shell dissolution was greater in undersaturated treatments compared to oversaturated treatments. Survival increased linearly with aragonite saturation state, though discrete treatment comparisons indicated that survival was similar in all but the lowest saturation state treatment. These results indicate that, under starvation conditions, pteropod survival may not be greatly affected by current and expected near-future aragonite saturation state in the NE Pacific, but shell dissolution may. Given that subsurface waters in Puget Sound's main basin are undersaturated with respect to aragonite in the winter and can be undersaturated in the summer, the condition and persistence of the species in this estuary warrants further study.

  5. Locally driven interannual variability of near-surface pH and ΩA in the Strait of Georgia

    Science.gov (United States)

    Moore-Maley, Ben L.; Allen, Susan E.; Ianson, Debby

    2016-03-01

    Declines in mean ocean pH and aragonite saturation state (ΩA) driven by anthropogenic CO2 emissions have raised concerns regarding the trends of pH and ΩA in estuaries. Low pH and ΩA can be harmful to a variety of marine organisms, especially those with calcium carbonate shells, and so may threaten the productive ecosystems and commercial fisheries found in many estuarine environments. The Strait of Georgia is a large, temperate, productive estuarine system with numerous wild and aquaculture shellfish and finfish populations. We determine the seasonality and variability of near-surface pH and ΩA in the Strait using a one-dimensional, biophysical, mixing layer model. We further evaluate the sensitivity of these quantities to local wind, freshwater, and cloud forcing by running the model over a wide range of scenarios using 12 years of observations. Near-surface pH and ΩA demonstrate strong seasonal cycles characterized by low pH, aragonite-undersaturated waters in winter and high pH, aragonite-supersaturated waters in summer. The aragonite saturation horizon generally lies at ˜20 m depth except in winter and during strong Fraser River freshets when it shoals to the surface. Periods of strong interannual variability in pH and aragonite saturation horizon depth arise in spring and summer. We determine that at different times of year, each of wind speed, freshwater flux, and cloud fraction are the dominant drivers of this variability. These results establish the mechanisms behind the emerging observations of highly variable near-surface carbonate chemistry in the Strait.

  6. Using palynology to re-assess the Dead Sea laminated sediments - Indeed varves?

    Science.gov (United States)

    López-Merino, Lourdes; Leroy, Suzanne A. G.; Eshel, Amram; Epshtein, Valentina; Belmaker, Reuven; Bookman, Revital

    2016-05-01

    Lacustrine laminated sediments are often varves representing annual rhythmic deposition. The Dead Sea high-stand laminated sections consist of mm-scale alternating detrital and authigenic aragonite laminae. Previous studies assumed these laminae were varves deposited seasonally. However, this assumption has never been robustly validated. Here we report an examination of the seasonal deposition of detrital-aragonite couplets from two well-known Late Holocene laminated sections at the Ze'elim fan-delta using palynology and grain-size distribution analyses. These analyses are complemented by the study of contemporary flash-flood samples and multivariate statistical analysis. Because transport affects the pollen preservation state, well-preserved (mostly) air-borne transported pollen was analysed separately from badly-preserved pollen and fungal spores, which are more indicative of water transport and reworking from soils. Our results indicate that (i) both detrital and aragonite laminae were deposited during the rainy season; (ii) aragonite laminae have significantly lower reworked and fungal spore concentrations than detrital and flash-flood samples; and (iii) detrital laminae are composed of recycling of local and distal sources, with coarser particles that were initially deposited in the Dead Sea watershed and later transported via run-off to the lake. This is in line with previous carbon balance studies that showed that aragonite precipitation occurs after the massive input of TCO2 associated with run-off episodes. Consequently, at least for the Holocene Ze'elim Formation, laminated sediments cannot be considered as varves. Older Quaternary laminated sequences should be re-evaluated.

  7. Growth and development of spring towers at Shiqiang, Yunnan Province, China

    Science.gov (United States)

    Jones, Brian; Peng, Xiaotong

    2017-01-01

    Throughout the world, high artesian pressures in hydrothermal areas have led to the growth of tall spring towers that have their vents at their summits. The factors that control their development and formative precipitates are poorly understood because these springs, irrespective of location, are mostly inactive. Spring towers found at Shiqiang (Yunnan Province, China), which are up to 4 m high and 3 m in diameter, are formed largely of calcite and aragonite crystal bushes, euhedral calcite crystals and coated grains with alternating Fe-poor and Fe-rich zones, calcite rafts, and cements formed of various combinations of calcite, aragonite, strontianite, Mg-Si reticulate, needle fiber calcite, calcified and non-calcified microbes, diatoms, and insects. Collectively, the limestones that form the towers can be divided into (1) Group A that are friable, porous and form the cores of the towers and have δ18OSMOW values of + 15.7 to + 19.7‰ (average 17.8‰) and δ13CPDB values of + 5.1 to + 6.9‰ (average 5.9‰), and (2) Group B that are hard and well lithified and found largely around the vents and the tower sides, and have δ18OSMOW values of + 13.0 to + 22.0‰ (average 17.6‰) and δ13CPDB values of + 1.4 to + 3.6‰ (average 2.6‰). The precipitates and the isotopic values indicate that these were thermogene springs. Growth of the Shiqiang spring towers involved (1) Phase IA when precipitation of calcite and aragonite bushes formed the core of the tower and Phase IB when calcite, commonly Fe-rich, was precipitated locally, (2) Phase II that involved the precipitation of white cements, formed of calcite, aragonite, strontianite, and Mg-Si reticulate coatings in cavities amid the Phase I precipitates, and (3) Phase III, which formed probably after spring activity ceased, when needle-fiber calcite was precipitated and the mounds were invaded by microbes (some now calcified), diatoms, and insects. At various times during this complex history, pore waters mediated

  8. Experimental subsolidus phase relations in the system CaCO3-CaMg(CO3)2 up to 6.5 GPa and implications for subducted marbles

    Science.gov (United States)

    Hermann, Jörg; Troitzsch, Ulrike; Scott, Dean

    2016-10-01

    The dissociation of dolomite to aragonite + magnesite and the reaction of dolomite + aragonite to Mg-calcite have been experimentally determined by piston cylinder experiments in the range of 650-1000 °C and 2-6.5 GPa. Friction decay within the salt sleeves used as pressure medium was monitored by continuously logging the travel distance of the piston. Piston movement ceased after the first 24 h of the experiment, and all experiments were kept at the steady-state conditions for an additional 24-196 h. The reaction of dolomite to aragonite + magnesite has a positive slope and has been bracketed at 650 °C between 5.1 and 5.8 GPa and at 750 °C between 5.7 and 6.5 GPa. The reaction is sluggish with a 0.6-GPa interval where all three phases coexist. The reaction dolomite + aragonite to Mg-calcite has been determined in 0.5-GPa intervals from 660 °C at 2 GPa to 940 °C at 6.5 GPa. The composition of Mg-calcite at the reaction curve is buffered and changes systematically from X(Ca) of 0.90 at 2 GPa to 0.57 at 6.5 GPa. The solvus between dolomite and Mg-calcite shrinks slightly with increasing pressure, providing evidence for a small negative slope of the critical curve dolomite = Mg-calcite. The degree of disorder in dolomite has been determined in some of the retrieved samples by Rietveld refinement based on X-ray diffraction patterns. The order parameter S decreases gradually from 1 to 0.7 as a function of temperature as the critical curve is approached and then drops dramatically after crossing it. No ordering on quench has been observed. The experimental results permit the construction of a petrogenetic grid for the system dolomite, aragonite, Mg-calcite, and magnesite, which has an invariant point at ~7.5 GPa and 980 °C, representing the maximum pressure stability of dolomite. X(Ca) isopleths of Mg-calcite coexisting with dolomite serve mainly as a thermometer, whereas in the presence of aragonite they are a useful barometer. The experimental results have been

  9. Calibration of the carbonate `clumped isotope' paleotemperature proxy using mollusc shells and benthic foraminiferal tests

    Science.gov (United States)

    Came, R. E.; Curry, W. B.; Weidman, C. R.; Eiler, J. M.

    2007-12-01

    It has recently been shown that the carbonate `clumped isotope' thermometer can provide temperature constraints that depend only on the isotopic composition of carbonate (in particular, on the proportion of 13C and 18O that form bonds with each other), and that do not require assumptions about the isotopic composition of the water in which the carbonate formed (Ghosh et al., 2006). Furthermore, this novel method permits the calculation of seawater δ18O based on the clumped isotope temperature estimates and the simultaneously obtained δ18O of carbonate, thereby enabling the extraction of global ice volume estimates for both the recent and distant geologic past. Here we present clumped isotope analyses of several naturally occurring marine carbonates that calcified at known temperatures in the modern ocean. First, we analyzed benthic foraminiferal tests from six high-quality multicore tops collected in the Florida Strait, spanning a temperature range of 9.3-20.2 degrees C. Second, we analyzed shallow-water mollusc shells from a variety of different climate regimes, spanning a temperature range of 2.5-26.0 degrees C. We find that the calcitic foraminiferal species Cibicidoides spp. agrees well with the inorganic calcite precipitation experiments of Ghosh et al. (2006), while the aragonitic species Hoeglundina elegans is significantly offset. Similarly, clumped isotope results obtained from aragonitic mollusc shells also reveal an offset from the Ghosh et al. (2006) trend, although the offset observed in mollusc aragonite is quite different in nature from that observed in foraminiferal aragonite. Assuming our estimates of the growth temperatures of these naturally occurring organisms are correct, these results suggest that there are vital effects associated with the stable isotope compositions of the aragonite-precipitating organisms examined in this study; further work will be required to determine their cause. Nevertheless, the internal coherence of trends for

  10. Interpreting the Marine Calcium Isotope Record: Influence of Reef Builders

    Science.gov (United States)

    Boehm, F.; Eisenhauer, A.; Farkas, J.; Kiessling, W.; Veizer, J.; Wallmann, K.

    2008-12-01

    The calcium isotopic composition of seawater as recorded in brachiopod shells varied substantially during the Paleozoic (Farkas et al. 2007, Geochim. Cosmochim. Acta, 71, 5117-5134). The most prominent feature of the record is an excursion to higher 44Ca/40Ca values that started during the Early Carboniferous and lasted until the Permian. The shift occurred shortly after the transition from a calcite-sea to an aragonite-sea (Sandberg 1983, Nature 305, 19-22; Stanley and Hardie 1998, Pal3, 144, 3-19). It therefore has been interpreted to reflect a change in the average calcium isotope fractionation of carbonates produced in the oceans. Aragonite is depleted by about 0.6 permil in 44Ca/40Ca compared to calcite (Gussone et al. 2005, Geochim. Cosmochim. Acta, 69, 4485-4494). Consequently a transient shift from calcite dominated to an aragonite dominated calcium carbonate sedimentation could have caused the observed 0.5 permil isotope shift. We compare the marine calcium isotope record with a new compilation of the Phanerozoic trends in the skeletal mineralogy of marine invertebrates (Kiessling et al. 2008, Nature Geoscience, 1, 527-530). The compilation is based on data collected in the PaleoReef database and the Paleobiology Database, which include information on Phanerozoic reef complexes and taxonomic collection data of Phanerozoic biota, respectively. We find a strong positive correlation between the calcium isotope ratios and the abundance of aragonitic reef builders from the Silurian until the Permian at a sample resolution of about 10 million years. The two records, however, diverge in the Triassic, when reefs were dominated by aragonite but the calcium isotope values remained at a relatively low level. We also find a good correlation between calcium isotopes and the proportion of aragonite in the general record of Phanerozoic biota. However, in this case the records start to diverge already in the latest Carboniferous. The observations suggest that the

  11. Behaviour of calcium carbonate in sea water

    Science.gov (United States)

    Cloud, P.E.

    1962-01-01

    Anomalies in the behaviour of calcium carbonate in natural solutions diminish when considered in context. Best values found by traditional oceanographie methods for the apparent solubility product constant K'CaCO3 in sea water at atmospheric pressure are consistent mineralogically-at 36 parts per thousand salinity and T-25??C, K'aragonlte is estimated as 1.12 ?? 10-6 and K'calcite as 0.61 ?? 10-6. At 30??C the corresponding values are 0.98 ?? 10-6 for aragonite and 0.53 ?? 10-6 for calcite. Because the K' computations do not compensate for ionic activity, however, they cannot give thermodynamically satisfactory results. It is of interest, therefore, that approximate methods and information now available permit the estimation from the same basic data of an activity product constant KCaCO3 close to that found in solutions to which Debye-Hu??ckel theory applies. Such methods indicate approximate Karagonite 7.8 ?? 10-9 for surface sea water at 29??C; Kcalcite would be proportionately lower. Field data and experimental results indicate that the mineralogy of precipitated CaCO3 depends primarily on degree of supersaturation, thus also on kinetic or biologic factors that facilitate or inhibit a high degree of supersaturation. The shallow, generally hypersaline bank waters west of Andros Island yield aragonitic sediments with O18 O16 ratios that imply precipitation mainly during the warmer months, when the combination of a high rate of evaporation, increasing salinity (and ionic strength), maximal temperatures and photosynthetic removal of CO2 result in high apparent supersaturation. The usual precipitate from solutions of low ionic strength is calcite, except where the aragonite level of supersaturation is reached as a result of diffusion phenomena (e.g. dripstones), gradual and marked evaporation, or biologic intervention. Published data also suggest the possibility of distinct chemical milieus for crystallographic variations in skeletal calcium carbonate. It appears

  12. Evidences of microbial mediation in the formation of MDAC in the Gulf of Cadiz

    Science.gov (United States)

    Magalhaes, V. H.; Pinheiro, L. M.; Birguel, D.; Peckmann, J.; Niemann, H.; Santos, L.; Vasconcelos, C.; McKenzie, J.; Ivanov, M.

    2006-12-01

    The study of methane-derived authigenic carbonates (MDAC) in the Gulf of Cadiz allowed the identification and collection of different types of authigenic carbonates: (I) dolomite crusts, dolomite nodules, chimneys or filled burrows and (II) aragonitic slabs or pavements. Both correspond to the cementation of sediments by the precipitation of authigenic carbonates, and the different lithologic types correspond to different geochemical environment of formation. Authigenic carbonates yielded 13C values indicating methane as the major carbon source with ratios as low as -46.9(per mil PDB). Likewise, the crusts and chimneys can be interpreted as a record of extensive methane seepage in this particular area of the Gulf of Cadiz. SEM observations revealed large amounts of structures and textures that clearly indicate microbial activity. In the cement of the dolomite chimneys, which consists of minor aggregates of rhombohedric calcite, high-Mg calcite and dolomite, SEM observations allowed the identification of a large variety of microbial-induced fabrics, such as: (1) microbial filaments; (2) high Mg-calcite and dolomite crystal aggregates calcifying and mimetizing filaments and flattening themselves against dolomite and calcite minerals; (3) rods with brush-like terminations; (4) dumbbell-like and cauliflower structures. The identification of microbial and mucous biofilms is frequent in aragonite pavements, occurring as a coating, draped between the aragonite fibres and needles of the stromatolitic layers. Also, aragonite batons, ball-capped batons and nanograins are observed. Specific 13C-depleted biomarkers indicators of archaea involved in the anaerobic oxidation of methane (AOM) as PMI, squalane, crocetane/phytane have been identified in dolomite chimney samples. The aragonite crusts showed even better preserved biomarkers. PMI is accompanied by unsaturated derivatives with 1 to 3 double bonds. Several bacterial lipid biomarkers, also with 13C-depleted compositions

  13. The long-term impact of magnesium in seawater on foraminiferal mineralogy: Mechanism and consequences

    Science.gov (United States)

    Dijk, I.; Nooijer, L. J.; Hart, M. B.; Reichart, G.-J.

    2016-03-01

    Foraminifera are unicellular protists, primarily known for their calcium carbonate shells that provide an extensive fossil record. This record, ranging from Cambrian to present shows both major shifts and gradual changes in the relative occurrence of taxa producing different polymorphs of carbonate. Here we present evidence for coupling between shifts in calcite- versus aragonite-producing species and periods with, respectively, low and high seawater Mg/Ca throughout the Phanerozoic. During periods when seawater Mg/Ca is extinction rates of species producing the mineral phase not favored by the seawater Mg/Ca of that time may be responsible for this alteration. These results imply that the current high seawater Mg/Ca will, in the long term, favor prevalence of high-Mg and aragonite-producing foraminifera over calcite-producing taxa, possibly shifting the balance toward a community in which calcite production is less dominant.

  14. Increase in acidifying water in the western Arctic Ocean

    Science.gov (United States)

    Qi, Di; Chen, Liqi; Chen, Baoshan; Gao, Zhongyong; Zhong, Wenli; Feely, Richard A.; Anderson, Leif G.; Sun, Heng; Chen, Jianfang; Chen, Min; Zhan, Liyang; Zhang, Yuanhui; Cai, Wei-Jun

    2017-02-01

    The uptake of anthropogenic CO2 by the ocean decreases seawater pH and carbonate mineral aragonite saturation state (Ωarag), a process known as Ocean Acidification (OA). This can be detrimental to marine organisms and ecosystems. The Arctic Ocean is particularly sensitive to climate change and aragonite is expected to become undersaturated (Ωarag oceans. However, the extent and expansion rate of OA in this region are still unknown. Here we show that, between the 1990s and 2010, low Ωarag waters have expanded northwards at least 5°, to 85° N, and deepened 100 m, to 250 m depth. Data from trans-western Arctic Ocean cruises show that Ωarag Arctic Ocean than the Pacific and Atlantic oceans, with the western Arctic Ocean the first open-ocean region with large-scale expansion of `acidified’ water directly observed in the upper water column.

  15. Scanning electron microscopic structure of the prismatic layer in the Bivalvia

    Institute of Scientific and Technical Information of China (English)

    Iwao KOBAYASHI

    2008-01-01

    The shell structure of the Bivalvia has been observed with the use of optical and electron microscopes since the early 1900's. The prismatic structure is one of the more attractive shell structures in bivalved mollusks. This structure is composed of the aggregation of polygonal prisms arranged densely. Each prism is made of small calcite crystallites arranged perpendicular to a growth shell surface. Organic materials, named organic sheaths, accumulate around prisms and stain well with heamatox-ylin-eosin.The Bivalvia, which make prismatic structures, are divided into two groups. One group has the inner shell layer made up of a nacreous structure, and the other has the inner shell layer made up of a foliated structure. The aragonite prismatic layer and the prismatic layer are clo-sely related to each other, as is the aragonite prismatic layer to the composite prismatic one.

  16. Chemical composition of a saline lake on Enderbury Island, Phoenix Island Group, Pacific Ocean

    Science.gov (United States)

    Gulbrandsen, Robert A.; Brown, David W.

    1973-01-01

    Ion activity products for the dissolution of calcite, aragonite, gypsum, monetite, brushite, dolomite, magnesite, hydroxyapatite, and fluorapatite were calculated for a South Pacific guano island brine with an ionic strength of 6.4. Environmental conditions for the brine at the time of analysis and of sampling indicated saturation with respect to calcite, aragonite, gypsum, hydroxyapatite and fluorapatite; a comparison of the ion activity products and equilibrium constants indicated saturation or supersaturation with respect to most minerals found in lake sediments or elsewhere on the island. The results suggest that chemical thermodynamic calculations for brines may have some usefulness despite the many assumptions and estimations that must be made.

  17. Mineral proximity influences mechanical response of proteins in biological mineral-protein hybrid systems.

    Science.gov (United States)

    Ghosh, Pijush; Katti, Dinesh R; Katti, Kalpana S

    2007-03-01

    The organic phase of nacre, which is composed primarily of proteins, has an extremely high elastic modulus as compared to that of bulk proteins, and also undergoes large deformation before failure. One reason for this unusually high modulus could be the mineral-organic interactions. In this work, we elucidate the specific role of mineral proximity on the structural response of proteins in biological structural composites such as nacre through molecular modeling. The "glycine-serine" domain of a nacre protein Lustrin A has been used as a model system. It is found that the amount of work needed to unfold is significantly higher when the GS domain is pulled in the proximity of aragonite. These results indicate that the proximity of aragonite has a significant effect on the unfolding mechanisms of proteins when pulled. These results will provide very useful information in designing synthetic biocomposites, as well as further our understanding of mechanical response in structural composites in nature.

  18. Texture and nano-scale internal microstructure of otoliths in the Atlantic molly, Poecilia mexicana: a high-resolution EBSD study.

    Science.gov (United States)

    Schulz-Mirbach, T; Götz, A; Griesshaber, E; Plath, M; Schmahl, W W

    2013-08-01

    Otoliths of modern bony fishes are massive polycrystalline structures consisting mainly of calcium carbonate (primarily aragonite), and 1-10% organic residuals. Unlike other biomineralisates like shells, teeth and bones, they are not optimized for mechanical loads but serve the senses of hearing and balance in the inner ear. We examined internal structural variation of otoliths through microstructural and texture analyses. Our study applied the electron backscattered diffraction technique (EBSD) to whole sections of saccular otoliths on cave- and surface-dwelling fish. Application of high spatial resolution EBSD on otoliths of the livebearing fish Poecilia mexicana allowed for an investigation of crystal orientation despite the small size (<150 nm) of aragonite crystallites. Crystallites at the rims of otoliths had a higher structural organization than those situated near the center, where no dominant orientation pattern was discernible. Moreover, the medial (sulcal) face of otoliths, which makes contact with the sensory epithelium, was more structured than the lateral (antisulcal) face.

  19. Interaction of ions in water system containing copper-zinc alloy for boiler energy saving

    Institute of Scientific and Technical Information of China (English)

    MING Xing; LIANG Jinsheng; OU Xiuqin; TANG Qingguo; DING Yan

    2006-01-01

    Copper-zinc alloy element for boiler energy saving was put in the intake of simulated boiler system to investigate the interaction and transfer of ions in water system both theoretically and experimentally. The fouling was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray detector (EDX). The results show that the transfer of calcium and magnesium ions in heat-transfer-surface-water system is affected by zinc ions dissolved from the alloy because of primary battery reaction. Some calcium ions of calcium carbonate crystal are replaced by zinc ions, the growth of aragonite crystal nucleus is retarded, and the transition of calcium carbonate from aragonite to calcite is hampered.

  20. Taphonomy and palaeoecology of the gastropod fauna from a Late Cretaceous rocky shore, Sweden

    DEFF Research Database (Denmark)

    Sørensen, Anne Mehlin; Surlyk, Finn

    2011-01-01

    A gastropod fauna comprising 17 species, each represented by a limited number of specimens, is described from a Late Cretaceous, late early Campanian rocky shore at Ivö Klack, southern Sweden. The gastropod fauna is associated with the most diverse ancient rocky shore fauna ever found. However......, the low gastropod species diversity compared to the faunas of modern rocky shores is ascribed to taphonomic factors, notably dissolution of the aragonitic shells, but the predominance of epifaunal herbivores is indicative of a guild structure similar to that found on modern rocky shores. The presence...... preservation of such drill holes difficult, since the majority of infaunal prey such as burrowing bivalves has aragonitic shells which are not preserved. The relatively high number of species in comparison to many other Late Cretaceous rocky shore faunas, offers an opportunity to compare gastropod guild...

  1. [Calcium carbide of different crystal formation synthesized by calcium carbide residue].

    Science.gov (United States)

    Lu, Zhong-yuan; Kang, Ming; Jiang, Cai-rong; Tu, Ming-jing

    2006-04-01

    To recycle calcium carbide residue effectively, calcium carbide of different crystal form, including global aragonite, calcite and acicular calcium carbide was synthesized. Both the influence of pretreatment in the purity of calcium carbide, and the influence of temperatures of carbonization reaction, release velocity of carbon dioxide in the apparition of calcium carbide of different crystal form were studied with DTA-TG and SEM. The result shows that calcium carbide residue can take place chemistry reaction with ammonia chlorinate straight. Under the condition that pH was above 7, the purity of calcium carbide was above 97%, and the whiteness was above 98. Once provided the different temperatures of carbonization reaction and the proper release velocity of carbon dioxide, global aragonite, calcite and acicular calcium carbide were obtained.

  2. Laser ablation ICP-MS screening of corals for diagenetically affected areas applied to Tahiti corals from the last deglaciation

    Science.gov (United States)

    Hathorne, Ed C.; Felis, Thomas; James, Rachael H.; Thomas, Alex

    2011-03-01

    Fossil corals are unique archives of past seasonal climate variability, providing vital information about seasonal climate phenomena such as ENSO and monsoons. However, submarine diagenetic processes can potentially obscure the original climate signals and lead to false interpretations. Here we demonstrate the potential of laser ablation ICP-MS to rapidly detect secondary aragonite precipitates in fossil Porites colonies recovered by Integrated Ocean Drilling Program (IODP) Expedition 310 from submerged deglacial reefs off Tahiti. High resolution (100 μm) measurements of coralline B/Ca, Mg/Ca, S/Ca, and U/Ca ratios are used to distinguish areas of pristine skeleton from those afflicted with secondary aragonite. Measurements of coralline Sr/Ca, U/Ca and oxygen isotope ratios, from areas identified as pristine, reveal that the seasonal range of sea surface temperature in the tropical south Pacific during the last deglaciation (14.7 and 11 ka) was similar to that of today.

  3. New Insight into the Toughening Mechanisms of Seashell: From Arch Shape to Multilayer Structure

    Directory of Open Access Journals (Sweden)

    Quan Yuan

    2016-01-01

    Full Text Available A seashell is a closed three-dimensional curved surface formed by two symmetrical open shells. Three-point bending is performed on a pure aragonite straight beam (PASB model and a multilayer structure curved beam (MSCB model to elucidate the structure-property relationships of seashells. The integrity of the PASB is broken because of the introduction of a soft layer, but this drawback is compensated by the peculiar arch shape and the internal multilayer structure. The effective modulus, stiffness, and fracture energy of MSCB increase with an increase in volume fraction, aspect ratio of aragonite platelet, overlap ratio of hard layers, and ratio of the elastic modulus of the hard layer to the shear modulus of the soft layer. New design disciplines drawn from the MSCB model are peculiar arch shape, internal multilayer structure of larger volume fraction, and aspect ratio of hard layers and nanoscaled soft layers.

  4. Electromigration and Deposition of Micro-Scale Calcium Carbonate Structures with Controlled Morphology and Polymorphism

    Science.gov (United States)

    2013-04-01

    17  Figure A2. The transformation from vaterite nanoparticles (a) and from amorphous CaCO3 to calcite rhombs...19  Figure A4. Transformation from metastable amorphous CaCO3 to stable calcite was observed in the 20-V-2-hr polycarbonate... Calcite rhombs (a), aragonite crystals (b), and vaterite to calcite transformation (c), are shown in the micrographs. Infilling polycarbonate pores (d

  5. Improved Understanding of In Situ Chemical Oxidation Soil Reactivity

    Science.gov (United States)

    2007-12-01

    P.A., 2005. Degradation of volatile organic compounds with thermally activated persulfate oxidation, Chemosphere, 61, 551-560. Huling, S.G., Arnold...quartz quartz4 quartz quartz quartz4 quartz4 quartz - plagioclase feldspar calcite calcite calcite - calcite (plagioclase) aragonite...labile compounds are consumed at high rates while the degradation of the recalcitrant fraction is at a low rate. As such, a first-order reaction model

  6. Thermal-Induced Wear Mechanisms of Sheet Nacre in Dry Friction

    OpenAIRE

    Stempflé, Philippe; Djilali, T.; Kouitat Njiwa, Richard; Rousseau, Marthe; Lopez, Evelyne; Bourrat, Xavier

    2009-01-01

    International audience; Sheet nacre is a natural biocomposite with a multiscale structure including a mineral phase of calcium carbonate (97 wt.%) and two organic matrices (3 wt.%). The mineral phase is constituted by an arrangement of CaCO3 biocrystal nanograins (ca 40 nm in size) drowned in an ‘‘intracrystalline'' organic matrix (4 nm thick) in order to form a microsized flat organomineral aragonite platelet. These platelets are themselves surrounded by an ‘‘intercrystalline'' organic matri...

  7. Ocean acidification research alongside extended continental shelf exploration in the western Arctic Ocean

    Science.gov (United States)

    Wynn, J. G.; Robbins, L. L.; Knorr, P. O.; Byrne, R. H.; Takahashi, T.; Onac, B. P.

    2013-12-01

    Research investments funded to fulfill the requirements of the UN Convention on the Law of the Sea in the western Arctic have allowed simultaneous acquisition of marine chemistry data, including baseline monitoring of changes in ocean acidification. Our participation in the Extended Continental Shelf cruises on the USCGC Healy in the western Arctic have allowed us to collect data focused on understanding processes driving rapid changes in seawater chemistry that result from increased oceanic uptake of CO2 (ocean acidification), increased freshwater runoff, changes in sea ice growth and decay processes and changes in biogeochemical processes. Carbonate mineral saturation data collected during HLY1002, HLY1102, and HLY1202 (summers 2010-2012) document undersaturation with respect to aragonitearagonite) in ~20% of the surface waters of the Canada and Makarov Basins, in direct association with areas of recently accelerated sea ice loss. Conservative tracer studies using salinity, stable oxygen isotopic composition, dissolved silica and barium augment this work by elucidating contributions from distinct water sources. These data show that while surface water in this entire area retains abundant freshwater from meteoric sources, it is freshwater additions from melting of multiyear sea ice which is most closely linked to the areas of aragonite undersaturation. Depth profiles from 20 oceanographic stations taken during the cruises show a ~100 m thick lens of Ωaragonite undersaturated water at ~150 m depth in the western Arctic, but not further north than 85°N. The surface waters in the Canada and Makarov Basins have pCO2 values much lower than the atmospheric pCO2 (~390 uatm), ranging between 350 μatm and 100 μatm, and are a strong sink for atmospheric CO2. The strong sink areas are found in the Chukchi Sea and western Beaufort shelf areas. These studies represent the frontiers of ocean acidification research in the western Arctic, in which baseline data have been

  8. U-Th dating of calcitic corals from the Gulf of Aqaba indicates freshwater activity during sapropels S5 and S4

    Science.gov (United States)

    Yehudai, M.; Lazar, B.; BAR (KOHN), N.; Agnon, A.; Shaked, Y.; Stein, M.

    2014-12-01

    Most of the fossil corals in the uplifted reef terraces along the Gulf of Aqaba (GOA, which is currently one of ‎the most hyper-arid regions on Earth) were extensively altered to calcite. This observation indicates extensive interaction with freshwater, possibly when the terraces were uplifted through a coastal aquifer that existed along the shores of the GOA, implying a wetter climate during time of recrystallization from aragonite to calcite. Thus, dating of the recrystallization events should yield timing of past wet conditions in the current hyper-arid area of the GOA. In the current study 16 samples of aragonitic and calcitic corals were collected from several uplifted coral terraces off the coast south to the city of Aqaba. While aragonite corals were dated with the conventional closed system (with no initial Th) age equation, the dating of the calcitic corals required the development of adequate equations that allow the calculation of both the initial cystallization age of the coral and time of recrystallization to calcite. The two age calculations were based on the assumptions that each reef terrace went through a single major recrystallization event and that the pristine aragonite corals had an initial U concentration in the range of 2.5-3 ppm (typical for pristine modern corals). Two recrystallization events were identified: at 124±30 ka BP and 106±7 ka BP, which coincide with the timing of sapropel events S5 and S4 when the African monsoon induced enhanced wetness in the desert area (e.g. Torfstein et al., 2014). The original reef deposition ages were calculated to be: ~ 129-127±8 ka BP, 112±3 ka BP and 5.7±0.3 ka BP, matching the interglacial peaks of global sea level high stands MIS5e, MIS5c and the mid-Holocene high stand.

  9. Natural variability in the surface ocean carbonate ion concentration

    Directory of Open Access Journals (Sweden)

    N. S. Lovenduski

    2015-11-01

    Full Text Available We investigate variability in the surface ocean carbonate ion concentration ([CO32−] on the basis of a~long control simulation with an Earth System Model. The simulation is run with a prescribed, pre-industrial atmospheric CO2 concentration for 1000 years, permitting investigation of natural [CO32−] variability on interannual to multi-decadal timescales. We find high interannual variability in surface [CO32−] in the tropical Pacific and at the boundaries between the subtropical and subpolar gyres in the Northern Hemisphere, and relatively low interannual variability in the centers of the subtropical gyres and in the Southern Ocean. Statistical analysis of modeled [CO32−] variance and autocorrelation suggests that significant anthropogenic trends in the saturation state of aragonitearagonite are already or nearly detectable at the sustained, open-ocean time series sites, whereas several decades of observations are required to detect anthropogenic trends in Ωaragonite in the tropical Pacific, North Pacific, and North Atlantic. The detection timescale for anthropogenic trends in pH is shorter than that for Ωaragonite, due to smaller noise-to-signal ratios and lower autocorrelation in pH. In the tropical Pacific, the leading mode of surface [CO32−] variability is primarily driven by variations in the vertical advection of dissolved inorganic carbon (DIC in association with El Niño–Southern Oscillation. In the North Pacific, surface [CO32−] variability is caused by circulation-driven variations in surface DIC and strongly correlated with the Pacific Decadal Oscillation, with peak spectral power at 20–30-year periods. North Atlantic [CO32−] variability is also driven by variations in surface DIC, and exhibits weak correlations with both the North Atlantic Oscillation and the Atlantic Multidecadal Oscillation. As the scientific community seeks to detect the anthropogenic influence on ocean carbonate chemistry, these results

  10. Are there "black holes" in carbonate deposystems?

    OpenAIRE

    Wright, V.P.; Cherns, L.

    2009-01-01

    The likelihood that extensive dissolution of aragonite (and high magnesian calcite) takes place during very early burial, even in relatively shallow tropical settings, has wide implications for interpreting and modelling ancient limestones. Some low energy environments may constitute net sinks (“black holes”) for carbonates. If this is the case attempts to model sediment budgets and develop depth-productivity profiles for carbonate systems require as yet unavailable quantitative data on the e...

  11. Use of nanoindentation technique for a better understanding of the fracture toughness of Strombus gigas conch shell

    Energy Technology Data Exchange (ETDEWEB)

    Romana, L., E-mail: laurence.romana@univ-ag.fr [Groupe de Technologie des Surfaces et des Interfaces, Université des Antilles et de la Guyane, 97 159 Pointe à Pitre, French West Indies, Guadeloupe (France); Thomas, P.; Bilas, P. [Groupe de Technologie des Surfaces et des Interfaces, Université des Antilles et de la Guyane, 97 159 Pointe à Pitre, French West Indies, Guadeloupe (France); Mansot, J.L. [Groupe de Technologie des Surfaces et des Interfaces, Université des Antilles et de la Guyane, 97 159 Pointe à Pitre, French West Indies, Guadeloupe (France); Centre Commun de Caractérisation des Matériaux, 97 159 Pointe à Pitre, French West Indies, Guadeloupe (France); Merrifiels, M. [Groupe de Technologie des Surfaces et des Interfaces, Université des Antilles et de la Guyane, 97 159 Pointe à Pitre, French West Indies, Guadeloupe (France); Bercion, Y. [Centre Commun de Caractérisation des Matériaux, 97 159 Pointe à Pitre, French West Indies, Guadeloupe (France); Aranda, D. Aldana [CINVESTAV IPN Unidad Merida, Recursos del Mar, Laboratorio de Biología y Acuacultura de Moluscos, Km 6 antigua Carretera a Progreso, Cp 97310 Cordemex (Mexico)

    2013-02-15

    In this work the nanochemical properties of the composite organomineral biomaterial constituting Strombus gigas conch shell are studied by means of dynamic mechanical analyses associated to nanoidentation technique. The measurements are performed on shell samples presenting different surface orientations relative to the growth axis of the conch shell. The influence of the organic component of the biomaterial on its nanomechanical properties is also investigated by studying fresh and dried S. gigas conch shells. Monocrystalline aragonite is used as a reference. For the understanding of nanochemical behaviour, special attention is paid to the pop in events observed on the load/displacement curves which results from nanofractures' initiation and propagation occuring during the load process. In order to better understand the mechanical properties systematic studies of the structure and morphology are performed using scanning electron microscopy, atomic force microscopy and X-ray diffractometry. The hardness and Young's modulus values measured on bio aragonite samples are close to those of the aragonite mineral standard. This surprising result shows that, H and E values are not related to the bio composition and lamellar structure of the bio aragonite. However, it was found that the organic layer and the micro architecture strongly influence the nanofracture initiation and propagation processes in the samples. Statistic study of the pop-in events can help to predict the macroscopic mechanical behaviour of the material. - Highlights: ► Nanomechanical properties of Strombus gigas conch shell ► Low influence of the crossed lamellar structure on H and E values at the nano scale ► Strong influence of the crossed lamellar on nanocracks initiation ► Correlation between mechanical behaviors at the macro and nano scales.

  12. Proceedings of the Coastal Benthic Boundary Layer Key West Workshop

    Science.gov (United States)

    1997-06-24

    plates of aragonitic green algae (Halimeda, Penicillus, and Udeota), molluscan shells, benthic and planktonic foraminifera , echinoid spines, sponge...Florida Shelf ( Gulf of Mexico waters) to the north, and the Florida Straits to the south. Seismic data from the shelf surrounding the Dry Tortugas...the west Florida carbonate platform. It is bordered to the north by the Gulf of Mexico and to the south by the Straits of Florida. The site is well

  13. Seafloor-precipitated carbonate fans in the Neoproterozoic Rainstorm Member, Johnnie Formation, Death Valley Region, USA

    OpenAIRE

    Pruss, Sara Brady; Corsetti, Frank A.; Fischer, Woodward W.

    2008-01-01

    Cm-sized carbonate seafloor fans occur in the Neoproterozoic Rainstorm Member of the Johnnie Formation, Death Valley, USA. The fans formed in a mixed carbonate-clastic succession near storm wave base at the base of parasequences on a storm-dominated ramp. Petrographic observations indicate that the fans were originally precipitated as aragonite and later inverted to calcite during diagenesis. Although not directly dated, the Rainstorm Member preserves a large magnitude negative carbon isotopi...

  14. Groundwater geochemistry observations in littoral caves of Mallorca (western Mediterranean: implications for deposition of phreatic overgrowths on speleothems

    Directory of Open Access Journals (Sweden)

    Bogdan P. Onac

    2014-05-01

    Full Text Available Phreatic overgrowths on speleothems (POS precipitate at the air-water interface in the littoral caves of Mallorca, Spain. Mainly composed of calcite, aragonite POS are also observed in specific locations. To characterize the geochemical environment of the brackish upper water column, water samples and salinity values were collected from water profiles (0-2.9 m in April 2012 and March 2013 near aragonite POS in Cova des Pas de Vallgornera and calcite POS in Coves del Drac (hereafter, Vallgornera and Drac. Degassing of CO2 from the water was evidenced by the existence of lower dissolved inorganic carbon (DIC concentration and enriched δ13CDIC values in a thin surface layer (the uppermost 0.4 m, which was observed in both profiles from Drac. This process is facilitated by the efficient exchange of cave air with the atmosphere, creating a CO2 partial pressure (pCO2 disparity between the cave water and air, resulting in the precipitation of calcite POS as CO2 degasses from the water. The degassed upper layer was not observed in either profile from Vallgornera, suggesting that less efficient cave ventilation restricts outgassing of CO2, which also results in accumulation of CO2 in the cave atmosphere. The presence of an existing uncorroded POS horizon, as well as higher concentrations and large amplitude fluctuations of cave air pCO2, may indicate that aragonite POS deposition is currently episodic in Vallgornera. Ion concentration data from monthly water samples collected in each cave between October 2012 and March 2013 indicate higher Mg:Ca, Sr:Ca, Ba:Ca and Sr:Mg ratios in Vallgornera. Salinity alone does not appear to be a viable proxy for ions that may promote aragonite precipitation or inhibit calcite precipitation. Instead, these ions may be contributed by more intense bedrock weathering or deep groundwater flow.

  15. Effect of carbonate chemistry alteration on the early embryonic development of the Pacific oyster (Crassostrea gigas.

    Directory of Open Access Journals (Sweden)

    Frédéric Gazeau

    Full Text Available Ocean acidification, due to anthropogenic CO₂ absorption by the ocean, may have profound impacts on marine biota. Calcareous organisms are expected to be particularly sensitive due to the decreasing availability of carbonate ions driven by decreasing pH levels. Recently, some studies focused on the early life stages of mollusks that are supposedly more sensitive to environmental disturbances than adult stages. Although these studies have shown decreased growth rates and increased proportions of abnormal development under low pH conditions, they did not allow attribution to pH induced changes in physiology or changes due to a decrease in aragonite saturation state. This study aims to assess the impact of several carbonate-system perturbations on the growth of Pacific oyster (Crassostrea gigas larvae during the first 3 days of development (until shelled D-veliger larvae. Seawater with five different chemistries was obtained by separately manipulating pH, total alkalinity and aragonite saturation state (calcium addition. Results showed that the developmental success and growth rates were not directly affected by changes in pH or aragonite saturation state but were highly correlated with the availability of carbonate ions. In contrast to previous studies, both developmental success into viable D-shaped larvae and growth rates were not significantly altered as long as carbonate ion concentrations were above aragonite saturation levels, but they strongly decreased below saturation levels. These results suggest that the mechanisms used by these organisms to regulate calcification rates are not efficient enough to compensate for the low availability of carbonate ions under corrosive conditions.

  16. Characterization of the multilayered shell of a limpet, Lottia kogamogai (Mollusca: Patellogastropoda), using SEM-EBSD and FIB-TEM techniques.

    Science.gov (United States)

    Suzuki, Michio; Kameda, Jun; Sasaki, Takenori; Saruwatari, Kazuko; Nagasawa, Hiromichi; Kogure, Toshihiro

    2010-08-01

    The microstructure and its crystallographic aspect of the shell of a limpet, Lottiakogamogai, have been investigated, as the first step to clarify the mechanism of shell formation in limpet. The shell consists of five distinct layers stacked along the shell thickness direction. Transmission electron microscopy (TEM) with the focused ion beam (FIB) sample preparation technique was primarily adopted, as well as scanning electron microscopy (SEM) with electron back-scattered diffraction (EBSD). The five layers were termed as M+3, M+2, M+1, M, M-1 from the outside to the inside in previous works, where M means myostracum. The outmost M+3 layer consists of calcite with a "mosaic" structure; granular submicron sub-grains with small-angle grain boundaries often accompanying dislocation arrays. M+2 layer consists of flat prismatic aragonite crystals with a leaf-like cross section, stacked obliquely to the shell surface. It looks that the prismatic crystals are surrounded by organic sheets, forming a compartment structure. M+1 and M-1 layers adopt a crossed lamellar structure consisting of aragonite flat prisms with rectangular cross section. M layer has a prismatic structure of aragonite perpendicular to the shell surface and with irregular shaped cross sections. Distinct organic sheets were not observed between the crystals in M+1, M and M-1 layers. The {110} twins are common in all aragonite M+2, M+1, M and M-1 layers, with the twin boundaries parallel to the prisms. These results for the microstructure of each layer should be considered in the discussion of the formation mechanism of the limpet shell structure.

  17. Skeletal mineralogy of coral recruits under high temperature and pCO2

    Directory of Open Access Journals (Sweden)

    T. Foster

    2016-03-01

    Our results show that elevated pCO2 alone is unlikely to drive changes in the skeletal mineralogy of young corals. Not having an ability to switch from aragonite to calcite precipitation may leave corals and ultimately coral reef ecosystems more susceptible to predicted ocean acidification. An important area for prospective research would be the investigation of the combined impact of high pCO2 and reduced Mg ∕ Ca ratio on coral skeletal mineralogy.

  18. Skeletal mineralogy of coral recruits under high temperature and pCO2

    Directory of Open Access Journals (Sweden)

    T. Foster

    2015-08-01

    Full Text Available Aragonite, which is the polymorph of CaCO3 precipitated by modern corals during skeletal formation, has a higher solubility than the more stable polymorph calcite. This higher solubility leaves animals that produce aragonitic skeletons more vulnerable to anthropogenic ocean acidification. It is therefore, important to determine whether scleractinian corals have the plasticity to adapt and produce calcite in their skeletons in response to changing environmental conditions. Both high pCO2 and lower Mg / Ca ratios in seawater are thought to have driven changes in the skeletal mineralogy of major marine calcifiers in the past ∼540 myr. Experimentally reduced Mg / Ca ratios in ambient seawater have been shown to induce some calcite precipitation in both adult and newly settled modern corals, however, the impact of high pCO2 on the mineralogy of recruits is unknown. Here we determined the skeletal mineralogy of one-month old Acropora spicifera coral recruits grown under high temperature (+3 °C and pCO2 (∼900 μatm conditions, using X-ray diffraction and Raman spectroscopy. We found that newly settled coral recruits produced entirely aragonitic skeletons regardless of the treatment. Our results show that elevated pCO2 alone is unlikely to drive changes in the skeletal mineralogy of young corals. Not having an ability to switch from aragonite to calcite precipitation may leave corals and ultimately coral reef ecosystems more susceptible to predicted ocean acidification. An important area for prospective research would be to investigate the combined impact of high pCO2 and reduced Mg / Ca ratio on coral skeletal mineralogy.

  19. Differential expression of three galaxin-related genes during settlement and metamorphosis in the scleractinian coral Acropora millepora

    OpenAIRE

    Miller David J; Hayward David C; Lin Zhiyi; Reyes-Bermudez Alejandro; Ball Eldon E

    2009-01-01

    Abstract Background The coral skeleton consists of CaCO3 deposited upon an organic matrix primarily as aragonite. Currently galaxin, from Galaxea fascicularis, is the only soluble protein component of the organic matrix that has been characterized from a coral. Three genes related to galaxin were identified in the coral Acropora millepora. Results One of the Acropora genes (Amgalaxin) encodes a clear galaxin ortholog, while the others (Amgalaxin-like 1 and Amgalaxin-like 2) encode larger and ...

  20. Cathodoluminescent bimineralic ooids from the Pleistocene of the Florida continental shelf

    Science.gov (United States)

    Major, R. P.; Halley, Robert B.; Lukas, Karen J.

    1988-01-01

    A bored and encrusted late Pleistocene ooid grainstone was recovered from the seafloor at a depth of approximately 40 m on the outer continental shelf of eastern Florida. Ooid cortices are dominantly bimineralic, generally consisting of inner layers of radial magnesian calcite and outer layers of tangential aragonite. Ooid nuclei are dominantly rounded cryptocrystalline grains, although quartz grains and a variety of skeletal grains also occur as nuclei. Ooids are partially cemented by blocky calcite, and interparticle porosity is partially filled by micrite.

  1. Transition of microbiological and sedimentological features associated with the geochemical gradient in a travertine mound in northern Sumatra, Indonesia

    Science.gov (United States)

    Sugihara, Chiya; Yanagawa, Katsunori; Okumura, Tomoyo; Takashima, Chizuru; Harijoko, Agung; Kano, Akihiro

    2016-08-01

    Modern travertines, carbonate deposits in Ca-rich hydrothermal water with high pCO2, often display a changing environment along the water path, with corresponding variability in the microbial communities. We investigated a travertine-bearing hot spring at the Blue Pool in northern Sumatra, Indonesia. The thermal water of 62 °C with high H2S (200 μM) and pCO2 ( 1 atm) developed a travertine mound 70 m wide. The concentrations of the gas components H2S and CO2, decrease immediately after the water is discharged, while the dissolved oxygen, pH, and aragonite saturation increase in the downstream direction. Responding to the geochemical gradient in the water, the surface biofilms change color from white to pink, light-green, dark-green, and brown as the water flows from the vent; this corresponds to microbial communities characterized by chemolithoautotrophs (Halothiobacillaceae), purple sulfur bacteria (Chromatiaceae), Anaerolineaceae, and co-occurrence of green non-sulfur bacteria (Chloroflexales)-Cyanobacteria, and green sulfur bacteria (Chlorobiales), respectively. In an environment with a certain level of H2S (> 1 μM), sulfur digestion and anoxygenic photosynthesis can be more profitable than oxygenic photosynthesis by Cyanobacteria. The precipitated carbonate mineral consists of aragonite and calcite, with the proportion of aragonite increasing downstream due to the larger Mg2 +/Ca2 + ratio in the water or the development of thicker biofilm. Where the biofilm is well developed, the aragonite travertines often exhibit laminated structures that were likely associated with the daily metabolism of these bacteria. The microbiological and sedimentological features at the Blue Pool may be the modern analogs of geomicrobiological products in the early Earth. Biofilm of anoxygenic photosynthetic bacteria had the potential to form ancient stromatolites that existed before the appearance of cyanobacteria.

  2. Impact of paleoclimate on the distribution of microbial communities in the subsurface sediment of the Dead Sea.

    Science.gov (United States)

    Thomas, C; Ionescu, D; Ariztegui, D

    2015-11-01

    A long sedimentary core has been recently retrieved from the Dead Sea Basin (DSB) within the framework of the ICDP-sponsored Dead Sea Deep Drilling Project. Contrasting climatic intervals were evident by distinctive lithological facies such as laminated aragonitic muds and evaporites. A geomicrobiological investigation was conducted in representative sediments of this core. To identify the microbial assemblages present in the sediments and their evolution with changing depositional environments through time, the diversity of the 16S rRNA gene was analyzed in gypsum, aragonitic laminae, and halite samples. The subsurface microbial community was largely dominated by the Euryarchaeota phylum (Archaea). Within the latter, Halobacteriaceae members were ubiquitous, probably favored by their 'high salt-in' osmotic adaptation which also makes them one of the rare inhabitants of the modern Dead Sea. Bacterial community members were scarce, emphasizing that the 'low salt-in' strategy is less suitable in this environment. Substantial differences in assemblages are observed between aragonitic sediments and gypsum-halite ones, independently of the depth and salinity. The aragonite sample, deposited during humid periods when the lake was stratified, consists mostly of the archaeal MSBL1 and bacterial KB1 Candidate Divisions. This consortium probably relies on compatible solutes supplied from the lake by halotolerant species present in these more favorable periods. In contrast, members of the Halobacteriaceae were the sole habitants of the gypsum-halite sediments which result from a holomictic lake. Although the biomass is low, these variations in the observed subsurface microbial populations appear to be controlled by biological conditions in the water column at the time of sedimentation, and subsequently by the presence or absence of stratification and dilution in the lake. As the latter are controlled by climatic changes, our data suggest a relationship between local

  3. Nacre-like ceramic/polymer laminated composite for use in body-armor applications

    OpenAIRE

    2016-01-01

    Nacre is a biological material constituting the innermost layer of the shells of gastropods and bivalves. It consists of polygonal tablets of aragonite, tessellated to form individual layers and having the adjacent layers as well as the tablets within a layer bonded by a biopolymer. Due to its highly complex hierarchical microstructure, nacre possesses an outstanding combination of mechanical properties, the properties which are far superior to the ones that are predicted using the techniques...

  4. Biogeochemical Controls on Authigenic Carbonate Formation at the Chapopote "Asphalt Volcano", Bay of Campeche

    Science.gov (United States)

    Naehr, T. H.; Bohrmann, G.; Birgel, D.; MacDonald, I. R.

    2007-12-01

    Unusual hydrocarbon seep features, so-called "asphalt volcanoes" were explored in the Bay of Campeche, southern Gulf of Mexico, in the spring of 2006. Guided by data from satellite imagery that showed evidence for persistent oil seeps in the region, we investigated lava-like flows of solidified asphalt along the rim of a dissected salt dome at a water depth of about 3000 m. Fresh asphalt contains copious thermogenic gas and gas hydrate. Slabs of authigenic carbonate form surface crusts with layers of oil pooled beneath. Sediments are anoxic with H2S concentrations of 8 to 13 mM. Gas hydrate forms layers and mounds in the surface sediments. Alkalinity profiles show values from 29 to 35 mM, indicating oxidation of hydrocarbons by reduction of seawater sulfate. Molecular and isotopic compositions of gas hydrate and sediment headspace indicate moderately mature, thermogenic gas. Oily sediment extracts and asphalt pieces are composed of a degraded mixture of hydrocarbons with a peak at n-C30 and a few resolved C29 to C32 hopanes. Authigenic carbonate crusts from Chapopote are porous, aragonite-cemented mudstones. Peloidal textures are common, as are bivalve shells and at least two generations of aragonite-cemented intraclasts. The carbon isotopic composition of the authigenic aragonite cements varies between -28.6 ‰ and -17.9 ‰ (PDB), indicating a contribution of carbon from non-methane liquid hydrocarbons to the total pool of dissolved CO2. δ18O values of the carbonates range from +3.2 ‰ to +4.5 ‰ (PDB), suggesting aragonite formation under near-equilibrium conditions in the shallow subsurface. Molecular fossils extracted from one carbonate sample contain abundant 13C-depleted archeal lipids, derived from anaerobic methanotrophs, suggesting that organisms mediating the anaerobic oxidation of methane are closely associated with carbonate authigenesis at the Chapopote asphalt seep site.

  5. Coastal ocean acidification: The other eutrophication problem

    Science.gov (United States)

    Wallace, Ryan B.; Baumann, Hannes; Grear, Jason S.; Aller, Robert C.; Gobler, Christopher J.

    2014-07-01

    Increased nutrient loading into estuaries causes the accumulation of algal biomass, and microbial degradation of this organic matter decreases oxygen levels and contributes towards hypoxia. A second, often overlooked consequence of microbial degradation of organic matter is the production of carbon dioxide (CO2) and a lowering of seawater pH. To assess the potential for acidification in eutrophic estuaries, the levels of dissolved oxygen (DO), pH, the partial pressure of carbon dioxide (pCO2), and the saturation state for aragonitearagonite) were horizontally and vertically assessed during the onset, peak, and demise of low oxygen conditions in systems across the northeast US including Narragansett Bay (RI), Long Island Sound (CT-NY), Jamaica Bay (NY), and Hempstead Bay (NY). Low pH conditions (3000 μatm), were acidic pH (<7.0), and were undersaturated with regard to aragonitearagonite < 1), even near-normoxic but eutrophic regions of these estuaries were often relatively acidified (pH < 7.7) during late summer and/or early fall. The close spatial and temporal correspondence between DO and pH and the occurrence of extremes in these conditions in regions with the most intense nutrient loading indicated that they were primarily driven by microbial respiration. Given that coastal acidification is promoted by nutrient-enhanced organic matter loading and reaches levels that have previously been shown to negatively impact the growth and survival of marine organisms, it may be considered an additional symptom of eutrophication that warrants managerial attention.

  6. Simulation of global ocean acidification and chemical habitats of shallow- and cold-water coral reefs

    Directory of Open Access Journals (Sweden)

    Mei-Di Zheng

    2014-12-01

    Full Text Available Using the UVic Earth System Model, this study simulated the change of seawater chemistry and analyzed the chemical habitat surrounding shallow- and cold-water coral reefs from the year 1800 to 2300 employing RCP2.6, RCP4.5, RCP6.0, and RCP8.5 scenarios. The model results showed that the global ocean will continue to absorb atmospheric CO2. Global mean surface ocean temperature will rise 1.1–2.8 K at the end of the 21st century across RCP scenarios. Meanwhile, the global mean surface ocean pH will drop 0.14–0.42 and the ocean surface mean concentration of carbonate will decrease 20%–51% across the RCP scenarios. The saturated state of sea water with respect to calcite carbonate minerals (Ω will decrease rapidly. During the pre-industrial period, 99% of the shallow-water coral reefs were surrounded by seawater with Ω > 3.5 and 87% of the deep-sea coral reefs were surrounded by seawater with aragonite supersaturation. Within the 21st century, except for the high mitigation scenario of RCP2.6, almost none shallow-water coral reefs will be surrounded by seawater with Ω > 3.5. Under the intensive emission scenario of RCP8.5, by the year 2100, the aragonite saturation horizon will rise to 308 m under the sea surface from 1138 m at the pre-industrial period, thus 73% of the cold-water coral reefs will be surrounded by seawater with aragonite undersaturation. By the year 2300, only 5% of the cold-water coral reefs will be surrounded by seawater with aragonite supersaturation.

  7. Empirically testing vaterite structural models using neutron diffraction and thermal analysis

    OpenAIRE

    Chakoumakos, Bryan C.; Pracheil, Brenda M.; Ryan P. Koenigs; Ronald M. Bruch; Mikhail Feygenson

    2016-01-01

    Otoliths, calcium carbonate (CaCO3) ear bones, are among the most commonly used age and growth structures of fishes. Most fish otoliths are comprised of the most dense CaCO3 polymorph, aragonite. Sturgeon otoliths, in contrast, have been characterized as the rare and structurally enigmatic polymorph, vaterite—a metastable polymorph of CaCO3. Vaterite is an important material ranging from biomedical to personal care applications although its crystal structure is highly debated. We characterize...

  8. Mineral and Protein-Bound Water and Latching Action Control Mechanical Behavior at Protein-Mineral Interfaces in Biological Nanocomposites

    OpenAIRE

    Pijush Ghosh; Katti, Dinesh R.; Kalpana S. Katti

    2008-01-01

    The nacre structure consists of laminated interlocked mineral platelets separated by nanoscale organic layers. Here, the role of close proximity of mineral to the proteins on mechanical behavior of the protein is investigated through steered molecular dynamics simulations. Our simulations indicate that energy required for unfolding protein in the proximity of mineral aragonite is several times higher than that for isolated protein in the absence of the mineral. Here, we present details of spe...

  9. A humidity sensitive two-dimensional tunable amorphous photonic structure in the bivalve ligament of Meretrix linnaeus.

    Science.gov (United States)

    Zhang, Weigang; Zhang, Gangsheng

    2015-12-01

    A humidity sensitive two-dimensional tunable amorphous photonic structure (2D TAPS) in the bivalve ligament of Meretrix linnaeus (LML) was reported in this paper. The structural color and microstructure of LML were investigated by reflection spectra and scanning electron microscopy, respectively. The results indicate that the LML has complex structural colors from blue to orange in the wet state from ventral to dorsal, which are derived from the aragonite fiber diameter increases continuously from ventral to dorsal of the ligament. The reflection peak wavelength of the wet LML can blue-shift from 522 nm to 480 nm with the air drying time increased from 0 to 60 min, while the reflectivity decreases gradually and only a weak reflection peak at last, relevant color changes from green to light blue. The structural color in the LML is produced by a two-dimensional amorphous photonic structure consists of aligned aragonite fibers and proteins, in which the diameters of the aragonite fiber and the inter-fiber spacing are 104±11 nm and 126±16 nm, respectively. Water can reversibly tune the reflection peak wavelength and reflectivity of this photonic structure, and the regulation achieved through dynamically tune the degree of order and lattice constant of the ligament in the different wet states.

  10. SEM observation of structural (non-mineralogical) alteration inside the previously crystallized nacreous layer of Crenomytilus grayanus (Bivalvia: Mytilidae).

    Science.gov (United States)

    Zuykov, Michael; Pelletier, Emilien; Kolyuchkina, Galina

    2013-01-01

    A microstructural and mineralogical study shows the transition of aragonitic nacreous tablets to aragonitic prisms inside previously secreted nacre, i.e. without contact with the mantle or extrapallial fluid, in a field-collected mytilid bivalve Crenomytilus grayanus (D.). The intermediate zone between nacre and new prisms is represented by nacre tablets "stuck together" or by disordered calcium carbonate material. The modified nacre forms aragonitic lenses of prisms (ALPs). These lenses may reach 500 μm in thickness below the tunnels excavated by the shell borers. ALPs are similar to myostracal prisms in mineralogy, morphology, and orientation, but differ from those in the outer shell layer. The process of ALPs formation is different to that of normal shell formation (e.g. nacre-prisms transition between prismatic and nacreous layers), remote biomineralization, extra shell thickening, as well as, shell repair, erosion, deformation or disease. Response to shell excavation by boring organisms is discussed as the reason for the appearance of ALPs.

  11. Aspartic acid racemization dating of Holocene brachiopods and bivalves from the southern Brazilian shelf, South Atlantic

    Science.gov (United States)

    Barbour Wood, Susan L.; Krause, Richard A.; Kowalewski, Michał; Wehmiller, John; Simões, Marcello G.

    2006-09-01

    The extent of racemization of aspartic acid (Asp) has been used to estimate the ages of 9 shells of the epifaunal calcitic brachiopod Bouchardia rosea and 9 shells of the infaunal aragonitic bivalve Semele casali. Both taxa were collected concurrently from the same sites at depths of 10 m and 30 m off the coast of Brazil. Asp D/L values show an excellent correlation with radiocarbon age at both sites and for both taxa ( r2Site 9 B. rosea = 0.97, r2Site 1 B. rosea = 0.997, r2Site 9 S. casali = 0.9998, r2Site 1 S. casali = 0.93). The Asp ratios plotted against reservoir-corrected AMS radiocarbon ages over the time span of multiple millennia can thus be used to develop reliable and precise geochronologies not only for aragonitic mollusks (widely used for dating previously), but also for calcitic brachiopods. At each collection site, Bouchardia specimens display consistently higher D/L values than specimens of Semele. Thermal differences between sites are also notable and in agreement with theoretical expectations, as extents of racemization for both taxa are greater at the warmer, shallower site than at the cooler, deeper one. In late Holocene marine settings, concurrent time series of aragonitic and calcitic shells can be assembled using Asp racemization dating, and parallel multi-centennial to multi-millennial records can be developed simultaneously for multiple biomineral systems.

  12. Facile Synthesis of Calcium Carbonate Nanoparticles from Cockle Shells

    Directory of Open Access Journals (Sweden)

    Kh. Nurul Islam

    2012-01-01

    Full Text Available A simple and low-cost method for the synthesis of calcium carbonate nanoparticles from cockle shells was described. Polymorphically, the synthesized nanoparticles were aragonites which are biocompatible and thus frequently used in the repair of fractured bone and development of advanced drug delivery systems, tissue scaffolds and anticarcinogenic drugs. The rod-shaped and pure aragonite particles of 30±5 nm in diameter were reproducibly synthesized when micron-sized cockle shells powders were mechanically stirred for 90 min at room temperature in presence of a nontoxic and nonhazardous biomineralization catalyst, dodecyl dimethyl betaine (BS-12. The findings were verified using a combination of analytical techniques such as variable pressure scanning electron microscopy (VPSEM, transmission electron microscopy (TEM, Fourier transmission infrared spectroscopy (FT-IR, X-ray diffraction spectroscopy (XRD, and energy dispersive X-ray analyser (EDX. The reproducibility and low cost of the method suggested that it could be used in industry for the large scale synthesis of aragonite nanoparticles from cockle shells, a low cost and easily available natural resource.

  13. Chemical-mechanical stability of the hierarchical structure of shell nacre

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The hierarchical structure and mechanical property of shell nacre are experimentally investigated from the new aspects of chemical stability and chemistry-mechanics coupling. Through chemical deproteinization or demineralization methods together with characterization techniques at micro/nano scales,it is found that the nacre of abalone,haliotis discus hannai,contains a hierarchical structure stacked with irregular aragonite platelets and interplatelet organic matrix thin layers. Yet the aragonite platelet itself is a nanocomposite consisting of nanoparticles and intraplatelet organic matrix framework. The mean diameter of the nanoparticles and the distribution of framework are quite different for different platelets. Though the interplatelet and in-traplatelet organic matrix can be both decomposed by sodium hydroxide solution,the chemical stability of individual aragonite platelets is much higher than that of the microstructure stacked with them. Further,macroscopic bending test or nanoindentation experiment is performed on the micro/nanostructure of nacre after sodium hydroxide treatment. It is found that the Young’s modulus of both the stacked microstructure and nanocomposite platelet reduced. The reduction of the microstructure is more remark than that of the platelet. Therefore the chemical-mechanical stability of the nanocomposite platelet itself is much higher than that of the stacked microstructure of nacre.

  14. Localization of intracrystalline organic macromolecules in mollusk shells

    Science.gov (United States)

    Suzuki, Michio; Okumura, Taiga; Nagasawa, Hiromichi; Kogure, Toshihiro

    2011-12-01

    As a crucial first step for understanding the organic-inorganic interaction in biomineralization of mollscan shells, localization of the intracrystalline organic macromolecules in biogenic calcium carbonate crystals of the nacreous, prismatic ( Pinctada fucata) and foliated ( Cellana toreuma) microstructures were investigated using Fresnel contrast analysis in a transmission electron microscope. Spherular Fresnel contrasts in the crystals correspond to organic substances, which was confirmed by the detection of 1s→π * (CC) transition peak at 284 eV in electron energy loss spectroscopy. Nano-sized (5-10 nm) spherules in the aragonite tablets constituting the nacreous layer of P. fucata specifically concentrate in the vicinity of the interlamellar membrane between the aragonite tablets. The dominant sizes of the organic macromolecules extracted by dissolving the aragonite tablets in the nacreous layer of P. fucata were estimated using the gel-filtration analysis to be roughly 10 and 4 nm, which dimensionally corresponds to the sizes observed by Fresnel contrast imaging in the tablets. These results will serve for understanding the functions of intracrystalline organic macromolecules in mollusk shells.

  15. Carbonate replacement of lacustrine gypsum deposits in two Neogene continental basins, eastern Spain

    Science.gov (United States)

    Anadón, P.; Rosell, L.; Talbot, M. R.

    1992-07-01

    Bedded nonmarine gypsum deposits in the Miocene Teruel and Cabriel basins, eastern Spain, are partly replaced by carbonate. The Libros gypsum (Teruel Graben) is associated with fossiliferous carbonate wackestones and finely laminated, organic matter-rich mudstones which accumulated under anoxic conditions in a meromictic, permanent lake. The gypsum is locally pseudomorphed by aragonite or, less commonly, replaced by calcite. Low δ 13C values indicate that sulphate replacement resulted from bacterial sulphate reduction processes that were favoured by anacrobic conditions and abundant labile organic matter in the sediments. Petrographic evidence and oxygen isotopic composition suggest that gypsum replacement by aragonite occurred soon after deposition. A subsequent return to oxidising conditions caused some aragonite to be replaced by diagenetic gypsum. Native sulphur is associated with some of these secondary gypsum occurrences. The Los Ruices sulphate deposits (Cabriel Basin) contain beds of clastic and selenitic gypsum which are associated with limestones and red beds indicating accumulation in a shallow lake. Calcite is the principal replacement mineral. Bacterial sulphate reduction was insignificant in this basin because of a scarcity of organic matter. Stable isotope composition of diagenetic carbonate indicates that gypsum replacement occurred at shallow burial depths due to contact with dilute groundwaters of meteoric origin. Depositional environment evidently has a major influence upon the diagenetic history of primary sulphate deposits. The quantity of preserved organic matter degradable by sulphate-reducing bacteria is of particular importance and, along with groundwater composition, is the main factor controlling the mechanism of gypsum replacement by carbonate.

  16. Threshold of carbonate saturation state determined by a CO2 control experiment

    Directory of Open Access Journals (Sweden)

    A. Negishi

    2011-08-01

    Full Text Available Acidification of the oceans by increasing anthropogenic CO2 emissions will cause a decrease in biogenic calcification and an increase in carbonate dissolution. Previous studies suggest that carbonate dissolution will occur in polar regions and in the deep-sea oceans where saturation state with respect to carbonate minerals (Ω will be 1. Recent reports demonstrated nocturnal carbonate dissolution reefs, despite Ω_a > 1, probably relate to the dissolution of the minor reef carbonate (Mg-calcite, which is more soluble than aragonite. However, the threshold of Ω for the dissolution of natural sediments has not been clearly determined, and it is unknown whether these dissolution processes actually occur under natural conditions. This work describes the measurement of the dissolution rates of coral aragonite and Mg calcite excreted by marine organisms under conditions of Ω_a > 1 with controlled seawater pCO2. Laboratory experimental data of the present study show that bulk carbonate sediments sampled from a coral reef start to dissolve when Ω_a = 3.7, and dissolution rates increase with falling Ω_a. Mg-calcite derived from foraminifera and coralline algae dissolved when Ω_a reached 3.4, whereas coralline aragonite started to dissolve when Ω_a was almost 1.0. We show that nocturnal carbonate dissolution of coral reefs occurs mainly by the dissolution of foraminifera and coralline algae in reef sediment.

  17. Evidence of compositional and ultrastructural shifts during the development of calcareous tubes in the biofouling tubeworm, Hydroides elegans.

    Science.gov (United States)

    Chan, Vera Bin San; Vinn, Olev; Li, Chaoyi; Lu, Xingwen; Kudryavtsev, Anatoliy B; Schopf, J William; Shih, Kaimin; Zhang, Tong; Thiyagarajan, Vengatesen

    2015-03-01

    The serpulid tubeworm, Hydroides elegans, is an ecologically and economically important species whose biology has been fairly well studied, especially in the context of larval development and settlement on man-made objects (biofouling). Nevertheless, ontogenetic changes associated with calcareous tube composition and structures have not yet been studied. Here, the ultrastructure and composition of the calcareous tubes built by H. elegans was examined in the three early calcifying juvenile stages and in the adult using XRD, FTIR, ICP-OES, SEM and Raman spectroscopy. Ontogenetic shifts in carbonate mineralogy were observed, for example, juvenile tubes contained more amorphous calcium carbonate and were predominantly aragonitic whereas adult tubes were bimineralic with considerably more calcite. The mineral composition gradually shifted during the tube development as shown by a decrease in Sr/Ca and an increase of Mg/Ca ratios with the tubeworm's age. The inner tube layer contained calcite, whereas the outer layer contained aragonite. Similarly, the tube complexity in terms of ultrastructure was associated with development. The sequential appearance of unoriented ultrastructures followed by oriented ultrastructures may reflect the evolutionary history of serpulid tube biominerals. As aragonitic structures are more susceptible to dissolution under ocean acidification (OA) conditions but are more difficult to be removed by anti-fouling treatments, the early developmental stages of the tubeworms may be vulnerable to OA but act as the important target for biofouling control.

  18. Fresh-water cementation of a 1,000-year-old oolite

    Science.gov (United States)

    Halley, R. B.; Harris, P. M.

    1979-01-01

    Calcite cementation of aragonite ooid sand is producing oolite on Joulters Cays, Bahamas. During the last 1,000 years, calcite cement has formed at an average rate of between 27 and 55 cm3 /m3 /yr and is derived from dissolution of ooid aragonite in fresh water. The dissolution-reprecipitation of carbonate minerals in the aquifer results in ground waters of unusually high Sr content. Sea water and mixtures of fresh and sea water appear to inhibit cementation. A pronounced cement fabric change occurs across the water table and has produced an obvious petrographic record of fresh-water diagenesis. Above the water table, cement is typically near grain contact positions, where water is held by capillarity; below the water table, cement is more randomly distributed around grains. At the water table a transition zone, 1 meter thick, marks the boundary between cement textures. No porosity reduction is associated with cementation; calcite cement precipitation is apparently compensated by an equal or greater amount of aragonite dissolution in the interval undergoing cementation. Permeability is more variable above the water table than below it, reflecting early channelling of flow patterns in the vadose zone. Effective permeability below the water table is one to two orders of magnitude higher than above the water table because of entrained gas in the vadose zone. This permeability difference promotes preservation of unstable minerals above the water table and continued diagenetic alteration below the water table.

  19. Adverse effects of ocean acidification on early development of squid (Doryteuthis pealeii.

    Directory of Open Access Journals (Sweden)

    Maxwell B Kaplan

    Full Text Available Anthropogenic carbon dioxide (CO2 is being absorbed into the ocean, altering seawater chemistry, with potentially negative impacts on a wide range of marine organisms. The early life stages of invertebrates with internal and external aragonite structures may be particularly vulnerable to this ocean acidification. Impacts to cephalopods, which form aragonite cuttlebones and statoliths, are of concern because of the central role they play in many ocean ecosystems and because of their importance to global fisheries. Atlantic longfin squid (Doryteuthis pealeii, an ecologically and economically valuable taxon, were reared from eggs to hatchlings (paralarvae under ambient and elevated CO2 concentrations in replicated experimental trials. Animals raised under elevated pCO2 demonstrated significant developmental changes including increased time to hatching and shorter mantle lengths, although differences were small. Aragonite statoliths, critical for balance and detecting movement, had significantly reduced surface area and were abnormally shaped with increased porosity and altered crystal structure in elevated pCO2-reared paralarvae. These developmental and physiological effects could alter squid paralarvae behavior and survival in the wild, directly and indirectly impacting marine food webs and commercial fisheries.

  20. Adverse effects of ocean acidification on early development of squid (Doryteuthis pealeii).

    Science.gov (United States)

    Kaplan, Maxwell B; Mooney, T Aran; McCorkle, Daniel C; Cohen, Anne L

    2013-01-01

    Anthropogenic carbon dioxide (CO2) is being absorbed into the ocean, altering seawater chemistry, with potentially negative impacts on a wide range of marine organisms. The early life stages of invertebrates with internal and external aragonite structures may be particularly vulnerable to this ocean acidification. Impacts to cephalopods, which form aragonite cuttlebones and statoliths, are of concern because of the central role they play in many ocean ecosystems and because of their importance to global fisheries. Atlantic longfin squid (Doryteuthis pealeii), an ecologically and economically valuable taxon, were reared from eggs to hatchlings (paralarvae) under ambient and elevated CO2 concentrations in replicated experimental trials. Animals raised under elevated pCO2 demonstrated significant developmental changes including increased time to hatching and shorter mantle lengths, although differences were small. Aragonite statoliths, critical for balance and detecting movement, had significantly reduced surface area and were abnormally shaped with increased porosity and altered crystal structure in elevated pCO2-reared paralarvae. These developmental and physiological effects could alter squid paralarvae behavior and survival in the wild, directly and indirectly impacting marine food webs and commercial fisheries.

  1. Drastic Aridification Caused the Decline of Oasis Civilizations on the Silk Route during the Eighth Century

    Science.gov (United States)

    Wei, K.; Song, S.; Huang, C.

    2003-12-01

    Availability of water, and response to shortage of it, plays an important role in shaping human history. Near a century ago, Ellsworth Huntington (1907) suggested that the developments of ancient civilizations in Inner Asian and their invasions into China and Europe were pulsed by climatic changes. In revisiting this proposition, here we present a paleoclimatic record of the past 5000 years deduced from carbon isotopic ratio of organic carbon and percentage of aragonite in bulk sediments of a radiometrically dated sedimentary core of Lake Bosten, Xinjiang, China. Together the two proxies of aridity provide a detailed record of climatic fluctuation of the Inner Asia. The arid periods are well characterized by high content of authigenic aragonite and heavier values of carbon isotopic ratio of organic carbon in the bulk sediments (implying dominance of C4 plants which thrived under arid condition). Conversely, the humid/wet periods are marked by lighter carbon isotopic values (indicating presence of C3 plants of humid climateœcand absence of aragonite. The Western Region (Xi-Y"1) area of China enjoyed a long period of stable and humid condition from 2nd century B.C. to the 8th century when many oasis city-states were established and Buddhism spread from India. A drastic deterioration of climate during the eighth century appears to cause the decline of those once strived ancient civilizations in the eastern side of the Tarim Basin along the Silk Routes.

  2. Effects of sample storage and shell orientation on LA-ICPMS trace element measurements on deep-sea mussels

    Science.gov (United States)

    Génio, Luciana; Simon, Klaus; Kiel, Steffen; Cunha, Marina R.

    2015-01-01

    Geochemical markers are being increasingly applied to fundamental questions in population and community ecology in marine habitats because they allow inferences on individuals dispersal, but vital effects, small sample size and instrumental limitation are still challenging particularly in deep-sea studies. Here we use shells of the deep-sea bivalve Idas modiolaeformis to assess potential effects of sample storage, mineralogy, and valve orientation on LA-ICPMS measurements. Trace element concentrations of 24Mg, 43Ca, 88Sr, 137Ba, 208Pb, and 238U are not affected by the two most commonly used storage methods of biologic deep-sea samples (frozen at –20°C and fixed in 95% ethanol); thus combined analysis of differently preserved specimens is possible when the number of individuals is insufficient and distinct sample fixation is needed for multiple purposes. Valve orientation had a strong impact on quantification of trace elements in the calcitic but not in the aragonitic layer of adult shells. Hence, to enable comparisons between adult shells and entirely aragonitic embryonic shells, a reference map of site-specific signatures can potentially be generated using the aragonitic layer of the adult shells. Understanding ontogenetic changes and environmental effects in trace element incorporation is critical before geochemical fingerprinting can be used as a tool for larval dispersal studies in the deep-sea. PMID:26643064

  3. The influence of Pacific Equatorial Water on fish diversity in the southern California Current System

    Science.gov (United States)

    McClatchie, Sam; Thompson, Andrew R.; Alin, Simone R.; Siedlecki, Samantha; Watson, William; Bograd, Steven J.

    2016-08-01

    The California Undercurrent transports Pacific Equatorial Water (PEW) into the Southern California Bight from the eastern tropical Pacific Ocean. PEW is characterized by higher temperatures and salinities, with lower pH, representing a source of potentially corrosive (aragonite,Ωfish diversity. We use hydrographic data to characterize the interannual and seasonal variability of estimated pH and aragonite saturation with depth. Although there is substantial variability in PEW presence as measured by spice on the 26.25-26.75 isopycnal layer, as well as in pH and aragonite saturation, we found fish diversity to be stable over the decades 1985-1996 and 1999-2011. We detected significant difference in species structure during the 1998 La Niña period, due to reduced species evenness. Species richness due to rare species was higher during the 1997/1998 El Niño compared to the La Niña but the effect on species structure was undetectable. Lack of difference in the species abundance structure in the decade before and after the 1997/1999 ENSO event showed that the assemblage reverted to its former structure following the ENSO perturbation, indicating resilience. While the interdecadal species structure remained stable, the long tail of the distributions shows that species richness increased between the decades consistent with intrusion of warm water with more diverse assemblages into the southern California region.

  4. Holocene carbonate record of Lake Kivu reflects the history of hydrothermal activity

    Science.gov (United States)

    Votava, Jillian E.; Johnson, Thomas C.; Hecky, Robert E.

    2017-01-01

    The sediment record of Lake Kivu reveals a complex volcanogenic and climatic Holocene history. Investigation of the inorganic carbonate record dates the onset of carbonate deposition in the mid-Holocene in Kivu’s deep northern and eastern basins and identifies conditions enabling deposition. The magnitude and timing of carbonate-rich sedimentation is not so much controlled by climate but, instead, linked strongly to hydrothermal activity in the basin. Sublacustrine springs supply the vast majority of the calcium and carbonate ions required for supersaturation with respect to aragonite. This major hydrothermal activity that permanently stratifies Lake Kivu today was initiated ˜3,100 y before present (3.1 ka), when carbonate-rich sediments first appeared in the Holocene record. Aragonite is the dominant CaCO3 mineral present in the lake deposits. Both δ13C and δ18O of the aragonite are enriched above the expected kinetic fractionation of meteoric waters, suggesting a volcanogenic influence on the formation waters. Repeated major fluctuations in the carbonate record after 3.1 ka therefore most likely reflect the historical variation in hydrothermal inputs.

  5. U-Th dating of calcite corals from the Gulf of Aqaba

    Science.gov (United States)

    Yehudai, Maayan; Lazar, Boaz; Bar, Neta; Kiro, Yael; Agnon, Amotz; Shaked, Yonathan; Stein, Mordechai

    2017-02-01

    Most of the fossil corals in the elevated reef terraces along the Gulf of Aqaba (GOA) were extensively altered to calcite. This observation indicates extensive interaction with freshwater, possibly when the terraces passed through a coastal aquifer that existed along the shores of the GOA, implying a wetter climate during the time of recrystallization from aragonite to calcite. Thus, dating of the recrystallization events should yield the timing of past wetter conditions in the current hyper-arid area of the GOA. In the present study, 18 aragonite and calcite corals were collected from several elevated coral reef terraces off the coast, south of the city of Aqaba. While aragonite corals were dated with the conventional closed system age equation (assuming zero initial Th), the dating of the calcite corals required the development of adequate equations to allow the calculation of both the initial formation age of the aragonite corals and the time of recrystallization to calcite. The two age calculations were based on the assumptions that each reef terrace went through a single and rapid recrystallization event and that the pristine aragonite corals were characterized by a rather uniform initial U concentration, typical for pristine modern corals. Two recrystallization events were identified at 104 ± 6 ka and 124 ± 8 ka. The ages coincide with the timing of sapropel events S4 and S5, respectively, when the African monsoon induced enhanced wetness in the desert area. Considering the age uncertainties, the times of formation of the two major reef terraces are estimated to be ∼124 ka (reef terrace R2) and ∼130 ka (reef terrace R3), matching the peaks in the global sea level during the last interglacial MIS 5e stage. Apparently, sea level of the GOA did not fluctuate a lot during the period between ∼130 ka and ∼104 ka and remained close to the Marine Isotopic stage (MIS) 5e highstand. The availability of freshwater (during the sapropel periods) and limited sea

  6. The Impact of Seawater Saturation State on Early Skeletal Development in Larval Corals: Insights into Scleractinian Biomineralization

    Science.gov (United States)

    Cohen, A. L.; McCorkle, D. C.; de Putron, S.

    2007-12-01

    Understanding the response of coral calcification to changes in seawater saturation state (ocean acidification) could provide important insights into the fundamental processes of scleractinian biomineralization. In particular, larval calcification, which involves initiation of skeletogenesis by a previously non-calcifying planktonic planula, offers a unique opportunity to examine the role and limitations of biological control over an essentially physicochemical process. Larvae of the brooding Atlantic coral Favia fragum were settled in unmodified seawater onto clay tiles within 12h of spawning, and placed into non-through flow 30 L aquaria prior to initiation of calcification. Seawater chemistry was pre-adjusted via HCl addition and continuous bubbling with laboratory air, yielding four aragonite saturation states: Omega(aragonite) = 3.71 (unmodified), 2.4, 1.04, and 0.22. The aquaria were held at 25 °C on a 12h/12h light/dark cycle, and sets of tiles harvested at 1, 5 and 8 days post-spawning. Accretion of aragonite (confirmed by Raman spectroscopy) in all treatments indicates that the settled larvae were able to elevate the saturation state of aquarium seawater sequestered within their calcifying space. However, external aqueous carbonate chemistry had a striking effect on larval mortality, on the nature and timing of basal plate formation, on skeletal growth rates (based on the length and cross-sectional area of septa), and on the structure and organization of aragonite crystals within the septa (imaged using SEM). Larval survival rates at the two lower saturation states was only 40% of that in the control and Omega = 2.35 treatments, and skeletal growth decreased by 30 % (relative to the control) in seawater with saturation state comparable to that predicted for the mid-latitude surface ocean by 2100 AD. SEM imaging of the larval skeletons revealed significant differences in the morphology of aragonite crystals accreted under different conditions. In stark

  7. Bony fish and their contribution to marine inorganic carbon cycling

    Science.gov (United States)

    Salter, Michael; Perry, Chris; Wilson, Rod; Harborne, Alistair

    2016-04-01

    Conventional understanding of the marine inorganic carbon cycle holds that CaCO3 (mostly as low Mg-calcite and aragonite) precipitates in the upper reaches of the ocean and sinks to a point where it either dissolves or is deposited as sediment. Thus, it plays a key role controlling the distribution of DIC in the oceans and in regulating their capacity to absorb atmospheric CO2. However, several aspects of this cycle remain poorly understood and have long perplexed oceanographers, such as the positive alkalinity anomaly observed in the upper water column of many of the world's oceans, above the aragonite and calcite saturation horizons. This anomaly would be explained by extensive dissolution of a carbonate phase more soluble than low Mg-calcite or aragonite, but major sources for such phases remain elusive. Here we highlight marine bony fish as a potentially important primary source of this 'missing' high-solubility CaCO3. Precipitation of CaCO3 takes place within the intestines of all marine bony fish as part of their normal physiological functioning, and global production models suggest it could account for up to 45 % of total new marine CaCO3 production. Moreover, high Mg-calcite containing >25 % mol% MgCO3 - a more soluble phase than aragonite - is a major component of these precipitates. Thus, fish CaCO3 may at least partially explain the alkalinity anomaly in the upper water column. However, the issue is complicated by the fact that carbonate mineralogy actually varies among fish species, with high Mg-calcite (HMC), low Mg-calcite (LMC), aragonite, and amorphous calcium carbonate (ACC) all being common products. Using data from 22 Caribbean fish species, we have generated a novel production model that resolves phase proportions. We evaluate the preservation/dissolution potential of these phases and consider potential implications for marine inorganic carbon cycling. In addition, we consider the dramatic changes in fish biomass structure that have resulted

  8. Synchrotron FT-IR analyses of microstructured biomineral domains: Hints to the biomineralization processes in freshwater cultured pearls.

    Science.gov (United States)

    Soldati, A. L.; Vicente-Vilas, V.; Gasharova, B.; Jacob, D. E.

    2009-04-01

    Recent investigations in freshwater cultured pearls (bio-carbonate) by micro-Raman spectroscopy (Wehrmeister et al., 2008; Soldati et al., 2008), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) imaging (Jacob et al., 2008) show that the pearl biomineralisation starts with a self assembling process in which an existing gel matrix of amorphous calcium carbonate (ACC) and organic substances reorganizes and conglomerates in small domains; these conglomerates then form prisms and mature nacreous tablets of aragonite or vaterite. Raman spectroscopy shows that the calcium carbonate polymorphs have decreasing luminescence in the order ACC>Vaterite>Aragonite, coinciding with decreasing quantities of S and P (related to the organic matrix) measured by Laser Ablation Inductively Coupled Plasma Mass Spectroscopy (LA-ICP-MS) and Electron Probe Micro Analyzer (EPMA). Although little is known about the process of transformation of the ACC gel into vaterite and aragonite, it is speculated that this probably involves dehydration and change of the accompanying organic matrix. This is also supported by our laboratory FT-IR analysis. However, due to the small size of the areas of ACC (about 10 ?m) and the biogenic crystals an in-situ high spatially resolved IR-method is needed to record how the water content and organic matrix change in the biomineralisation sequence, to understand which processes take place in the self-organization. The beamline IR-1 at the ANKA synchrotron source (Karlsruhe, Germany) was used for this experiment. Freshwater cultured pearls from China cultured in Hyriopsis cumingii mussels by tissue nucleation methods (so-called beadless pearls) as well as by bead implantation methods (aragonite nucleus) were studied. The pearls were cut in half with a diamond-plated saw and polished with diamond paste on a copper plate. Micro-Raman spectroscopy maps (Department of Geosciences, at the Johannes Gutenberg-University, Mainz) were generated

  9. Resilience of cold-water scleractinian corals to ocean acidification: Boron isotopic systematics of pH and saturation state up-regulation

    Science.gov (United States)

    McCulloch, Malcolm; Trotter, Julie; Montagna, Paolo; Falter, Jim; Dunbar, Robert; Freiwald, André; Försterra, Günter; López Correa, Matthias; Maier, Cornelia; Rüggeberg, Andres; Taviani, Marco

    2012-06-01

    The boron isotope systematics has been determined for azooxanthellate scleractinian corals from a wide range of both deep-sea and shallow-water environments. The aragonitic coral species, Caryophyllia smithii, Desmophyllum dianthus, Enallopsammia rostrata, Lophelia pertusa, and Madrepora oculata, are all found to have relatively high δ11B compositions ranging from 23.2‰ to 28.7‰. These values lie substantially above the pH-dependent inorganic seawater borate equilibrium curve, indicative of strong up-regulation of pH of the internal calcifying fluid (pHcf), being elevated by ˜0.6-0.8 units (ΔpH) relative to ambient seawater. In contrast, the deep-sea calcitic coral Corallium sp. has a significantly lower δ11B composition of 15.5‰, with a corresponding lower ΔpH value of ˜0.3 units, reflecting the importance of mineralogical control on biological pH up-regulation. The solitary coral D. dianthus was sampled over a wide range of seawater pHT and shows an approximate linear correlation with ΔpHDesmo = 6.43 - 0.71pHT (r2 = 0.79). An improved correlation is however found with the closely related parameter of seawater aragonite saturation state, where ΔpHDesmo = 1.09 - 0.14Ωarag (r2 = 0.95), indicating the important control that carbonate saturation state has on calcification. The ability to up-regulate internal pHcf, and consequently Ωcf, of the calcifying fluid is therefore a process present in both azooxanthellate and zooxanthellate aragonitic corals, and is attributed to the action of Ca2+-ATPase in modulating the proton gradient between seawater and the site of calcification. These findings also show that the boron isotopic compositions (δ11Bcarb) of aragonitic corals are highly systematic and consistent with direct uptake of the borate species within the biologically controlled extracellular calcifying medium. We also show that the relatively strong up-regulation of pH and consequent elevation of the internal carbonate saturation state (Ωcf ˜8

  10. Late Quaternary sea level and environmental changes from relic carbonate deposits of the western margin of India

    Indian Academy of Sciences (India)

    V Purnachandra Rao; G Rajagopalan; K H Vora; F Almeida

    2003-03-01

    Relic carbonate deposits along the western margin of India occur as dolomite crusts, aragonite sands (pelletal / oolitic) and aragonite-cemented limestones, oyster shells, corals, encrusted coralline algal and foraminiferal-dominated nodules. The petrology and mineralogy of the deposits indicate that except for aragonite sands and foraminiferal nodules, the others were formed in shallow marine conditions and serve as sea level indicators. Radiocarbon dates were measured for 62 relic deposits covering the entire margin. The age of these deposits on the continental shelf off Cape Comorin and Mangalore, between 110 and 18m depth, ranges between 12, 610 14C yr BP and 6,390 14C yr BP. On the northwestern margin of India, especially on the carbonate platform (between 64 and 100 m), the age ranges from 17,250 to 6,730 14C yr BP. The relic deposits of the Gulf of Kachchh at depths between 35 and 25m are dated at 12,550-9,630 14C yr BP. The age vs. depth plot of the relic deposits further indicates that the Gulf of Kachchh was inundated much early, atleast by 15 ka, after the Last Glacial Maximum, and was subjected to uplift and subsidence during the Holocene. The carbonate platform subsided during the early Holocene. Some of the relic deposits between Cape Comorin and Mangalore plot on or, closely follow the glacio-eustatic sea level curve. Despite abundant siliciclastic flux discharged by the Narmada and Tapti during the early Holocene, the platform off these rivers is largely devoid of this flux and carbonate sedimentation continued until 6,700 14C yr BP. We suggest that the river-derived ediment flux diverted southwards under the influence of the SW monsoon current and, thereby, increased the turbidity on the shelf and slope southeast of the carbonate platform and facilitated the formation of deeper water foraminiferal nodules off Vengurla-Goa.

  11. Response of the Arctic pteropod Limacina helicina to projected future environmental conditions.

    Directory of Open Access Journals (Sweden)

    Steeve Comeau

    Full Text Available Thecosome pteropods (pelagic mollusks can play a key role in the food web of various marine ecosystems. They are a food source for zooplankton or higher predators such as fishes, whales and birds that is particularly important in high latitude areas. Since they harbor a highly soluble aragonitic shell, they could be very sensitive to ocean acidification driven by the increase of anthropogenic CO(2 emissions. The effect of changes in the seawater chemistry was investigated on Limacina helicina, a key species of Arctic pelagic ecosystems. Individuals were kept in the laboratory under controlled pCO(2 levels of 280, 380, 550, 760 and 1020 microatm and at control (0 degrees C and elevated (4 degrees C temperatures. The respiration rate was unaffected by pCO(2 at control temperature, but significantly increased as a function of the pCO(2 level at elevated temperature. pCO(2 had no effect on the gut clearance rate at either temperature. Precipitation of CaCO(3, measured as the incorporation of (45Ca, significantly declined as a function of pCO(2 at both temperatures. The decrease in calcium carbonate precipitation was highly correlated to the aragonite saturation state. Even though this study demonstrates that pteropods are able to precipitate calcium carbonate at low aragonite saturation state, the results support the current concern for the future of Arctic pteropods, as the production of their shell appears to be very sensitive to decreased pH. A decline of pteropod populations would likely cause dramatic changes to various pelagic ecosystems.

  12. Distribution of total alkalinity and pH in the Ross Sea (Antarctica waters during austral summer 2008

    Directory of Open Access Journals (Sweden)

    Paola Rivaro

    2014-10-01

    Full Text Available Measurements of total alkalinity (AT and pH were made in the Ross Sea in January–February 2008 in order to characterize the carbonate system in the Ross Sea and to evaluate the variability associated with different water masses. The main water masses of the Ross Sea, Antarctic Surface Water, High Salinity Shelf Water (HSSW, Deep Ice Shelf Water, Circumpolar Deep Water (CDW and Antarctic Bottom Water, were identified on the basis of the physical and chemical data. In particular, the AT ranged between 2275 and 2374 µmol kg−1 with the lowest values in the surface waters (2275–2346 µmol kg−1, where the influence of the sea-ice melting and of the variability of the physical properties was significant. In the deep layers of the water column, the AT maxima were measured in correspondence to the preferential pathways of the spreading HSSW. The pH had variable values in the surface layer (7.890–8.033 with the highest values in Terra Nova Bay and Ross Sea polynyas. A low pH (7.969±0.025 traced the intrusion of the CDW in the Ross Sea shelf area. All samples revealed waters that were oversaturated with respect to both calcite and aragonite, but near corrosive levels of aragonite saturation state (Ω ca. 1.1–1.2 were associated with the entrainment of CDW over the slope. Aragonite undersaturation is of particular concern for the zooplankton species comprising to calcifying organisms such as pteropods. The partial pressure of CO2 at the sea surface was undersaturated with respect to the atmospheric value, particularly in Terra Nova Bay and the Ross Sea polynyas, but a large variability in the sea–air CO2 fluxes was observed associated with different responses in the strength of the biological and physical processes.

  13. Compositional variations at ultra-structure length scales in coral skeleton

    Science.gov (United States)

    Meibom, Anders; Cuif, Jean-Pierre; Houlbreque, Fanny; Mostefaoui, Smail; Dauphin, Yannicke; Meibom, Karin L.; Dunbar, Robert

    2008-03-01

    Distributions of Mg and Sr in the skeletons of a deep-sea coral ( Caryophyllia ambrosia) and a shallow-water, reef-building coral ( Pavona clavus) have been obtained with a spatial resolution of 150 nm, using the NanoSIMS ion microprobe at the Muséum National d'Histoire Naturelle in Paris. These trace element analyses focus on the two primary ultra-structural components in the skeleton: centers of calcification (COC) and fibrous aragonite. In fibrous aragonite, the trace element variations are typically on the order of 10% or more, on length scales on the order of 1-10 μm. Sr/Ca and Mg/Ca variations are not correlated. However, Mg/Ca variations in Pavona are strongly correlated with the layered organization of the skeleton. These data allow for a direct comparison of trace element variations in zooxanthellate and non-zooxanthellate corals. In both corals, all trace elements show variations far beyond what can be attributed to variations in the marine environment. Furthermore, the observed trace element variations in the fibrous (bulk) part of the skeletons are not related to the activity of zooxanthellae, but result from other biological activity in the coral organism. To a large degree, this biological forcing is independent of the ambient marine environment, which is essentially constant on the growth timescales considered here. Finally, we discuss the possible detection of a new high-Mg calcium carbonate phase, which appears to be present in both deep-sea and reef-building corals and is neither aragonite nor calcite.

  14. Suitable environmental ranges for potential coral reef habitats in the tropical ocean.

    Science.gov (United States)

    Guan, Yi; Hohn, Sönke; Merico, Agostino

    2015-01-01

    Coral reefs are found within a limited range of environmental conditions or tolerance limits. Estimating these limits is a critical prerequisite for understanding the impacts of climate change on the biogeography of coral reefs. Here we used the diagnostic model ReefHab to determine the current environmental tolerance limits for coral reefs and the global distribution of potential coral reef habitats as a function of six factors: temperature, salinity, nitrate, phosphate, aragonite saturation state, and light. To determine these tolerance limits, we extracted maximum and minimum values of all environmental variables in corresponding locations where coral reefs are present. We found that the global, annually averaged tolerance limits for coral reefs are 21.7-29.6 °C for temperature, 28.7-40.4 psu for salinity, 4.51 μmol L-1 for nitrate, 0.63 μmol L-1 for phosphate, and 2.82 for aragonite saturation state. The averaged minimum light intensity in coral reefs is 450 μmol photons m-2 s-1. The global area of potential reef habitats calculated by the model is 330.5 × 103 km2. Compared with previous studies, the tolerance limits for temperature, salinity, and nutrients have not changed much, whereas the minimum value of aragonite saturation in coral reef waters has decreased from 3.28 to 2.82. The potential reef habitat area calculated with ReefHab is about 121×103 km2 larger than the area estimated from the charted reefs, suggesting that the growth potential of coral reefs is higher than currently observed.

  15. The mineralogical responses of marine calcifiers to CO2-induced ocean acidification

    Science.gov (United States)

    Ries, J. B.; Cohen, A. L.; McCorkle, D. C.

    2008-12-01

    We have conducted 6-month laboratory experiments to investigate the effect of pCO2-induced reductions in seawater CaCO3 saturation state on biocalcification by 18 aragonitic and calcitic (low-high Mg) taxa representing eight of the major marine calcifying groups: Chlorophyta; Rhodophyta; Crustacea; Bivalvia; Gastropoda; Annelida; Cnidaria; and Echinodermata. The CaCO3 saturation states of the experimental seawaters, constrained by intercalibrated determinations of pH, alkalinity, and DIC, were attained with bubbled air-CO2 mixtures of 400 (ambient), 600, 900, and 2850 ppm pCO2, yielding Ωarag of 2.5 (ambient), 2.0, 1.5, 0.7, respectively. We previously showed that while rates of net calcification obtained from buoyant weighing declined with increasing pCO2 for nearly half of the species investigated, a nearly equal number exhibited constant or, in some cases, increased calcification under moderately (600 ppm) or extremely (900 or 2850 ppm) elevated pCO2. The organisms' investigated in this study secrete various forms of CaCO3, which differ in crystallographic structure and therefore solubility: aragonite and high-Mg are generally more soluble than low-Mg calcite. We have employed powder x-ray diffraction, Raman spectroscopy, inductively-coupled-plasma mass-spectrometry, and scanning electron microscopy to quantify changes in the organisms' skeletal mineralogy (aragonite:calcite ratio) and Mg-content (MgCO3:CaCO3 ratio) that occurred in response to the prescribed reductions in seawater CaCO3 saturation state. We will compare calcification and mineralogical response patterns amongst the organisms to elucidate the role of mineral lability in driving species-specific responses to CO2-induced ocean acidification.

  16. Black Mn-Fe crusts as markers of abrupt palaeoenvironmental changes in El Soplao Cave (Cantabria, Spain

    Directory of Open Access Journals (Sweden)

    Gazquez Fernando

    2011-07-01

    Full Text Available Peculiar iron and manganese deposits coating walls, floors and ceilings of many galleries are one of the special features of the ElSoplao Cave (Cantabria, Spain. These speleothems appear to have been deposited over wall clay deposits, as well as formingpart of flowstones. Structure of crusts is essentially amorphous but several manganese and iron oxides were identified like goethiteand birnessite, though all occur with a low degree of crystallinity. In the outer layer of the crusts, alteration iron minerals appear thatderive from previous minerals in a process probably mediated by microorganisms. EDX microanalyses report fairly high values of Feand Mn in the crusts, though the Mn/Fe ratio varies considerably as a function of distance from the substrate/bedrock. The presentstudy proposes a genetic model for crust speleothems in El Soplao, based on oscillations of the phreatic level. The origin of thesedeposits is related to mobilization, under phreatic conditions, of polymetallic sulfides in the host rock. Metal ions (including Fe²+ andMn²+ released into the cave under reducing conditions, are oxidized and fixed in a process mediated by bacteria, giving rise to oxidesand hydroxides of low crystallinity. The presence of various black intercalated layers in aragonite flowstones indicate periods whencave conditions suddenly changed from vadose, when aragonite is precipitated, to phreatic and epiphreatic conditions, when theMn-Fe deposits are precipitated. Subsequently, vadose conditions were re-established, leading to the final stages of precipitation ofaragonite recorded in the flowstone and recent aragonite helictites on the surface of the Mn-Fe crusts.

  17. Carbonate organo-mineral micro- and ultrastructures in sub-fossil stromatolites: Marion lake, South Australia.

    Science.gov (United States)

    Perri, E; Tucker, M E; Spadafora, A

    2012-03-01

    Sub-fossil stromatolites (5000-3000 years old) occur on the marginal flat surrounding Marion Lake (South Australia). A micrite/microsparite crystal fabric characterises these fine-grained, well-laminated stromatolites, which lack trapped grains. The internal lamination is characterised by a sub-millimetric alternation of porous and dense laminae. The microfabric of the laminae is ubiquitously composed of a fine (10-20 μm) peloidal texture, with many thinner aphanitic layers. Aggregates of very fine, low-Mg calcite and aragonite constitute both peloidal and aphanitic micrite, which is coated, respectively, by spherulitic and fringing acicular microspar. Micrite, with a high organic matter content, is formed of coalescing nanospheres grading into small polyhedrons, probably composed mainly of aragonite, with less calcite enriched in Mg, Sr, Na and S. Bacteria-like microfossils and relics of extracellular polymeric substance (EPS) occur abundantly within this micritic framework. The former consist of empty moulds and mineralised bodies of coccoid forms, whereas EPS relics consist of sheet-like or filamentous structures that appear both mineralised and more often still preserved as a C-enriched dehydrated substance that represents the main organic matter component of the deposit. Acicular crystals, which show a prismatic elongate shape, are composed of Mg-depleted aragonite that lacks fossils or organic relicts. Degrading EPS and micro-organisms appear gradually to be replaced and entombed by the nanospherical precipitates, implying the existence of processes of organo-mineralisation within an original syn-sedimentary microbial community. Succeeding micron-scale crystals merge to form isolated or connected micritic aggregates (the peloids), followed by the gradual formation of the acicular crystals as purely inorganic precipitates.

  18. Imminent ocean acidification projected with the NCAR global coupled carbon cycle-climate model

    Directory of Open Access Journals (Sweden)

    M. Steinacher

    2008-11-01

    Full Text Available Ocean acidification from the uptake of anthropogenic carbon is simulated for the industrial period and IPCC SRES emission scenarios A2 and B1 with a global coupled carbon cycle-climate model. Earlier studies identified seawater saturation state with respect to aragonite, a mineral phase of calcium carbonate, as a key variable governing impacts on corals and other shell-forming organisms. Globally in the A2 scenario, water saturated by more than 300%, considered suitable for coral growth, vanishes by 2070 AD (CO2≈630 ppm, and the ocean volume fraction occupied by saturated water decreases from 42% to 25% over this century. The largest simulated pH changes worldwide occur in Arctic surface waters, where hydrogen ion concentration increases by up to 185%. Projected climate change amplifies the decrease in Arctic surface mean saturation and pH by more than 20%, mainly due to freshening and increased carbon uptake in response to sea ice retreat. Modeled saturation compares well with observation-based estimates along an Arctic transect and simulated changes have been corrected for remaining model-data differences in this region. Aragonite undersaturation in Arctic surface waters is projected to occur locally soon and to become more widespread as atmospheric CO2 continues to grow. The results imply that surface waters in the Arctic Ocean will become corrosive to aragonite, with potentially large implications for the marine ecosystem, if anthropogenic carbon emissions are not reduced and atmospheric CO2 not kept below 450 ppm.

  19. Imminent ocean acidification in the Arctic projected with the NCAR global coupled carbon cycle-climate model

    Directory of Open Access Journals (Sweden)

    M. Steinacher

    2009-04-01

    Full Text Available Ocean acidification from the uptake of anthropogenic carbon is simulated for the industrial period and IPCC SRES emission scenarios A2 and B1 with a global coupled carbon cycle-climate model. Earlier studies identified seawater saturation state with respect to aragonite, a mineral phase of calcium carbonate, as a key variable governing impacts on corals and other shell-forming organisms. Globally in the A2 scenario, water saturated by more than 300%, considered suitable for coral growth, vanishes by 2070 AD (CO2≈630 ppm, and the ocean volume fraction occupied by saturated water decreases from 42% to 25% over this century. The largest simulated pH changes worldwide occur in Arctic surface waters, where hydrogen ion concentration increases by up to 185% (ΔpH=−0.45. Projected climate change amplifies the decrease in Arctic surface mean saturation and pH by more than 20%, mainly due to freshening and increased carbon uptake in response to sea ice retreat. Modeled saturation compares well with observation-based estimates along an Arctic transect and simulated changes have been corrected for remaining model-data differences in this region. Aragonite undersaturation in Arctic surface waters is projected to occur locally within a decade and to become more widespread as atmospheric CO2 continues to grow. The results imply that surface waters in the Arctic Ocean will become corrosive to aragonite, with potentially large implications for the marine ecosystem, if anthropogenic carbon emissions are not reduced and atmospheric CO2 not kept below 450 ppm.

  20. Oxygen spectroscopy and polarization-dependent imaging contrast (PIC)-mapping of calcium carbonate minerals and biominerals.

    Science.gov (United States)

    DeVol, Ross T; Metzler, Rebecca A; Kabalah-Amitai, Lee; Pokroy, Boaz; Politi, Yael; Gal, Assaf; Addadi, Lia; Weiner, Steve; Fernandez-Martinez, Alejandro; Demichelis, Raffaella; Gale, Julian D; Ihli, Johannes; Meldrum, Fiona C; Blonsky, Adam Z; Killian, Christopher E; Salling, C B; Young, Anthony T; Marcus, Matthew A; Scholl, Andreas; Doran, Andrew; Jenkins, Catherine; Bechtel, Hans A; Gilbert, Pupa U P A

    2014-07-17

    X-ray absorption near-edge structure (XANES) spectroscopy and spectromicroscopy have been extensively used to characterize biominerals. Using either Ca or C spectra, unique information has been obtained regarding amorphous biominerals and nanocrystal orientations. Building on these results, we demonstrate that recording XANES spectra of calcium carbonate at the oxygen K-edge enables polarization-dependent imaging contrast (PIC) mapping with unprecedented contrast, signal-to-noise ratio, and magnification. O and Ca spectra are presented for six calcium carbonate minerals: aragonite, calcite, vaterite, monohydrocalcite, and both hydrated and anhydrous amorphous calcium carbonate. The crystalline minerals reveal excellent agreement of the extent and direction of polarization dependences in simulated and experimental XANES spectra due to X-ray linear dichroism. This effect is particularly strong for aragonite, calcite, and vaterite. In natural biominerals, oxygen PIC-mapping generated high-magnification maps of unprecedented clarity from nacre and prismatic structures and their interface in Mytilus californianus shells. These maps revealed blocky aragonite crystals at the nacre-prismatic boundary and the narrowest calcite needle-prisms. In the tunic spicules of Herdmania momus, O PIC-mapping revealed the size and arrangement of some of the largest vaterite single crystals known. O spectroscopy therefore enables the simultaneous measurement of chemical and orientational information in CaCO3 biominerals and is thus a powerful means for analyzing these and other complex materials. As described here, PIC-mapping and spectroscopy at the O K-edge are methods for gathering valuable data that can be carried out using spectromicroscopy beamlines at most synchrotrons without the expense of additional equipment.

  1. Adsorption Properties of Chalk Reservoir Materials

    DEFF Research Database (Denmark)

    Okhrimenko, Denis

    Understanding adsorption energetics and wetting properties of calcium carbonate surfaces is essential for developing remediation strategies for aquifers, improving oil recovery, minimising risk in CO2 storage and optimising industrial processes. This PhD was focussed on comparing the vapour....../gas adsorption properties of synthetic calcium carbonate phases (calcite, vaterite and aragonite) with chalk, which is composed of biogenic calcite (>98%). In combination with data from nanotechniques, the results demonstrate the complexity of chalk behavior and the role of nanoscale clay particles. The results...

  2. Iron Drinking Water Pipe Corrosion Products: Concentrators of Toxic Metals

    Science.gov (United States)

    2013-01-01

    2005): p. 537. 27. A. A. Finch and N. Allison: ’Coordination of Sr and Mg in calcite and aragonite’, Mineralogical Magaz/ne, 71, 5 (2007): p. 539...surfaces of calcite and kaolinite’, Geochimica et Cosmochimica Ada, 62, 9 (1998): p. 1481. 29. N. E. Pingitore Jr, F. W. Lytle, B. M. Davies, M. P...Eastman, P. G. Eller, and E. M. Larson: ’Mode of incorporation of Sr^* in calcite : Determination by X-ray absorption spectroscopy’, Geochimica et

  3. Photothermal characterization of thermally treated shells of Strombus Gigas

    Science.gov (United States)

    Hernández-Ayala, A.; Quintana, P.; Alvarado-Gil, J. J.; Aldana, D.

    2005-06-01

    The thermal properties of the marine shells of the mollusk Strombus gigas are studied using photoacoustic techniques. In order to generate changes in the layered structure of the shells, they were thermally treated in the range from ambient temperature up to 400ºC. Our results show that the thermal diffusivity and conductivity have a maximum at 200ºC due to the degradation of the organic matrix. At higher temperatures the thermal diffusivity and conductivity decrease due to the calcium carbonate structural phase transition from aragonite to calcite.

  4. Caracterização físico-química e microestrutural de conchas de moluscos bivalves provenientes de cultivos da região litorânea da ilha de Santa Catarina Physical chemistry and micro structural characterization of shells of bivalve mollusks from sea farmer around the Santa Catarina island

    OpenAIRE

    Denyo Silva; Nito Angelo Debacher; Armando Borges de Castilhos Junior; Fabio Rohers

    2010-01-01

    Samples of shells of oysters and mussels from sea farm around the Santa Catarina Island in south Brazil were collected and analyzed by DRX, FRX, SEM, CHN-S, FTIR, TG, AAS/Flame and AAS /GF. The results showed that the crystalline structure of mussel's shells is mainly formed by aragonite and the oyster's shells by calcite. The calcium percentage in both shells species was in the range of 33 to 35% and also 850 and 1200 mg/kg of strontium was detected in the shells of oysters and mussels, resp...

  5. Caracterização físico-química e microestrutural de conchas de moluscos bivalves provenientes de cultivos da região litorânea da ilha de Santa Catarina

    OpenAIRE

    Silva, Denyo; Debacher,Nito Angelo; Castilhos Junior,Armando Borges de; Rohers,Fabio

    2010-01-01

    Samples of shells of oysters and mussels from sea farm around the Santa Catarina Island in south Brazil were collected and analyzed by DRX, FRX, SEM, CHN-S, FTIR, TG, AAS/Flame and AAS /GF. The results showed that the crystalline structure of mussel's shells is mainly formed by aragonite and the oyster's shells by calcite. The calcium percentage in both shells species was in the range of 33 to 35% and also 850 and 1200 mg/kg of strontium was detected in the shells of oysters and mussels, resp...

  6. Effects of pore-scale precipitation on permeability and flow

    Science.gov (United States)

    Noiriel, Catherine; Steefel, Carl I.; Yang, Li; Bernard, Dominique

    2016-09-01

    The effects of calcite precipitation on porous media permeability and flow were evaluated with a combined experimental and modeling approach. X-ray microtomography images of two columns packed with glass beads and calcite (spar crystals) or aragonite (Bahamas ooids) injected with a supersaturated solution (log Ω = 1.42) were processed in order to calculate rates of calcite precipitation with a spatial resolution of 4.46 μm. Identification and localization of the newly precipitated crystals on the 3D images was performed and results used to calculate the crystal growth rates and velocities. The effects of carbonate precipitation were also evaluated in terms of the integrated precipitation rate over the length of the column, crystal shape, surface area and pore roughness changes. While growth was epitaxial on calcite spar, calcite rhombohedra formed on glass beads and clusters of polyhedrons formed on aragonite ooids. Near the column inlet, calcite precipitation occurred preferentially on carbonate grains compared to glass beads, with almost 100% of calcite spar surface area covered by new crystals versus 92% in the case of aragonite and 11% in the case of glass beads. Although the experimental chemistry and flow boundary conditions in the two columns were similar, their porosity-permeability evolution was different because the nucleation and subsequent crystal growth on the two substrates (i.e., calcite spar and aragonite ooids) was very different. The impact of mineral precipitation on pore-scale flow and permeability was evaluated using a pore-scale Stokes solver that accounted for the changes in pore geometry. For similar magnitude reductions in porosity, the decrease in permeability was highest within the sample that experienced the greatest increase in pore roughness. Various porous media models were generated to show the impact of different crystal growth patterns and pore roughness changes on flow and permeability-porosity relationship. Under constant flow

  7. Photonic crystal type structure in bivalve ligament of Pinctada maxima

    Institute of Scientific and Technical Information of China (English)

    ZHANG GangSheng

    2007-01-01

    The dry ligament of Pinctada maxima normally appears black; however, it can exhibit striking blue structural colors after being wetted by water. The field-mission SEM investigation shows that the ligament is made of lamellae, which, about 35 μm thick, are made of proteins and aragonite fibers of about 78 nm in diameter. In each single lamella, the fibers are highly aligned characterized by a 2D photonic crystal type structure. According to measured reflective spectra and theoretical simulations, the dry and wet ligaments possess photonic stop band at ultraviolet and blue wavelengths, respectively, which are responsible for structural colorations of ligament.

  8. Natural variability in the surface ocean carbonate ion concentration

    Directory of Open Access Journals (Sweden)

    N. S. Lovenduski

    2015-08-01

    Full Text Available We investigate variability in the surface ocean carbonate ion concentration ([CO32−] on the basis of a long control simulation with a fully-coupled Earth System Model. The simulation is run with a prescribed, pre-industrial atmospheric CO2 concentration for 1000 years, permitting investigation of natural [CO32−] variability on interannual to multi-decadal timescales. We find high interannual variability in surface [CO32−] in the tropical Pacific and at the boundaries between the subtropical and subpolar gyres in the Northern Hemisphere, and relatively low interannual variability in the centers of the subtropical gyres and in the Southern Ocean. Statistical analysis of modeled [CO32−] variance and autocorrelation suggests that significant anthropogenic trends in the saturation state of aragonitearagonite are already or nearly detectable at the sustained, open-ocean timeseries sites, whereas several decades of observations are required to detect anthropogenic trends in Ωaragonite in the tropical Pacific, North Pacific, and North Atlantic. The detection timescale for anthropogenic trends in pH is shorter than that for Ωaragonite, due to smaller noise-to-signal ratios and lower autocorrelation in pH. In the tropical Pacific, the leading mode of surface [CO32−] variability is primarily driven by variations in the vertical advection of dissolved inorganic carbon (DIC in association with El Niño–Southern Oscillation. In the North Pacific, surface [CO32−] variability is caused by circulation-driven variations in surface DIC and strongly correlated with the Pacific Decadal Oscillation, with peak spectral power at 20–30 year periods. North Atlantic [CO32−] variability is also driven by variations in surface DIC, and exhibits weak correlations with both the North Atlantic Oscillation and the Atlantic Multidecadal Oscillation. As the scientific community seeks to detect the anthropogenic influence on ocean carbonate chemistry, these

  9. Outer organic layer and internal repair mechanism protects pteropod Limacina helicina from ocean acidification

    Science.gov (United States)

    Peck, Victoria L.; Tarling, Geraint A.; Manno, Clara; Harper, Elizabeth M.; Tynan, Eithne

    2016-05-01

    Scarred shells of polar pteropod Limacina helicina collected from the Greenland Sea in June 2012 reveal a history of damage, most likely failed predation, in earlier life stages. Evidence of shell fracture and subsequent re-growth is commonly observed in specimens recovered from the sub-Arctic and further afield. However, at one site within sea-ice on the Greenland shelf, shells that had been subject to mechanical damage were also found to exhibit considerable dissolution. It was evident that shell dissolution was localised to areas where the organic, periostracal sheet that covers the outer shell had been damaged at some earlier stage during the animal's life. Where the periostracum remained intact, the shell appeared pristine with no sign of dissolution. Specimens which appeared to be pristine following collection were incubated for four days. Scarring of shells that received periostracal damage during collection only became evident in specimens that were incubated in waters undersaturated with respect to aragonite, ΩAr≤1. While the waters from which the damaged specimens were collected at the Greenland Sea sea-ice margin were not ΩAr≤1, the water column did exhibit the lowest ΩAr values observed in the Greenland and Barents Seas, and was likely to have approached ΩAr≤1 during the winter months. We demonstrate that L. helicina shells are only susceptible to dissolution where both the periostracum has been breached and the aragonite beneath the breach is exposed to waters of ΩAr≤1. Exposure of multiple layers of aragonite in areas of deep dissolution indicate that, as with many molluscs, L. helicina is able to patch up dissolution damage to the shell by secreting additional aragonite internally and maintain their shell. We conclude that, unless breached, the periostracum provides an effective shield for pteropod shells against dissolution in waters ΩAr≤1, and when dissolution does occur the animal has an effective means of self-repair. We suggest

  10. Bioinspired Design of Building Materials for Blast and Ballistic Protection

    Directory of Open Access Journals (Sweden)

    Yu-Yan Sun

    2016-01-01

    Full Text Available Nacre in abalone shell exhibits high toughness despite the brittle nature of its major constituent (i.e., aragonite. Its specific structure is a major contributor to the energy absorption capacity of nacre. This paper reviews the mechanisms behind the performance of nacre under shear, uniaxial tension, compression, and bending conditions. The remarkable combination of stiffness and toughness on nacre can motivate the development of bioinspired building materials for impact resistance applications, and the possible toughness designs of cement-based and clay-based composite materials with a layered and staggered structure were discussed.

  11. Mineralogical analyses in two caves from the Perşani Mountains

    Directory of Open Access Journals (Sweden)

    Ştefan Marincea

    2007-01-01

    Full Text Available After diffractometric X-ray analyses through the powder method, made on sampling tests from two caves in the Perşani Mountains karst, mineral associations made up of calcite, magnesium calcite, aragonite, dolomite, brushite, hydroxylapatite, carbonate-hydroxylapatite, gypsum and α-quartz were emphasized. Tables arepresented with the resulting data from the diffractometric analyses, including the computed parameters of the elementary cells of each mineral species. The materials are discussed comparatively with the existent data in the literature. In the final chapter there is a discussion upon the mineralogenesis of the determined species.

  12. Why Corals Care about Ocean Acidification: Insights from Ion Microprobe Analyses of Coral Crystals (Invited)

    Science.gov (United States)

    Cohen, A. L.; McCorkle, D. C.; de Putron, S.; Gaetani, G. A.; Rose, K. A.

    2009-12-01

    Ocean acidification caused by rising levels of atmospheric CO2 is considered a major threat to the future health of coral reef ecosystems across the global tropics and subtropics. Results from laboratory experiments with corals reared under elevated CO2 conditions suggest that coral growth rates may decline by up to 80% of modern values by the end of this century. The mechanism by which ocean acidification impacts the skeletal growth of corals however, is not well-understood, limiting our ability to predict how corals might respond to climate changes outside of the laboratory. We used micro-scale imaging (SEM) and analytical (SIMS) techniques to quantify morphological and compositional changes in the first aragonite crystals accreted by young corals as they metamorphosed from non-calcifying larvae to calcifying polyps in experimental aquaria with seawater saturation states (Ω) ranging from ambient (3.71) to strongly under-saturated (0.22). Aragonite was accreted by all corals, even those reared under strongly under-saturated conditions, indicating that Ω of fluid within the calcifying compartment is maintained well above that of the external seawater environment. However, significant and progressive changes in both crystal morphology and composition with increasing acidification indicate that Ω of the coral’s calcifying fluid changed in proportion to that of the aquarium seawater. With increasing acidification, the normal skeleton of densely-packed bundles of fine aragonite needles gave way to a disordered aggregate of highly faceted rhombs. Sr/Ca ratios of the crystals increased by 13% and Mg/Ca ratios decreased by 45%. By comparing these variations in elemental ratios with results from Rayleigh fractionation calculations, we show that these changes are consistent with a >80% decrease in the amount of aragonite precipitated by the corals from each “batch” of calcifying fluid. The inability of the corals in acidified treatments to achieve the levels of

  13. Minor element partitioning and mineralogy in limpets from the Ischia CO2 vent site

    Science.gov (United States)

    Langer, Gerald; Sadekov, Aleksey; Nehrke, Gernot; Baggini, Cecilia; Rodolfo-Metalpa, Riccardo; Hall-Spencer, Jason; Bijma, Jelle; Elderfield, Henry

    2015-04-01

    Specimens of the patellogastropod limpet Patella caerulea were collected within and outside a CO2 vent site at Ischia, Italy. The shells were sectioned transversally and scanned for polymorph distribution by means of confocal Raman microscopy. Minor element to calcium ratios were measured using laser-ablation-inductively-coupled-plasma-mass-spectroscopy (LA-ICPMS). Mg/Ca, Sr/Ca, and Li/Ca ratios were determined in calcitic as well as aragonitic parts of the shells. This approach allows for investigating the effects of the polymorph and the seawater carbonate chemistry on minor element partitioning separately.

  14. Spatiotemporal variability and long-term trends of ocean acidification in the California Current System

    Directory of Open Access Journals (Sweden)

    C. Hauri

    2012-08-01

    Full Text Available Due to seasonal upwelling, the upper ocean waters of the California Current System (CCS have a naturally low pH and aragonite saturation state (Ωarag, making this region particularly prone to the effects of ocean acidification. Here, we use the Regional Oceanic Modeling System (ROMS to conduct preindustrial and transient (1995–2050 simulations of ocean biogeochemistry in the CCS. The transient simulations were forced with increasing atmospheric pCO2 as projected by the NCAR CSM 1.4 model run under either the IPCC SRES A2 or B1 scenarios. Using ROMS, we investigate the timing of transition decades during which pH and Ωarag depart from their modeled preindustrial (1750 and present-day (2011 variability envelopes. We report these transition decades by noting the midpoint of the ten-year transition periods. In addition, we also analyze the timing of near permanent aragonite undersaturation in the upper 100 m of the water column. Our results show that an interplay of physical and biogeochemical processes create large seasonal variability in pH (∼ 0.14 and Ωarag (∼ 0.2. Despite this large variability, we find that present-day pH and Ωarag have already moved out of their preindustrial variability envelopes due to the rapidly increasing concentrations of atmospheric CO2. The simulations following the A2 emissions scenario suggest that nearshore surface pH of the northern and central CCS will move out of their present-day variability envelopes by 2045 and 2037, respectively. However, surface Ωarag of the northern and central CCS subregions are projected to depart from their present-day variability envelopes sooner, by 2030 and 2035, respectively. By 2025, the aragonite saturation horizon of the central CCS is projected to shoal into the upper 75 m for the duration of the annual cycle, causing near permanent undersaturation in subsurface waters. Overall, our

  15. Influences of riverine and upwelling waters on the coastal carbonate system off Central Chile and their ocean acidification implications

    Science.gov (United States)

    Vargas, Cristian A.; Contreras, Paulina Y.; Pérez, Claudia A.; Sobarzo, Marcus; Saldías, Gonzalo S.; Salisbury, Joe

    2016-06-01

    A combined data set, combining data from field campaigns and oceanographic cruises, was used to ascertain the influence of both river discharges and upwelling processes, covering spatial and temporal variation in dissolved inorganic carbon (DIC) and aragonite saturation state. This work was conducted in one of the most productive river-influenced upwelling areas in the South Pacific coasts (36°S). Additionally, further work was also conducted to ascertain the contribution of different DIC sources, influencing the dynamics of DIC along the land-ocean range. Six sampling campaigns were conducted across seven stations at the Biobío River basin, covering approximately 200 km. Three research cruises were undertaken simultaneously, covering the adjacent continental shelf, including 12 sampling stations for hydrographic measurements. Additionally, six stations were also sampled for chemical analyses, covering summer, winter, and spring conditions over 2010 and 2011. Our results evidenced that seaward extent of the river plume was more evident during the winter field campaign, when highest riverine DIC fluxes were observed. The carbonate system along the river-ocean continuum was very heterogeneous varying over spatial and temporal scales. High DIC and pCO2 were observed in river areas with larger anthropogenic effects. CO2 supersaturation at the river plume was observed during all campaigns due to the influence of low pH river waters in winter/spring and high-pCO2 upwelling waters in summer. δ13CDIC evidenced that main DIC sources along the river and river plume corresponded to the respiration of terrestrial organic matter. We have linked this natural process to the carbonate saturation on the adjacent river-influenced coastal area, suggesting that Ωaragonite undersaturation in surface/subsurface waters is largely modulated by the influence of both river discharge and coastal upwelling events in this productive coastal area. Conditions of low Ωaragonite might impact

  16. Role of mineral proximity on mechanics of organic macromolecules in a bio-nanocomposite

    Science.gov (United States)

    Ghosh, Pijush

    Nacre, the iridescent inner layer of seashells, is a material exhibiting extraordinary mechanical properties. Nacre is a laminated nanocomposite composed of pseudohexagonal platelets that are 2 micrometer to 3 micrometer in diameter and 250 nm to 500 nm tall with an organic phase about 20 nm thick between the platelets. Although nacre is composed of about 95% aragonitic calcium carbonate and 5% organics (mainly proteins), the fracture toughness exhibited by nacre is 3000 times higher than aragonite. Nacre has been studied as an inspiration for design of the next generation of high-performance biomimetic nanocomposites. In this research, the influence of the close proximity of mineral aragonite on mechanical response of the organic phase is studied for the first time. The major focus of this research is to study the influence of mineral proximity on the mechanical properties of proteins in a natural bio-nanocomposite nacre. This work seeks to understand the fundamental mechanisms behind unfolding of protein at mineral proximity. The results and knowledge from this research will help in designing the next generation of high-performance materials, particularly with hybrid organic and inorganic phases. The influence of mineral proximity on the mechanical property of a protein is found by pulling a model protein domain at mineral proximity and without the presence of mineral. The "Glycine-Serine" domain of a nacre protein, Lustrin A, has been used as a model system. Steered Molecular Dynamics has been used for our simulations. The CHARMm potential parameters necessary for aragonite are derived. The protein is pulled at three different velocities and for same duration of time in the presence and absence of the mineral. It is concluded that several times more energy are required to unfold a protein in the presence of the mineral compared to unfolding the protein alone. A detailed quantitative analysis to understand reasons for the enhancement of the load deformation

  17. Porous tablets of crystalline calcium carbonate via sintering of amorphous nanoparticles

    OpenAIRE

    Gebauer, Denis; Liu, Xing-Min; Aziz, Baroz; Hedin, Niklas; Zhao, Zhe

    2013-01-01

    Porous tablets of crystalline calcium carbonate were formed upon sintering of a precursor powder of amorphous calcium carbonate (ACC) under compressive stress (20 MPa) at relatively low temperatures (120–400 °C), induced by pulsed direct currents. Infrared spectroscopy ascertained the amorphous nature of the precursor powders. At temperatures of 120–350 °C and rates of temperature increase of 20–100 °C min−1, the nanoparticles of ACC transformed into crystallites of mainly aragonite, which is...

  18. Carbonate system in the water masses of the Southeast Atlantic sector of the Southern Ocean during February and March 2008

    Directory of Open Access Journals (Sweden)

    M. González-Dávila

    2011-05-01

    Full Text Available Carbonate system variables were measured in the South Atlantic sector of the Southern Ocean along a transect from South Africa to the southern limit of the Antarctic Circumpolar Current (ACC from February to March 2008. Eddies detached from the retroflection of the Agulhas Current increased the gradients observed along the fronts. Minima in the fugacity of CO2, fCO2, and maxima in pH on either side of the frontal zone were observed, noting that within the frontal zone fCO2 reached maximum values and pH was at a minimum.

    Vertical distributions of water masses were described by their carbonate system properties and their relationship to CFC concentrations. Upper Circumpolar Deep Water (UCDW and Lower Circumpolar Deep Water (LCDW offered pHT,25 values of 7.56 and 7.61, respectively. The UCDW also had higher concentrations of CFC-12 (>0.2 pmol kg−1 as compared to deeper waters, revealing that UCDW was mixed with recently ventilated waters. Calcite and aragonite saturation states (Ω were also affected by the presence of these two water masses with high carbonate concentrations. The aragonite saturation horizon was observed at 1000 m in the subtropical area and north of the Subantarctic Front. At the position of the Polar Front, and under the influence of UCDW and LCDW, the aragonite saturation horizon deepened from 800 m to 1500 m at 50.37° S, and reached 700 m south of 57.5° S. High latitudes proved to be the most sensitive areas to predicted anthropogenic carbon increase. Buffer coefficients related to changes in [CO2], [H+] and Ω with changes in dissolved inorganic carbon (CT and total alkalinity (AT offered minima values in the Antarctic Intermediate Water and UCDW layers. These coefficients suggest that a small increase in CT will sharply decrease the status of pH and carbonate saturation

  19. Synthesis of CaCO3 crystals using hydroxypropylmethyl cellulose hydrogel as template

    Institute of Scientific and Technical Information of China (English)

    ZHAO Jin; LI YanJun; CHENG GuoXiang

    2007-01-01

    Calcium carbonate crystallization was performed in hydrogel of hydroxypropylmethyl cellulose (HPMC). Results showed that the polyhydroxy functionalities in HPMC gel network facilitated the nucleation of aragonite which was not found in experiment without HPMC hydrogel and in experiment using methylcellulose (MC) hydrogel as template. On the other hand,due to the unique assembly of the macromolecules in HPMC hydrogel network,which was different from other hydrogels used in some previous reports,particular crystal morphology,corncob-like CaCO3,was obtained for the first time.

  20. ESR dating of Lymnaea baltica and Cerastoderma glaucum from low Ancylus level and transgressive Litorina Sea deposits

    Energy Technology Data Exchange (ETDEWEB)

    Molodkov, Anatoly [AN Ehstonskoj SSR, Tallin (Estonia). Inst. Geologii

    1996-11-01

    Freshwater gastropod (Lymnaea baltica) and brackish-water bivalve (Cerastoderma glaucum) shell samples from Ancylus Lake and Litorina Sea deposits on Hiiuma Island (north-west Estonia) were subjected to ESR measurements. All L. baltica shells studied were composed of calcite and displayed typical multicomponent ESR spectra. C. Glaucum shells normally show ESR spectra typical of aragonite with five radiation-induced lines. In the present work a C. glaucum with calcite-like spectra was encountered for the first time. The problem connected with accumulated palaeodose determination in shell fossils with unusual ESR spectra is highlighted. (author).

  1. Simulation on an aqueous solution of Calcium Carbonate%碳酸钙水溶液的模拟研究

    Institute of Scientific and Technical Information of China (English)

    游秀芬; 张雪峰; 游小嘉

    2012-01-01

    选取方解石水溶液和文石水溶液为研究对象,采用分子动力学方法,对构建的碳酸钙水溶液进行分子动力学模拟计算.计算结果表明:水分子的活性及渗透性随温度上升呈增大趋势,只有333 K温度下明显降低.方解石水溶液中Ca2+和CO32-的扩散系数随温度变化波动较大,文石水溶液中Ca2+和CO32-的扩散系数呈逐渐上升趋势.模拟得到的文石水溶液Ca2+-CO32-径向分布函数图和H2O径向分布函数图第一、二峰高度明显低于方解石水溶液.计算结果还显示离子与方解石晶面的相互作用能比文石晶面高0.02 kcal/mol.%In order to study the Calcium Carbonate crystallization, the aqueous solution of calcite and the aqueous solution of aragonite are treated as the research object by u-sing the Molecular dynamics simulate the Calcium Carbonate system. The conclusions are drew that the diffusion coefficient of water molecules increases ceaselessly with the increasing of the temperature and it's relatively small only when the temperature is 333 K. And it's also concluded that the diffusion coefficients of Ca2+ and COff in the a-queous solution of calcite vary relatively with the increasing of the temperature and those in the aqueous solution of aragonite increases ceaselessly. The radial distribution function graphs of Ca2+-CO?i~ and H2O the simulation has concluded display that the first and the second peak height is obviously lower than that of the aqueous solution of aragonite. Then it's calculated that the binding energy between the surface of calcite and 0. 02 kcal/mol higher than the surface of aragonite.

  2. Cyanobacterial calcification in modern microbialites at the submicrometer-scale

    Directory of Open Access Journals (Sweden)

    E. Couradeau

    2013-02-01

    Full Text Available The search for microfossils in the geological record has been a long-term challenge. Part of the problem comes from the difficulty of identifying such microfossils unambiguously, since they can be morphologically confused with abiotic biomorphs. One route to improve our ability to correctly identify microfossils consists in studying fossilization processes affecting bacteria in modern settings. We studied the initial stages of fossilization of cyanobacterial cells in modern microbialites from Lake Alchichica (Mexico, a Mg-rich hyperalkaline crater lake (pH 8.9 hosting currently growing stromatolites composed of aragonite [CaCO3] and hydromagnesite [Mg5(CO34(OH2 × 4(H2O]. Most of the biomass associated with the microbialites is composed of cyanobacteria. Scanning electron microscopy analyses coupled with confocal laser scanning microscopy observations were conducted to co-localize cyanobacterial cells and associated minerals. These observations showed that cyanobacterial cells affiliating to the order Pleurocapsales become specifically encrusted within aragonite with an apparent preservation of cell morphology. Encrustation gradients from non-encrusted to totally encrusted cells spanning distances of a few hundred micrometers were observed. Cells exhibiting increased levels of encrustation along this gradient were studied down to the nm-scale using a combination of focused ion beam (FIB milling, transmission electron microscopy (TEM and scanning transmission X-ray microscopy (STXM at the C, O and N K-edges. Two different types of aragonite crystals were observed: one type was composed of needle-shaped nano-crystals growing outward from the cell body with a crystallographic orientation perpendicular to the cell wall, and another type was composed of larger crystals that progressively filled the cell interior. Organic matter (OM, initially co-localized with the cell, decreased in concentration

  3. Centuries of marine radiocarbon reservoir age variation within archaeological Mesodesma Donacium shells from Southern Peru

    Science.gov (United States)

    Jones, K.B.; Hodgins, G.W.L.; Etayo-Cadavid, M. F.; Andrus, C.F.T.; Sandweiss, D.H.

    2010-01-01

    Mollusk shells provide brief (Peru. The ranges in marine 14C ages (and thus R) from the 2 shells are 530 and 170 14C yr; R from individual aragonite samples spans 130 ?? 60 to 730 ?? 170 14C yr. This intrashell 14C variability suggests that 14C dating of small (time-slice much less than 1 yr) marine samples from a variable-R (i.e. variable-upwelling) environment may introduce centuries of chronometric uncertainty. ?? 2010 by the Arizona Board of Regents on behalf of the University of Arizona.

  4. Phosphatised limestones and associated sediments from the western continental shelf of India

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, V.P.; Natarajan, R.; Parthiban, G.; Mascarenhas, A.

    . Aragonite, low-magnesium calcite and quartz are also present in some samples. Microprobe geochemistry of the phosphatised material of the algal nodules reveals the presence of land-derived siliciclastic detritus and the possibility of more than one source... the continental shelf off the central west coast of India. source of phosphate as 90% of the material in the 0025-3227/90/$03.50 © 1990 -- Elsevier Science Publishers B.V. 18 V. PURNACHANDRA RAO El" AL. algal nodules is composed of calcium carbonate. In between...

  5. Dolomite in caves: Recent dolomite formation in oxic, non-sulfate environments. Castañar Cave, Spain

    OpenAIRE

    Alonso-Zarza, Ana María; Martín Pérez, Andrea

    2008-01-01

    Dolomite is a common mineral in the rock record but rare in recent superficial environments. Where it does occur, it is related to anoxic, sulfate-rich environments and microbial activity. The occurrence of some dolomite deposits in caves, however, indicates that dolomite formation is also possible in oxic, non-sulfate settings. Dolomite is forming at 17 °C and in oxic-vadose conditions on the host rocks and aragonite speleothems of the Castañar Cave, Cáceres, Spain. It appears as...

  6. Mineral composition of sedimentary matter in the Caspian Sea

    Science.gov (United States)

    Lukashin, V. N.; Lisitzin, A. P.; Dara, O. M.; Kozina, N. V.; Klyuvitkin, A. A.; Novigatsky, A. N.

    2016-11-01

    Data on the mineral composition of sedimentary matter and its fluxes in the sediment system of the Caspian Sea are presented. River runoff, aerosols, particulate matter from sediment traps, and the upper layer (0-1 cm) of bottom sediments are considered. The contents of detrital minerals (quartz, albite, and K-feldspar), clay minerals (illite, chlorite, and kaolinite), and carbonates (calcite, Mg-calcite, dolomite, aragonite, and rhodochrosite) are determined. Gypsum was found in bottom sediments but is absent in the other object of the sediment system.

  7. Late Cretaceous scleractinian corals from the rocky shore of Ivö Klack, southern Sweden, including some of the northernmost zooxanthellate corals

    DEFF Research Database (Denmark)

    Sørensen, Anne Mehlin; Floris, S; Surlyk, Finn

    2011-01-01

    A relatively low diversity coral fauna comprising eight zooxanthellate, three azooxanthellate, and one unidentified species is described from a Late Cretaceous rocky shore at Ivö Klack, southern Sweden. All species, except the solitary azooxanthellate Paracyathus? sp., are represented by one or two...... specimens only, indicating low preservation potential similar to the aragonite-shelled gastropod fauna from the same locality. The fauna comprises one out of two northernmost zooxanthellate forms known and adds important environmental information to the fauna and depositional conditions of the rocky shore...

  8. Radiation does response of calcium carbonate crystal in marine shells samples

    Directory of Open Access Journals (Sweden)

    Changkian, S.

    2002-01-01

    Full Text Available A study of the evolution of element, crystal structure and thermoluminescence signal versus gamma irradiation dose were carried out for calcite shells samples. The composition of element was studied by X-ray fluorescence spectrometer. As identified by X-ray diffraction and SEM/EDS analysis, two polymorphs of calcium-carbonate were extracted: calcite and aragonite. The evolution of TL signal versus gamma irradiation dose using the TL reader (Harshaw 2000 was initially dependent on crystal structure and fading effect of the thermoluminescence signal .

  9. Cyanobacterial calcification in modern microbialites at the submicrometer scale

    Directory of Open Access Journals (Sweden)

    E. Couradeau

    2013-08-01

    Full Text Available The search for microfossils in the geological record has been a long-term challenge. Part of the problem comes from the difficulty of identifying such microfossils unambiguously, since they can be morphologically confused with abiotic biomorphs. One route to improve our ability to correctly identify microfossils involves studying fossilization processes affecting bacteria in modern settings. We studied the initial stages of fossilization of cyanobacterial cells in modern microbialites from Lake Alchichica (Mexico, a Mg-rich hyperalkaline crater lake (pH 8.9 hosting currently growing stromatolites composed of aragonite [CaCO3] and hydromagnesite [Mg5(CO34(OH2 · 4(H2O]. Most of the biomass associated with the microbialites is composed of cyanobacteria. Scanning electron microscopy analyses coupled with confocal laser scanning microscopy observations were conducted to co-localize cyanobacterial cells and associated minerals. These observations showed that cyanobacterial cells affiliated with the order Pleurocapsales become specifically encrusted within aragonite with an apparent preservation of cell morphology. Encrustation gradients from non-encrusted to totally encrusted cells spanning distances of a few hundred micrometers were observed. Cells exhibiting increased levels of encrustation along this gradient were studied down to the nm scale using a combination of focused ion beam (FIB milling, transmission electron microscopy (TEM and scanning transmission x-ray microscopy (STXM at the C, O and N K-edges. Two different types of aragonite crystals were observed: one type was composed of needle-shaped nano-crystals growing outward from the cell body with a crystallographic orientation perpendicular to the cell wall, and another type was composed of larger crystals that progressively filled the cell interior. Exopolymeric substances (EPS, initially co-localized with the cells, decreased in concentration and dispersed away from the cells while

  10. Pteropods from the Caribbean Sea: dissolution as an indicator of past ocean acidification

    Directory of Open Access Journals (Sweden)

    D. Wall-Palmer

    2011-07-01

    Full Text Available The aragonite shell–bearing thecosome pteropods are an important component of the oceanic plankton. However, with increasing pCO2 and the associated reduction in oceanic pH (ocean acidification, thecosome pteropods are thought to be particularly vulnerable to shell dissolution. The distribution and preservation of pteropods over the last 250,000 years have been investigated in marine sediment cores from the Caribbean Sea close to the island of Montserrat. Using the Limacina Dissolution Index (LDX, fluctuations in pteropod dissolution through the most recent glacial/interglacial cycles is documented. By comparison to the oxygen isotope record (global sea ice volume, we show that pteropod dissolution is closely linked to global changes in pCO2 and pH and is, therefore, a global signal. These data are in agreement with the findings of experiments upon living pteropods, which show that variations in pH can greatly affect aragonitic shells. The results of this study provide information which may be useful in the prediction of future changes to the pteropod assemblage caused by ocean acidification.

  11. Travertines associated with the Alhama-Jaraba thermal waters (NE, Spain): Genesis and geochemistry

    Science.gov (United States)

    Asta, Maria P.; Auqué, Luis F.; Sanz, Francisco J.; Gimeno, Maria J.; Acero, Patricia; Blasco, Mónica; García-Alix, Antonio; Gómez, Javier; Delgado-Huertas, Antonio; Mandado, Juan

    2017-01-01

    Freshwater carbonates are interesting archives in palaeoenvironmental reconstructions. However, more studies of those systems are needed to fully understand past environments. In this work the actively-forming travertines of the Alhama-Jaraba thermal system were studied for the first time in order to evaluate the relationship between the geochemical and mineralogical composition and the environmental conditions during their formation. With that aim, a combination of petrographical, mineralogical, geochemical and stable isotope analyses were carried out. These carbonates provide a natural laboratory for the study of the effect of different variables (natural and anthropogenic) on carbonate precipitation. The results showed that there is a close relationship between the mineralogy of the solid precipitates and the formation temperature, and only the samples formed from overheated waters (40-60 °C) show significant concentrations of aragonite. Aragonite-bearing samples show higher concentrations in Sr, Ba and U while calcitic solids are enriched in Mg. These differences could be attributed to mineralogy, temperature or different precipitation rates. The geochemical evaluation of the chemistry of both the solids and their parental waters suggests that differences in the rate of CO2-degassing and, in some cases, evaporation are the primary environmental controls on isotopic compositions. In addition, the results show that, if strong evaporation and CO2-degassing are involved, calcite precipitation occurs under conditions of isotopic disequilibrium with its parental water. The results of our study are useful to interpret old depositional environments and palaeotemperatures.

  12. Vertical and horizontal distribution of Desmophyllum dianthus in Comau Fjord, Chile: a cold-water coral thriving at low pH.

    Science.gov (United States)

    Fillinger, Laura; Richter, Claudio

    2013-01-01

    Cold-water corals provide an important habitat for a rich fauna along the continental margins and slopes. Although these azooxanthellate corals are considered particularly sensitive to ocean acidification, their responses to natural variations in pH and aragonite saturation are largely unknown due to the difficulty of studying their ecology in deep waters. Previous SCUBA investigations have shown an exceptionally shallow population of the cold-water coral Desmophyllum dianthus in near-surface waters of Comau Fjord, a stratified 480 m deep basin in northern Chilean Patagonia with suboxic deep waters. Here, we use a remotely operated vehicle to quantitatively investigate the distribution of D. dianthus and its physico-chemical drivers in so far uncharted naturally acidified waters. Remarkably, D. dianthus was ubiquitous throughout the fjord, but particularly abundant between 20 and 280 m depth in a pH range of 8.4 to 7.4. The persistence of individuals in aragonite-undersaturated waters suggests that present-day D. dianthus in Comau Fjord may show pre-acclimation or pre-adaptation to conditions of ocean acidification predicted to reach over 70% of the known deep-sea coral locations by the end of the century.

  13. Vertical and horizontal distribution of Desmophyllum dianthus in Comau Fjord, Chile: a cold-water coral thriving at low pH

    Directory of Open Access Journals (Sweden)

    Laura Fillinger

    2013-10-01

    Full Text Available Cold-water corals provide an important habitat for a rich fauna along the continental margins and slopes. Although these azooxanthellate corals are considered particularly sensitive to ocean acidification, their responses to natural variations in pH and aragonite saturation are largely unknown due to the difficulty of studying their ecology in deep waters. Previous SCUBA investigations have shown an exceptionally shallow population of the cold-water coral Desmophyllum dianthus in near-surface waters of Comau Fjord, a stratified 480 m deep basin in northern Chilean Patagonia with suboxic deep waters. Here, we use a remotely operated vehicle to quantitatively investigate the distribution of D. dianthus and its physico-chemical drivers in so far uncharted naturally acidified waters. Remarkably, D. dianthus was ubiquitous throughout the fjord, but particularly abundant between 20 and 280 m depth in a pH range of 8.4 to 7.4. The persistence of individuals in aragonite-undersaturated waters suggests that present-day D. dianthus in Comau Fjord may show pre-acclimation or pre-adaptation to conditions of ocean acidification predicted to reach over 70% of the known deep-sea coral locations by the end of the century.

  14. Influence of acid-soluble proteins from bivalve Siliqua radiata ligaments on calcium carbonate crystal growth

    Science.gov (United States)

    Huang, Zeng-Qiong; Zhang, Gang-Sheng

    2016-08-01

    In vitro biomimetic synthesis of calcium carbonate (CaCO3) in the presence of shell proteins is a heavily researched topic in biomineralization. However, little is known regarding the function of bivalve ligament proteins in the growth of CaCO3 crystals. In this study, using fibrous protein K58 from Siliqua radiata ligaments or coverslips as substrates, we report the results of our study of CaCO3 precipitation in the presence or absence of acid-soluble proteins (ASP) from inner ligament layers. ASP can disturb the controlling function of K58 or a coverslip on the crystalline phase, resulting in the formation of aragonite, calcite, and vaterite. In addition, we identified the following four primary components from ASP by mass spectroscopy: alkaline phosphatase (ALP), ABC transporter, keratin type II cytoskeletal 1 (KRT 1), and phosphate ABC transporter, phosphate-binding protein (PstS). Further analysis revealed that the first three proteins and especially ALP, which is important in bone mineralisation, could affect the polymorphism and morphology of CaCO3 crystals by trapping calcium ions in their domains. Our results indicate that ALP may play an important role in the formation of aragonite in S. radiata ligaments. This paper may facilitate our understanding of the biomineralization process.

  15. The relationship between the ratio of strontium to calcium and sea-surface temperature in a modern Porites astreoides coral: Implications for using P. astreoides as a paleoclimate archive

    Science.gov (United States)

    Tess E. Busch,; Flannery, Jennifer A.; Richey, Julie N.; Stathakopoulos, Anastasios

    2015-11-13

    An inverse relationship has been demonstrated between water temperature and the ratio of strontium to calcium (Sr/Ca) in coral aragonite for a number of Pacific species of the genus Porites. This empirically determined relationship has been used to reconstruct past sea-surface temperature (SST) from modern and Holocene age coral archives. A study was conducted to investigate this relationship for Porites astreoides to determine the potential for using these corals as a paleotemperature archive in the Caribbean and western tropical Atlantic Ocean. Skeletal aragonite from a P. astreoides colony growing offshore of the southeast coast of Florida was subsampled with a mean temporal resolution of 14 samples per year and analyzed for Sr/Ca. The resulting Sr/Ca time series yielded well-defined annual cycles that correspond to annual growth bands in the coral. Sr/Ca was regressed against a monthly SST record from C-MAN buoy station FWYF1 (located at Fowey Rocks, Florida), resulting in the following Sr/Ca-SST relationship: Sr/Ca = –0.040*SST + 10.128 (R = –0.77). A 10-year time series of Sr/Ca-derived SST yields annual cycles with a 10–12 degree Celsius seasonal amplitude, consistent with available local instrumental records. We conclude that Sr/Ca in Porites astreoides from the Caribbean/Atlantic region has high potential for developing subannually resolved modern and recent Holocene SST records.

  16. The exposure of the Great Barrier Reef to ocean acidification

    KAUST Repository

    Mongin, Mathieu

    2016-02-23

    The Great Barrier Reef (GBR) is founded on reef-building corals. Corals build their exoskeleton with aragonite, but ocean acidification is lowering the aragonite saturation state of seawater (Ωa). The downscaling of ocean acidification projections from global to GBR scales requires the set of regional drivers controlling Ωa to be resolved. Here we use a regional coupled circulation–biogeochemical model and observations to estimate the Ωa experienced by the 3,581 reefs of the GBR, and to apportion the contributions of the hydrological cycle, regional hydrodynamics and metabolism on Ωa variability. We find more detail, and a greater range (1.43), than previously compiled coarse maps of Ωa of the region (0.4), or in observations (1.0). Most of the variability in Ωa is due to processes upstream of the reef in question. As a result, future decline in Ωa is likely to be steeper on the GBR than currently projected by the IPCC assessment report.

  17. Oxygen isotope record of the 1997-1998 El Niño in Peruvian sea catfish (Galeichthys peruvianus) otoliths

    Science.gov (United States)

    Andrus, C. Fred T.; Crowe, Douglas E.; Romanek, Christopher S.

    2002-12-01

    Sagittal otoliths of the Peruvian sea catfish Galeichthys peruvianus were collected from the north coast of Peru during and after the 1997-1998 El Niño. The otoliths were analyzed via laser microprobe and micromilling techniques for oxygen isotope composition through ontogeny to document their use as an El Niño-Southern Oscillation (ENSO) proxy. Results were compared to theoretical calculations for the δ18O of otolith aragonite using measured sea surface temperatures (SST) and δ18O values for local seawater assuming equilibrium oxygen isotope fractionation was achieved. All otoliths recorded the 1997-1998 El Niño event as well as seasonal temperature variations. These ENSO events were recorded in otolith aragonite as significant negative excursions in δ18O that reflected the increased temperature of local marine waters. The combined otolith data were used to create a 10-year SST record, including ENSO events and local seasonal temperature variation, validating the use of otolith δ18O as a temperature proxy.

  18. Lime muds and their genesis off-Northwestern India during the late Quaternary

    Indian Academy of Sciences (India)

    V Purnachandra Rao; A Anil Kumar; S W A Naqvi; Allan R Chivas; B Sekar; Pratima M Kessarkar

    2012-06-01

    Two sediment types were found in five gravity cores collected from water depths between 56 m and 121 m along the northwestern continental margin of India: lime muds were abundant in the lower section while siliciclastic sediments dominated the upper section. Lime mud-dominated sediments in shelf cores contained 60%–75% carbonate, 0.3%–0.6% Sr and terrigenous minerals, whereas those at the shelf break were found to have < 90% carbonate, 0.6%–0.8% Sr and traces of terrigenous minerals. Aragonite needles showing blunt edges, jointed needles and needles wrapped in smooth aragonite cement were found to be common. Stable (O and C) isotopes of lime mud indicate a potentially freshwater contribution for shelf cores and purely marine contribution for those at the shelf break. Calibrated radiocarbon ages of the lime muds ranged from 17.6–11.9 ka in different cores. The results reported here suggest that the lime muds in the shallow shelf are probably reworked from the Gulf of Kachchh, whereas those at the shelf break were biodetrital, initially formed on the carbonate platform during low stands of sea level and then exported. The change in lime mud-dominated to siliciclastic-dominated sediments in the cores may be due to climate change and rapid rise in sea level during the early Holocene.

  19. Skeletal development in Acropora cervicornis: I. Patterns of calcium carbonate accretion in the axial corallite

    Science.gov (United States)

    Gladfeiter, E. H.

    1982-06-01

    Scanning electron microscopy and serial petrographic thin sections were used to investigate skeletal elongation and mineralization in the perforate coral, Acropora cervicornis. The axial corallite extends by the formation of randomly oriented fusiform crystals which are deposited on its distal edge. Aragonitic needle-like crystals grow in random directions from the surface of these fusiform crystals. Only those needle-like crystals growing toward the calicoblastic epithelium (i.e. crystals whose growth axis is perpendicular to the plane of the calicoblastic cell membrane) continue to elongate. Groups of these growing crystals join to form well-defined fasciculi which make up the primary skeletal elements comprising the septotheca. The resulting skeleton is highly porous with all surfaces covered by the continuous calicoblastic epithelium. This cell layer is separated by thin mesoglea from the flagellated gastrodermis which lines the highly ramified coelenteron. Porosity and permeability of the skeleton decrease with distance from the tip. Density correspondingly increases due to the addition of aragonite to the fasciculi whose boundaries become less distinct as channels fill with calcium carbonate.

  20. Could artificial ocean alkalinization protect tropical coral ecosystems from ocean acidification?

    Science.gov (United States)

    Feng, Ellias Y.; Keller, David P.; Koeve, Wolfgang; Oschlies, Andreas

    2016-07-01

    Artificial ocean alkalinization (AOA) is investigated as a method to mitigate local ocean acidification and protect tropical coral ecosystems during a 21st century high CO2 emission scenario. Employing an Earth system model of intermediate complexity, our implementation of AOA in the Great Barrier Reef, Caribbean Sea and South China Sea regions, shows that alkalinization has the potential to counteract expected 21st century local acidification in regard to both oceanic surface aragonite saturation Ω and surface pCO2. Beyond preventing local acidification, regional AOA, however, results in locally elevated aragonite oversaturation and pCO2 decline. A notable consequence of stopping regional AOA is a rapid shift back to the acidified conditions of the target regions. We conclude that AOA may be a method that could help to keep regional coral ecosystems within saturation states and pCO2 values close to present-day values even in a high-emission scenario and thereby might ‘buy some time’ against the ocean acidification threat, even though regional AOA does not significantly mitigate the warming threat.

  1. Naked Stony Corals: Skeleton Loss in Scleractinia

    Energy Technology Data Exchange (ETDEWEB)

    Medina, Monica; Collins, Allen G.; Takaoka, Tori L.; Kuehl,Jennifer; Boore, Jeffrey L.

    2005-12-01

    Hexacorallia includes the Scleractinia, or stony corals, characterized by having an external calcareous skeleton made of aragonite, and the Corallimorpharia, or mushroom corals, that lack such a skeleton. Although each group has traditionally been considered monophyletic, some molecular phylogenetic analyses have challenged this, suggesting that skeletal features are evolutionarily plastic, and reviving notions that the scleractinian skeleton may be ephemeral and that the group itself may be polyphyletic. Nevertheless, the most comprehensive phylogenetic study of Hexacorallia supported scleractinian monophyly (REF), and so this remains controversial. In order to resolve this contentious issue, we sequenced the complete mitochondrial genome sequences of nine scleractinians and four corallimorpharians and performed phylogenetic analysis that also included three outgroups (an octocoral and two sea anemones). Our data provide the first strong evidence that Scleractinia is paraphyletic and that the Corallimorpharia is derived from within the group, from which we conclude that skeletal loss has occurred in the latter group secondarily. It is possible that a driving force in such skeletal loss could be the high levels of CO{sub 2} in the ocean during the mid-Cretaceous, which would have impacted aragonite solubility. We estimate from molecular divergence measures that the Corallimorpharia arose in the mid-Cretaceous, approximately 87 million years ago (Ma), supporting this view. These data also permit us to date the origin of Scleractinia to 265 Ma, narrowing the gap between the group's phylogenetic origin and its earliest fossil record.

  2. Mineralization of Calcium Carbonate on Multifunctional Peptide Assembly Acting as Mineral Source Supplier and Template.

    Science.gov (United States)

    Murai, Kazuki; Kinoshita, Takatoshi; Nagata, Kenji; Higuchi, Masahiro

    2016-09-13

    Crystal phase and morphology of biominerals may be precisely regulated by controlled nucleation and selective crystal growth through biomineralization on organic templates such as a protein. We herein propose new control factors of selective crystal growth by the biomineralization process. In this study, a designed β-sheet Ac-VHVEVS-CONH2 peptide was used as a multifunctional template that acted as mineral source supplier and having crystal phase control ability of calcium carbonate (CaCO3) during a self-supplied mineralization. The peptides formed three-dimensional nanofiber networks composed of assembled bilayer β-sheets. The assembly hydrolyzed urea molecules to one carbonate anion and two ammonium cations owing to a charge relay effect between His and Ser residues under mild conditions. CaCO3 was selectively mineralized on the peptide assembly using the generated carbonate anions on the template. Morphology of the obtained CaCO3 was fiber-like structure, similar to that of the peptide template. The mineralized CaCO3 on the peptide template had aragonite phase. This implies that CaCO3 nuclei, generated using the carbonate anions produced by the hydrolysis of urea on the surface of the peptide assembly, preferentially grew into aragonite phase, the growth axis of which aligned parallel to the direction of the β-sheet fiber axis.

  3. Polarimetry of Pinctada fucata nacre indicates myostracal layer interrupts nacre structure.

    Science.gov (United States)

    Metzler, Rebecca A; Jones, Joshua A; D'Addario, Anthony J; Galvez, Enrique J

    2017-02-01

    The inner layer of many bivalve and gastropod molluscs consists of iridescent nacre, a material that is structured like a brick wall with bricks consisting of crystalline aragonite and mortar of organic molecules. Myostracal layers formed during shell growth at the point of muscle attachment to the shell can be found interspersed within the nacre structure. Little has been done to examine the effect the myostracal layer has on subsequent nacre structure. Here we present data on the structure of the myostracal and nacre layers from a bivalve mollusc, Pinctada fucata. Scanning electron microscope imaging shows the myostracal layer consists of regular crystalline blocks. The nacre before the layer consists of tablets approximately 400 nm thick, while after the myostracal layer the tablets are approximately 500 nm thick. A new technique, imaging polarimetry, indicates that the aragonite crystals within the nacre following the myostracal layer have greater orientation uniformity than before the myostracal layer. The results presented here suggest a possible interaction between the myostracal layer and subsequent shell growth.

  4. Extraction and Purification of Matrix Protein from the Nacre of Pearl Oyster Pinctada fucata

    Institute of Scientific and Technical Information of China (English)

    MA Caiping; ZHANG Cen; NIE Yancheng; XIE Liping; ZHANG Rongqing

    2005-01-01

    A soluble matrix protein P14 with an apparent molecular mass of 14.5 kDa was isolated from fragmented nacre of pearl oysters (Pinctada fucata) treated with 10% NaOH solution to investigate the nacre matrix proteins and their effect on the CaCO3 crystal. The protein was characterized by gel exclusion chromatography and reversed-phase high performance liquid chromatography after demineralization by 10% acetic acid. The X-ray diffraction pattern of P14 crystals indicates that P14 plays an important role in nacre biomineralization. P14 can induce aragonite formation, stimulate CaCO3 crystal formation, and accelerate aragonite precipitation. Heating of the acid insoluble nacre residue, which was named conchiolin, in 10% sodium dodecyl sulfate solution supplemented with 10% β-mercaptoethanol solution for 10-20 min at about 100(C gave two other soluble proteins having molecular masses of 19.4 kDa and 25.0 kDa. The present study suggests that these two proteins are linked to the insoluble organic matrix by disulfide bridges because the extraction yield increases when β-mercaptoethanol is added to the medium.

  5. I/Ca ratios in benthic foraminifera from the Peruvian oxygen minimum zone: analytical methodology and evaluation as proxy for redox conditions

    Directory of Open Access Journals (Sweden)

    N. Glock

    2014-07-01

    Full Text Available In this study we explore the correlation of I/Ca ratios in three calcitic and one aragonitic foraminiferal species. I/Ca ratios are evaluated as possible proxies for changes in ambient redox conditions across the Peruvian oxygen minimum zone to the ambient oxygen concentrations in the habitat of the foraminiferal species studied. We test cleaning and measurement methods to determine I/Ca ratios in benthic foraminifera from the Peruvian oxygen minimum zone. All species show a positive trend in their I/Ca ratios as a function of higher oxygen concentrations and these trends are all statistically significant except for the aragonitic species Hoeglundina elegans. The most promising species appears to be Uvigerina striata which shows a highly statistically significant correlation between I/Ca ratios and bottom water (BW oxygenation (I/Ca = 0.032(± 0.004[O2]BW + 0.29(± 0.03, R2 = 0.61, F = 75, P 2]BW correlations, and the individual variability of single tests severely interfere with the observed I/Ca–[O2]BW relationship.

  6. Calcium distribution in the subtropical Atlantic Ocean: Implications for calcium excess and saturation horizons

    Science.gov (United States)

    Rosón, Gabriel; Guallart, Elisa F.; Pérez, Fiz F.; Ríos, Aida F.

    2016-06-01

    This study constituted the first attempt to measure dissolved calcium ([Ca2 +]meas) in the subtropical North Atlantic, during a zonal transoceanic cruise along 24.5°N (WOCE A05 section), in summer 1992. [Ca2 +]meas was obtained in 20 full-depth equidistant stations along the section, showing that their gradients are rather sensitive to horizontal and vertical water mass distribution. Deep waters along 24.5°N systematically show a positive calcium excess of 20 ± 14 μmol·kg- 1, i.e., more [Ca2 +] than expected by CaCO3 dissolution and organic matter oxidation (estimated by total alkalinity and nitrate). CaCO3 settling and benthic dissolution accounts for 70% and the North Atlantic plus Arctic riverine inputs of HCO3- for the remaining 30%. Combining [Ca2 +]meas and CO2 data sets, carbonate mineral saturation states distributions for aragonite and calcite can be obtained. The two solubility ratios resulted, on average, 0.5% smaller than if conservative behavior for Ca2 + was assumed (an approach widely followed when [Ca2 +]meas is unknown). As a result, shallower saturation horizon depths for both carbonate states (19 dbar for aragonite and 10 dbar for calcite) are yielded if [Ca2 +]meas is taken into account instead than estimated from salinity.

  7. Marine Biogenic Minerals Hold Clues About Changes in Ocean Chemistry and Climate: Some Important Lessons Learned from Studies of Stable and Radioactive Isotopes of Be and Al

    Directory of Open Access Journals (Sweden)

    Devendra Lal

    2002-01-01

    Full Text Available The elements Be and Al exhibit very short residence time in ocean waters, and therefore serve as useful tracers for the study of biogeochemical processes in seawater. A unique feature of these tracers is that nuclear interactions of cosmic rays in the atmosphere produce appreciable amounts of two radioactive isotopes, 10Be (with a half-life of 1.5 my and 26Al (with a half-life of 0.7 my, which are introduced in the hydrosphere, cryosphere, and lithosphere via precipitation. Thus, these elements are labeled by their respective radioactive isotopes, which help quantitative tagging of their biogeochemical cycles. Finally, as we report here, several marine organisms incorporate them in their skeletal shells in certain fixed proportions to their concentrations in the seawater, so that it seems possible to study changes in the ocean chemistry and climate over the past several million years. We summarize here the recent discovery by Dong et al.[9] of significant enrichments of intrinsic Be and Al in marine foraminiferal calcite and coral aragonite, and of Al in opal (radiolarians and aragonite (corals, which should make it possible to determine 10Be/Be and 26Al/Al in oceans in the past. We also summarize their measured 10Be/9Be in foraminiferal calcite in Pacific Ocean cores, which reveal that the concentrations and ratios of the stable and cosmogenic isotopes of Be and Al have varied significantly in the past 30 ky. The implications of these results are discussed.

  8. Atlanta ariejansseni, a new species of shelled heteropod from the Southern Subtropical Convergence Zone (Gastropoda, Pterotracheoidea).

    Science.gov (United States)

    Wall-Palmer, Deborah; Burridge, Alice K; Peijnenburg, Katja T C A

    2016-01-01

    The Atlantidae (shelled heteropods) is a family of microscopic aragonite shelled holoplanktonic gastropods with a wide biogeographical distribution in tropical, sub-tropical and temperate waters. The aragonite shell and surface ocean habitat of the atlantids makes them particularly susceptible to ocean acidification and ocean warming, and atlantids are likely to be useful indicators of these changes. However, we still lack fundamental information on their taxonomy and biogeography, which is essential for monitoring the effects of a changing ocean. Integrated morphological and molecular approaches to taxonomy have been employed to improve the assessment of species boundaries, which give a more accurate picture of species distributions. Here a new species of atlantid heteropod is described based on shell morphology, DNA barcoding of the Cytochrome Oxidase I gene, and biogeography. All specimens of Atlanta ariejansseni sp. n. were collected from the Southern Subtropical Convergence Zone of the Atlantic and Indo-Pacific oceans suggesting that this species has a very narrow latitudinal distribution (37-48°S). Atlanta ariejansseni sp. n. was found to be relatively abundant (up to 2.3 specimens per 1000 m(3) water) within this narrow latitudinal range, implying that this species has adapted to the specific conditions of the Southern Subtropical Convergence Zone and has a high tolerance to the varying ocean parameters in this region.

  9. Structure-function studies of the lustrin A polyelectrolyte domains, RKSY and D4.

    Science.gov (United States)

    Wustman, Brandon A; Weaver, James C; Morse, Daniel E; Evans, John Spencer

    2003-01-01

    The lustrin superfamily represents a unique group of biomineralization proteins localized between layered aragonite mineral plates (i.e., nacre layers) in mollusk shell. These proteins not only exhibit elastomeric behavior within the mineralized matrix, but also adhesion to the aragonite-containing composite layer. One member of the lustrin superfamily, Lustrin A, has been sequenced; the protein is organized into defined, modular sequence domains that are hypothesized to perform separate functions (i.e., force unfolding, mineral adhesion, intermolecular binding) within the Lustrin A protein. Using nuclear magnetic resonance (NMR) and in vitro mineralization assays, we investigated structure-function relationships for two Lustrin A putative mineral binding domains, the 30 AA Arg, Lys, Tyr, Ser-rich (RKSY) and the 24 AA Asp-rich (D4) sequence regions domain of the Lustrin A protein. The results indicate that both sequences adopt open, unfolded structures that represent either extended or random coil states. Using geologic calcite overgrowth assays and scanning electron microscopic analyses, we observe that the RKSY polypeptide does not significantly perturb calcium carbonate growth. However, the D4 domain does influence crystal growth in a concentration-dependent manner. Collectively, our data indicate that D4, and not the RKSY domain, exhibits structure-function activity consistent with a mineral binding region.

  10. The exposure of the Great Barrier Reef to ocean acidification

    Science.gov (United States)

    Mongin, Mathieu; Baird, Mark E.; Tilbrook, Bronte; Matear, Richard J.; Lenton, Andrew; Herzfeld, Mike; Wild-Allen, Karen; Skerratt, Jenny; Margvelashvili, Nugzar; Robson, Barbara J.; Duarte, Carlos M.; Gustafsson, Malin S. M.; Ralph, Peter J.; Steven, Andrew D. L.

    2016-01-01

    The Great Barrier Reef (GBR) is founded on reef-building corals. Corals build their exoskeleton with aragonite, but ocean acidification is lowering the aragonite saturation state of seawater (Ωa). The downscaling of ocean acidification projections from global to GBR scales requires the set of regional drivers controlling Ωa to be resolved. Here we use a regional coupled circulation–biogeochemical model and observations to estimate the Ωa experienced by the 3,581 reefs of the GBR, and to apportion the contributions of the hydrological cycle, regional hydrodynamics and metabolism on Ωa variability. We find more detail, and a greater range (1.43), than previously compiled coarse maps of Ωa of the region (0.4), or in observations (1.0). Most of the variability in Ωa is due to processes upstream of the reef in question. As a result, future decline in Ωa is likely to be steeper on the GBR than currently projected by the IPCC assessment report. PMID:26907171

  11. Phase transitions of natural corals monitored by ESR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Vongsavat, V. [Department of Chemistry, Faculty of Science, Mahidol University, Rama VI Road, Rajathevi, Bangkok 10400 (Thailand); Winotai, P. [Department of Chemistry, Faculty of Science, Mahidol University, Rama VI Road, Rajathevi, Bangkok 10400 (Thailand); Meejoo, S. [Department of Chemistry, Faculty of Science, Mahidol University, Rama VI Road, Rajathevi, Bangkok 10400 (Thailand)]. E-mail: scsmj@mahidol.ac.th

    2006-01-15

    The main purpose of this work is to present a systematic study of structure of marine exoskeletons, Acropora coral and its structural transformation upon heat treatments. The coralline sample was ground and characterized as powder throughout this work. Structural identifications of all samples have been confirmed using X-ray diffraction and IR spectroscopy. It was clearly found that the fresh specimen is made of aragonite, a common phase of the mineral CaCO{sub 3}. Thermal analyses, DSC and TGA were used to monitor structural and thermal decompositions and an irreversible solid-state phase transition from aragonite to calcite of the marine carbonate. Next, the coral powder was annealed at specific temperatures over the range 350-900 deg. C, and the effects of heat treatment on the structure of coralline samples were carefully studied by Rietveld refinement method. In addition, we have examined Mn{sup 2+} paramagnetic ions and free radicals present in the coral and changes of those upon heating by using ESR spectroscopy. The local environments of Mn{sup 2+} ions were verified from the calculated ESR spectra using appropriate spin Hamiltonian parameters, i.e. gyromagnetic tensor g , zero-field splitting D and hyperfine tensor A . This work reported structures and compositions as well as physical, chemical and thermal properties of the coralline material upon heat treatments qualitatively and quantitatively.

  12. Gradual Ordering in Red Abalone Nacre

    Energy Technology Data Exchange (ETDEWEB)

    Gilbert, P. U. P. A.; Metzler, Rebecca A.; Zhou, Dong; Scholl, Andreas; Doran, Andrew; Young, Anthony; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan N.

    2008-09-03

    Red abalone (Haliotis rufescens) nacre is a layered composite biomineral that contains crystalline aragonite tablets confined by organic layers. Nacre is intensely studied because its biologically controlled microarchitecture gives rise to remarkable strength and toughness, but the mechanisms leading to its formation are not well understood. Here we present synchrotron spectromicroscopy experiments revealing that stacks of aragonite tablet crystals in nacre are misoriented with respect to each other. Quantitative measurements of crystal orientation, tablet size, and tablet stacking direction show that orientational ordering occurs not abruptly but gradually over a distance of 50 {micro}m. Several lines of evidence indicate that different crystal orientations imply different tablet growth rates during nacre formation. A theoretical model based on kinetic and gradual selection of the fastest growth rates produces results in qualitative and quantitative agreement with the experimental data and therefore demonstrates that ordering in nacre is a result of crystal growth kinetics and competition either in addition or to the exclusion of templation by acidic proteins as previously assumed. As in other natural evolving kinetic systems, selection of the fastest-growing stacks of tablets occurs gradually in space and time. These results suggest that the self-ordering of the mineral phase, which may occur completely independently of biological or organic-molecule control, is fundamental in nacre formation.

  13. Detection of interaction between biomineralising proteins and calcium carbonate microcrystals

    Directory of Open Access Journals (Sweden)

    Hanna Rademaker

    2011-04-01

    Full Text Available The natural composite nacre is characterised by astonishing mechanical properties, although the main constituent is a brittle mineral shaped as tablets interdispersed by organic layers. To mimic the natural formation process which takes place at ambient conditions an understanding of the mechanism responsible for a defined microstructure of nacre is necessary. Since proteins are assumed to be involved in this mechanism, it is advantageous to identify distinct proteins interacting with minerals from the totality of proteins contained in nacre. Here, we adopted and modified a recently published approach given by Suzuki et al. that gives a hint of specific protein–mineral interactions. Synthesised aragonite or calcite microcrystals were incubated with a protein mixture extracted from nacre of Haliotis laevigata. After incubation the mineral phase was dissolved and investigated for attached proteins. The results give a hint of one protein that seems to bind specifically to aragonite and not to calcite. The presented protocol seems to be suitable to detect mineral binding proteins quickly and therefore can point to proteins whose mineral binding capabilities should be investigated further.

  14. Detection of interaction between biomineralising proteins and calcium carbonate microcrystals.

    Science.gov (United States)

    Rademaker, Hanna; Launspach, Malte

    2011-01-01

    The natural composite nacre is characterised by astonishing mechanical properties, although the main constituent is a brittle mineral shaped as tablets interdispersed by organic layers. To mimic the natural formation process which takes place at ambient conditions an understanding of the mechanism responsible for a defined microstructure of nacre is necessary. Since proteins are assumed to be involved in this mechanism, it is advantageous to identify distinct proteins interacting with minerals from the totality of proteins contained in nacre. Here, we adopted and modified a recently published approach given by Suzuki et al. [1] that gives a hint of specific protein-mineral interactions. Synthesised aragonite or calcite microcrystals were incubated with a protein mixture extracted from nacre of Haliotis laevigata. After incubation the mineral phase was dissolved and investigated for attached proteins. The results give a hint of one protein that seems to bind specifically to aragonite and not to calcite. The presented protocol seems to be suitable to detect mineral binding proteins quickly and therefore can point to proteins whose mineral binding capabilities should be investigated further.

  15. Microbial and diagenetic steps leading to the mineralisation of Great Salt Lake microbialites

    Science.gov (United States)

    Pace, Aurélie; Bourillot, Raphaël; Bouton, Anthony; Vennin, Emmanuelle; Galaup, Serge; Bundeleva, Irina; Patrier, Patricia; Dupraz, Christophe; Thomazo, Christophe; Sansjofre, Pierre; Yokoyama, Yusuke; Franceschi, Michel; Anguy, Yannick; Pigot, Léa; Virgone, Aurélien; Visscher, Pieter T.

    2016-08-01

    Microbialites are widespread in modern and fossil hypersaline environments, where they provide a unique sedimentary archive. Authigenic mineral precipitation in modern microbialites results from a complex interplay between microbial metabolisms, organic matrices and environmental parameters. Here, we combined mineralogical and microscopic analyses with measurements of metabolic activity in order to characterise the mineralisation of microbial mats forming microbialites in the Great Salt Lake (Utah, USA). Our results show that the mineralisation process takes place in three steps progressing along geochemical gradients produced through microbial activity. First, a poorly crystallized Mg-Si phase precipitates on alveolar extracellular organic matrix due to a rise of the pH in the zone of active oxygenic photosynthesis. Second, aragonite patches nucleate in close proximity to sulfate reduction hotspots, as a result of the degradation of cyanobacteria and extracellular organic matrix mediated by, among others, sulfate reducing bacteria. A final step consists of partial replacement of aragonite by dolomite, possibly in neutral to slightly acidic porewater. This might occur due to dissolution-precipitation reactions when the most recalcitrant part of the organic matrix is degraded. The mineralisation pathways proposed here provide pivotal insight for the interpretation of microbial processes in past hypersaline environments.

  16. Mineralogy of the hardpan formation processes in the interface between sulfide-rich sludge and fly ash: Applications for acid mine drainage mitigation

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Lopez, R.; Nieto, J.M.; Alvarez-Valero, A.M.; De Almodovar, G.R. [University of Huelva, Huelva (Spain). Dept. of Geology

    2007-11-15

    In the present study, experiments in non-saturated leaching columns were conducted to characterize the neoformed phases that precipitate at the interface between two waste residues having different chemical characteristics: an acid mine drainage producer residue (i.e., pyritic sludge) and an acidity neutralizer residue (i.e., coal combustion fly ash). A heating source was placed on top of one of the columns to accelerate oxidation and precipitation of newly formed phases, and thus, to observe longer-scale processes. When both residues are deposited together, the resulting leachates are characterized by alkaline pH, and low sulfate and metal concentrations. Two mechanisms help to improve the quality of the leachates. Over short-time scales, the leaching of pyrite at high pH (as a consequence of fly ash addition) favors the precipitation of ferrihydrite, encapsulating the pyrite grains and attenuating the oxidation process. Over longer time scales, a hardpan is promoted at the interface between both residues due to the precipitation of ferrihydrite, jarosite, and a Ca phase-gypsum or aragonite, depending on carbonate ion activity. Geochemical modeling of leachates using PHREEQC software predicted supersaturation in the observed minerals. The development of a relatively rigid crust at the interface favors the isolation of the mining waste from weathering processes, helped by the cementation of fly ash owing to aragonite precipitation, which ensures total isolation and neutralization of the mine residues.

  17. Greenhouse conditions induce mineralogical changes and dolomite accumulation in coralline algae on tropical reefs

    Science.gov (United States)

    Diaz-Pulido, Guillermo; Nash, Merinda C.; Anthony, Kenneth R. N.; Bender, Dorothea; Opdyke, Bradley N.; Reyes-Nivia, Catalina; Troitzsch, Ulrike

    2014-02-01

    Human-induced ocean acidification and warming alter seawater carbonate chemistry reducing the calcification of reef-building crustose coralline algae (CCA), which has implications for reef stability. However, due to the presence of multiple carbonate minerals with different solubilities in seawater, the algal mineralogical responses to changes in carbonate chemistry are poorly understood. Here we demonstrate a 200% increase in dolomite concentration in living CCA under greenhouse conditions of high pCO2 (1,225 μatm) and warming (30 °C). Aragonite, in contrast, increases with lower pCO2 (296 μatm) and low temperature (28 °C). Mineral changes in the surface pigmented skeleton are minor and dolomite and aragonite formation largely occurs in the white crust beneath. Dissolution of high-Mg-calcite and particularly the erosive activities of endolithic algae living inside skeletons play key roles in concentrating dolomite in greenhouse treatments. As oceans acidify and warm in the future, the relative abundance of dolomite in CCA will increase.

  18. Variability of the carbonate chemistry in a shallow, seagrass-dominated ecosystem: implications for ocean acidification experiments

    Science.gov (United States)

    Challener, Roberta; Robbins, Lisa L.; Mcclintock, James B.

    2016-01-01

    Open ocean observations have shown that increasing levels of anthropogenically derived atmospheric CO2 are causing acidification of the world's oceans. Yet little is known about coastal acidification and studies are just beginning to characterise the carbonate chemistry of shallow, nearshore zones where many ecologically and economically important organisms occur. We characterised the carbonate chemistry of seawater within an area dominated by seagrass beds (Saint Joseph Bay, Florida) to determine the extent of variation in pH and pCO2 over monthly and daily timescales. Distinct diel and seasonal fluctuations were observed at daily and monthly timescales respectively, indicating the influence of photosynthetic and respiratory processes on the local carbonate chemistry. Over the course of a year, the range in monthly values of pH (7.36-8.28), aragonite saturation state (0.65-5.63), and calculated pCO2 (195-2537 μatm) were significant. When sampled on a daily basis the range in pH (7.70-8.06), aragonite saturation state (1.86-3.85), and calculated pCO2 (379-1019 μatm) also exhibited significant range and indicated variation between timescales. The results of this study have significant implications for the design of ocean acidification experiments where nearshore species are utilised and indicate that coastal species are experiencing far greater fluctuations in carbonate chemistry than previously thought.

  19. Cooption of secretory phospholipase (SPLA2) for different aspects of gravity receptor-associated mineralization in vertebrate phylogeny

    Science.gov (United States)

    Thalmann, R.; Lu, W.

    2009-04-01

    Vertebrate gravity-associated minerals consists of either a single large stone (otolith), or an assembly of minute biomineral particles, otoconia ("ear dust"). Otoliths and both, amphibian and reptilian otoconia, consist of aragonite, whereas avian and mammalian otoconia consist of calcite. Vertebrate gravity-associated minerals are the product of site-directed biologically-controlled mineralization. Insoluble frame work molecules specify sites of nucleation and direction of crystal growth. Soluble matrix proteins modulate growth kinetics and crystal morphology. It is most remarkable that the principal insoluble frame work protein, otolin, is the same for both, otolith and otoconia. Otolin is a novel type of collagen, homologous to the network-forming collagen type X prevalent in mature chondrocytes. The principal soluble matrix proteins of calcitic, aragonitic, and most likely also of vateritic otoconia are all homologs of SPLA2, which is most prevalent in pancreatic secretion and snake venoms. Otonin90 (OC90), the principal soluble matrix protein of calcitic otoconia consists of two SPLA-like (SPLAL) domains, which are connected by a sizeable linker segment and contain significant terminal extensions. The MW of the protein backbone amounts to approximately 50 kDa. The molecule contains, in addition massive post-translational modifications, 80% of which are accounted for by sulfated GAGs, resulting in a total MW of 100 KDa. The protein backbone is moderately acidic, pI 4.4, but the pI of the whole molecule is 2.9, indicating a substantial acidity of the GAG component. In adapting SPLA2 for mineral modulation the enzymatic site is modified and presumed nonfunctional. The seven SH- bonds are rigorously conserved in both, OC90 and otoconin22 (OC22). It appears that the SH-bonds of the parent SPLA2 are intended to stabilize the molecule to ensure continued enzymatic activity in the hostile environment of the gut. It therefore seems logical that SPLA2 was coopted for

  20. Hierarchical structure of the otolith of adult wild carp

    Energy Technology Data Exchange (ETDEWEB)

    Li Zhuo; Gao Yonghua [State key laboratory of new ceramics and fine processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Feng Qingling, E-mail: biomater@mail.tsinghua.edu.cn [State key laboratory of new ceramics and fine processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China)

    2009-04-30

    The otolith of adult wild carp contains a pair of asterisci, a pair of lappilli and a pair of sagittae. Current research works are mainly restricted to the field of the daily ring structure. The purpose of this work is to explore the structural characteristics of carp's otolith in terms of hierarchy from nanometer to millimeter scale by transmission election microscope (TEM) and scanning electron microscope (SEM). Based on the observation, carp's lapillus is composed of ordered aragonite crystals. Seven hierarchical levels of the microstructure were proposed and described with the scheme representing a complete organization in detail. SEM studies show not only the clear daily growth increment, but also the morphology within the single daily increment. The domain structure of crystal orientation in otolith was observed for the first time. Furthermore, TEM investigation displays that the lapillus is composed of aragonite crystals with nanometer scale. Four hierarchical levels of the microstructure of the sagitta are also proposed. The asteriscus which is composed of nanometer scale vaterite crystals is considered to have a uniform structure.

  1. High-pressure behavior of otavite (CdCO{sub 3})

    Energy Technology Data Exchange (ETDEWEB)

    Minch, R., E-mail: robert.minch@fh-kiel.d [Institut fuer Geowissenschaften, Christian-Albrechts-Universitaet zu Kiel, D-24118 Kiel (Germany); Seoung, D.-H. [Department of Earth System Science, Yonsei University, Seoul (Korea, Republic of); Ehm, L. [Mineral Physics Institute, Stony Brook University, Stony Brook, NY 11794 (United States); National Synchrotron Light Source, Brookhaven National Laboratory, Upton, NY 11973 (United States); Winkler, B. [Institut fuer Geowissenschaften, Abteilung fuer Kristallographie, Universitaet Frankfurt, D-60438 Frankfurt am Main (Germany); Knorr, K. [BrukerAXS GmbH, 76187 Karlsruhe (Germany); Peters, L. [Institut fuer Geowissenschaften, Christian-Albrechts-Universitaet zu Kiel, D-24118 Kiel (Germany); Borkowski, L.A. [Mineral Physics Institute, Stony Brook University, Stony Brook, NY 11794 (United States); Parise, J.B. [Department of Geosciences, Stony Brook University, Stony Brook, NY 11794 (United States); Lee, Y. [Department of Earth System Science, Yonsei University, Seoul (Korea, Republic of); Dubrovinsky, L. [Bayerisches Geoinstitut, Universitaet Bayreuth, D-95447 Bayreuth (Germany); Depmeier, W. [Institut fuer Geowissenschaften, Christian-Albrechts-Universitaet zu Kiel, D-24118 Kiel (Germany)

    2010-10-22

    Research highlights: {yields} The calcite-type structure of CdCO{sub 3} is stable up to at least {approx}19 GPa. {yields} DFT calculations suggest a calcite-aragonite-type phase transition in CdCO{sub 3} at 30 GPa. {yields} Experimental data propose a phase transition to occur at {approx}19 GPa in unknown structure. {yields} Higher pressure stability of otavite with respect to calcite can be attributed only to the significantly different electron configuration of Cd{sup 2+} and Ca{sup 2+}. {yields} The pressure homologue rule does not necessarily hold for cations with different valence spheres. - Abstract: The high-pressure, room temperature behavior of otavite (CdCO{sub 3}) was investigated by angle-dispersive synchrotron radiation powder diffraction up to 40 GPa, Raman spectroscopy up to 23 GPa and quantum mechanical calculations based on density functional theory. The calcite-type structure of CdCO{sub 3} is stable up to at least {approx}19 GPa as shown by Raman spectroscopy. The compression mechanism was obtained from structure refinements against the diffraction data. The quantum mechanical calculations propose a calcite-aragonite phase transition to occur at about 30 GPa. The existence of a pressure-induced phase transition is supported by the Raman and diffraction experiments. Evidence for the transformation is given by broadening of X-ray reflections and external Raman bands starting from about 19 GPa in both experiments.

  2. Mineral and Protein-Bound Water and Latching Action Control Mechanical Behavior at Protein-Mineral Interfaces in Biological Nanocomposites

    Directory of Open Access Journals (Sweden)

    Pijush Ghosh

    2008-01-01

    Full Text Available The nacre structure consists of laminated interlocked mineral platelets separated by nanoscale organic layers. Here, the role of close proximity of mineral to the proteins on mechanical behavior of the protein is investigated through steered molecular dynamics simulations. Our simulations indicate that energy required for unfolding protein in the proximity of mineral aragonite is several times higher than that for isolated protein in the absence of the mineral. Here, we present details of specific mechanisms which result in higher energy for protein unfolding in the proximity of mineral. At the early stage of pulling, peaks in the load-displacement (LD plot at mineral proximity are quantitatively correlated to the interaction energy between atoms involved in the latching phenomenon of amino acid side chain to aragonite surface. Water plays an important role during mineral and protein interaction and water molecules closer to the mineral surface are highly oriented and remain rigidly attached as the protein strand is pulled. Also, the high magnitude of load for a given displacement originates from attractive interactions between the protein, protein-bound water, and mineral. This study provides an insight into mineral-protein interactions that are predominant in biological nanocomposites and also provides guidelines towards design of biomimetic nanocomposites.

  3. Characterization of organic matrix components of pearl oyster ,Pinctada fucata and their implications in shell formation

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Mollusks make their shells by biomineralization using Ca2+ and CO32- from natural environment.In molluscan shells,two types of CaCO3 crystal which are aragonite and calcite form the species-dependent microstructures.It is believed that shell organic matrices act for control of the crystal types and microstructures.Shell of Pinetada fucata is divided into aragonitic nacreous layer and calcitic prismtic layer.In the recent years,several novel matrix components have been identified in pearl oyster shells by subsequent solubilization of the insoluble matrix,even in the nacreous layer which abounds in the data.In them,we focused our attention on a component,of which the N-terminal amino acid sequence was determined,and attempted cloning genes encoding it.As a result,several clones with typical sequence for the ORF (open reading frame) region were identified and the amino acid sequences were deduced.Further analysis of northern hybridization clarified the tissue specific expressions of the transcripts of the identified genes.

  4. Microbial composition of biofilms associated with lithifying rubble of Acropora palmata branches.

    Science.gov (United States)

    Beltrán, Yislem; Cerqueda-García, Daniel; Taş, Neslihan; Thomé, Patricia E; Iglesias-Prieto, Roberto; Falcón, Luisa I

    2016-01-01

    Coral reefs are among the most productive ecosystems on the planet, but are rapidly declining due to global-warming-mediated changes in the oceans. Particularly for the Caribbean region, Acropora sp. stony corals have lost ∼80% of their original coverage, resulting in vast extensions of dead coral rubble. We analyzed the microbial composition of biofilms that colonize and lithify dead Acropora palmata rubble in the Mexican Caribbean and identified the microbial assemblages that can persist under scenarios of global change, including high temperature and low pH. Lithifying biofilms have a mineral composition that includes aragonite and magnesium calcite (16 mole% MgCO(3)) and calcite, while the mineral phase corresponding to coral skeleton is basically aragonite. Microbial composition of the lithifying biofilms are different in comparison to surrounding biotopes, including a microbial mat, water column, sediments and live A. palmata microbiome. Significant shifts in biofilm composition were detected in samples incubated in mesocosms. The combined effect of low pH and increased temperature showed a strong effect after two-week incubations for biofilm composition. Findings suggest that lithifying biofilms could remain as a secondary structure on reef rubble possibly impacting the functional role of coral reefs.

  5. Archaeal populations in two distinct sedimentary facies of the subsurface of the Dead Sea.

    Science.gov (United States)

    Thomas, C; Ionescu, D; Ariztegui, D

    2014-10-01

    Archaeal metabolism was studied in aragonitic and gypsum facies of the Dead Sea subsurface using high-throughput DNA sequencing. We show that the communities are well adapted to the peculiar environment of the Dead Sea subsurface. They harbor the necessary genes to deal with osmotic pressure using high- and low-salt-in strategies, and to cope with unusually high concentrations of heavy metals. Methanogenesis was identified for the first time in the Dead Sea and appears to be an important metabolism in the aragonite sediment. Fermentation of residual organic matter, probably performed by some members of the Halobacteria class is common to both types of sediments. The latter group represents more than 95% of the taxonomically identifiable Archaea in the metagenome of the gypsum sediment. The potential for sulfur reduction has also been revealed and is associated in the sediment with EPS degradation and Fe-S mineralization as revealed by SEM imaging. Overall, we show that distinct communities of Archaea are associated with the two different facies of the Dead Sea, and are adapted to the harsh chemistry of its subsurface, in different ways.

  6. Micro-structure and chemical composition of vateritic deformities occurring in the bivalve Corbicula fluminea (Müller, 1774).

    Science.gov (United States)

    Frenzel, Max; Harper, Elizabeth M

    2011-05-01

    Vateritic deformities occurring in the invasive heterodont bivalve Corbicula fluminea from several locations in the UK were characterised in detail for the first time using scanning electron microscopy, X-ray diffraction and different geochemical techniques (electron microprobe, ICP-AES, and mass spectrometry). Large volumes of vaterite are produced abnormally in the animals' shells in the form of yellow-green bulges. These are distinguished from the aragonitic parts of the shell by their characteristic micro-structures, content of organic material, trace elemental composition and carbon stable isotope signatures. The most commonly observed micro-structures include columnar vaterite, lamellar vaterite and different irregular structures occurring in all parts of the shell. There are indications that organic material is present largely as intracrystalline impurities or nano-scale phases and not as envelopes around microstructural units. These micro-structures are novel, nothing equivalent having yet been described for other vateritic systems. Euhedral vaterite crystals also occur occasionally. The vaterite has generally higher Mg/Ca and lower Na/Ca, K/Ca than the aragonite. In addition, δ¹³C is also always lower. Microstructural characteristics would suggest loss of biological control probably due to physiological stress(es) inducing the switch to vaterite production. The vaterite might be stabilised by its higher content of organic material and magnesium.

  7. Calcite as a bone substitute. Comparison with hydroxyapatite and tricalcium phosphate with regard to the osteoblastic activity

    Energy Technology Data Exchange (ETDEWEB)

    Monchau, F., E-mail: Francine.monchau@univ-artois.fr [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Hivart, Ph.; Genestie, B. [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Chai, F. [Laboratoire Medicaments et Biomateriaux a Liberation Controlee (INSERM U 1008, Universite Lille Nord de France), Groupe de Recherche sur les Biomateriaux (Universite Lille-2), Faculte de Medecine, 1, place de Verdun, 59045 Lille cedex (France); and others

    2013-01-01

    Close to the bone mineral phase, the calcic bioceramics, such as hydroxyapatite (HA) and {beta}-tricalcium phosphate ({beta}-TCP), are commonly used as substitutes or filling materials in bone surgery. Besides, calcium carbonate (CaCO{sub 3}) is also used for their excellent biocompatibility and bioactivity. However, the problem with the animal-origin aragonite demands the new technique to synthesize pure calcite capable of forming 3D bone implant. This study aims to manufacture and evaluate a highly-pure synthetic crystalline calcite with good cytocompatibility regarding to the osteoblasts, comparing to that of HA and {beta}-TCP. After the manufacture of macroporous bioceramic scaffolds with the identical internal architecture, their cytocompatibility is studied through MC3T3-E1 osteoblasts with the tests of cell viability, proliferation, vitality, etc. The results confirmed that the studied process is able to form a macroporous material with a controlled internal architecture, and this synthesized calcite is non-cytotoxic and facilitate the cell proliferation. Indeed requiring further improvement, the studied calcite is definitely an interesting alternative not only to coralline aragonite but also to calcium phosphate ceramics, particularly in bone sites with the large bone remodelling. Highlights: Black-Right-Pointing-Pointer Macroporous calcite manufacturing with controlled architecture as bone substitute Black-Right-Pointing-Pointer Cytotoxicity: adaptation of the colony-forming method with the target cells: MC3T3-E1 osteoblasts Black-Right-Pointing-Pointer Study of osteoblast proliferation and activity on calcite, HA and TCP.

  8. Greenhouse conditions induce mineralogical changes and dolomite accumulation in coralline algae on tropical reefs.

    Science.gov (United States)

    Diaz-Pulido, Guillermo; Nash, Merinda C; Anthony, Kenneth R N; Bender, Dorothea; Opdyke, Bradley N; Reyes-Nivia, Catalina; Troitzsch, Ulrike

    2014-01-01

    Human-induced ocean acidification and warming alter seawater carbonate chemistry reducing the calcification of reef-building crustose coralline algae (CCA), which has implications for reef stability. However, due to the presence of multiple carbonate minerals with different solubilities in seawater, the algal mineralogical responses to changes in carbonate chemistry are poorly understood. Here we demonstrate a 200% increase in dolomite concentration in living CCA under greenhouse conditions of high pCO2 (1,225 μatm) and warming (30 °C). Aragonite, in contrast, increases with lower pCO2 (296 μatm) and low temperature (28 °C). Mineral changes in the surface pigmented skeleton are minor and dolomite and aragonite formation largely occurs in the white crust beneath. Dissolution of high-Mg-calcite and particularly the erosive activities of endolithic algae living inside skeletons play key roles in concentrating dolomite in greenhouse treatments. As oceans acidify and warm in the future, the relative abundance of dolomite in CCA will increase.

  9. Diet control on carbon isotopic composition of land snail shell carbonate

    Institute of Scientific and Technical Information of China (English)

    LIU ZongXiu; GU ZhaoYan; WU NaiQin; XU Bing

    2007-01-01

    Carbon isotope compositions for both the carbonate shells and soft bodies (organic tissue) of living land snails collected mostly from the Loess Plateau, China have been measured. The result shows that δ13C values range from -13.1‰ to -4.3‰ for the aragonite shell samples and from -26.8‰ to -18.0‰ for the soft body samples. Although the shells are enriched in 13C relative to the bodies averagely by 14.2(±0.8)‰, the shell δ13Ca values are closely correlated to the body δ13Corg values, expressed as δ13Ca = 1.021 δ13Corg + 14.38 (R = 0.965; N = 31). This relationship indicates that δ13Ca is primarily a function of the isotopic composition of the snail diets since previous studies have proved that the snail body is the same as their food in carbon isotope composition. In other words, carbon isotope compo-sition of the carbonate shell can be used as a proxy to estimate the dietary 13C abundance of the land snails. The data also support that the 13C enrichment of the carbonate shells results mainly from the equilibrium fractionations between the metabolic CO2, HCO3- in the hemolymph and shell aragonite, and partially from kinetic fractionations when snail shells form during their activity.

  10. Identifying vital effects in Halimeda algae with Ca isotopes

    Directory of Open Access Journals (Sweden)

    C. L. Blättler

    2014-12-01

    Full Text Available Geochemical records of biogenic carbonates provide some of the most valuable records of the geological past, but are often difficult to interpret without a mechanistic understanding of growth processes. In this experimental study, Halimeda algae are used as a test organism to untangle some of the specific factors that influence their skeletal composition, in particular their Ca-isotope composition. Algae were stimulated to precipitate both calcite and aragonite by growth in artificial Cretaceous seawater, resulting in experimental samples with somewhat malformed skeletons. The Ca-isotope fractionation of the algal calcite (−0.6‰ appears to be much smaller than that for the algal aragonite (−1.4‰, similar to the behaviour observed in inorganic precipitates. However, the carbonate from Halimeda has higher Ca-isotope ratios than inorganic forms by approximately 0.25‰, likely because of Rayleigh distillation within the algal intercellular space. In identifying specific vital effects and the magnitude of their influence on Ca-isotope ratios, this study suggests that mineralogy has a first-order control on the marine Ca-isotope cycle.

  11. The exposure of the Great Barrier Reef to ocean acidification.

    Science.gov (United States)

    Mongin, Mathieu; Baird, Mark E; Tilbrook, Bronte; Matear, Richard J; Lenton, Andrew; Herzfeld, Mike; Wild-Allen, Karen; Skerratt, Jenny; Margvelashvili, Nugzar; Robson, Barbara J; Duarte, Carlos M; Gustafsson, Malin S M; Ralph, Peter J; Steven, Andrew D L

    2016-02-23

    The Great Barrier Reef (GBR) is founded on reef-building corals. Corals build their exoskeleton with aragonite, but ocean acidification is lowering the aragonite saturation state of seawater (Ωa). The downscaling of ocean acidification projections from global to GBR scales requires the set of regional drivers controlling Ωa to be resolved. Here we use a regional coupled circulation-biogeochemical model and observations to estimate the Ωa experienced by the 3,581 reefs of the GBR, and to apportion the contributions of the hydrological cycle, regional hydrodynamics and metabolism on Ωa variability. We find more detail, and a greater range (1.43), than previously compiled coarse maps of Ωa of the region (0.4), or in observations (1.0). Most of the variability in Ωa is due to processes upstream of the reef in question. As a result, future decline in Ωa is likely to be steeper on the GBR than currently projected by the IPCC assessment report.

  12. Atlanta ariejansseni, a new species of shelled heteropod from the Southern Subtropical Convergence Zone (Gastropoda, Pterotracheoidea)

    Science.gov (United States)

    Wall-Palmer, Deborah; Burridge, Alice K.; Peijnenburg, Katja T.C.A.

    2016-01-01

    Abstract The Atlantidae (shelled heteropods) is a family of microscopic aragonite shelled holoplanktonic gastropods with a wide biogeographical distribution in tropical, sub-tropical and temperate waters. The aragonite shell and surface ocean habitat of the atlantids makes them particularly susceptible to ocean acidification and ocean warming, and atlantids are likely to be useful indicators of these changes. However, we still lack fundamental information on their taxonomy and biogeography, which is essential for monitoring the effects of a changing ocean. Integrated morphological and molecular approaches to taxonomy have been employed to improve the assessment of species boundaries, which give a more accurate picture of species distributions. Here a new species of atlantid heteropod is described based on shell morphology, DNA barcoding of the Cytochrome Oxidase I gene, and biogeography. All specimens of Atlanta ariejansseni sp. n. were collected from the Southern Subtropical Convergence Zone of the Atlantic and Indo-Pacific oceans suggesting that this species has a very narrow latitudinal distribution (37–48°S). Atlanta ariejansseni sp. n. was found to be relatively abundant (up to 2.3 specimens per 1000 m3 water) within this narrow latitudinal range, implying that this species has adapted to the specific conditions of the Southern Subtropical Convergence Zone and has a high tolerance to the varying ocean parameters in this region. PMID:27551204

  13. Investigation of scale inhibition mechanisms based on the effect of scale inhibitor on calcium carbonate crystal forms

    Institute of Scientific and Technical Information of China (English)

    ZHANG GuiCai; GE JiJiang; SUN MingQin; PAN BinLin; MAO Tao; SONG ZhaoZheng

    2007-01-01

    To probe the scale inhibition mechanisms, calcium carbonate scale occurring before and after the addition of scale inhibitors was collected. The results from scale SEM confirm that, without scale inhibitor, calcium carbonate scale shows rhombohedron and hexagon, which are the characteristic feathers of calcite. After addition of inhibitors, morphology of scale is changed, and the more efficient the scale inhibitor is, the more greatly the morphology is modified. To elucidate the scale constitute, they were further analyzed by FT-IR, XRD. Besides calcite, vaterite and aragonite occur in calcium carbonate scale after addition of inhibitors, and the higher scale inhibition efficiency is, the more vaterite presents in scale. It can be concluded that the alteration of morphology is ascribed to the change of crystal form. There are three stages in the crystallizing process including occurrence and disappearing of unstable phase, occurrence and disappearing of metastable phase, development of stable phase. Without scale inhibitors, metastable phases usually transform into stable phase, thus the main constitute of formed scale is calcite. When scale inhibitors are added, both formation and transformation of metastable phases are inhibited, which results in the occurrence of aragonite and vaterite. From the fact that more vaterite presents in scale with a more efficient scale inhibitor added, we can see that the function of scale inhibitor is realized mainly by controlling the crystallizing process at the second stage.

  14. Investigation of scale inhibition mechanisms based on the effect of scale inhibitor on calcium carbonate crystal forms

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    To probe the scale inhibition mechanisms,calcium carbonate scale occurring before and after the ad- dition of scale inhibitors was collected.The results from scale SEM confirm that,without scale inhibitor, calcium carbonate scale shows rhombohedron and hexagon,which are the characteristic feathers of calcite.After addition of inhibitors,morphology of scale is changed,and the more efficient the scale inhibitor is,the more greatly the morphology is modified.To elucidate the scale constitute,they were further analyzed by FT-IR,XRD.Besides calcite,vaterite and aragonite occur in calcium carbonate scale after addition of inhibitors,and the higher scale inhibition efficiency is,the more vaterite presents in scale.It can be concluded that the alteration of morphology is ascribed to the change of crystal form. There are three stages in the crystallizing process including occurrence and disappearing of unstable phase,occurrence and disappearing of metastable phase,development of stable phase.Without scale inhibitors,metastable phases usually transform into stable phase,thus the main constitute of formed scale is calcite.When scale inhibitors are added,both formation and transformation of metastable phases are inhibited,which results in the occurrence of aragonite and vaterite.From the fact that more vaterite presents in scale with a more efficient scale inhibitor added,we can see that the function of scale inhibitor is realized mainly by controlling the crystallizing process at the second stage.

  15. Inorganic carbon in a high latitude estuary-fjord system in Canada's eastern Arctic

    Science.gov (United States)

    Turk, D.; Bedard, J. M.; Burt, W. J.; Vagle, S.; Thomas, H.; Azetsu-Scott, K.; McGillis, W. R.; Iverson, S. J.; Wallace, D. W. R.

    2016-09-01

    Rapidly changing conditions in the Arctic can have a significant impact on biogeochemical cycles and can be particularly important in high latitude estuary-fjord systems with abundant and diverse freshwater sources. This study provides a first look into the inorganic carbon system and its relation to freshwater sources in Cumberland Sound in the east coast of Baffin Island, Nunavut, Canada. These data contribute to the very limited set of inorganic carbon measurements in high latitude estuary-fjord systems. During the ice-free conditions in August 2011, the meteoric freshwater fractions (MW) in the upper 40 m ranged from 11 to 21% and no sea ice melt (SIM) was present in the Sound. Surface waters were undersaturated with pCO2 (260 and 300 μatm), and DIC and TA ranged between 1779 and 1966 μmol DIC kg-1, and 1922 and 2140 μmol TA kg-1, respectively. Aragonite saturation (ΩAr) state ranged from 1.9 in the surface to 1.4 in the subsurface waters. Data show decreasing TA and ΩAr with increasing MW fraction and suggest that Cumberland Sound waters would become aragonite undersaturated (ΩAr melt. In August 2012, MW fractions at the surface were between 8 and 11.5%, and SIM between 7 and 23%. Significant interannual variability of summertime SIM could potentially result in ΩAr undersaturation.

  16. Nacre tablet thickness records formation temperature in modern and fossil shells

    Science.gov (United States)

    Gilbert, Pupa U. P. A.; Bergmann, Kristin D.; Myers, Corinne E.; Marcus, Matthew A.; DeVol, Ross T.; Sun, Chang-Yu; Blonsky, Adam Z.; Tamre, Erik; Zhao, Jessica; Karan, Elizabeth A.; Tamura, Nobumichi; Lemer, Sarah; Giuffre, Anthony J.; Giribet, Gonzalo; Eiler, John M.; Knoll, Andrew H.

    2017-02-01

    Nacre, the iridescent outer lining of pearls and inner lining of many mollusk shells, is composed of periodic, parallel, organic sheets alternating with aragonite (CaCO3) tablet layers. Nacre tablet thickness (TT) generates both nacre's iridescence and its remarkable resistance to fracture. Despite extensive studies on how nacre forms, the mechanisms controlling TT remain unknown, even though they determine the most conspicuous of nacre's characteristics, visible even to the naked eye. Thermodynamics predicts that temperature (T) will affect both physical and chemical components of biomineralized skeletons. The chemical composition of biominerals is well-established to record environmental parameters, and has therefore been extensively used in paleoclimate studies. The physical structure, however, has been hypothesized but never directly demonstrated to depend on the environment. Here we observe that the physical TT in nacre from modern and fossil shallow-water shells of the bivalves Pinna and Atrina correlates with T as measured by the carbonate clumped isotope thermometer. Based on the observed TT vs. T correlation, we anticipate that TT will be used as a paleothermometer, useful to estimate paleotemperature in shallow-water paleoenvironments. Here we successfully test the proposed new nacre TT thermometer on two Jurassic Pinna shells. The increase of TT with T is consistent with greater aragonite growth rate at higher T, and with greater metabolic rate at higher T. Thus, it reveals a complex, T-dependent biophysical mechanism for nacre formation.

  17. Mineralogy of Holocene Sediments from the Southwestern Black Sea Shelf (Turkey) in Relation to Provenance, Sea-level and Current Regimes

    Institute of Scientific and Technical Information of China (English)

    Emel BAYHAN; Mustafa ERG(I)N; Abidin TEMEL; Seref KESK(I)N

    2005-01-01

    Grain size and mineral composition of core sediments were used to investigate influences of various terrestrial and marine conditions,which have prevailed on the southwestern Black Sea shelf during the Holocene.Siliciclastic mud with small amounts of sand and gravel from nearby coastal hinterland is the principal sediment type,whereas sediments deposited near the shelf edge and the (I)stanbul Strait and off the Duru Lake (a paleo-river mouth)constitued large quantities of sand and gravel of both biogenic and terrigenic origin.Variable amounts of aragonite,1 nm-micas,quartz,feldspars,calcite and dolomite constitute the dominant non-clay minerals in bulk sediments.The clay mineral assemblage in the < 2 μm fraction is made up of smectite,illite,kaolinite and chlorite.Aragonite and calcite are mainly derived from benthic accumulations,whereas feldspars (mainly plagioclase) and smectite reflect magmaticvolcanic provenance and the distribution of 1 nm-micas and chlorite correlate with nearby metamorphic sources onland.Nevertheless,grain size and mineral distribution generally indicate a combination of effects of wind and wave climate,longshore and offshore cyclonic currents,changing sea-level stands and nearby source rock and morphological conditions.It is also suggested that at least part of clay minerals could be derived from the northwesterly Danube River input.

  18. Biomineralisation in Mollusc shells

    Science.gov (United States)

    Dauphin, Y.; Cuif, J. P.; Salomé, M.; Williams, C. T.

    2009-04-01

    The main components of Mollusc shells are carbonate minerals: calcite and aragonite. ACC is present in larval stages. Calcite and aragonite can be secreted simultaneously by the mantle. Despite the small number of varieties, the arrangement of the mineral components is diverse, and dependant upon the taxonomy. They are also associated with organic components much more diverse, the diversity of which reflects the large taxonomic diversity. From TGA analyses, the organic content (water included) is high (>5% in some layers). The biomineralisation process is not a passive precipitation process, but is strongly controlled by the organism. The biological-genetic control is shown by the constancy of the arrangement of the layers, the mineralogy and the microstructure in a given species. Microstructural units (i.e. tablets, prisms etc.) have shapes that do not occur in non-biogenic counterparts. Nacreous tablets, for example, are flattened on their crystallographic c axis, which is normally the axis of maximum growth rate for non-biogenic aragonite. Morever, their inner structure is species-specific: the arrangements of nacreous tablets in Gastropoda - Cephalopoda, and in Bivalvia differ, and the inner arrangement of the nacreous tablets is different in ectocochlear and endocochlear Cephalopoda. The organic-mineral ratios also differ in the various layers of a shell. Differences in chemical composition also demonstrates the biological-genetic control: for example, aragonite has a low Sr content unknown in non-biogenic samples; two aragonitic layers in a shell have different Sr and Mg contents, S is higher in calcitic layers. Decalcification releases soluble (SOM) and insoluble (IOM) organic components. Insoluble components form the main part of the intercrystalline membranes, and contain proteins, polysaccharides and lipids. Soluble phases are present within the crystals and the intercrystalline membranes. These phases are composed of more or less glycosylated proteins

  19. Sr/Ca and Mg/Ca vital effects correlated with skeletal architecture in a scleractinian deep-sea coral and the role of Rayleigh fractionation

    Science.gov (United States)

    Gagnon, Alexander C.; Adkins, Jess F.; Fernandez, Diego P.; Robinson, Laura F.

    2007-09-01

    Deep-sea corals are a new tool in paleoceanography with the potential to provide century long records of deep ocean change at sub-decadal resolution. Complicating the reconstruction of past deep-sea temperatures, Mg/Ca and Sr/Ca paleothermometers in corals are also influenced by non-environmental factors, termed vital effects. To determine the magnitude, pattern and mechanism of vital effects we measure detailed collocated Sr/Ca and Mg/Ca ratios, using a combination of micromilling and isotope-dilution ICP-MS across skeletal features in recent samples of Desmophyllum dianthus, a scleractinian coral that grows in the near constant environment of the deep-sea. Sr/Ca variability across skeletal features is less than 5% (2σ relative standard deviation) and variability of Sr/Ca within the optically dense central band, composed of small and irregular aragonite crystals, is significantly less than the surrounding skeleton. The mean Sr/Ca of the central band, 10.6 ± 0.1 mmol/mol (2σ standard error), and that of the surrounding skeleton, 10.58±0.09 mmol/mol, are statistically similar, and agree well with the inorganic aragonite Sr/Ca-temperature relationship at the temperature of coral growth. In the central band, Mg/Ca is greater than 3 mmol/mol, more than twice that of the surrounding skeleton, a general result observed in the relative Mg/Ca ratios of D. dianthus collected from separate oceanographic locations. This large vital effect corresponds to a ˜ 10 °C signal, when calibrated via surface coral Mg/Ca-temperature relationships, and has the potential to complicate paleoreconstructions. Outside the central band, Mg/Ca ratios increase with decreasing Sr/Ca. We explain the correlated behavior of Mg/Ca and Sr/Ca outside the central band by Rayleigh fractionation from a closed pool, an explanation that has been proposed elsewhere, but which is tested in this study by a simple and general relationship. We constrain the initial solution and effective partition

  20. Will Coral Islands maintain their growth over the next century? A deterministic model of sediment availability at Lady Elliot Island, Great Barrier Reef.

    Science.gov (United States)

    Hamylton, Sarah

    2014-01-01

    A geomorphic assessment of reef system calcification is conducted for past (3200 Ka to present), present and future (2010-2100) time periods. Reef platform sediment production is estimated at 569 m3 yr-1 using rate laws that express gross community carbonate production as a function of seawater aragonite saturation, community composition and rugosity and incorporating estimates of carbonate removal from the reef system. Key carbonate producers including hard coral, crustose coralline algae and Halimeda are mapped accurately (mean R2 = 0.81). Community net production estimates correspond closely to independent census-based estimates made in-situ (R2 = 0.86). Reef-scale outputs are compared with historic rates of production generated from (i) radiocarbon evidence of island deposition initiation around 3200 years ago, and (ii) island volume calculated from a high resolution island digital elevation model. Contemporary carbonate production rates appear to be remarkably similar to historical values of 573 m3 yr-1. Anticipated future seawater chemistry parameters associated with an RCP8.5 emissions scenario are employed to model rates of net community calcification for the period 2000-2100 on the basis of an inorganic aragonite precipitation law, under the assumption of constant benthic community character. Simulations indicate that carbonate production will decrease linearly to a level of 118 m3 yr-1 by 2100 and that by 2150 aragonite saturation levels may no longer support the positive budgetary status necessary to sustain island accretion. Novel aspects of this assessment include the development of rate law parameters to realistically represent the variable composition of coral reef benthic carbonate producers, incorporation of three dimensional rugosity of the entire reef platform and the coupling of model outputs with both historical radiocarbon dating evidence and forward hydrochemical projections to conduct an assessment of island evolution through time

  1. On the origin and early diagenesis of early Triassic carbonate mud (Dolomites, Italy)

    Science.gov (United States)

    Preto, Nereo; Westphal, Hildegard; Birgel, Daniel; Carampin, Raul; Dal Corso, Jacopo; Gattolin, Giovanni; Montinaro, Alice; Peckmann, Jörn

    2015-04-01

    The earliest Triassic (early Induan) deposits of the Italian Southern Alps are shallow water oolites, and lime-mudstone formed in an open shelf (mid to outer carbonate ramp) sedimentary environment, deposited after the end-Permian extinction that killed all carbonate producers. The origin of these lime-mudstones is thus enigmatic. We used a multidisciplinary petrographic and geochemical approach to identify the origin and early diagenesis of early Triassic lime-mudstones of the Dolomites (Northern Italy). This fine carbonate is made of pitted crystals of microsparite, ~ 25 μm in diameter, exhibiting zonation both in fluorescence and cathodoluminescence. Field and standard petrographic observations exclude an origin from fragmentation or abrasion of carbonate grains. Strontium content, measured in-situ with electron microprobe, has a bimodal distribution with values locally as high as > 4000 ppm. Lipid biomarker analysis revealed molecular fossils of bacteria (terminally-branched alkanes, hopanes, and scarce methylhopanes) along with compounds of low source specificity (n-alkanes), whereas biomarkers of algae (steranes) were not detected. This suggests that, differently from modern Caribbean shelfs, this fine carbonate did not originate from the disgregation of green algae. A Pristane to Phytane ratio < 1 also suggests deposition under anoxic conditions, in agreement with the known status of "superanoxia" of earliest Triassic oceans. Overall, our observations suggest an aragonitic mineralogy of the carbonate mud, followed by calcite replacement and cementation in the marine burial early diagenetic environment. Our data strongly suggest that the early Triassic carbonate mud of the Dolomites was precipitated in the water column, similarly to the modern whitings of the Bahamas, and then settled on a shelf bottom below wave base. Our study shows that these lime-mudstones contain aragonite replaced by calcite and calcite cement, in variable proportions. The δ13C of

  2. Observations on ichnology, taphonomy and epibiota in the freshwater realm

    Science.gov (United States)

    Lawfield, Andrew Martin William

    Ichnology concerns the study of interactions between organisms and both soft and hard substrates. Actualistic observation of a modern day river channel molluscan assemblage including unionid and sphaeriid bivalves and gastropods within the Saint John River, Fredericton, New Brunswick, Canada reveals their production of almond shaped Lockeia like resting traces, together with varied, horizontally aligned furrowed, meandering, looping and spiral plan view locomotion/grazing traces. These traces occur within a shifting sand softground substrate. An emersion event associated with a low water level allowed collection of unionid samples, amongst which Elliptio complanata predominates, alongside Lampsilis radiata and Anodonta implicata. Detailed analysis of shell material, with methodologies including scanning electron microscopy (SEM) reveals microboring, various taphonomic signatures and the development of biofilm and extracellular polymeric substances (EPS). These are often associated with one another and their location closely influenced by the shell structure. Taphonomic decay of the shells was noted, with the external periostracum and prismatic aragonite layers decaying, particularly in the umbonal region. Physical puncturing and tearing penetrate the periostracum. Exposed regions of nacreous aragonite are smoothed by a combination of chemical interaction with the water column and physical abrasion from agitated silt and sand sediments. Surface pitting and circular to ovoid penetrations with morphologies comparable to Oichnus borings are noted and their formation is tentatively attributed to bacterial decay processes. In marine settings, the outer protective periostracum of molluscs often possesses physical and chemical defence mechanisms intended to inhibit the attachment of epibiota. Our observations suggest their absence from unionids, with final instar larval or pupal stage Trichoptera, including Goera, Neophylax and Helicopsyche selectively attached to regions

  3. Estimates of ikaite export from sea ice to the underlying seawater in a sea ice-seawater mesocosm

    Science.gov (United States)

    Geilfus, Nicolas-Xavier; Galley, Ryan J.; Else, Brent G. T.; Campbell, Karley; Papakyriakou, Tim; Crabeck, Odile; Lemes, Marcos; Delille, Bruno; Rysgaard, Søren

    2016-09-01

    the effect of oceanic acidification on the aragonite saturation state (Ωaragonite) in fall and in winter in ice-covered areas, at the time when Ωaragonite is smallest.

  4. Impacts of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on the dissolution kinetics of whole-shell biogenic carbonates

    Science.gov (United States)

    Ries, Justin B.; Ghazaleh, Maite N.; Connolly, Brian; Westfield, Isaac; Castillo, Karl D.

    2016-11-01

    Anthropogenic increase of atmospheric pCO2 since the Industrial Revolution has caused seawater pH to decrease and seawater temperatures to increase-trends that are expected to continue into the foreseeable future. Myriad experimental studies have investigated the impacts of ocean acidification and warming on marine calcifiers' ability to build protective shells and skeletons. No studies, however, have investigated the combined impacts of ocean acidification and warming on the whole-shell dissolution kinetics of biogenic carbonates. Here, we present the results of experiments designed to investigate the effects of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on gross rates of whole-shell dissolution for ten species of benthic marine calcifiers: the oyster Crassostrea virginica, the ivory barnacle Balanus eburneus, the blue mussel Mytilus edulis, the conch Strombus alatus, the tropical coral Siderastrea siderea, the temperate coral Oculina arbuscula, the hard clam Mercenaria mercenaria, the soft clam Mya arenaria, the branching bryozoan Schizoporella errata, and the coralline red alga Neogoniolithon sp. These experiments confirm that dissolution rates of whole-shell biogenic carbonates decrease with calcium carbonate (CaCO3) saturation state, increase with temperature, and vary predictably with respect to the relative solubility of the calcifiers' polymorph mineralogy [high-Mg calcite (mol% Mg > 4) ≥ aragonite > low-Mg calcite (mol% Mg 1) with respect to both aragonite and calcite reveals fundamental differences between the dissolution kinetics of whole-shell biogenic CaCO3 and inorganic CaCO3. Thus, applying stoichiometric solubility products derived for inorganic CaCO3 to model gross dissolution of biogenic carbonates may substantially underestimate the impacts of ocean acidification on net calcification (gross calcification minus gross dissolution) of systems ranging in scale from individual organisms to entire ecosystems (e.g., net

  5. Spatiotemporal variability and long-term trends of ocean acidification in the California Current System

    Directory of Open Access Journals (Sweden)

    C. Hauri

    2013-01-01

    Full Text Available Due to seasonal upwelling, the upper ocean waters of the California Current System (CCS have a naturally low pH and aragonite saturation state (Ωarag, making this region particularly prone to the effects of ocean acidification. Here, we use the Regional Oceanic Modeling System (ROMS to conduct preindustrial and transient (1995–2050 simulations of ocean biogeochemistry in the CCS. The transient simulations were forced with increasing atmospheric pCO2 and increasing oceanic dissolved inorganic carbon concentrations at the lateral boundaries, as projected by the NCAR CSM 1.4 model for the IPCC SRES A2 scenario. Our results show a large seasonal variability in pH (range of ~ 0.14 and Ωarag (~ 0.2 for the nearshore areas (50 km from shore. This variability is created by the interplay of physical and biogeochemical processes. Despite this large variability, we find that present-day pH and Ωarag have already moved outside of their simulated preindustrial variability envelopes (defined by ±1 temporal standard deviation due to the rapidly increasing concentrations of atmospheric CO2. The nearshore surface pH of the northern and central CCS are simulated to move outside of their present-day variability envelopes by the mid-2040s and late 2030s, respectively. This transition may occur even earlier for nearshore surface Ωarag, which is projected to depart from its present-day variability envelope by the early- to mid-2030s. The aragonite saturation horizon of the central CCS is projected to shoal into the upper 75 m within the next 25 yr, causing near-permanent undersaturation in subsurface waters. Due to the model's overestimation of Ωarag, this transition may occur even earlier than simulated by the model. Overall, our study shows that the CCS joins the Arctic and Southern oceans as one of only a few known ocean regions presently approaching the dual threshold of

  6. Investigation of Bio-Inspired Hybrid Materials through Polymer Infiltration of Thermal Spray Formed Ceramic Templates

    Science.gov (United States)

    Flynn, Katherine Claire

    High strength and toughness are often mutually exclusive in engineered materials. This is especially true of ceramics and polymers. Ceramics exhibit high strength and stiffness, but are brittle while polymers are flaw tolerant but prone to deformation at low stresses. Nature overcomes this restriction in materials by strategically combining brittle components with tough organics, leading to materials with both a high strength and toughness. One of the most impressive natural composites is nacre consisting of mainly a brittle mineral phase, 95vol% calcium carbonate (aragonite), and 5vol% biopolymer (a combination of proteins and polysaccahrides). Nature combines constituents with poor macroscale properties and achieves levels that surpass those expected despite being formed of mostly mineral CaCO3 tablets. Interestingly, nacreous assemblies can display a toughness 3,000 times higher than their major constituent, aragonite. Similarities have been observed between nacre and sprayed ceramics in terms of their microstructures and mechanical behavior. Both assemblies follow a design hierarchy and layered organization over several length scales. The mineral phase in nacre has evolved on the microscale and nanometer interlayers of biopolymer bond neighboring tablets. In addition, these tablets have a certain degree of waviness, nanoscale roughness, and mineral bridges thereby further enhancing linkages to one another. These inherent microstructural features significantly improve the mechanical properties of nacreous assemblies. On the other hand, sprayed ceramics are formed from micron sized splats, larger than aragonite nacreous tablets, with comparable (nanoscale) roughness, resulting from grain termination sites. Together these features of sprayed ceramics respond similarly to nacre, showing a great extent of mechanical nonlinearity and hysteresis, which is mostly absent in structural ceramics. Due to the splat-by-splat deposition process, sprayed ceramics contain a

  7. Timing of methane efflux along the Norwegian and US Atlantic margin

    Science.gov (United States)

    Sahy, Diana; Condon, Daniel; Lepland, Aivo; Crémière, Antoine; Noble, Stephen; Ruppel, Carolyn

    2016-04-01

    Methane-related authigenic carbonates (MDAC) provide a robust archive of past methane emissions from cold seeps located along continental margins. MDAC are amenable to U-Th geochronology which can be used to assess the timing and drivers of fluid flow (Teichert et al., 2003; Bayon et al., 2013). The difficulty of sourcing MDAC typically precludes the assembly of datasets with sufficient geographic coverage and resolution to investigate the processes triggering and sustaining methane seeps on a regional scale. To address this, two collaborative projects led by the British, Norwegian and US geological surveys are currently underway, targeting methane seeps located along the Norwegian and US Atlantic margins (Skarke et al., 2014). MDAC samples collected for the two projects come from a range of depths (300-2000 m), and are linked to a variety of processes (e.g. collapse of grounded ice sheet, salt diapirism, dissociation of upper slope gas hydrates, emissions from deep reservoirs through fault networks). MDAC typically present as matrix-supported conglomerate /sandstone/ siltstone, and consist of detrital material of variable grainsize (depending on locality) encased in an aragonite and/or calcite cement. Interconnected voids within the MDAC, which likely represent fluid conduits, are often at least partially filled with clean (>90%), layered aragonite. The latter are ideal materials for U-Th geochronology, and can yield U-Th dates with precision approaching 0.5 % (2σ), with thicker (ca. 2 cm) layered cavity fills showing resolvable growth histories on the order of 1 kyr. While measurements on cavity-filling aragonite give a snapshot of seep activity, quantifying the entire methane emission history of a sample, and crucially, the timing of the onset of emissions, requires the analysis of MDAC groundmass. Such analyses are more challenging as initial detrital 230Th included in the samples must be accounted for. While precise dating of the onset of methane emissions at

  8. Sedimentary and structural controls on seismogenic slumping within mass transport deposits from the Dead Sea Basin

    Science.gov (United States)

    Alsop, G. I.; Marco, S.; Weinberger, R.; Levi, T.

    2016-10-01

    Comparatively little work has been undertaken on how sedimentary environments and facies changes can influence detailed structural development in slump sheets associated with mass transport deposits (MTDs). The nature of downslope deformation at the leading edge of MTDs is currently debated in terms of frontally emergent, frontally confined and open-toed models. An opportunity to study and address these issues occurs within the Dead Sea Basin, where six individual slump sheets (S1-S6) form MTDs in the Late Pleistocene Lisan Formation. All six slumps, which are separated from one another by undeformed beds, are traced towards the NE for up to 1 km, and each shows a change in sedimentary facies from detrital-rich in the SW, to more aragonite-rich in the NE. The detrital-rich facies is sourced predominantly from the rift margin 1.5 km further SW, while the aragonite-rich facies represents evaporitic precipitation in the hyper saline Lake Lisan. The stacked system of MTDs translates downslope towards the NE and follows a pre-determined sequence controlled by the sedimentary facies. Each individual slump roots downwards into underlying detrital-rich layers and displays a greater detrital content towards the SW, which is marked by increasing folding, while increasing aragonite content towards the NE is associated with more discrete thrusts. The MTDs thin downslope towards the NE, until they pass laterally into undeformed beds at the toe. The amount of contraction also reduces downslope from a maximum of 50% to < 10% at the toe, where upright folds form diffuse 'open-toed' systems. We suggest that MTDs are triggered by seismic events, facilitated by detrital-rich horizons, and controlled by palaeoslope orientation. The frequency of individual failures is partially controlled by local environmental influences linked to detrital input and should therefore be used with some caution in more general palaeoseismic studies. We demonstrate that MTDs display 'open toes' where

  9. Rayleigh-based, multi-element coral thermometry: A biomineralization approach to developing climate proxies

    Science.gov (United States)

    Gaetani, G.A.; Cohen, A.L.; Wang, Z.; Crusius, J.

    2011-01-01

    This study presents a new approach to coral thermometry that deconvolves the influence of water temperature on skeleton composition from that of “vital effects”, and has the potential to provide estimates of growth temperatures that are accurate to within a few tenths of a degree Celsius from both tropical and cold-water corals. Our results provide support for a physico-chemical model of coral biomineralization, and imply that Mg2+ substitutes directly for Ca2+ in biogenic aragonite. Recent studies have identified Rayleigh fractionation as an important influence on the elemental composition of coral skeletons. Daily, seasonal and interannual variations in the amount of aragonite precipitated by corals from each “batch” of calcifying fluid can explain why the temperature dependencies of elemental ratios in coral skeleton differ from those of abiogenic aragonites, and are highly variable among individual corals. On the basis of this new insight into the origin of “vital effects” in coral skeleton, we developed a Rayleigh-based, multi-element approach to coral thermometry. Temperature is resolved from the Rayleigh fractionation signal by combining information from multiple element ratios (e.g., Mg/Ca, Sr/Ca, Ba/Ca) to produce a mathematically over-constrained system of Rayleigh equations. Unlike conventional coral thermometers, this approach does not rely on an initial calibration of coral skeletal composition to an instrumental temperature record. Rather, considering coral skeletogenesis as a biologically mediated, physico-chemical process provides a means to extract temperature information from the skeleton composition using the Rayleigh equation and a set of experimentally determined partition coefficients. Because this approach is based on a quantitative understanding of the mechanism that produces the “vital effect” it should be possible to apply it both across scleractinian species and to corals growing in vastly different environments. Where

  10. Photoluminescence and electron-vibrational interaction in 4f{sup n-1}5d states of Ce{sup 3+} or Pr{sup 3+} ions doped LnBO{sub 3} (Ln=Lu, Y, La) orthoborates materials

    Energy Technology Data Exchange (ETDEWEB)

    Guerbous, L., E-mail: guerbous@yahoo.fr [Laser Department, Nuclear Techniques Division, Algiers Nuclear Research Center, 02, bd Frantz Fanon, BP 399, Algiers 16000 (Algeria); Seraiche, M. [Laser Department, Nuclear Techniques Division, Algiers Nuclear Research Center, 02, bd Frantz Fanon, BP 399, Algiers 16000 (Algeria); Department of Materials and Components, Faculty of Physics, USTHB (Algeria); Krachni, O. [Departement de Physique, Faculte des Sciences, Universite Ferhat Abbas Setif 19000 (Algeria)

    2013-02-15

    Calcite, vaterite and aragonite type rare earth LnBO{sub 3} (Ln=Lu, Y, La) orthoborate powders, doped with 1% cerium or praseodymium, were prepared by the classical solid state reaction method. The structure and the morphology of these powder materials were checked by X-ray Diffraction, Fourier Transform Infra Red Spectroscopy (FTIR) and Scanning Electron Microscopy. Room temperature excitation and emission spectra of four compounds: LuBO{sub 3} with calcite and vaterite structure, YBO{sub 3} (vaterite type structure) and LaBO{sub 3} with aragonite, doped with 1% cerium or praseodymium ions, have been measured and investigated. The effect of Ce{sup 3+} and Pr{sup 3+} crystalline environment in these compounds on the position of their 5d (4f5d) levels has been discussed. This work is also devoted to the problem of the electron-vibrational interaction (EVI) in 4f-5d optical transitions in orthoborate materials. The emission and excitation 4f-5d transitions resulted in broad vibronic bands whose shape functions were described and found. The main EVI parameters, such as the Huang-Rhys factor, effective phonon energy, and zero-phonon line position, were estimated. These values are checked by modeling the Ce{sup 3+} 5d-4f and Pr{sup 3+} 4f5d-4f{sup 2} emission lines shapes, in which good agreement with experimental spectra confirms validity of the performed analysis. - Highlights: Black-Right-Pointing-Pointer Ce{sup 3+} and Pr{sup 3+}-doped calcite, vaterite and aragonite LnBO{sub 3} (Ln=Lu, Y, La) orthoborates were successfully prepared by the solid state reaction method. Black-Right-Pointing-Pointer The effect of Ce{sup 3+} and Pr{sup 3+} crystalline environment in orthoborates on the position of their 5d levels has been discussed. Black-Right-Pointing-Pointer The main electron-vibrational interaction parameters (EVI), such as the Huang-Rhys factor, effective phonon energy, and zero-phonon line position, were estimated and discussed.

  11. Experiments on different materials (polyamide, stainless & galvanized steel) influencing geothermal CaCO3 scaling formation: Polymorphs & elemental incorporation

    Science.gov (United States)

    Wedenig, Michael; Dietzel, Martin; Boch, Ronny; Hippler, Dorothee

    2016-04-01

    Thermal water is increasingly used for heat and electric power production providing base-load capable renewable and virtually unlimited geothermal energy. Compared to other energy sources geothermal facilities are less harmful to the environment, i.e. chemically and visually. In order to promote the economic viability of these systems compared to other traditional and renewable energy sources, production hindering processes such as corrosion and scaling of components arising from the typically high salinity thermal waters have to be considered as important economic factors. In this context, using proper materials being in contact with the thermal water is crucial and a playground for further improvements. Aim of the study presented, are basic experiments and observations of scaling and corrosive effects from hydrothermal water interacting with different materials and surfaces (stainless steel, polyamide, galvanized steel) and in particular the nucleation and growth effects of these materials regarding the precipitation of solid carbonate phases. The incorporation of Mg, Sr and Ba cations into the carbonate scalings are investigated as environmental proxy. For this purpose, hydrothermal carbonate precipitating experiments were initialized by mixing NaHCO3 and Ca-Mg-Sr-Ba-chloride solutions at temperatures ranging from 40 to 80 °C in glass reactors hosting artificial substrates of the above mentioned materials. The experiments show a strong dependence of the precipitation behaviour of calcium carbonate polymorphs on the particular material being present. Stainless steel and polyamide seem to restrict aragonite formation, whereas galvanized steel supports aragonite nucleation. Vaterite formation is promoted by polyamide surfaces. Importantly, vaterite is more soluble (less stable) compared to the other anhydrous calcium carbonate polymorphs, i.e. vaterite can be more easily re-dissolved. Thus, the use of polyamide components might reduce the amount and durability of

  12. Carbonate mineral saturation states in the East China Sea: present conditions and future scenarios

    Directory of Open Access Journals (Sweden)

    W.-C. Chou

    2013-10-01

    Full Text Available To assess the impact of rising atmospheric CO2 and eutrophication on the carbonate chemistry of the East China Sea shelf waters, saturation states (Ω for two important biologically relevant carbonate minerals – calcite (Ωc and aragonite (Ωa – were calculated throughout the water column from dissolved inorganic carbon (DIC and total alkalinity (TA data collected in spring and summer of 2009. Results show that the highest Ωc (∼9.0 and Ωa (∼5.8 values were found in surface water of the Changjiang plume area in summer, whereas the lowest values (Ωc = ∼2.7 and Ωa = ∼1.7 were concurrently observed in the bottom water of the same area. This divergent behavior of saturation states in surface and bottom waters was driven by intensive biological production and strong stratification of the water column. The high rate of phytoplankton production, stimulated by the enormous nutrient discharge from the Changjiang, acts to decrease the ratio of DIC to TA, and thereby increases Ω values. In contrast, remineralization of organic matter in the bottom water acts to increase the DIC to TA ratio, and thus decreases Ω values. The projected result shows that continued increases of atmospheric CO2 under the IS92a emission scenario will decrease Ω values by 40–50% by the end of this century, but both the surface and bottom waters will remain supersaturated with respect to calcite and aragonite. Nevertheless, superimposed on such Ω decrease is the increasing eutrophication, which would mitigate or enhance the Ω decline caused by anthropogenic CO2 uptake in surface and bottom waters, respectively. Our simulation reveals that, under the combined impact of eutrophication and augmentation of atmospheric CO2, the bottom water of the Changjiang plume area will become undersaturated with respect to aragonite (Ωa = ∼0.8 by the end of this century, which would threaten the health of the benthic ecosystem.

  13. Deepwater carbonate deposition in response to re-flooding of carbonate bank and atoll-tops at glacial terminations

    Science.gov (United States)

    Jorry, Stéphan J.; Droxler, André W.; Francis, Jason M.

    2010-08-01

    The late Quaternary has experienced large glacial/interglacial climatic variations and related 10's to 100 meters high-amplitude sea level fluctuations at Milankovich frequencies from 10's to 100 kyr during which carbonate platform tops have been exposed and re-flooded in many occasions. This study focuses on the accumulation of calci-turbidites, the aragonite onset/sharp increase in fine sediments and their timing in deep basins adjacent to carbonate platforms. A particular emphasis is developed on the occurrence of the first gravity flow event and aragonite onset/sharp increase and their linkage to the initial re-flooding of the platform tops during deglaciations. Three basins adjacent to isolated platforms in the Bahamas, the Northern Nicaragua Rise, and the Gulf of Papua, were selected to represent pure carbonate versus mixed systems, in quiescent versus tectonically active settings, and various carbonate bank top morphologies, ranging from atoll to relatively deeply and narrowly flooded flat top banks. In spite of these differences, each record illustrates a clear relationship between the timing of platform top re-flooding and initiation of significant carbonate export by gravity flows and low-density plumes into the surrounding basins. The concept of "re-flooding window" is introduced to characterize the prolific period of time during which bank and atoll-tops are flooded enough to produce large export of bank-derived aragonite and of calci-turbidites in adjacent basins. According to our datasets, the main re-flooding windows have occurred mainly on the last part of the sea level rise at each glacial termination (T), those periods being marked by some of the highest rates of sea level rise. The analysis of a long-piston core from the earthquakes-prone Walton Basin (Northern Nicaragua Rise) demonstrates that sea level, not seismic activities, played a major role as trigger mechanism for the initiation of gravity flows since the last four glacial

  14. Differential Effects of Ocean Acidification on Coral Calcification: Insights from Geochemistry.

    Science.gov (United States)

    Holcomb, M.; Decarlo, T. M.; Venn, A.; Tambutte, E.; Gaetani, G. A.; Tambutte, S.; Allemand, D.; McCulloch, M. T.

    2014-12-01

    Although ocean acidification is expected to negatively impact calcifying animals due to the formation of CaCO3 becoming less favorable, experimental evidence is mixed. Corals have received considerable attention in this regard; laboratory culture experiments show there to be a wide array of calcification responses to acidification. Here we will show how relationships for the incorporation of various trace elements and boron isotopes into synthetic aragonite can be used to reconstruct carbonate chemistry at the site of calcification. In turn the chemistry at the site of calcification can be determined under different ocean acidification scenarios and differences in the chemistry at the site of calcification linked to different calcification responses to acidification. Importantly we will show that the pH of the calcifying fluid alone is insufficient to estimate calcification responses, thus a multi-proxy approach using multiple trace elements and isotopes is required to understand how the site of calcification is affected by ocean acidification.

  15. Caracterização físico-química e microestrutural de conchas de moluscos bivalves provenientes de cultivos da região litorânea da ilha de Santa Catarina Physical chemistry and micro structural characterization of shells of bivalve mollusks from sea farmer around the Santa Catarina island

    Directory of Open Access Journals (Sweden)

    Denyo Silva

    2010-01-01

    Full Text Available Samples of shells of oysters and mussels from sea farm around the Santa Catarina Island in south Brazil were collected and analyzed by DRX, FRX, SEM, CHN-S, FTIR, TG, AAS/Flame and AAS /GF. The results showed that the crystalline structure of mussel's shells is mainly formed by aragonite and the oyster's shells by calcite. The calcium percentage in both shells species was in the range of 33 to 35% and also 850 and 1200 mg/kg of strontium was detected in the shells of oysters and mussels, respectively. The content of organic matter was larger in the mussel's shells and the thermal degradation of both shells species occurred by three events at different temperatures from 250 to 830 ºC.

  16. Shock-induced devolatilization of calcite

    Science.gov (United States)

    Boslough, M. B.; Ahrens, T. J.; Vizgirda, J.; Becker, R. H.; Epstein, S.

    1982-01-01

    Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

  17. Determination of calcium carbonate and sodium carbonate melting curves up to Earth's transition zone pressures with implications for the deep carbon cycle

    Science.gov (United States)

    Li, Zeyu; Li, Jie; Lange, Rebecca; Liu, Jiachao; Militzer, Burkhard

    2017-01-01

    Melting of carbonated eclogite or peridotite in the mantle influences the Earth's deep volatile cycles and bears on the long-term evolution of the atmosphere. Existing data on the melting curves of calcium carbonate (CaCO3) and sodium carbonate (Na2CO3) are limited to 7 GPa and therefore do not allow a full understanding of carbon storage and cycling in deep Earth. We determined the melting curves of CaCO3 and Na2CO3 to the pressures of Earth's transition zone using a multi-anvil apparatus. Melting was detected in situ by monitoring a steep and large increase in ionic conductivity, or inferred from sunken platinum markers in recovered samples. The melting point of CaCO3 rises from 1870 K at 3 GPa to ∼2000 K at 6 GPa and then stays within 50 K of 2000 K between 6 and 21 GPa. In contrast, the melting point of Na2CO3 increases continuously from ∼1123 K at 3 GPa to ∼1950 K at 17 GPa. A pre-melting peak in the alternating current through solid CaCO3 is attributed to the transition from aragonite to calcite V. Accordingly the calcite V-aragonite-liquid invariant point is placed at 13 ± 1 GPa and 1970 ± 40 K, with the Clapeyron slope of the calcite V to aragonite transition constrained at ∼70 K/GPa. The experiments on CaCO3 suggest a slight decrease in the melting temperature from 8 to 13 GPa, followed by a slight increase from 14 to 21 GPa. The negative melting slope is consistent with the prediction from our ab initio simulations that the liquid may be more compressible and become denser than calcite V at sufficiently high pressure. The positive melting slope at higher pressures is supported by the ab initio prediction that aragonite is denser than the liquid at pressures up to 30 GPa. At transition zone pressures the melting points of CaCO3 are comparable to that of Na2CO3 but nearly 400 K and 500 K lower than that of MgCO3. The fusible nature of compressed CaCO3 may be partially responsible for the majority of carbonatitic melts found on Earth's surface

  18. Stable isotopes (δ 18O and δ 13C), trace and minor element compositions of Recent scleractinians and Last Glacial bivalves at the Santa Maria di Leuca deep-water coral province, Ionian Sea

    Science.gov (United States)

    Correa, Matthias López; Montagna, Paolo; Vendrell-Simón, Begoña; McCulloch, Malcolm; Taviani, Marco

    2010-03-01

    The aragonitic skeletons of bathyal cold-water corals have a high potential as geochemical in situ archives for paleoceanography. Oxygen isotopes and stable carbon isotopes (δ 18O and δ 13C) have been analyzed, as well as trace and minor element compositions (e.g. Mg/Ca, Sr/Ca, U/Ca, B/Ca and P/Ca) in Lophelia pertusa, one of the most important frame-builders at the Santa Maria di Leuca (SML) deep-water coral hotspot in the Central Mediterranean. The Apulian Bank is swept by strong currents of the Adriatic Deep Water Outflow. The temperature of 13.9 °C is the highest temperature recorded for L. pertusa and provides an important end-member of environmental conditions for geochemical analyses on living Atlantic and Mediterranean cold-water corals. Temperature and salinity (38.77 PSU) are stable throughout the year, and thus virtually no changes should be observed in the stable oxygen isotope signal—if the coral precipitates its skeleton in equilibrium with seawater. We measured various marine properties, such as the seawater oxygen isotope composition (δ 18O sw), stable carbon isotope composition (δ 13C DIC) of dissolved inorganic carbon (DIC), and dissolved inorganic nutrient concentrations (PO 4, NO 3, NO 2, NH 3 and SiO 2). Bottom water at the coral sites shows a mean oxygen isotope composition of 1.47‰ δ 18O sw-VSMOW, and δ 13C DIC showed a mean of 1.1‰ VPDB. A section of a living L. pertusa with a thick theca calcification was probed with a Merchantek MicroMill at a high spatial sampling resolution with 10 samples per 1 mm. This reduced the signal-smoothing inherent to conventional sampling. The δ 18O ag of coral aragonite ranges between -2.0‰ and +2.8‰ VPDB and the δ 13C ag ranges between -7.77‰ and +1.47‰ VPDB. The Gaussian data distribution for both parameters, including heavy equilibrium values, suggests the completeness of the captured isotopic variability. The strict linear correlation of δ 13C and δ 18O displays a strong 'kinetic

  19. Eutrophication-induced acidification of coastal waters in the northern Gulf of Mexico: Insights into origin and processes from a coupled physical-biogeochemical model

    Science.gov (United States)

    Laurent, Arnaud; Fennel, Katja; Cai, Wei-Jun; Huang, Wei-Jen; Barbero, Leticia; Wanninkhof, Rik

    2017-01-01

    Nutrient inputs from the Mississippi/Atchafalaya River system into the northern Gulf of Mexico promote high phytoplankton production and lead to high respiration rates. Respiration coupled with water column stratification results in seasonal summer hypoxia in bottom waters on the shelf. In addition to consuming oxygen, respiration produces carbon dioxide (CO2), thus lowering the pH and acidifying bottom waters. Here we present a high-resolution biogeochemical model simulating this eutrophication-driven acidification and investigate the dominant underlying processes. The model shows the recurring development of an extended area of acidified bottom waters in summer on the northern Gulf of Mexico shelf that coincides with hypoxic waters. Not reported before, acidified waters are confined to a thin bottom boundary layer where the production of CO2 by benthic metabolic processes is dominant. Despite a reduced saturation state, acidified waters remain supersaturated with respect to aragonite.

  20. The early Holocene humid period in the Tayma palaeolake, NW Arabian Peninsula -- A high-resolution micro-facies and geochemical approach

    Science.gov (United States)

    Neugebauer, Ina; Plessen, Birgit; Dinies, Michèle; Engel, Max; Tjallingii, Rik; Brauer, Achim

    2016-04-01

    The Tayma palaeolake is a rare archive of the early Holocene humid period in northern Arabia (Dinies et al. 2015; Engel et al. 2012). Here we present a ca. 1 m thick and 500 years spanning annually laminated sediment section that was deposited in the centre of the former lake from ca. 8500 to 8000 calibrated years (cal. yrs) BP, as determined by AMS 14C dating of pollen concentrates (Dinies et al. 2015). High-resolution micro-facies analyses based on thin section microscopy, μXRF element scanning, δ18Ocarb and δ13Ccarb measurements on single carbonate laminae, as well as geochemical measurements on bulk samples for TOC, CaCO3, C/N ratio, δ18Ocarb, δ13Ccarb, δ13Corg and δ15N determination were performed in order to investigate the sedimentological and geochemical changes along the varved sequence in great detail. The finely laminated marl sediments are mainly composed of sub-mm thick laminae of endogenic aragonite, organic matter and diatoms, as well as occasional, often graded silt-clay layers. Following an early lake phase from ca. 8700 to 8500 cal. yrs BP characterized by coarsely laminated, presumably non-annual marl sediments that are rich in ostracods, three main varved phases can be distinguished within the investigated section: (1) aragonitic-organic varves from ca. 8500 to 8300 cal. yrs BP, (2) diatom-organic varves from ca. 8300 to 8100 cal. yrs BP that frequently include aragonite laminae and occasionally gastropod and ostracod shells, and (3) organic varves from ca. 8100 to 8000 cal. yrs BP with decreasing diatom and aragonite laminae and an increasing frequency of gypsum layers. After this period, gypsum becomes abundant and fine lamination appears only sporadically. In addition, we observe increasing trends of TOC, C/N and δ13Ccarb and decreasing δ18Ocarb during phase 1 and excess δ18Ocarb, δ13Ccarb and TOC values during phase 2, pointing towards the maximum lake productivity and increased seasonal precipitation. We interpret this

  1. Corals concentrate dissolved inorganic carbon to facilitate calcification.

    Science.gov (United States)

    Allison, Nicola; Cohen, Itay; Finch, Adrian A; Erez, Jonathan; Tudhope, Alexander W

    2014-01-01

    The sources of dissolved inorganic carbon (DIC) used to produce scleractinian coral skeletons are not understood. Yet this knowledge is essential for understanding coral biomineralization and assessing the potential impacts of ocean acidification on coral reefs. Here we use skeletal boron geochemistry to reconstruct the DIC chemistry of the fluid used for coral calcification. We show that corals concentrate DIC at the calcification site substantially above seawater values and that bicarbonate contributes a significant amount of the DIC pool used to build the skeleton. Corals actively increase the pH of the calcification fluid, decreasing the proportion of DIC present as CO2 and creating a diffusion gradient favouring the transport of molecular CO2 from the overlying coral tissue into the calcification site. Coupling the increases in calcification fluid pH and [DIC] yields high calcification fluid [CO3(2-)] and induces high aragonite saturation states, favourable to the precipitation of the skeleton.

  2. Seep-carbonate lamination controlled by cyclic particle flux

    Science.gov (United States)

    Himmler, Tobias; Bayon, Germain; Wangner, David; Enzmann, Frieder; Peckmann, Jörn; Bohrmann, Gerhard

    2016-11-01

    Authigenic carbonate build-ups develop at seafloor methane-seeps, where microbially mediated sulphate-dependent anaerobic oxidation of methane facilitates carbonate precipitation. Despite being valuable recorders of past methane seepage events, their role as archives of atmospheric processes has not been examined. Here we show that cyclic sedimentation pulses related to the Indian monsoon in concert with authigenic precipitation of methane-derived aragonite gave rise to a well-laminated carbonate build-up within the oxygen minimum zone off Pakistan (northern Arabian Sea). U-Th dating indicates that the build-up grew during past ~1,130 years, creating an exceptional high-resolution archive of the Indian monsoon system. Monsoon-controlled formation of seep-carbonates extends the known environmental processes recorded by seep-carbonates, revealing a new relationship between atmospheric and seafloor processes.

  3. Nighttime dissolution in a temperate coastal ocean ecosystem increases under acidification.

    Science.gov (United States)

    Kwiatkowski, Lester; Gaylord, Brian; Hill, Tessa; Hosfelt, Jessica; Kroeker, Kristy J; Nebuchina, Yana; Ninokawa, Aaron; Russell, Ann D; Rivest, Emily B; Sesboüé, Marine; Caldeira, Ken

    2016-03-18

    Anthropogenic emissions of carbon dioxide (CO2) are causing ocean acidification, lowering seawater aragonite (CaCO3) saturation state (Ω arag), with potentially substantial impacts on marine ecosystems over the 21(st) Century. Calcifying organisms have exhibited reduced calcification under lower saturation state conditions in aquaria. However, the in situ sensitivity of calcifying ecosystems to future ocean acidification remains unknown. Here we assess the community level sensitivity of calcification to local CO2-induced acidification caused by natural respiration in an unperturbed, biodiverse, temperate intertidal ecosystem. We find that on hourly timescales nighttime community calcification is strongly influenced by Ω arag, with greater net calcium carbonate dissolution under more acidic conditions. Daytime calcification however, is not detectably affected by Ω arag. If the short-term sensitivity of community calcification to Ω arag is representative of the long-term sensitivity to ocean acidification, nighttime dissolution in these intertidal ecosystems could more than double by 2050, with significant ecological and economic consequences.

  4. Three-dimensional distribution of polymorphs and magnesium in a calcified underwater attachment system by diffraction tomography.

    Science.gov (United States)

    Leemreize, Hanna; Almer, Jonathan D; Stock, Stuart R; Birkedal, Henrik

    2013-09-01

    Biological materials display complicated three-dimensional hierarchical structures. Determining these structures is essential in understanding the link between material design and properties. Herein, we show how diffraction tomography can be used to determine the relative placement of the calcium carbonate polymorphs calcite and aragonite in the highly mineralized holdfast system of the bivalve Anomia simplex. In addition to high fidelity and non-destructive mapping of polymorphs, we use detailed analysis of X-ray diffraction peak positions in reconstructed powder diffraction data to determine the local degree of Mg substitution in the calcite phase. These data show how diffraction tomography can provide detailed multi-length scale information on complex materials in general and of biomineralized tissues in particular.

  5. Dynamics of sheet nacre formation in bivalves.

    Science.gov (United States)

    Rousseau, Marthe; Meibom, Anders; Gèze, Marc; Bourrat, Xavier; Angellier, Martine; Lopez, Evelyne

    2009-03-01

    Formation of nacre (mother-of-pearl) is a biomineralization process of fundamental scientific as well as industrial importance. However, the dynamics of the formation process is still not understood. Here, we use scanning electron microscopy and high spatial resolution ion microprobe depth-profiling to image the full three-dimensional distribution of organic materials around individual tablets in the top-most layer of forming nacre in bivalves. Nacre formation proceeds by lateral, symmetric growth of individual tablets mediated by a growth-ring rich in organics, in which aragonite crystallizes from amorphous precursors. The pivotal role in nacre formation played by the growth-ring structure documented in this study adds further complexity to a highly dynamical biomineralization process.

  6. Sr/Ca and {delta} {sup 18}O ratios measured from Acropora nobilis and Porites lutea: Is Sr/Ca paleo-thermometry always reliable?; Mesures conjointes des rapports Sr/Ca et {delta} {sup 18}O effectuees sur Acropora nobilis et Porites lutea: le paleothermometre Sr/Ca est-il toujours fiable?

    Energy Technology Data Exchange (ETDEWEB)

    Boiseau, M.; Trupin, L.; Juillet-Leclerc, A. [Centre National de la Recherche Scientifique (CNRS), 91 - Gif-sur-Yvette (France). Centre des Faibles Radioactivites; Cornu, H. [Centre National de la Recherche Scientifique (CNRS), Lab. d' oceanographie dynamique et de climatologie, Unite mixte CNRS-ORSTOM-UPCM, 75 - Paris (France)

    1997-11-01

    We measured the Sr/Ca and {sup 18}O/{sup 16}O ratios in Acropora nobilis and Porites lutea, from the Mayotte lagoon. As the variations of {delta}{sup 18}O{sub seawater} are negligible, coral {delta}{sup 18}O{sub aragonite} reflects only seasonal temperature variations. While there is a good agreement between the Sr/Ca ratio and {delta}{sup 18}O for Acropora nobilis, it is not the case for Porites lutea. Coral biological and environmental parameters cannot explain the discrepancies between Sr/Ca ratios and isotopic measurements. However transport mechanisms of Sr{sup 2+} and Ca{sup 2+} and the presence of two mineralogical structures of strontium may affect the Sr/Ca ratio.

  7. The metabolic response of pteropods to acidification reflects natural CO2-exposure in oxygen minimum zones

    Directory of Open Access Journals (Sweden)

    K. F. Wishner

    2012-02-01

    Full Text Available Shelled pteropods (Thecosomata are a group of holoplanktonic mollusks that are believed to be especially sensitive to ocean acidification because their aragonitic shells are highly soluble. Despite this concern, there is very little known about the physiological response of these animals to conditions of elevated carbon dioxide. This study examines the oxygen consumption and ammonia excretion of five pteropod species, collected from tropical regions of the Pacific Ocean, to elevated levels of carbon dioxide (0.10%, 1000 ppm. Our results show that pteropods that naturally migrate into oxygen minimum zones, such as Hyalocylis striata, Clio pyramidata, Cavolinia longirostris and Creseis virgula, were not affected by carbon dioxide at the levels and duration tested. Diacria quadridentata, which does not migrate, responds to high carbon dioxide conditions with reduced oxygen consumption and ammonia excretion. This indicates that the natural chemical environment of individual species may influence their resilience to ocean acidification.

  8. Organic matter of fossil origin in the amberine speleothems from El Soplao Cave (Cantabria, Northern Spain

    Directory of Open Access Journals (Sweden)

    Gázquez Fernando

    2012-01-01

    Full Text Available Unusual amberine-coloured speleothems were recently found in El Soplao Cave (Cantabria, Spain. Chromophore elements such as Fe, Mn, Cd, Co or Ti were not present in significant quantities. Rather, our data show that their colour comes from leachates of fossilized organic material hosted in the carbonaceous Urgonian facies of the host rock. These leachates are related to the Cretaceous amber deposit that has been recently discovered in the vicinity of El Soplao Cave. The presence of humic and fulvic acids of fossil origin were confirmed by IR and Raman spectroscopic analysis of the carbonaceous strata and the speleothems. In addition, the mineralogy of the amberine speleothems was studied. Alternating bands made of calcite and aragonite reveal that periods of humidity and aridity occurred within the cave during the speleothem genesis.

  9. Geochemistry of Precambrian carbonates - 3-shelf seas and non-marine environments of the Archean

    Science.gov (United States)

    Veizer, Jan; Clayton, R. N.; Hinton, R. W.; Von Brunn, Victor; Mason, T. R.

    1990-01-01

    Samples from the Pangola and Ventersdorp Supergroups (Kaapvaal Craton, South Africa) and from the Fortescue and Hamersley Groups (Pilbara Block, Australia) were analyzed, using XRF, AAS, and isotope-analysis techniques to investigate the mineralogical, chemical, and isotopic features of these representatives of contemporary shelf carbonates (Pangola and Hamersley samples) and nonmarine carbonates (the Ventersdorp and Fortescue samples). Results show that, mineralogically, the shelf carbonates are almost exclusively dolostones, while the lacustrine facies are predominantly limestones. Geological, trace-element, and oxygen-isotope results of the shelf carbonates suggest that their original mineralogy may have been aragonite, and that the Pangola dolostones may represent a direct dolomitization product of this precursor. By contrast, the stabilization of the Hamersley carbonates may have involved an additional step of transformation of a metastable precursor into limestone.

  10. The Ring Monstrance from the Loreto treasury in Prague: handheld Raman spectrometer for identification of gemstones.

    Science.gov (United States)

    Jehlička, Jan; Culka, Adam; Baštová, Markéta; Bašta, Petr; Kuntoš, Jaroslav

    2016-12-13

    A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and unambiguous detection of common gemstones mounted in complex jewels. Here, complex religious artefacts and the Ring Monstrance from the Loreto treasury (Prague, Czech Republic; eighteenth century) were investigated. These discriminations are based on the very good correspondence of the wavenumbers of the strongest Raman bands of the minerals. Very short laser illumination times and efficient collection of scattered light were sufficient to obtain strong diagnostic Raman signals. The following minerals were documented: quartz and its varieties, beryl varieties (emerald), corundum varieties (sapphire), garnets (almandine, grossular), diamond as well as aragonite in pearls. Miniature Raman spectrometers can be recommended for common gemmological work as well as for mineralogical investigations of jewels and cultural heritage objects whenever the antiquities cannot be transported to a laboratory.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

  11. Major geochemical processes in the evolution of carbonate-Aquifer systems

    Science.gov (United States)

    Hanshaw, B.B.; Back, W.

    1979-01-01

    As a result of recent advances by carbonate petrologists and geochemists, hydrologists are provided with new insights into the origin and explanation of many aquifer characteristics and hydrologic phenomena. Some major advances include the recognition that: (1) most carbonate sediments are of biological origin; (2) they have a strong bimodal size-distribution; and (3) they originate in warm shallow seas. Although near-surface ocean water is oversaturated with respect to calcite, aragonite, dolomite and magnesite, the magnesium-hydration barrier effectively prevents either the organic or inorganic formation of dolomite and magnesite. Therefore, calcareous plants and animals produce only calcite and aragonite in hard parts of their bodies. Most carbonate aquifers that are composed of sand-size material have a high initial porosity; the sand grains that formed these aquifers originated primarily as small shells, broken shell fragments of larger invertebrates, or as chemically precipitated oolites. Carbonate rocks that originated as fine-grained muds were initially composed primarily of aragonite needles precipitated by algae and have extremely low permeability that requires fracturing and dissolution to develop into aquifers. Upon first emergence, most sand beds and reefs are good aquifers; on the other hand, the clay-sized carbonate material initially has high porosity but low permeability, a poor aquifer property. Without early fracture development in response to influences of tectonic activity these calcilutites would not begin to develop into aquifers. As a result of selective dissolution, inversion of the metastable aragonite to calcite, and recrystallization, the porosity is collected into larger void spaces, which may not change the overall porosity, but greatly increases permeability. Another major process which redistributes porosity and permeability in carbonates is dolomitization, which occurs in a variety of environments. These environments include back

  12. Combining µXANES and µXRD mapping to analyse the heterogeneity in calcium carbonate granules excreted by the earthworm Lumbricus terrestris.

    Science.gov (United States)

    Brinza, Loredana; Schofield, Paul F; Hodson, Mark E; Weller, Sophie; Ignatyev, Konstantin; Geraki, Kalotina; Quinn, Paul D; Mosselmans, J Frederick W

    2014-01-01

    The use of fluorescence full spectral micro-X-ray absorption near-edge structure (µXANES) mapping is becoming more widespread in the hard energy regime. This experimental method using the Ca K-edge combined with micro-X-ray diffraction (µXRD) mapping of the same sample has been enabled on beamline I18 at Diamond Light Source. This combined approach has been used to probe both long- and short-range order in calcium carbonate granules produced by the earthworm Lumbricus terrestris. In granules produced by earthworms cultured in a control artificial soil, calcite and vaterite are observed in the granules. However, granules produced by earthworms cultivated in the same artificial soil amended with 500 p.p.m. Mg also contain an aragonite. The two techniques, µXRD and µXANES, probe different sample volumes but there is good agreement in the phase maps produced.

  13. Study and characterization of ceramic materials from natural origin for application in jewellery design using laser texturing as innovation; Estudo e caracterizacao de materiais ceramicos de origem natural para aplicacao no design de joias utilizando a texturizacao a laser como diferencial de inovacao

    Energy Technology Data Exchange (ETDEWEB)

    Elesbao, T.R.; Carus, L.A.; Tabarelli, A.C.; Vieira, R.P.; Takimi, A.S., E-mail: taianeelesbao@hotmail.com [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Departamento de Materiais

    2012-07-01

    Technological development has been largely responsible for changes in the jewelry market. Seeking to contribute to the development of new products, this study analyzed the technique of laser texturing, aiming to add commercial and aesthetic values to the mother of pearl, material used in the jewelry field. The methodology was divided into physico-chemical characterization of the mother-of-pearl and of the resulting residue of laser texturing and analysis of the interaction of laser with the surface of the mother-of-pearl. The characterizations carried out were: Infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Results indicate that the studied material is composed mainly by the aragonite crystal phase, different from that resulting residue from texturing process. Although the process remove some of the gem material, the effect water characteristic of the mother-of-pearl is maintained, suggesting that technology combined with research and design can increase the value of this material. (author)

  14. Relationship between ionoluminescence emission and bond distance (M-O) in carbonates

    Energy Technology Data Exchange (ETDEWEB)

    Calvo del Castillo, H. [Universidad Autonoma de Madrid, Fac. Ciencias, Dpto. Qca. Agricola, Geologia y Geoquimica, 28049, Cantoblanco, Madrid (Spain); Sil, J.L. Ruvalcaba [Universidad Nacional Autonoma de Mexico, Instituto de Fisica, 04510 Ciudad Universitaria, Mexico, DF (Mexico)]. E-mail: sil@fisica.unam.mx; Alvarez, M.A. [Universidad de Sevilla, Dpto. Qca. Agricola y Cristalografia, Fac. de Quimica, Sevilla (Spain); Beneitez, P. [Universidad Autonoma de Madrid, Fac. Ciencias, Dpto. Qca.-Fisica Aplicada, 28049, Cantoblanco, Madrid (Spain); Millan, M.A. [Universidad Autonoma de Madrid, Fac. Ciencias, Dpto. Qca. Agricola, Geologia y Geoquimica, 28049, Cantoblanco, Madrid (Spain); Calderon, T. [Universidad Autonoma de Madrid, Fac. Ciencias, Dpto. Qca. Agricola, Geologia y Geoquimica, 28049, Cantoblanco, Madrid (Spain)

    2006-08-15

    Ionoluminescence emission spectra induced by 2 MeV protons are reported for a range of carbonates. A major feature in these spectra, are the Mn{sup 2+} luminescence centres that appear within all the samples. The emission wavelengths for the Mn{sup 2+} are linearly correlated to the metal-oxygen bonding length, both in rhombohedral and orthorhombic lattices for the minerals studied. The Mn{sup 2+} band, is in each case related to the corresponding energy level diagram of the mineral's crystal lattice, as this ion perturbs the crystal field term, which for emission in rhombohedral calcite has a value of 1000 cm{sup -1}, and for orthorhombic sites in aragonite is 1200 cm{sup -1}.

  15. Structure and composition of the septal nacreous layer of Nautilus macromphalus L. (Mollusca, Cephalopoda).

    Science.gov (United States)

    Dauphin, Yannicke

    2006-01-01

    The nacreous layer of Mollusca is the best-known aragonitic structure and is the usual model for biomineralization. However, data are based on less than 10 species. In situ observations of the septal nacreous layer of the cephalopod Nautilus shell has revealed that the tablets are composed of acicular laths. These laths are composed of round nanograins surrounded by an organic sheet. No hole has been observed in the decalcified interlamellar membranes. A set of combined analytical data shows that the organic matrices extracted from the nacreous layer are glycoproteins. In both soluble and insoluble matrices, S amino acids are rare and the soluble organic matrices have a higher sulfated sugar content than the insoluble matrices. It is possible that the observed differences in the structure and composition of the nacreous layers of the outer wall and septa of the Nautilus shell have a dual origin: evolution and functional adaptation. However, we have no appropriate data as yet to answer this question.

  16. Fish as major carbonate mud producers and missing components of the tropical carbonate factory

    Science.gov (United States)

    Perry, Chris T.; Salter, Michael A.; Harborne, Alastair R.; Crowley, Stephen F.; Jelks, Howard L.; Wilson, Rod W.

    2011-01-01

    Carbonate mud is a major constituent of recent marine carbonate sediments and of ancient limestones, which contain unique records of changes in ocean chemistry and climate shifts in the geological past. However, the origin of carbonate mud is controversial and often problematic to resolve. Here we show that tropical marine fish produce and excrete various forms of precipitated (nonskeletal) calcium carbonate from their guts ("low" and "high" Mg-calcite and aragonite), but that very fine-grained (mostly 4 mole % MgCO3) are their dominant excretory product. Crystallites from fish are morphologically diverse and species-specific, but all are unique relative to previously known biogenic and abiotic sources of carbonate within open marine systems. Using site specific fish biomass and carbonate excretion rate data we estimate that fish produce ~6.1 x 106 kg CaCO3/year across the Bahamian archipelago, all as mud-grade (the factories function both today and in the past.

  17. Microfacies and diagenesis of the reefal limestone, Callovian Tuwaiq Mountain Limestone Formation, central Saudi Arabia

    Science.gov (United States)

    EL-Sorogy, Abdelbaset S.; Almadani, Sattam A.; Al-Dabbagh, Mohammad E.

    2016-03-01

    In order to document the microfacies and diagenesis of the reefal limestone in the uppermost part of the Callovian Tuwaiq Mountain Limestone Formation at Khashm Al-Qaddiyah area, central Saudi Arabia, scleractinian corals and rock samples were collected and thin sections were prepared. Coral framestone, coral floatstone, pelloidal packstone, bioclastic packstone, bioclastic wacke/packstone, algal wackestone and bioclastic foraminiferal wacke/packstone were the recorded microfacies types. Cementation, recrystallization, silicification and dolomitization are the main diagenetic alterations affected the aragonitic skeletons of scleractinian corals. All coral skeletons were recrystallized, while some ones were dolomitized and silicified. Microfacies types, as well as the fossil content of sclearctinian corals, bivalves, gastropods, brachiopods and foraminifera indicated a deposition in environments ranging from shelf lagoon with open circulation in quiet water below wave base to shallow reef flank and organic build up for the uppermost reefal part of the Tuwaiq Formation in the study area.

  18. Synthetic nacre by predesigned matrix-directed mineralization

    Science.gov (United States)

    Mao, Li-Bo; Gao, Huai-Ling; Yao, Hong-Bin; Liu, Lei; Cölfen, Helmut; Liu, Gang; Chen, Si-Ming; Li, Shi-Kuo; Yan, You-Xian; Liu, Yang-Yi; Yu, Shu-Hong

    2016-10-01

    Although biomimetic designs are expected to play a key role in exploring future structural materials, facile fabrication of bulk biomimetic materials under ambient conditions remains a major challenge. Here, we describe a mesoscale “assembly-and-mineralization” approach inspired by the natural process in mollusks to fabricate bulk synthetic nacre that highly resembles both the chemical composition and the hierarchical structure of natural nacre. The millimeter-thick synthetic nacre consists of alternating organic layers and aragonite platelet layers (91 weight percent) and exhibits good ultimate strength and fracture toughness. This predesigned matrix-directed mineralization method represents a rational strategy for the preparation of robust composite materials with hierarchically ordered structures, where various constituents are adaptable, including brittle and heat-labile materials.

  19. Monthly sea surface temperature records reconstructed by δ18O of reef-building coral in the east of Hainan Island,South China Sea

    Institute of Scientific and Technical Information of China (English)

    HE; Xuexian(何学贤); LIU; Dunyi(刘敦一); PENG; Zicheng(彭子成); LIU; Weiguo(刘卫国)

    2002-01-01

    Stable oxygen isotopic compositions of a coral colony of Porites lutea obtained on a core allowed the reconstruction of a 56-a (1943-1998) proxy record of the sea surface temperatures. This coral δ18O data are from the east of Hainan Island water (22°20′N, 110°39′E), South China Sea. The relationship between δ18O in the skeletal aragonite carbonate and the sea surface temperature (SST) is SST = -5.36 δ18OPDB-3.51 (r = 0.73, n = 470), dδ18O/d(SST) = -0.187‰/ ℃; and the thermometer was set at monthly resolution. The 56-a (1943-1998) proxy record of the sea surface temperatures reflected the same change trend in the northern part of South China Sea as the air temperature change trend in China.

  20. MINERAL BRIDGES OF NACRE AND ITS EFFECTS

    Institute of Scientific and Technical Information of China (English)

    宋凡; 白以龙

    2001-01-01

    Nacre, or mother-of-pearl, is a kind of composites of aragonite platelets sandwiched between organic materials. Its excellent mechanical properties are thought to stem from the microarchitecture that is traditionally described as a "brick and mortar" arrangement. In this paper, a new microstructure, referred to as mineral bridge in the biomineralization, is directly observed in the organic matrix layers (mortar) of nacre. This is an indication that the organic matrix layer of nacre should be treated as a three-dimensional interface and the microarchitecture of nacre ought to be considered as a "brick-bridge-mortar" structure rather than the traditional one. Experiments and analyses show that the mineral bridges not only improve the mechanical properties of the organic matrix layers but also play an important role in the pattern of the crack extension in nacre.

  1. [Study on the mechanism of liesegang pattern development during carbonating of traditional sticky rice-lime mortar].

    Science.gov (United States)

    Wei, Guo-feng; Fang, Shi-qiang; Zhang, Bing-jian; Wang, Xiao-qi; Li, Zu-guang

    2012-08-01

    Liesegang patterns in traditional sticky rice-lime mortar undergoing carbonation were investigated by means of FTIR, XRD and SEM. Results indicate that well-developed Liesegang patterns only occur in the mortar prepared with aged lime and sticky rice. The smaller Ca(OH)2 particle size in aged lime and the control of the sticky rice for the crystallization of calcium carbonate lead to the small pores in this mortar. These small pores can make Ca2+ and CO3(2-) highly supersaturated, which explains the reason why Liesegang pattern developed in the sticky rice-aged lime mortar. The formed metastable aragonite proves that Liesegang pattern could be explained based on the post-nucleation theory.

  2. Synchrotron Radiation X-Ray Fluorescence nanoanalyses of the metallome of a ~3.3 Ga-old microbial biofilm from the Barberton greenstone belt, South Africa.

    Science.gov (United States)

    Hubert, A.; Lemelle, L.; Salome, M.; Cloetens, P.; Westall, F.; Simionovici, A.

    2012-04-01

    Combining in situ nanometer-scale techniques on the fossilized Josefsdal Chert Microbial Biofilm (JCMB) reveals a distinct vertical structural and compositional organisation: the lower part is calcified as aragonite, while the upper non-calcified kerogenous layer is characterised by up to 1% sulphur [1]. The in situ analysis of all the metals as a group represents a useful microbial fingerprint [2] and we will continue to explore it. Synchrotron Radiation X-Ray Fluorescence maps of high spatial resolution (AIP Conference Proceedings, 1221, 131-138. 4. Bleuet P., et al., 2008. App. Phys. Lett., 92, 213111-1-3. 5. Golosio B., et al., 2003. Appl. Phys., 94, 145-157. 6. M. Haschke, 2003. PhD dissertation, T.U. Berlin. 7. Simionovici A. S., et al., 2010. Proceedings of the Meteoritical Society Conference, N.Y., USA. 8. Solé V.A., et al., 2006, Elsevier, 62, 63-68.

  3. Raman spectroscopy as a tool for polyunsaturated compound characterization in gastropod and limnic terrestrial shell specimens

    Science.gov (United States)

    de Oliveira, Leandra N.; de Oliveira, Vanessa E.; D'ávila, Sthefane; Edwards, Howell G. M.; de Oliveira, Luiz Fernando C.

    2013-10-01

    The colours of mollusc shells were determined using the Raman spectroscopy and these analyses suggest that the conjugated polyenes (carotenoids) and psittacofulvins are the organic pigments incorporated into their skeletal structures responsible by their colorations. The symmetric stretching vibration of the carbonate ion gives rise to a very strong Raman band at ca. 1089 cm-1 and a weak band at 705 cm-1, for all samples; the second band characterizes the aragonite as the inorganic matrix and can be used as a marker. The specimens show bands at 1523-1500 and at 1130-1119 cm-1, assigned to the ν1 and ν2 modes of the polyenic chain vibrations, respectively. Another band at 1293 cm-1, assigned to the CHdbnd CH in-plane rocking mode of the olefinic hydrogen is also observed in all samples, which reinforces the psittacofulvin compound as the main pigment present in the analyzed samples.

  4. High pressure behavior of otavite (CdCo3)

    Energy Technology Data Exchange (ETDEWEB)

    Minch, R.; Ehm, L.; Seoung, D.H.; Winkler, B.; Knorr, K.; Peters, L.; Borkowski, L.A.; Parise, J.B.; Lee, Y.; Dubrovinsky, L.; Depmeier, W.

    2010-08-24

    The high-pressure, room temperature behavior of otavite (CdCO{sub 3}) was investigated by angle-dispersive synchrotron radiation powder diffraction up to 40 GPa, Raman spectroscopy up to 23 GPa and quantum mechanical calculations based on density functional theory. The calcite-type structure of CdCO{sub 3} is stable up to at least {approx}19 GPa as shown by Raman spectroscopy. The compression mechanism was obtained from structure refinements against the diffraction data. The quantum mechanical calculations propose a calcite-aragonite phase transition to occur at about 30 GPa. The existence of a pressure-induced phase transition is supported by the Raman and diffraction experiments. Evidence for the transformation is given by broadening of X-ray reflections and external Raman bands starting from about 19 GPa in both experiments.

  5. High-precision uranium-series dating of lacustrine carbon-ates from Daihai Lake

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Ages of small aragonite samples retrieved from sediments from the Daihai Lake are determined by using the Thermal Ionization Mass Spectrometry (TIMS) technique. The ages of the samples range from (8740±601) to (10446±489) a, with a precision of 2%-3% for non-corrected dating ages and 4.7%-9.8% for corrected ages respectively, and are consistent within the deviation range. At about 10.5 ka BP, the grain-size of the sediments coarsens sharply, the frequency curves of grain-size distribution show coarse grain dominated single-double kurtosis, indicating cooling, de-creased hydrodynamic conditions and increased wind influ-ence procedure. This is in good agreement with previous results obtained from the Daihai Lake, which suggests that the climate was cold and the lake surface was shrinking. The TIMS ages of the sediments are therefore believed to be credible.

  6. Electron microscopy study of red mud after seawater neutralisation; Estudo por microscopia eletronica de transmissao de lama vermelha tratada com agua do mar

    Energy Technology Data Exchange (ETDEWEB)

    Toledo, S.P.; Kiyohara, P.K. [Universidade de Sao Paulo (IF/LME/USP), SP (Brazil); Antunes, M.L.P., E-mail: malu@sorocaba.unesp.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Sorocaba, SP (Brazil); Frost, Ray [Queensland University of Technology (United States)

    2012-07-01

    Red Mud, residue of Bayer process for extracting alumina from bauxite, is produced in large quantity. This residue is very alkaline and can cause damage to health and the environment. One way to minimize the environmental impact of this residue is neutralization by sea water. The Brazilian Red Mud was treated with sea water. It appears that the initial pH of the samples is reduced to 8. The analysis by x-ray diffraction allows to identify the formation of hydrotalcite and aragonite. The transmission electron microscopy images show that this consists of particles with dimensions between 0.02 to 2 μm. It was possible to identify by EDS/MET particles of magnesium, confirming the formation of hydrotalcite. (author)

  7. Physical basis for materials synthesis using biomineralization

    Energy Technology Data Exchange (ETDEWEB)

    De Yoreo, J; Orme, C; Dove, P; Teng, H

    2000-05-16

    -structured materials, the fundamental physical controls on carbonate biomineral formation remain poorly understood. Carbonates are formed in diverse environments almost exclusively by living organisms. These naturally occurring marine and fresh water minerals most commonly occur as the polymorphs of calcite, aragonite and vaterite which are nucleated and grown in the exoskeletons and tissues of marine and freshwater organisms ranging from simple bacteria and algae to crustaceans, molluscs, or sponges. It is known that the soluble fraction associated with mineralizing parts of organisms plays a primary role in crystal formation. In the formation of molluscan shells, this fraction is distinguished by the common presence of aspartic acid rich amino acid mixtures. It is also known that carbonates exposed to different polyamino acids exhibit different crystal habits. Belcher et al. showed that exposing growing CaCO{sub 3} crystals alternately to solutions containing polyanionic proteins associated with the aragonitic and calcitic layers of mollusc shells led to sequential switching of the crystal structure of the newly grown material between that of aragonite and calcite. Further work has demonstrated that these protein mixtures alter the morphology of the calcite growth surface and that they contain two fractions effecting growth: a step-binding fraction that inhibits step advancement on calcite surfaces, and a surface binding fraction that appears to lead to the subsequent nucleation of aragonite. Wierzbicki et al. found that polyaspartate molecules (ASP{sub 20}) bind to calcite surfaces. Finally, modeling of ASP{sub 15} binding to calcite planes predicts large binding energies for well defined orientations. This and related evidence shows that systematic relationships between crystal morphology and surface interactions with the reactive groups of the organic molecules must exist. However, the interplay between surface chemistry and the physical processes of nucleation and crystal growth

  8. Comparative genomics explains the evolutionary success of reef-forming corals

    KAUST Repository

    Bhattacharya, Debashish

    2016-05-24

    Transcriptome and genome data from twenty stony coral species and a selection of reference bilaterians were studied to elucidate coral evolutionary history. We identified genes that encode the proteins responsible for the precipitation and aggregation of the aragonite skeleton on which the organisms live, and revealed a network of environmental sensors that coordinate responses of the host animals to temperature, light, and pH. Furthermore, we describe a variety of stress-related pathways, including apoptotic pathways that allow the host animals to detoxify reactive oxygen and nitrogen species that are generated by their intracellular photosynthetic symbionts, and determine the fate of corals under environmental stress. Some of these genes arose through horizontal gene transfer and comprise at least 0.2% of the animal gene inventory. Our analysis elucidates the evolutionary strategies that have allowed symbiotic corals to adapt and thrive for hundreds of millions of years.

  9. Shell microstructure and its inheritance in the calcitic helcionellid Mackinnonia

    Directory of Open Access Journals (Sweden)

    Michael J. Vendrasco

    2015-02-01

    Full Text Available Mackinnonia davidi from the Cambrian (Series 2 of Australia has a prismatic outer shell layer and, as newly described here, a calcitic semi-nacre inner layer. The pattern is the same as in stenothecids such as Mellopegma, providing more evidence for a strong phylogenetic signal in the shell microstructure of Cambrian molluscs. In addition, calcite now appears to have been common in helcionellids and other molluscs during the early and middle Cambrian, with many species exhibiting foliated calcite. This is surprising given the dominance of aragonite in molluscs, both modern and from post-Cambrian fossil deposits with exceptional shell microstructure preservation, including localities from the Ordovician of the Cincinnati region, USA.

  10. Nacre in Molluscs from the Ordovician of the Midwestern United States

    Directory of Open Access Journals (Sweden)

    Steven D.J. Baumann

    2013-01-01

    Full Text Available Nacre was previously thought to be primitive in the Mollusca, but no convincing Cambrian examples are known. This aragonitic microstructure with crystal tablets that grow within an organic framework is thought to be the strongest, most fracture-resistant type of shell microstructure. Fossils described herein from the Ordovician of Iowa, Indiana, and Ohio provide supporting evidence for the hypothesis that sometime between the middle Cambrian and late Ordovician, nacre originated in cephalopod, bivalve, and possibly gastropod lineages. The correlation of independent origins of fracture-resistant nacre with increasing shell-crushing abilities of predators during the Cambrian-Ordovician suggests an early pulse in the evolutionary arms race between predators and molluscan prey.

  11. Decadal trends in air-sea CO2 exchange in the Ross Sea (Antarctica)

    Science.gov (United States)

    Tagliabue, Alessandro; Arrigo, Kevin R.

    2016-05-01

    Highly productive Antarctic shelf systems, like the Ross Sea, play important roles in regional carbon budgets, but the drivers of local variations are poorly quantified. We assess the variability in the Ross Sea carbon cycle using a regional physical-biogeochemical model. Regionally, total partial pressure of CO2 (pCO2) increases are largely controlled by the biological pump and broadly similar to those in the offshore Southern Ocean. However, this masks substantial local variability within the Ross Sea, where interannual fluctuations in total pCO2 are driven by the biological pump and alkalinity, whereas those for anthropogenic pCO2 are related to physical processes. Overall, the high degree of spatial variability in the Ross Sea carbon cycle causes extremes in aragonite saturation that can be as large as long-term trends. Therefore, Antarctic shelf polynya systems like the Ross Sea will be strongly affected by local processes in addition to larger-scale phenomena.

  12. Dolomitization in a mixing zone of near-seawater composition, Late Pleistocene, northeastern Yucatan Peninsula

    Science.gov (United States)

    Ward, W. C.; Halley, Robert B.

    1985-01-01

    Patches of dolomite occur in cores of reefal limestone from the shallow subsurface on the northeastern coast of the Yucatan Peninsula. This limestone accumulated during an interglacial high stand of sea level about 200,000 years ago. Dolomitization was preceded by freshwater diagenesis, including precipitation of sparry calcite cement, stabilization of Mg-calcitic skeletal fragments, and partial dissolution of aragonitic components. This suggests a predolomitization lowering of sea level with the consequent freshening of pore water. The subsequent precipitation of dolomite indicates a return to high sea level with the consequent increase in Mg/Ca ratio of pore water. Dolomitization took place during a brief high stand of sea level, either shortly after deposition about 200,000 yr BP, r, more likely, about 125,000 yr BP.

  13. Alternative diagenetic models for cretaceous talus deposits, Deep Sea Drilling Project Site 536, Gulf of Mexico: Chapter 8 in Initial reports of the Deep Sea Drilling Project

    Science.gov (United States)

    Halley, Robert B.; Pierson, B. J.; Schlager, Wolfgang

    1984-01-01

    Talus deposits recovered from Site 536 show evidence of aragonite dissolution, secondary porosity development, and calcite cementation. Although freshwater diagenesis could account for the petrographic features of the altered talus deposits, it does not uniquely account for isotopic or trace-element characteristics. Also, the hydrologic setting required for freshwater alteration is not easily demonstrated for the Campeche Bank. A mixing-zone model does not account for the available trace-element data, but does require somewhat less drastic assumptions about the size of the freshwater lens. Although a seawater (bottom-water) alteration model requires no hydrologic difficulties, unusual circumstances are required to account for the geochemical characteristics of the talus deposits using this model.

  14. Radon, carbon dioxide and fault displacements in central Europe related to the Tōhoku Earthquake.

    Science.gov (United States)

    Briestenský, M; Thinová, L; Praksová, R; Stemberk, J; Rowberry, M D; Knejflová, Z

    2014-07-01

    Tectonic instability may be measured directly using extensometers installed across active faults or it may be indicated by anomalous natural gas concentrations in the vicinity of active faults. This paper presents the results of fault displacement monitoring at two sites in the Bohemian Massif and Western Carpathians. These data have been supplemented by radon monitoring in the Mladeč Caves and by carbon dioxide monitoring in the Zbrašov Aragonite Caves. A significant period of tectonic instability is indicated by changes in the fault displacement trends and by anomalous radon and carbon dioxide concentrations. This was recorded around the time of the catastrophic MW=9.0 Tōhoku Earthquake, which hit eastern Japan on 11 March 2011. It is tentatively suggested that the Tōhoku Earthquake in the Pacific Ocean and the unusual geodynamic activity recorded in the Bohemian Massif and Western Carpathians both reflect contemporaneous global tectonic changes.

  15. Crystallization in organo-mineral micro-domains in the crossed-lamellar layer of Nerita undata (Gastropoda, Neritopsina).

    Science.gov (United States)

    Nouet, Julius; Baronnet, Alain; Howard, Lauren

    2012-02-01

    Crossed-lamellar shell microstructure consists of a sophisticated arrangement of interspersed lamellae, which is very commonly found in Gastropoda or Bivalvia shell layers. Its smallest constitutive microstructural units are usually described as sub-micrometric fibers, or rods, and form very ordered and regular patterns. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) imaging confirms the presence of even smaller building units in the form of organo-mineral granules, and we further investigate their internal structure within aragonite crossed-lamellar internal layer of Nerita undata (Gastropoda, Neritopsina) shell. Their coalescence may have controlled anisotropically the propagation of the crystallographic coherence through this complex microstructure, as suggested by the propagation of the microtwinning pattern between neighboring granules.

  16. Cryogenic Origin for Mars Analog Carbonates in the Bockfjord Volcanic Complex Svalbard (Norway)

    Science.gov (United States)

    Amundsen, H. E. F.; Benning, L.; Blake, D. F.; Fogel, M.; Ming, D.; Skidmore, M.; Steele, A.

    2011-01-01

    The Sverrefjell and Sigurdfjell eruptive centers in the Bockfjord Volcanic Complex (BVC) on Svalbard (Norway) formed by subglacial eruptions ca. 1 Ma ago. These eruptive centers carry ubiquitous magnesian carbonate deposits including dolomitemagnesite globules similar to those in the Martian meteorite ALH84001. Carbonates in mantle xenoliths are dominated by ALH84001 type carbonate globules that formed during quenching of CO2-rich mantle fluids. Lava hosted carbonates include ALH84001 type carbonate globules occurring throughout lava vesicles and microfractures and massive carbonate deposits associated with vertical volcanic vents. Massive carbonates include < or equal 5 cm thick magnesite deposits protruding downwards into clear blue ice within volcanic vents and carbonate cemented lava breccias associated with volcanic vents. Carbonate cements comprise layered deposits of calcite, dolomite, huntite, magnesite and aragonite associated with ALH84001 type carbonate globules lining lava vesicles. Combined Mossbauer, XRD and VNIR data show that breccia carbonate cements at Sverrefjell are analog to Comanche carbonates at Gusev crater.

  17. Microwave-assisted synthesis of spheroidal vaterite CaCO 3 in ethylene glycol-water mixed solvents without surfactants

    Science.gov (United States)

    Chen, Yinxia; Ji, Xianbing; Wang, Xiaobo

    2010-10-01

    Spheroidal vaterite CaCO 3 composed of irregular nanoparticals have been synthesized by a fast microwave-assisted method. The structures are fabricated by the reaction of Ca(CH 3COO) 2 with (NH 4) 2CO 3 at 90 °C in ethylene glycol-water mixed solvents without any surfactants. The diameters of the spheroidal vaterite CaCO 3 range from 1 to 2 μm, and the average size of the nanoparticals is about 70 nm. Bundle-shaped aragonite and rhombohedral calcite are also obtained by adjusting the experimental parameters. Our experiments show that the ratio of ethylene glycol to water, microwave power, reaction time, and two sources of ammonium ions and acetate anions are key parameters for the fabrication of spheroidal vaterite CaCO 3. A possible growth mechanism for the spheroidal structures has been proposed, which suggests that the spheroidal vaterite CaCO 3 is formed by an aggregation mechanism.

  18. Hydrogeochemical Simulation of Water-Rock Interaction Under Water Flood Recovery in Renqiu Oilfield, Hebei Province, China

    Institute of Scientific and Technical Information of China (English)

    冯启言; 韩宝平

    2002-01-01

    Hydrogeochemical simulation is an effective method to study water-rock interaction.In this paper, PHREEQM was used for the simulation of water-rock interaction under water flooding in the Renqiu Oilfield. Calculated results revealed that when fresh water was injected into the reservoir, Cl- and Na+ would decrease without involvement in water-rock interaction.Erosion to dolomite will lead to an increase in Ca2 + , Mg2 + and CaHCO3+. Saturation index of calcite and aragonite decreased first and then increased. With fresh water accounting for up to 70 %, mixed water has the strongest erosion ability. Deoiled water has erosion ability under high temperature and high partial pressure of CO2. Pyrite and gypsum were sensitive to deoiled water, which can cause the dissolution of pyrite and the precipitation of gypsum. Micrographs revealed a great deal of information about water-rock interaction.

  19. A New Method for Fabrication of Nanohydroxyapatite and TCP from the Sea Snail Cerithium vulgatum

    Directory of Open Access Journals (Sweden)

    O. Gunduz

    2014-01-01

    Full Text Available Biphasic bioceramic nanopowders of hydroxyapatite (HA and β-tricalcium phosphate (TCP were prepared from shells of the sea snail Cerithium vulgatum (Bruguière, 1792 using a novel chemical method. Calcination of the powders produced was carried out at varying temperatures, specifically at 400°C and 800°C, in air for 4 hours. When compared to the conventional hydrothermal transformation method, this chemical method is very simple, economic, due to the fact that it needs inexpensive and safe equipment, because the transformation of the aragonite and calcite of the shells into the calcium phosphate phases takes place at 80°C under the atmospheric pressure. The powders produced were determined using infrared spectroscopy (FT-IR, X-ray diffraction, and scanning electron microscopy (SEM. The features of the powders produced along with the fact of their biological origin qualify these powders for further consideration and experimentation to fabricate nanoceramic biomaterials.

  20. Late Quaternary sedimentary features of Bear Lake, Utah and Idaho

    Science.gov (United States)

    Smoot, J.P.

    2009-01-01

    Bear Lake sediments were predominantly aragonite for most of the Holocene, reflecting a hydrologically closed lake fed by groundwater and small streams. During the late Pleistocene, the Bear River flowed into Bear Lake and the lake waters spilled back into the Bear River drainage. At that time, sediment deposition was dominated by siliciclastic sediment and calcite. Lake-level fluctuation during the Holocene and late Pleistocene produced three types of aragonite deposits in the central lake area that are differentiated primarily by grain size, sorting, and diatom assemblage. Lake-margin deposits during this period consisted of sandy deposits including well-developed shoreface deposits on margins adjacent to relatively steep gradient lake floors and thin, graded shell gravel on margins adjacent to very low gradient lake-floor areas. Throughout the period of aragonite deposition, episodic drops in lake level resulted in erosion of shallow-water deposits, which were redeposited into the deeper lake. These sediment-focusing episodes are recognized by mixing of different mineralogies and crystal habits and mixing of a range of diatom fauna into poorly sorted mud layers. Lake-level drops are also indicated by erosional gaps in the shallow-water records and the occurrence of shoreline deposits in areas now covered by as much as 30 m of water. Calcite precipitation occurred for a short interval of time during the Holocene in response to an influx of Bear River water ca. 8 ka. The Pleistocene sedimentary record of Bear Lake until ca. 18 ka is dominated by siliciclastic glacial fl our derived from glaciers in the Uinta Mountains. The Bear Lake deep-water siliciclastic deposits are thoroughly bioturbated, whereas shallow-water deposits transitional to deltas in the northern part of the basin are upward-coarsening sequences of laminated mud, silt, and sand. A major drop in lake level occurred ca. 18 ka, resulting in subaerial exposure of the lake floor in areas now covered by

  1. Effect of precipitation procedure and detection technique on particle size distribution of CaCO 3

    Science.gov (United States)

    Martos, C.; Coto, B.; Peña, J. L.; Rodríguez, R.; Merino-Garcia, D.; Pastor, G.

    2010-09-01

    The deposition of inorganic salts ("scales") such as calcium carbonate is an important flow assurance problem during crude oil production. The knowledge of the features of the precipitated solids, mainly the particle size and morphology, is crucial to understand the nature of the solids and to avoid or reduce the effect of their deposition. For instance, the use of additives is one of the most usual procedures to mitigate this problem. Additives interact with scale-forming substances either by increasing the induction time, or by inhibiting crystal growth, changing the morphology of solids. In this work, CaCO 3 was precipitated by two different experimental methods: by mixing sodium carbonate and calcium chloride at 25 °C (method 1), and by changing the pH (method 2). Precipitated solids were analyzed by means of the following techniques: laser diffraction (LD), focused-beam reflectance measurement (FBRM), scanning electron microscopy (SEM), and X-ray diffraction (XRD), in order to select a method for the determination of particle size of solids similar to scales, in order to study these deposits at the beginning of their formation and to evaluate the effect of additives in the scales particle size. Results were compared to those of scale deposits extracted from crude oil pipelines. SEM and XRD characterization showed that both the precipitation methods lead to calcium carbonate as a mixture of calcite, aragonite and vaterite, with rhombohedral morphology for method 1 and spherical for method 2. The effects of temperature, kinetics and Mg 2+ presence in the morphology of CaCO 3 were evaluated. Thus, the solids obtained by static bottle test and real scales are mainly formed by long needle-shaped aragonite. The comparison of the several particle size characterization methods determinates that an LD is a fast and sensitive technique for spherical and non-spherical solids, and it is a convenient technique for the analysis of scales extracted from oil pipelines.

  2. Effect of ocean acidification on the early life stages of the blue mussel (Mytilus edulis

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    C. H. R. Heip

    2010-04-01

    Full Text Available Several experiments have shown a decrease of growth and calcification of organisms at decreased pH levels but relatively few studies have focused on early life stages which are believed to be more sensitive to environmental disturbances such as hypercapnia. Here, we present experimental data demonstrating that the growth of planktonic mussel (Mytilus edulis larvae is significantly affected by a decrease of pH to a level expected for the end of the century. Even though there was no significant effect of a 0.25–0.34 pH unit decrease on hatching and mortality rates during the first 2 days of development nor during the following 13-day period prior to settlement, final shells were, respectively, 4.5±1.3 and 6.0±2.3% smaller at pHNBS~7.8 than at a control pHNBS of ~8.1. Moreover, a decrease of 12.0±5.4% of shell thickness was observed. More severe impacts were found with a decrease of ~0.5 pHNBS unit during the first 2 days of development which could be attributed to a decrease of calcification due toslight undersaturation of seawater with respect to aragonite. Indeed, important effects on both hatching and D-veliger shell growth were found. Hatching rates were 24±4% lower while D-veliger shells were 12.7±0.9% smaller at pHNBS~7.6 than at a control pHNBS of ~8.1. Although these results show that blue mussel larvae are still able to develop a shell in seawater undersaturated with respect to aragonite, decreases of hatching rates and shell growth suggest a negative impact of ocean acidification on the future survival of bivalve populations potentially leading to significant ecological and economical losses.

  3. Geochemical and Mineralogical Characteristics of Pleistocene Lignites and Associated Sediments of Marathousa Coal Field,Central Peloponnese,Greece

    Institute of Scientific and Technical Information of China (English)

    A.E.KELEPERTSIS; E.KONTIS

    1997-01-01

    The mineralogy and geochemistry data are presented for thirty-seven shales,four concretions,two carbonate sediments and seven lignites from the Marathousa coal field of the Megalopolis Basin in Greece.The argillaceous rocks consist of chlorite,illite,kaolinte,albite,quartz.opal-A,calcite and dolomite;the concretions of aragonite,gypsum and pyrite;and the carbonate rocks of calcite,quartz and illite.The mineral matter in the lignites consists of gypsum,quartz,albite,chlorite,illite,opal-A,dolomite,pyrite,and rarely calcite and kaolinite Athree-factor model explains the total variaition of major and trace elements in the argillaceous sediments.The first factor is an aluminosilicate factor and involves the following elements:Al,Si,Mg,Na,K,Ti,Mn,Nb,Y,Rb,Zn,Cu,Ni,Cr,Nband V,associated with chlorite,albite and illite.The second factor involves the elements Ca,Sr,Ba,Znand Sc and is related to carbonate lithology and mainly the carbonate concretions with gypsum.The third factor involves Fe and Ce with a weak association with Mn.The diagenesis of the Marathousa sediments and lignites was not very advanced as indicated by (a) the total thickness of the sequence (500m),(b) the presence of biogenic silica(opal-A) and (c) the age of the deposit(Pleistocene).FOr these reasons the rpresence of chlorite,illite and kaolinite in the sediments and lignite is due not to diagenetic reactions but to weathering of the flysch and metamorphic rocks at the edges of the Megalopolis Basin and transport of the weathering products(illite,chlorite,kaolinite)into the basin of deposition.The diagenetic minerals of the Marathousa sequence include pyrite,gypsum,dolomite and aragonite.

  4. Effects of drying, heating, annealing, and roasting on carbonate skeletal material, with geochemical and diagenetic implications

    Science.gov (United States)

    Gaffey, Susan J.; Kolak, Jonathan J.; Bronnimann, Charles E.

    1991-06-01

    Carbonate skeletons subjected to drying, heating, annealing, or roasting at elevated temperatures as part of routine sample preparation for chemical analyses or geochemical experiments differ significantly from skeletal materials as they occur in nature. Heating of skeletal samples can degrade organic material, expel H 2O and OH -, reduce the concentration of some trace elements, and change the mineralogy and texture of the material. Thermal degradation of organics and expulsion of water in inclusions, which can occur at temperatures of 100-105°C, cause fracturing and pitting of skeletal samples; areas of pitting reflect original concentrations of volatile phases within the skeleton. Coralline aragonites are partially or completely altered to calcite at temperatures of 150°C or higher; the degree of alteration varies with temperature and duration of heating, and genus of the coral. High Mg calcites (HMCs) tend to form calcian dolomite and multiple HMCs of lower Mg content on heating, but the rate of alteration is related to the taxonomic group rather than the Mg content; echinoids alter very rapidly (dolomite detectable by X-ray diffraction formed in Clypeaster heated for 6 h at 200°C), while the coralline red alga Neogoniolithon showed no alteration after heating at 400°C for 23 h. Mineralogical alteration of coralline aragonites and echinoid HMCs is positively correlated with water loss. Skeletal carbonates comprise a very diverse and heterogeneous suite of materials, and their diversity and heterogeneity are reflected in their responses to heating. Variations in rate and degree of alteration on heating, in many cases between different subsamples of material produced by the same organism, make it difficult to obtain a consistent product from heat treatment. Many workers have used high temperature experiments to model diagenetic processes, and the results of this study have implications for diagenetic alteration as well as for laboratory analyses and

  5. The discovery of stromatolites developing at 3570 m above sea level in a high-altitude volcanic lake Socompa, Argentinean Andes.

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    María E Farías

    Full Text Available We describe stromatolites forming at an altitude of 3570 m at the shore of a volcanic lake Socompa, Argentinean Andes. The water at the site of stromatolites formation is alkaline, hypersaline, rich in inorganic nutrients, very rich in arsenic, and warm (20-24°C due to a hydrothermal input. The stromatolites do not lithify, but form broad, rounded and low-domed bioherms dominated by diatom frustules and aragonite micro-crystals agglutinated by extracellular substances. In comparison to other modern stromatolites, they harbour an atypical microbial community characterized by highly abundant representatives of Deinococcus-Thermus, Rhodobacteraceae, Desulfobacterales and Spirochaetes. Additionally, a high proportion of the sequences that could not be classified at phylum level showed less than 80% identity to the best hit in the NCBI database, suggesting the presence of novel distant lineages. The primary production in the stromatolites is generally high and likely dominated by Microcoleus sp. Through negative phototaxis, the location of these cyanobacteria in the stromatolites is controlled by UV light, which greatly influences their photosynthetic activity. Diatoms, dominated by Amphora sp., are abundant in the anoxic, sulfidic and essentially dark parts of the stromatolites. Although their origin in the stromatolites is unclear, they are possibly an important source of anaerobically degraded organic matter that induces in situ aragonite precipitation. To the best of our knowledge, this is so far the highest altitude with documented actively forming stromatolites. Their generally rich, diverse and to a large extent novel microbial community likely harbours valuable genetic and proteomic reserves, and thus deserves active protection. Furthermore, since the stromatolites flourish in an environment characterized by a multitude of extremes, including high exposure to UV radiation, they can be an excellent model system for studying microbial

  6. Calcification is not the Achilles' heel of cold-water corals in an acidifying ocean.

    Science.gov (United States)

    Rodolfo-Metalpa, Riccardo; Montagna, Paolo; Aliani, Stefano; Borghini, Mireno; Canese, Simonepietro; Hall-Spencer, Jason M; Foggo, Andy; Milazzo, Marco; Taviani, Marco; Houlbrèque, Fanny

    2015-06-01

    Ocean acidification is thought to be a major threat to coral reefs: laboratory evidence and CO2 seep research has shown adverse effects on many coral species, although a few are resilient. There are concerns that cold-water corals are even more vulnerable as they live in areas where aragonite saturation (Ωara ) is lower than in the tropics and is falling rapidly due to CO2 emissions. Here, we provide laboratory evidence that net (gross calcification minus dissolution) and gross calcification rates of three common cold-water corals, Caryophyllia smithii, Dendrophyllia cornigera, and Desmophyllum dianthus, are not affected by pCO2 levels expected for 2100 (pCO2  1058 μatm, Ωara 1.29), and nor are the rates of skeletal dissolution in D. dianthus. We transplanted D. dianthus to 350 m depth (pHT 8.02; pCO2  448 μatm, Ωara 2.58) and to a 3 m depth CO2 seep in oligotrophic waters (pHT 7.35; pCO2  2879 μatm, Ωara 0.76) and found that the transplants calcified at the same rates regardless of the pCO2 confirming their resilience to acidification, but at significantly lower rates than corals that were fed in aquaria. Our combination of field and laboratory evidence suggests that ocean acidification will not disrupt cold-water coral calcification although falling aragonite levels may affect other organismal physiological and/or reef community processes.

  7. Probe imaging studies of magnetic susceptibility and permeability for sensitive characterisation of carbonate reservoir rocks

    Science.gov (United States)

    Ivakhnenko, Aleksandr; Bigaliyeva, Akmaral; Dubinin, Vladislav

    2016-04-01

    In this study were disclosed the main principals of identifying petrophysical properties of carbonate reservoirs such as porosity, permeability and magnetic susceptibility. While exploring and developing reservoir there are significant diversity of tasks that can be solved by appropriate knowledge of properties which are listed above. Behavior of fluid flow, distribution of hydrocarbons and other various industrial applications can be solved by measuring areal distribution of these petrophysical parameters. The results demonstrate how magnetic probe and hysteresis measurements correlate with petrophysical parameters in carbonate reservoirs. We made experimental measurements and theoretical calculations of how much magnetic susceptibility depends on the porosity of the rocks and analyzed data with graphics. In theoretical model of the carbonate rocks we considered calcite, dolomite, quartz and combinations of calcite and dolomite, calcite and Fe-dolomite, calcite and quartz, calcite and aragonite with increasing concentrations of the dolomite, Fe-dolomite, quartz and aragonite up to 50% with step of 5%. Here we defined dependence of magnetic susceptibility from the porosity: the higher porosity measurements, the less slope of magnetic susceptibility, consequently mass magnetization is higher for diamagnetic and lower for paramagnetic carbonate rocks, but in the both cases magnetic susceptibility tries to reach zero with increasing of the total porosity. Rock measurements demonstrate that reservoir zones of the low diamagnetic magnetic susceptibility are generally correlated with higher permeability and also porosity distribution. However for different carbonate reservoirs we establish different relationships depending on the complexity of their mineralogy and texture. Application of integral understanding in distribution of permeability, porosity and mineral content in heterogeneous carbonates represented by this approach can be useful tool for carbonate reservoir

  8. Diagenetic Pattern in the Citarate Carbonate Rocks, Cilograng Area, Lebak Regency, Banten Province

    Directory of Open Access Journals (Sweden)

    N. I. Basuki

    2014-06-01

    Full Text Available DOI: 10.17014/ijog.v7i3.142The carbonate sequence overlies conformably the tuffaceous sandstone unit, and in turn is conformably underlain by the tuff-sandstone unit, both of which are members of the Citarate Formation. The Citarate carbonate rocks were deposited in an open platform back reef environment, which was temporarily drowned by local sea level rise. Regional Middle Miocene deformation formed NNE-WSW trend faults and E-W trend folds in the researched area. This paper discusses the nature of diagenetic alteration of the Citarate carbonate rocks based on petrographic analyses of twenty surface samples. Carbonate rocks from bottom to top comprise algae packstone, packstone-grainstone, coral-algae packstone, and foraminifer wackestone-packstone. Fragments of coral, coralline red algae, and large foraminifera are the dominant bioclasts in most of the observed samples, whereas echinoids and bivalves are less abundant; they are set in a recrystallized micrite matrix. Planktonic foraminifera are abundant only in few samples. Fragments of plagioclase, igneous volcanic rocks, pyroclastic rocks (tuff, and much less abundant quartz are commonly present in all the studied samples. A generalized diagenesis includes early marine cementation by fibrous aragonite, compaction, aragonite dissolution and/or neomorphism, precipitation of equant-grained calcite cement in a phreatic environment, dissolution to form moldic porosities, dolomitization, the formation of stylolites and fractures, and precipitation of late ferroan calcite during burial. Multiple carbonate cements occur as pore-filling phases, with ferroan calcite cementation taking place during later-stage burial. Secondary porosities were formed during different stages in diagenetic processes, such as dissolution, dolomitization, and stylolite and fracture formations. Although precipitation of nonferroan and ferroan calcite cement occluded porosities, porosity enhancement during early selective

  9. Insights into Carbonate Formation through the Incorporation of Trace Metals into Ooids

    Science.gov (United States)

    Fairbank, V. E.; Robinson, L. F.; Parkinson, I. J.; Elliott, T.

    2014-12-01

    Trace metal ratios are widely used as paleoclimate proxies for past ocean conditions. In particular Mg/Ca and Sr/Ca ratios in biogenic carbonates have been used as paleothermometers. Of course the use of these trace metal ratios as reliable climate proxies does not come without complications. As well as biologically mediated "vital effects", there have also been other secondary controls on trace metal incorporation reported, including salinity, carbonate ion concentration and growth rate. Within this study a range of trace metal ratios and their isotopes have been measured for modern ooid samples forming under a range of environmental conditions. Since ooids are thought to form through inorganic precipitation (although microbial mediation may play a role), the "vital effects" seen in biogenic carbonates should be minimised or absent. Therefore, ooids should be expected to incorporate trace metals similarly to carbonate precipitated in experimental studies. Through studying modern ooids we can test this hypothesis, as well as looking at the factors that affect the incorporation of trace metals into calcium carbonates without the control of typical "vital effects".The sample set includes both pure aragonite and pure calcite ooids, as well as samples with intermediate mineralogy as determined by in situ Raman spectroscopy. The distribution coefficients for purely aragonite or calcite ooids are offset from the reported inorganic precipitate values, with DSr being larger, while DMg has been found to be lower. The incorporation of Mg and Sr across the sample set is inversely correlated and does not seem to be explained by mineralogy alone. Here we explore alternative secondary factors contributing to the incorporation of these trace elements into oolitic carbonate. This will be accomplished by utilising stable Sr isotope fractionation during incorporation and using kinetic models and distribution coefficients to investigate the controls on Mg and Sr partitioning into

  10. Development of gravity-sensing organs in altered gravity

    Science.gov (United States)

    Wiederhold, M. L.; Gao, W. Y.; Harrison, J. L.; Hejl, R.

    1997-01-01

    Experiments are described in which the development of the gravity-sensing organs was studied in newt larvae reared in microgravity on the IML-2 mission and in Aplysia embryos and larvae reared on a centrifuge at 1 to 5 g. In Aplysia embryos, the statolith (single dense mass on which gravity and linear acceleration act) was reduced in size in a graded fashion at increasing g. In early post-metamorphic Aplysia or even in isolated statocysts from such animals, the number of statoconia produced is reduced at high g. Newt larvae launched before any of the otoconia were formed and reared for 15 days in microgravity had nearly adult labyrinths at the end of the IML-2 mission. The otoliths of the saccule and utricle were the same size in flight and ground-reared larvae. However, the system of aragonitic otoconia produced in the endolymphatic sac in amphibians was much larger and developed earlier in the flight-reared larvae. At later developmental stages, the aragonitic otoconia enter and fill the saccule. One flight-reared larva was maintained for nine months post-flight and the size of the saccular otolith, as well as the volume of otoconia within the endolymphatic sac, were considerably larger than in age-matched, ground-reared newts. This suggests that rearing in microgravity initiates a process that continues for several months after introduction to 1-g, which greatly increases the volume of otoconia. The flight-reared animal had abnormal posture, pointing its head upward, whereas normal ground-reared newts always keep their head horizontal. This suggests that rearing for even a short period in microgravity can have lasting functional consequences in an animal subsequently reared in 1-g conditions on Earth.

  11. Ocean acidification and temperature increase impact mussel shell shape and thickness: problematic for protection?

    Science.gov (United States)

    Fitzer, Susan C; Vittert, Liberty; Bowman, Adrian; Kamenos, Nicholas A; Phoenix, Vernon R; Cusack, Maggie

    2015-11-01

    Ocean acidification threatens organisms that produce calcium carbonate shells by potentially generating an under-saturated carbonate environment. Resultant reduced calcification and growth, and subsequent dissolution of exoskeletons, would raise concerns over the ability of the shell to provide protection for the marine organism under ocean acidification and increased temperatures. We examined the impact of combined ocean acidification and temperature increase on shell formation of the economically important edible mussel Mytilus edulis. Shell growth and thickness along with a shell thickness index and shape analysis were determined. The ability of M. edulis to produce a functional protective shell after 9 months of experimental culture under ocean acidification and increasing temperatures (380, 550, 750, 1000 μatm pCO 2, and 750, 1000 μatm pCO 2 + 2°C) was assessed. Mussel shells grown under ocean acidification conditions displayed significant reductions in shell aragonite thickness, shell thickness index, and changes to shell shape (750, 1000 μatm pCO 2) compared to those shells grown under ambient conditions (380 μatm pCO 2). Ocean acidification resulted in rounder, flatter mussel shells with thinner aragonite layers likely to be more vulnerable to fracture under changing environments and predation. The changes in shape presented here could present a compensatory mechanism to enhance protection against predators and changing environments under ocean acidification when mussels are unable to grow thicker shells. Here, we present the first assessment of mussel shell shape to determine implications for functional protection under ocean acidification.

  12. Mineral parageneses, regional architecture, and tectonic evolution of Franciscan metagraywackes, Cape Mendocino-Garberville-Covelo 30' x 60' quadrangles, northwest California

    Science.gov (United States)

    Ernst, W.G.; McLaughlin, R.J.

    2012-01-01

    The Franciscan Complex is a classic subduction-zone assemblage. In northwest California, it comprises a stack of west vergent thrust sheets: westernmost Eastern Belt outliers; Central Belt mélange; Coastal Belt Yager terrane; Coastal Belt Coastal terrane; Coastal Belt King Range/False Cape terranes. We collected samples and determined P-T conditions of recrystallization for 88 medium-fine-grained metasandstones to assess their subduction-exhumation histories and assembly of the host allochthons. Feebly recrystallized Yager, Coastal, and King Range strata retain clear detrital features. Scattered neoblastic prehnite occurs in several Coastal terrane metasandstones; traces of possible pumpellyite are present in three Yager metaclastic rocks. Pumpellyite ± lawsonite ± aragonite-bearing Central Belt metasandstones are moderately deformed and reconstituted. Intensely contorted, thoroughly recrystallized Eastern Belt affinity quartzose metagraywackes contain lawsonite + jadeitic pyroxene ± aragonite ± glaucophane. We microprobed neoblastic phases in 23 rocks, documenting mineral parageneses that constrain the tectonic accretion and metamorphic P-T evolution of these sheets. Quasi-stable mineral assemblages typify Eastern Belt metasandstones, but mm-sized domains in the Central and Coastal belt rocks failed to achieve chemical equilibrium. Eastern Belt slabs rose from subduction depths approaching 25–30 km, whereas structurally lower Central Belt mélanges returned from ∼15–18 km. Coastal Belt assemblages suggest burial depths less than 5–8 km. Eastern and Central belt allochthons sequentially decoupled from the downgoing oceanic lithosphere and ascended into the accretionary margin; K-feldspar-rich Coastal Belt rocks were stranded along the continental edge without undergoing appreciable subduction, probably during Paleogene unroofing of the older, deeply subducted units of the Franciscan Complex in east-vergent crustal wedges.

  13. Optics and remote sensing of Bahamian carbonate sediment whitings and potential relationship to wind-driven Langmuir circulation

    Directory of Open Access Journals (Sweden)

    H. M. Dierssen

    2008-12-01

    Full Text Available Regions of milky white seas or "whitings" periodically occur to the west of Andros Island along the Great Bahama Bank where the bottom sediment consists of fine-grained aragonite mud. We present comprehensive measurements of inherent optical properties within a whiting patch and discuss the potential for monitoring the frequency, extent, and quantity of suspended matter from ocean colour satellite imagery. Sea spectral reflectance measured in situ and remotely from space revealed highly reflective waters elevated across the visible spectrum (i.e., "whitened" with a peak at 490 nm. Particulate backscattering was an order of magnitude higher than that measured at other stations throughout the region. The whiting also had one of the highest backscattering ratios measured in natural waters (0.05–0.06 consistent with water dominated by aragonite particles with a high index of refraction. Regular periodicity of 40 and 212 s evident in the light attenuation coefficient over the sampling period indicated patches of fluctuating turbidity on spatial scales that could be produced from regular rows of Langmuir cells penetrating the 5-m water column. We suggest that previously described mechanisms for sediment resuspension in whitings, such as tidal bursting and fish activity, are not fully consistent with these data and propose that wind-driven Langmuir cells reaching the full-depth of the water column may represent a plausible mechanism for sediment resuspension and subsequent whiting formation. Optics and remote sensing provide important tools for quantifying the linkages between physical and biogeochemical processes in these dynamic shallow water ecosystems.

  14. Coral records of reef-water pH across the central Great Barrier Reef, Australia: assessing the influence of river runoff on inshore reefs

    Science.gov (United States)

    D'Olivo, J. P.; McCulloch, M. T.; Eggins, S. M.; Trotter, J.

    2015-02-01

    The boron isotopic (δ11Bcarb) compositions of long-lived Porites coral are used to reconstruct reef-water pH across the central Great Barrier Reef (GBR) and assess the impact of river runoff on inshore reefs. For the period from 1940 to 2009, corals from both inner- and mid-shelf sites exhibit the same overall decrease in δ11Bcarb of 0.086 ± 0.033‰ per decade, equivalent to a decline in seawater pH (pHsw) of ~0.017 ± 0.007 pH units per decade. This decline is consistent with the long-term effects of ocean acidification based on estimates of CO2 uptake by surface waters due to rising atmospheric levels. We also find that, compared to the mid-shelf corals, the δ11Bcarb compositions of inner-shelf corals subject to river discharge events have higher and more variable values, and hence higher inferred pHsw values. These higher δ11Bcarb values of inner-shelf corals are particularly evident during wet years, despite river waters having lower pH. The main effect of river discharge on reef-water carbonate chemistry thus appears to be from reduced aragonite saturation state and higher nutrients driving increased phytoplankton productivity, resulting in the drawdown of pCO2 and increase in pHsw. Increased primary production therefore has the potential to counter the more transient effects of low-pH river water (pHrw) discharged into near-shore environments. Importantly, however, inshore reefs also show a consistent pattern of sharply declining coral growth that coincides with periods of high river discharge. This occurs despite these reefs having higher pHsw, demonstrating the overriding importance of local reef-water quality and reduced aragonite saturation state on coral reef health.

  15. Equilibrium magnesium isotope fractionation between aqueous Mg2+ and carbonate minerals: Insights from path integral molecular dynamics

    Science.gov (United States)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Natarajan, Suresh K.; Vuilleumier, Rodolphe; Mauri, Francesco

    2015-08-01

    The theoretical determination of the isotopic fractionation between an aqueous solution and a mineral is of utmost importance in Earth sciences. While for crystals, it is well established that equilibrium isotopic fractionation factors can be calculated using a statistical thermodynamic approach based on the vibrational properties, several theoretical methods are currently used to model ions in aqueous solution. In this work, we present a systematic study to determine the reduced partition function ratio (β-factor) of aqueous Mg2+ using several levels of theory within the simulations. In particular, using an empirical force field, we compare and discuss the performance of the exact results obtained from path integral molecular dynamics (PIMD) simulations, with respect to the more traditional methods based on vibrational properties and the cluster approximation. The results show the importance of including configurational disorder for the estimation of the equilibrium isotope fractionation factor. We also show that using the vibrational frequencies computed from snapshots taken from equilibrated classical molecular dynamics represents a good approximation for the study of aqueous ions. Based on these conclusions, the β-factor of aqueous Mg2+ have been estimated from a Car-Parrinello molecular dynamics (CPMD) simulation with an ab initio force field, and combined with the β-factors of carbonate minerals (magnesite, dolomite, calcite and aragonite). Mg β-factor of Mg-bearing aragonite, calculated here for the first time, displays a lower value than the three other carbonate minerals. This is explained by a strong distortion of the cationic site leading to a decrease of the coordination number during Ca-Mg substitution. Overall, the equilibrium magnesium isotope fractionation factors between aqueous Mg2+ and carbonate minerals that derive from this methodological study support the previous theoretical results obtained from embedded cluster models.

  16. Mineralization of vestimentiferan tubes at methane seeps on the Congo deep-sea fan

    Science.gov (United States)

    Haas, Antonie; Little, Crispin T. S.; Sahling, Heiko; Bohrmann, Gerhard; Himmler, Tobias; Peckmann, Jörn

    2009-02-01

    Vestimentiferan tube worms are prominent members of modern methane seep communities and are totally reliant as adults on symbiotic sulphide-oxidizing bacteria for their nutrition. The sulphide is produced in the sediment by a biochemical reaction called the anaerobic oxidation of methane (AOM). A well-studied species from the Gulf of Mexico shows that seep vestimentiferans 'mine' sulphide from the sediment using root-like, thin walled, permeable posterior tube extensions, which can also be used to pump sulphate and possibly hydrogen ions from the soft tissue back into the sediment to increase the local rate of AOM. The 'root-balls' of exhumed seep vestimentiferans are intimately associated with carbonate nodules, which are a result of AOM. We have studied vestimentiferan specimens and associated carbonates from seeps at the Kouilou pockmark field on the Congo deep-sea fan and find that some of the posterior 'root' tubes of living specimens are enclosed with carbonate indurated sediment and other, empty examples are partially or completely replaced by the carbonate mineral aragonite. This replacement occurs from the outside of the tube wall inwards and leaves fine-scale relict textures of the original organic tube wall. The process of mineralization is unknown, but is likely a result of post-mortem microbial decay of the tube wall proteins by microorganisms or the precipitation from locally high flux of AOM derived carbonate ions. The aragonite-replaced tubes from the Kouilou pockmarks show similar features to carbonate tubes in ancient seep deposits and make it more likely that many of these fossil tubes are those of vestimentiferans. These observations have implications for the supposed origination of this group, based on molecular divergence estimates.

  17. The skeletal proteome of the coral Acropora millepora: the evolution of calcification by co-option and domain shuffling.

    Science.gov (United States)

    Ramos-Silva, Paula; Kaandorp, Jaap; Huisman, Lotte; Marie, Benjamin; Zanella-Cléon, Isabelle; Guichard, Nathalie; Miller, David J; Marin, Frédéric

    2013-09-01

    In corals, biocalcification is a major function that may be drastically affected by ocean acidification (OA). Scleractinian corals grow by building up aragonitic exoskeletons that provide support and protection for soft tissues. Although this process has been extensively studied, the molecular basis of biocalcification is poorly understood. Notably lacking is a comprehensive catalog of the skeleton-occluded proteins-the skeletal organic matrix proteins (SOMPs) that are thought to regulate the mineral deposition. Using a combination of proteomics and transcriptomics, we report the first survey of such proteins in the staghorn coral Acropora millepora. The organic matrix (OM) extracted from the coral skeleton was analyzed by mass spectrometry and bioinformatics, enabling the identification of 36 SOMPs. These results provide novel insights into the molecular basis of coral calcification and the macroevolution of metazoan calcifying systems, whereas establishing a platform for studying the impact of OA at molecular level. Besides secreted proteins, extracellular regions of transmembrane proteins are also present, suggesting a close control of aragonite deposition by the calicoblastic epithelium. In addition to the expected SOMPs (Asp/Glu-rich, galaxins), the skeletal repertoire included several proteins containing known extracellular matrix domains. From an evolutionary perspective, the number of coral-specific proteins is low, many SOMPs having counterparts in the noncalcifying cnidarians. Extending the comparison with the skeletal OM proteomes of other metazoans allowed the identification of a pool of functional domains shared between phyla. These data suggest that co-option and domain shuffling may be general mechanisms by which the trait of calcification has evolved.

  18. Crystallographic control on the substructure of nacre tablets.

    Science.gov (United States)

    Checa, Antonio G; Mutvei, Harry; Osuna-Mascaró, Antonio J; Bonarski, Jan T; Faryna, Marek; Berent, Katarzyna; Pina, Carlos M; Rousseau, Marthe; Macías-Sánchez, Elena

    2013-09-01

    Nacre tablets of mollusks develop two kinds of features when either the calcium carbonate or the organic portions are removed: (1) parallel lineations (vermiculations) formed by elongated carbonate rods, and (2) hourglass patterns, which appear in high relief when etched or in low relief if bleached. In untreated tablets, SEM and AFM data show that vermiculations correspond to aligned and fused aragonite nanogloblules, which are partly surrounded by thin organic pellicles. EBSD mapping of the surfaces of tablets indicates that the vermiculations are invariably parallel to the crystallographic a-axis of aragonite and that the triangles are aligned with the b-axis and correspond to the advance of the {010} faces during the growth of the tablet. According to our interpretation, the vermiculations appear because organic molecules during growth are expelled from the a-axis, where the Ca-CO3 bonds are the shortest. In this way, the subunits forming nacre merge uninterruptedly, forming chains parallel to the a-axis, whereas the organic molecules are expelled to the sides of these chains. Hourglass patterns would be produced by preferential adsorption of organic molecules along the {010}, as compared to the {100} faces. A model is presented for the nanostructure of nacre tablets. SEM and EBSD data also show the existence within the tablets of nanocrystalline units, which are twinned on {110} with the rest of the tablet. Our study shows that the growth dynamics of nacre tablets (and bioaragonite in general) results from the interaction at two different and mutually related levels: tablets and nanogranules.

  19. Phylomineralogy of the coralline red algae: correlation of skeletal mineralogy with molecular phylogeny.

    Science.gov (United States)

    Smith, A M; Sutherland, J E; Kregting, L; Farr, T J; Winter, D J

    2012-09-01

    The coralline algae in the orders Corallinales and Sporolithales (subclass Corallinophycidae), with their high degree of mineralogical variability, pose a challenge to projections regarding mineralogy and response to ocean acidification. Here we relate skeletal carbonate mineralogy to a well-established phylogenetic framework and draw inferences about the effects of future changes in sea-water chemistry on these calcified red algae. A collection of 191 coralline algal specimens from New Zealand, representing 13 genera and 28 species, included members of three families: Corallinaceae, Hapalidiaceae, and Sporolithaceae. While most skeletal specimens were entirely calcitic (range: 73-100 wt.% calcite, mean 97 wt.% calcite, std dev=5, n=172), a considerable number contained at least some aragonite. Mg in calcite ranged from 10.5 to 16.4 wt.% MgCO(3), with a mean of 13.1 wt.% MgCO(3) (std dev=1.1, n=172). The genera Mesophyllum and Lithophyllum were especially variable. Growth habit, too, was related to mineralogy: geniculate coralline algae do not generally contain any aragonite. Mg content varied among coralline families: the Corallinaceae had the highest Mg content, followed by the Sporolithaceae and the Hapalidiaceae. Despite the significant differences among families, variation and overlap prevent the use of carbonate mineralogy as a taxonomic character in the coralline algae. Latitude (as a proxy for water temperature) had only a slight relationship to Mg content in coralline algae, contrary to trends observed in other biomineralising taxa. Temperate magnesium calcites, like those produced by coralline algae, are particularly vulnerable to ocean acidification. Changes in biomineralisation or species distribution may occur over the next few decades, particularly to species producing high-Mg calcite, as pH and CO(2) dynamics change in coastal temperate oceans.

  20. Shellfish face uncertain future in high CO2 world: influence of acidification on oyster larvae calcification and growth in estuaries.

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    A Whitman Miller

    Full Text Available BACKGROUND: Human activities have increased atmospheric concentrations of carbon dioxide by 36% during the past 200 years. One third of all anthropogenic CO(2 has been absorbed by the oceans, reducing pH by about 0.1 of a unit and significantly altering their carbonate chemistry. There is widespread concern that these changes are altering marine habitats severely, but little or no attention has been given to the biota of estuarine and coastal settings, ecosystems that are less pH buffered because of naturally reduced alkalinity. METHODOLOGY/PRINCIPAL FINDINGS: To address CO(2-induced changes to estuarine calcification, veliger larvae of two oyster species, the Eastern oyster (Crassostrea virginica, and the Suminoe oyster (Crassostrea ariakensis were grown in estuarine water under four pCO(2 regimes, 280, 380, 560 and 800 microatm, to simulate atmospheric conditions in the pre-industrial era, present, and projected future concentrations in 50 and 100 years respectively. CO(2 manipulations were made using an automated negative feedback control system that allowed continuous and precise control over the pCO(2 in experimental aquaria. Larval growth was measured using image analysis, and calcification was measured by chemical analysis of calcium in their shells. C. virginica experienced a 16% decrease in shell area and a 42% reduction in calcium content when pre-industrial and end of 21(st century pCO(2 treatments were compared. C. ariakensis showed no change to either growth or calcification. Both species demonstrated net calcification and growth, even when aragonite was undersaturated, a result that runs counter to previous expectations for invertebrate larvae that produce aragonite shells. CONCLUSIONS AND SIGNIFICANCE: Our results suggest that temperate estuarine and coastal ecosystems are vulnerable to the expected changes in water chemistry due to elevated atmospheric CO(2 and that biological responses to acidification, especially calcifying

  1. Physicochemical and pharmacological assessment of a traditional biomedicine: Mukta shouktic bhasma

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    Nitin Dubey

    2009-11-01

    Full Text Available Mukta shouktic bhasma (MSB is a traditional Ayurvedic medicinal preparation. This biomedicine is synthesized through special calcination of mother of pearl as mentioned in the classical Ayurvedic text. Physicochemical characterization of MSB was carried out using modern techniques such as transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction analysis, Fourier transform infra-red spectroscopy, inductively coupled plasma analysis, energy dispersive X-ray analysis, and thermogravimetric analysis. The study showed that the raw material mukta shouktic (mother of pearl is an organo-mineral matrix containing calcium carbonate in aragonite form. The aragonite form of calcium carbonatetransforms to a stable calcite form during the process of bhasma formation and forms the main crystalline component of MSB. The heat treatment does result in partial conversion of calcite to calcium oxide, which appears as calcium hydroxide(not more than 2% w/w in the final product. The organic content of processed material degraded gradually. Physical evaluation revealed that MSB is a fine grayish white powder having a poor flow property with narrow particle size distribution of 1.22 to 22.52 m having a mean particle size of 10.20±0.45 m. A clearly identifiable fraction of MSB particles was below 50 nanometer. The presence of nanosized particles in MSB might impart the therapeutic property of this medicine. Trace element analysis of MSB revealed the presence of metals, like arsenic, lead, chromium, cadmium, mercury, and tin under regulatory acceptable limits at the prescribed dose of MSB. Energy dispersive X-ray analysis revealed calcium as the major element (40.22 wt % in MSB. Microbial load for the formulation was found to be within limits. Animals were found to be safe up to a maximum dose of 2000 mg/kg body weight in acute toxicity studies. A significant (P<0.05 reduction in hyperpyrexia in rat was produced by MSB.

  2. Out of their depth? Isolated deep populations of the cosmopolitan coral Desmophyllum dianthus may be highly vulnerable to environmental change.

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    Karen J Miller

    Full Text Available Deep sea scleractinian corals will be particularly vulnerable to the effects of climate change, facing loss of up to 70% of their habitat as the Aragonite Saturation Horizon (below which corals are unable to form calcium carbonate skeletons rises. Persistence of deep sea scleractinian corals will therefore rely on the ability of larvae to disperse to, and colonise, suitable shallow-water habitat. We used DNA sequence data of the internal transcribed spacer (ITS, the mitochondrial ribosomal subunit (16S and mitochondrial control region (MtC to determine levels of gene flow both within and among populations of the deep sea coral Desmophyllum dianthus in SE Australia, New Zealand and Chile to assess the ability of corals to disperse into different regions and habitats. We found significant genetic subdivision among the three widely separated geographic regions consistent with isolation and limited contemporary gene flow. Furthermore, corals from different depth strata (shallow 1500 m even on the same or nearby seamounts were strongly differentiated, indicating limited vertical larval dispersal. Genetic differentiation with depth is consistent with the stratification of the Subantarctic Mode Water, Antarctic Intermediate Water, the Circumpolar Deep and North Pacific Deep Waters in the Southern Ocean, and we propose that coral larvae will be retained within, and rarely migrate among, these water masses. The apparent absence of vertical larval dispersal suggests deep populations of D. dianthus are unlikely to colonise shallow water as the aragonite saturation horizon rises and deep waters become uninhabitable. Similarly, assumptions that deep populations will act as refuges for shallow populations that are impacted by activities such as fishing or mining are also unlikely to hold true. Clearly future environmental management strategies must consider both regional and depth-related isolation of deep-sea coral populations.

  3. 13C-18O isotope signatures and ‘clumped isotope’ thermometry in foraminifera and coccoliths

    Science.gov (United States)

    Tripati, Aradhna K.; Eagle, Robert A.; Thiagarajan, Nivedita; Gagnon, Alexander C.; Bauch, Henning; Halloran, Paul R.; Eiler, John M.

    2010-10-01

    Accurate constraints on past ocean temperatures and compositions are critical for documenting climate change and resolving its causes. Most proxies for temperature are not thermodynamically based, appear to be subject to biological processes, require regional calibrations, and/or are influenced by fluid composition. As a result, their interpretation becomes uncertain when they are applied in settings not necessarily resembling those in which they were empirically calibrated. Independent proxies for past temperature could provide an important means of testing and/or expanding on existing reconstructions. Here we report measurements of abundances of stable isotopologues of calcitic and aragonitic benthic and planktic foraminifera and coccoliths, relate those abundances to independently estimated growth temperatures, and discuss the possible scope of equilibrium and kinetic isotope effects. The proportions of 13C- 18O bonds in these samples exhibits a temperature dependence that is generally similar to that previously been reported for inorganic calcite and other biologically precipitated carbonate-containing minerals (apatite from fish, reptile, and mammal teeth; calcitic brachiopods and molluscs; aragonitic coral and mollusks). Most species that exhibit non-equilibrium 18O/ 16O (δ 18O) and 13C/ 12C (δ 13C) ratios are characterized by 13C- 18O bond abundances that are similar to inorganic calcite and are generally indistinguishable from apparent equilibrium, with possible exceptions among benthic foraminiferal samples from the Arctic Ocean where temperatures are near-freezing. Observed isotope ratios in biogenic carbonates can be explained if carbonate minerals generally preserve a state of ordering that reflects the extent of isotopic equilibration of the dissolved inorganic carbon species.

  4. Comparison of Mediterranean Pteropod Shell Biometrics and Ultrastructure from Historical (1910 and 1921) and Present Day (2012) Samples Provides Baseline for Monitoring Effects of Global Change

    Science.gov (United States)

    Gattuso, Jean-Pierre; Bijma, Jelle

    2017-01-01

    Anthropogenic carbon perturbation has caused decreases in seawater pH and increases in global temperatures since the start of the 20th century. The subsequent lowering of the saturation state of CaCO3 may make the secretion of skeletons more problematic for marine calcifiers. As organisms that precipitate thin aragonite shells, thecosome pteropods have been identified as being particularly vulnerable to climate change effects. Coupled with their global distribution, this makes them ideal for use as sentinel organisms. Recent studies have highlighted shell dissolution as a potential indicator of ocean acidification; however, this metric is not applicable for monitoring pH changes in supersaturated basins. In this study, the novel approach of high resolution computed tomography (CT) scanning was used to produce quantitative 3-dimensional renderings pteropod shells to assess the potential of using this method to monitor small changes in shell biometrics that may be driven by climate change drivers. An ontogenetic analysis of the shells of Cavolinia inflexa and Styliola subula collected from the Mediterranean was used to identify suitable monitoring metrics. Modern samples were then compared to historical samples of the same species, collected during the Mediterranean leg of the Thor (1910) and Dana (1921) cruises to assess whether any empirical differences could be detected. Shell densities were calculated and scanning electron microscopy was used to compare the aragonite crystal morphology. pH for the collection years was hind-cast using temperature and salinity time series with atmospheric CO2 concentrations from ice core data. Historical samples of S. subula were thicker than S. subula shells of the same size from 2012 and C. inflexa shells collected in 1910 were significantly denser than those from 2012. These results provide a baseline for future work to develop monitoring techniques for climate change in the oceans using the novel approach of high-resolution CT

  5. Quantifying the influence of CO2 seasonality on future ocean acidification

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    T. P. Sasse

    2015-04-01

    Full Text Available Ocean acidification is a predictable consequence of rising atmospheric carbon dioxide (CO2, and is highly likely to impact the entire marine ecosystem – from plankton at the base to fish at the top. Factors which are expected to be impacted include reproductive health, organism growth and species composition and distribution. Predicting when critical threshold values will be reached is crucial for projecting the future health of marine ecosystems and for marine resources planning and management. The impacts of ocean acidification will be first felt at the seasonal scale, however our understanding how seasonal variability will influence rates of future ocean acidification remains poorly constrained due to current model and data limitations. To address this issue, we first quantified the seasonal cycle of aragonite saturation state utilizing new data-based estimates of global ocean surface dissolved inorganic carbon and alkalinity. This seasonality was then combined with earth system model projections under different emissions scenarios (RCPs 2.6, 4.5 and 8.5 to provide new insights into future aragonite under-saturation onset. Under a high emissions scenario (RCP 8.5, our results suggest accounting for seasonality will bring forward the initial onset of month-long under-saturation by 17 years compared to annual-mean estimates, with differences extending up to 35 ± 17 years in the North Pacific due to strong regional seasonality. Our results also show large-scale under-saturation once atmospheric CO2 reaches 486 ppm in the North Pacific and 511 ppm in the Southern Ocean independent of emission scenario. Our results suggest that accounting for seasonality is critical to projecting the future impacts of ocean acidification on the marine environment.

  6. Earth system commitments due to delayed mitigation

    Science.gov (United States)

    Pfister, Patrik L.; Stocker, Thomas F.

    2016-01-01

    As long as global CO2 emissions continue to increase annually, long-term committed Earth system changes grow much faster than current observations. A novel metric linking this future growth to policy decisions today is the mitigation delay sensitivity (MDS), but MDS estimates for Earth system variables other than peak temperature (ΔT max) are missing. Using an Earth System Model of Intermediate Complexity, we show that the current emission increase rate causes a ΔT max increase roughly 3-7.5 times as fast as observed warming, and a millenial steric sea level rise (SSLR) 7-25 times as fast as observed SSLR, depending on the achievable rate of emission reductions after the peak of emissions. These ranges are only slightly affected by the uncertainty range in equilibrium climate sensitivity, which is included in the above values. The extent of ocean acidification at the end of the century is also strongly dependent on the starting time and rate of emission reductions. The preservable surface ocean area with sufficient aragonite supersaturation for coral reef growth is diminished globally at an MDS of roughly 25%-80% per decade. A near-complete loss of this area becomes unavoidable if mitigation is delayed for a few years to decades. Also with respect to aragonite, 12%-18% of the Southern Ocean surface become undersaturated per decade, if emission reductions are delayed beyond 2015-2040. We conclude that the consequences of delaying global emission reductions are much better captured if the MDS of relevant Earth system variables is communicated in addition to current trends and total projected future changes.

  7. Climatic modulation of recent trends in ocean acidification in the California Current System

    Science.gov (United States)

    Turi, G.; Lachkar, Z.; Gruber, N.; Münnich, M.

    2016-01-01

    We reconstruct the evolution of ocean acidification in the California Current System (CalCS) from 1979 through 2012 using hindcast simulations with an eddy-resolving ocean biogeochemical model forced with observation-based variations of wind and fluxes of heat and freshwater. We find that domain-wide pH and {{{Ω }}}{arag} in the top 60 m of the water column decreased significantly over these three decades by about -0.02 decade-1 and -0.12 decade-1, respectively. In the nearshore areas of northern California and Oregon, ocean acidification is reconstructed to have progressed much more rapidly, with rates up to 30% higher than the domain-wide trends. Furthermore, ocean acidification penetrated substantially into the thermocline, causing a significant domain-wide shoaling of the aragonite saturation depth of on average -33 m decade-1 and up to -50 m decade-1 in the nearshore area of northern California. This resulted in a coast-wide increase in nearly undersaturated waters and the appearance of waters with {{{Ω }}}{arag}\\lt 1, leading to a substantial reduction of habitat suitability. Averaged over the whole domain, the main driver of these trends is the oceanic uptake of anthropogenic CO2 from the atmosphere. However, recent changes in the climatic forcing have substantially modulated these trends regionally. This is particularly evident in the nearshore regions, where the total trends in pH are up to 50% larger and trends in {{{Ω }}}{arag} and in the aragonite saturation depth are even twice to three times larger than the purely atmospheric CO2-driven trends. This modulation in the nearshore regions is a result of the recent marked increase in alongshore wind stress, which brought elevated levels of dissolved inorganic carbon to the surface via upwelling. Our results demonstrate that changes in the climatic forcing need to be taken into consideration in future projections of the progression of ocean acidification in coastal upwelling regions.

  8. Projections of ocean acidification over the next three centuries using a simple global climate carbon-cycle model

    Science.gov (United States)

    Hartin, C. A.; Bond-Lamberty, B.; Patel, P.; Mundra, A.

    2015-12-01

    Continued oceanic uptake of anthropogenic CO2 is projected to significantly alter the chemistry of the upper oceans, potentially having serious consequences for the marine ecosystems. Projections of ocean acidification are primarily determined from prescribed emission pathways within large scale earth system models. Rather than running the cumbersome earth system models, we can use a reduced-form model to quickly emulate the CMIP5 models for projection studies under arbitrary emission pathways and for uncertainty analyses of the marine carbonate system. In this study we highlight the capability of Hector v1.1, a reduced-form model, to project changes in the upper ocean carbonate system over the next three centuries. Hector is run under historical emissions and a high emissions scenario (Representative Concentration Pathway 8.5), comparing its output to observations and CMIP5 models that contain ocean biogeochemical cycles. Ocean acidification changes are already taking place, with significant changes projected to occur over the next 300 years. We project a low latitude (> 55°) surface ocean pH decrease from preindustrial conditions by 0.4 units to 7.77 at 2100, and an additional 0.27 units to 7.50 at 2300. Aragonite saturations decrease by 1.85 units to 2.21 at 2100 and an additional 0.80 units to 1.42 at 2300. Under a high emissions scenario, for every 1 °C of future warming we find a 0.107 unit pH decrease and a 0.438 unit decrease in aragonite saturations. Hector reproduces the global historical trends, and future projections with equivalent rates of change over time compared to observations and CMIP5 models. Hector is a robust tool that can be used for quick ocean acidification projections, accurately emulating large scale climate models under multiple emission pathways.

  9. Establishing criteria to distinguish oil- from methane-seep carbonates

    Science.gov (United States)

    Smrzka, Daniel; Zwicker, Jennifer; Bach, Wolfgang; Bohrmann, Gerhard; Peckmann, Jörn

    2016-04-01

    Hydrocarbon seeps harbor biota depending on chemosynthesis that is preserved in the fossil record as part of authigenic carbonate deposits. Seep environments are characterized by emanation of methane-rich fluids, yet an increasing number of seeps have been discovered in recent years that are typified by seepage of crude oil. Fluid composition is an important factor governing the composition and diversity of seep-dwelling fauna at modern seeps, as different species have differing tolerances and requirements with regard to the emitted compounds. In this regard, oil seepage has a profound influence on the diversity and distribution of seep-endemic macrofauna and microbial communities. Despite current efforts to better understand oil seeps and their ecology, the confident identification of oil seeps in the geologic record still poses fundamental problems. We present new geochemical data that allow for a more reliable identification of oil seepage during the Phanerozoic. Clear, fibrous aragonite cements of modern and putative ancient oil- and methane-seep deposits were analyzed for their rare earth element (REE) content. This cement is common in seep limestones and represents a product of the anaerobic oxidation of methane and higher hydrocarbons. Clear aragonite is particularly pure and virtually free of detrital inclusions, making it an ideal mineral for comparative geochemical analyses. Its REE composition reveals that oil-seep deposits are significantly enriched in REEs compared to methane- seep deposits. Furthermore, bulk total organic carbon (TOC) measurements suggest that modern and putative ancient oil seep carbonates are enriched in organic carbon. The combined data serve as a promising tool for identifying oil seepage in the fossil record. Our results provide the foundation for an improved understanding of the adaptation of chemosynthesis-based life to oil as an energy source.

  10. Metagenome-based diversity analyses suggest a significant contribution of non-cyanobacterial lineages to carbonate precipitation in modern microbialites

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    Purificacion eLopez-Garcia

    2015-08-01

    Full Text Available Cyanobacteria are thought to play a key role in carbonate formation due to their metabolic activity, but other organisms carrying out oxygenic photosynthesis (photosynthetic eukaryotes or other metabolisms (e.g. anoxygenic photosynthesis, sulfate reduction, may also contribute to carbonate formation. To obtain more quantitative information than that provided by more classical PCR-dependent methods, we studied the microbial diversity of microbialites from the Alchichica crater lake (Mexico by mining for 16S/18S rRNA genes in metagenomes obtained by direct sequencing of environmental DNA. We studied samples collected at the Western (AL-W and Northern (AL-N shores of the lake and, at the latter site, along a depth gradient (1, 5, 10 and 15 m depth. The associated microbial communities were mainly composed of bacteria, most of which seemed heterotrophic, whereas archaea were negligible. Eukaryotes composed a relatively minor fraction dominated by photosynthetic lineages, diatoms in AL-W, influenced by Si-rich seepage waters, and green algae in AL-N samples. Members of the Gammaproteobacteria and Alphaproteobacteria classes of Proteobacteria, Cyanobacteria and Bacteroidetes were the most abundant bacterial taxa, followed by Planctomycetes, Deltaproteobacteria (Proteobacteria, Verrucomicrobia, Actinobacteria, Firmicutes and Chloroflexi. Community composition varied among sites and with depth. Although cyanobacteria were the most important bacterial group contributing to the carbonate precipitation potential, photosynthetic eukaryotes, anoxygenic photosynthesizers and sulfate reducers were also very abundant. Cyanobacteria affiliated to Pleurocapsales largely increased with depth. Scanning electron microscopy (SEM observations showed considerable areas of aragonite-encrusted Pleurocapsa-like cyanobacteria at microscale. Multivariate statistical analyses showed a strong positive correlation of Pleurocapsales and Chroococcales with aragonite formation at

  11. Effect of permethrin, anthracene and mixture exposure on shell components, enzymatic activities and proteins status in the Mediterranean clam Venerupis decussata

    Energy Technology Data Exchange (ETDEWEB)

    Sellami, Badreddine, E-mail: sellamibadreddine@gmail.com [Laboratory of Environment Biomonitoring, Coastal Ecology Unit, Faculty of Sciences of Bizerta, University of Carthage, 7021 Zarzouna (Tunisia); Khazri, Abdelhafidh [Laboratory of Environment Biomonitoring, Coastal Ecology Unit, Faculty of Sciences of Bizerta, University of Carthage, 7021 Zarzouna (Tunisia); Mezni, Amine [Unit of Research 99/UR12-30, Department of Chemistry, Faculty of Sciences of Bizerte, 7021 Jarzouna (Tunisia); Louati, Héla; Dellali, Mohamed; Aissa, Patricia; Mahmoudi, Ezzeddine; Beyrem, Hamouda [Laboratory of Environment Biomonitoring, Coastal Ecology Unit, Faculty of Sciences of Bizerta, University of Carthage, 7021 Zarzouna (Tunisia); Sheehan, David, E-mail: d.sheehan@ucc.ie [Environmental Research Institute and Department of Biochemistry, University College Cork, Western Gateway Building, Western Road, Cork (Ireland)

    2015-01-15

    Highlights: • We assessed toxicity of anthracene, permethrin and their mixture on clams. • Tissue and stressor-dependent changes were observed in biochemical responses. • Permethrin induces phase transition from aragonite to calcite in shell structure. • Interactive effects were observed on digestive gland and gill biomarkers. • Both approaches give new vision to risk assessment of organic pollution. - Abstract: Anthracene (ANT) and permethrin (PER) are two of the more toxic compounds reaching the marine environment. This study aimed to determine the impact of these molecules on Venerupis decussata, an economically important species cultured on the Tunisian coast. Shell structure and its possible transformation upon exposure to the two contaminants were studied by X-ray diffraction and gravimetric analyses. Results revealed a phase transition in shell composition from aragonite to calcite after PER exposure, to a mixture of PER and ANT (Mix) but not for ANT alone. Catalase (CAT), superoxide dismutase (SOD) and glutathione transferase (GST) activities were determined in digestive gland and gills after exposure to ANT, PER and Mix to assess the impact of the contamination on the oxidative status of V. decussata. Enzyme activities increased in the digestive gland after PER treatment and in the gills after ANT treatment. PER exposure significantly reduced the levels of free thiols and increased levels of carbonylated proteins in the digestive gland, as compared to controls. In contrast, ANT exposure significantly reduced free thiols and increased the number of carbonylated proteins in the gills. Mix induced additive effects as measured by both enzymatic and proteomic approaches. The present study suggests that PER has a strong effect on shell structure; that PER and ANT exposure generate compound-dependent oxidative stress in the tissues of V. decussata and that a mixture of the two compounds has synergistic effects on biochemical response.

  12. Optics and remote sensing of Bahamian carbonate sediment whitings and potential relationship to wind-driven Langmuir circulation

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    H. M. Dierssen

    2009-03-01

    Full Text Available Regions of milky white seas or "whitings" periodically occur to the west of Andros Island along the Great Bahama Bank where the bottom sediment consists of fine-grained aragonite mud. We present measurements of inherent optical properties within a sediment whiting patch and discuss the potential for monitoring the frequency, extent, and quantity of suspended matter from ocean colour satellite imagery. Sea spectral reflectance measured in situ and remotely from space revealed highly reflective waters elevated across the visible spectrum (i.e., "whitened" with a peak at 490 nm. Particulate backscattering was an order of magnitude higher than that measured at other stations throughout the region. The whiting also had one of the highest backscattering ratios measured in natural waters (0.05–0.06 consistent with water dominated by aragonite particles with a high index of refraction. Regular periodicity of 40 and 212 s evident in the light attenuation coefficient over the sampling period indicated patches of fluctuating turbidity on spatial scales that could be produced from regular rows of Langmuir cells penetrating the 5-m water column. We suggest that previously described mechanisms for sediment resuspension in whitings, such as tidal bursting and fish activity, are not fully consistent with these data and propose that wind-driven Langmuir cells reaching the full-depth of the water column may represent a plausible mechanism for sediment resuspension and subsequent whiting formation. Optics and remote sensing provide important tools for quantifying the linkages between physical and biogeochemical processes in these dynamic shallow water ecosystems.

  13. Underground electromagnetic activity in two regions with contrasting seismicity: a case study from the Eastern Alps and Bohemian Massif

    Science.gov (United States)

    Baroň, Ivo; Koktavý, Pavel; Stemberk, Josef; Macků, Robert; Trčka, Tomáš; Škarvada, Pavel; Lenhardt, Wolfgang; Meurers, Bruno; Rowberry, Mattew; Marti, Xavi; Plan, Lukas; Grasemann, Berhnard; Mitrovic, Ivanka

    2016-04-01

    Electromagnetic emissions (EME) occur during the fracturing of solid materials under laboratory conditions and may represent potential earthquake precursors. We recorded EME from May 2015 to October 2015 in two caves situated in contrasting seismotectonic settings. Zbrašov Aragonite Caves are located close to the seismically quiescent contact between the Bohemian Massif and the Outer Western Carpathians while Obir Caves are located near the seismically active Periadriatic Fault on the southern margin of the Eastern Alps. The specific monitoring points are located at depths of tens of metres below the ground surface as such places are assumed to represent favourably shielded environments. The EME signals were continuously monitored by two custom-made Emission Data Loggers (EDLOG), comprising both analogue and digital parts. The crucial analogue component within the EDLOG is a wideband shielded magnetic loop antenna. To be able to observe EME related rock deformation and microfracturing we recorded signals between 10 and 200 kHz with a sampling frequency of 500 kHz. An ultralow noise preamplifier placed close to the antenna increases the signal-to-noise ratio. Further signal processing consisted of filtering, such as antialiasing and interference rejection, and additional amplification to fit the signal to the full scale range of the AD convertor. The digital part of the EDLOG comprises a range of PC components such as high-capacity replaceable data storage and unbuffered RAM, high-speed multichannel DAQ cards, and custom made control software in the programming environment LabVIEW. During our EME monitoring all the raw data were stored. This has allowed us to perform advanced data processing and detailed analysis. During the study period some artificial EME signals were observed in Zbrašov Aragonite Caves. This artificial noise may have overprinted any natural signals and is most likely to relate to the pumping of CO2. In contrast, markedly different signals were

  14. Microbial bio-mineralization processes in hydrothermal travertine: the case study of two active travertine systems (Tuscany, Italy).

    Science.gov (United States)

    Barilaro, Federica; Bontognali, Tomaso R. R.; Mc Kenzie, Judith A.; Vasconcelos, Crisogono

    2015-04-01

    Modern hydrothermal travertine deposits, occurring today at Bagni San Filippo (Radicofani Basin) and at Bagni di Saturnia (Albegna Valley) in Tuscany, Central Italy, have been investigated with the main purpose to improve the understanding of the processes that control calcium carbonate precipitation in hydrothermal-spring settings. Present-day thermal activity at Bagni di Saturnia is characterized by a 37.5°C thermal spring with a rate of about 800 l/s, with a pH of ca. 6.4. Thermal water discharges at Bagni San Filippo reach a rate of 20 litres per second at a maximum temperature of 50°C and a pH of ca. 7. The springs expel water enriched in H2S-CO2-SO42- and HCO3- and divalent cations (Ca and Mg). In the studied areas, travertine precipitation occurs in association with living microbial mats and biofilms, composed of a heterogeneous community of green algae, filamentous cyanobacteria and other types of prokaryotes, anoxygenic photosynthetic bacteria and heterotrophic heat-tolerant bacteria, with a variable amount of extracellular polymeric substances (EPS). Nine categories of fabric types, dominantly calcite and aragonite in composition, showing a wide range of macro- and micro-porosity, have been identified. High magnification analysis of dendritic and laminated boundstone, crystalline crust cementstone, raft boundstone, coated bubble boundstone, micrite mudstone and coated reed boundstone fabric types, suggests that precipitation occurs in association with organic matter. Diatoms, cyanobacteria filaments and other bacteria are then associated with the EPS and often appear totally or partially entombed (passively or actively) in it. Organic extracellular polymeric substances (EPS) and often the external surface of cyanobacterial sheaths are the location where the calcite minerals nucleate and grow. Precipitation begins with organomineral nano-globules consisting of nanometre-size, from sub-spherical to globular-like, raised structures (5 to 80 nm diameter

  15. 碳酸钙形成过程中重金属离子的配分问题研究(1)--理论基础和实验方法%Study on Heavy Metals Partitioning in Carbonate Calcium Formation (1)--Theoretic Background and Experimental Methods

    Institute of Scientific and Technical Information of China (English)

    陈万春; 加藤喜久雄; 陈中笑; 陈溯

    2000-01-01

    碳酸钙有方解石、霞石和球霞石3种同质异构形态,其中方解石是天然碳酸钙的最常见形式,也是碳酸盐在地表的稳定形态.作者研究和论述了重金属离子在碳酸盐形成过程中配分问题.文章分两部分:第一部分介绍配分问题研究的理论基础、实验方法和重金属离子的配分特征;第二部分介绍配分问题的研究机制.本文为第一部分.在这篇文章中,作者提出了重金属离子配分系数的计算方程;评述了方解石、霞石和球霞石及其固溶体的生成条件和合成方法;总结了晶体内微量元素的分析方法;讨论了重金属离子的配分特征.实验结果表明:Mg2+离子抑制球霞石的形成;Sr2+离子促进霞石的形成;F-离子抑制Mg2+在方解石晶面的吸附;Sr2+离子的分凝系数随生长速率的增加而增加;Co2+,Mg2+,Cd2+的分凝系数随生长速率的增加而降低.%Calcium carbonate has three different crystal forms, such as calcite, aragonite and vaterite. Calcite is the most common form of native calcium carbonate known and is one of the stable forms of carbonate on the earth's surface also. Authors have been summarized the research progress on heavy metals partitioning in carbonate calcium formation. The review is divided two parts. The topic for the part 1 is theoretic background and experimental methods. The topic for the part 2 is research progress and partitioning mechanism. Here is the part 1. In this paper,the equations for calculating partitioning coefficient of heavy metal ions were propo-sed. The growth conditions and synthetic methods for calcite, aragonite and vaterite and its solid solution have been evaluated. The analytical methods for trace elements were summarized. The partitioning behaviors of heavy metal ions were discussed. The experimental results shown that: the presence of Mg2+ inhibits vaterite formation;the presence of Sr2+ favors aragonite formation;F- inhibits adsorption of Mg2+ ions on

  16. Exploring the impact of temperature and fluid chemistry on Ca and Sr isotope composition of Arctica islandica shells via experimental alteration

    Science.gov (United States)

    Goos, Manuela; Eisenhauer, Anton; Liebetrau, Volker; Böhm, Florian; Fietzke, Jan; Nehrke, Gernot; Buhl, Dieter; Mavromatis, Vasileios; Dietzel, Martin

    2016-04-01

    Carbonate shells of marine organisms record by their chemical and isotopic composition environmental conditions like temperature, salinity and pH during their formation. However, primary signals can be overprinted by diagenesis, which has to be considered for the interpretation of environmental proxy data and on the other side may provide additional information about distinct reaction pathways throughout diagenesis (e.g. Allison et al, 2007). Aragonitic Arctica islandica shells widely used as proxy archives (e.g. Schöne et al, 2005) were chosen for hydrothermal alteration experiments in order to get a more detailed insight into diagenetic effects. Here we present results of experiments in which Arctica islandica shell fragments were exposed to North Sea seawater at temperatures of 100r{ }C and 175r{ }C at distinct reaction times. Strontium isotope composition of the experimental medium was adjusted from an original composition of δ 88/86SrSRM987= 0.391(1)‰ and 87Sr/86Sr= 0.70921(1) to δ 88/86SrSRM987= 0.179(1)‰ and 87Sr/86Sr= 0.70789(1) by sulfate extraction and Sr replacement procedures. The artificially altered shell material (six sub-samples of six shell fragments) and the corresponding solutions were prepared and analyzed. Results show that at 100r{ }C aragonite is still the predominant phase, but show lower peak intensities with Raman and XRD near the surface of the shell fragments. At 175r{ }C the aragonitic shell material recrystallized almost completely to calcite. In addition a rim of weakly ordered dolomite (10μ m) was found around these samples. Analysis of element concentrations of initial and final solutions show that at 175r{ }C Sr and Ca concentrations increase (Sr: 79 to 183 μ mol/l; Ca: 8 to 30 mmol/l), while Mg concentration decreases (Mg: 42 to 22 mmol/l). A corresponding Sr and Ca depletion along with an increase of Mg occurred in the samples, especially in the dolomite rim. At 100r{ }C only minor increase of Sr, Ca and Mg

  17. Low Florida coral calcification rates in the Plio-Pleistocene

    Science.gov (United States)

    Brachert, Thomas C.; Reuter, Markus; Krüger, Stefan; Klaus, James S.; Helmle, Kevin; Lough, Janice M.

    2016-08-01

    In geological outcrops and drill cores from reef frameworks, the skeletons of scleractinian corals are usually leached and more or less completely transformed into sparry calcite because the highly porous skeletons formed of metastable aragonite (CaCO3) undergo rapid diagenetic alteration. Upon alteration, ghost structures of the distinct annual growth bands often allow for reconstructions of annual extension ( = growth) rates, but information on skeletal density needed for reconstructions of calcification rates is invariably lost. This report presents the bulk density, extension rates and calcification rates of fossil reef corals which underwent minor diagenetic alteration only. The corals derive from unlithified shallow water carbonates of the Florida platform (south-eastern USA), which formed during four interglacial sea level highstands dated approximately 3.2, 2.9, 1.8, and 1.2 Ma in the mid-Pliocene to early Pleistocene. With regard to the preservation, the coral skeletons display smooth growth surfaces with minor volumes of marine aragonite cement within intra-skeletal porosity. Within the skeletal structures, voids are commonly present along centres of calcification which lack secondary cements. Mean extension rates were 0.44 ± 0.19 cm yr-1 (range 0.16 to 0.86 cm yr-1), mean bulk density was 0.96 ± 0.36 g cm-3 (range 0.55 to 1.83 g cm-3) and calcification rates ranged from 0.18 to 0.82 g cm-2 yr-1 (mean 0.38 ± 0.16 g cm-2 yr-1), values which are 50 % of modern shallow-water reef corals. To understand the possible mechanisms behind these low calcification rates, we compared the fossil calcification rates with those of modern zooxanthellate corals (z corals) from the Western Atlantic (WA) and Indo-Pacific calibrated against sea surface temperature (SST). In the fossil data, we found a widely analogous relationship with SST in z corals from the WA, i.e. density increases and extension rate decreases with increasing SST, but over a significantly larger

  18. Mg isotopes in biocarbonates: new insight into vital effects associated to echinoderms and bivalves calcification

    Science.gov (United States)

    Planchon, F.; Hermans, J.; Borremans, C.; Dubois, P.; Poulain, C.; Paulet, Y.; Andre, L.

    2007-12-01

    Mg isotopes can be helpful tracers to reveal the fundamental pathways of Mg incorporation during biomineralisation. We report in this study a detailed characterisation of the Mg isotopic signatures of different biominerals: high magnesium calcitic skeletons of selected echinoderms (sea urchins and starfish) and low magnesium aragonitic shells of a bivalve species (clam). State of the art analytical procedures were applied including sample purification step followed by high precision measurements using MC-ICP-MS (Nu instrument) in dry plasma conditions. 26Mg/24Mg and 25Mg/24Mg are expressed as per mil deviations from the DSM3 (Dead Sea Metal 3) reference standard in delta notation (d26Mg and d25Mg). For echinoderms, we considered: (a) adult specimens of six starfish species (Asteria r., Marthasterias g., Anseropoda p., Asterina g., Echinaster s. and Henricia o.), sampled in Brittany (France); (b) a sea urchin species (Paracentrotus lividus) with field samples (Mediterranean Sea, Marseille, France) and culture specimen under T and S controlled conditions. In vivo endoskeletons display negative, but different d26Mg values of -3.06 for starfish (with uniform interspecies signatures) and -2.65 for sea urchin. Relative to seawater signature (-0.82), all echinoderms favour the incorporation of light isotopes during biocalcification. The d26Mg depletion is lower than theoretically expected from a inorganic calcite precipitation from seawater (at -3.5). These differences suggest that on its route from seawater to the shell, Mg isotopes are partly biologically fractionationated through "vital effects" leaving heavier Mg isotopic signatures. Taken into account that calcification in echinoderms is an intra- cellular process involving transient amorphous calcium carbonate (ACC) phase, the observed bio-fractionation factors can be related to: (1) changes in the isotopic composition of the precipitating intracellular fluids due to active pumping in and out of the cell; (2) a

  19. Geochemical and sedimentological evidence for the massive dissociation and formation of subsurface gas hydrates on the Umitaka Spur, eastern margin of Japan Sea

    Science.gov (United States)

    Hiruta, A.; Matsumoto, R.; Snyder, G.; Tomaru, H.; Aoyama, C.; Machiyama, H.; Hiromatsu, M.; Hiruta, T.

    2006-12-01

    .3~-6.6 permil VPDB) were recovered close to north plume site whereas aragonite nodules (-41.1~-9.8 permil VPDB) were at active plume sites. Delta 18O values of aragonites (2.9~5.2 permil VPDB) and calcites (1.8~4.5 permil VPDB corrected for Mg content[4]) is generally heavier that calcite. Assuming that the water temperature of 0 to 1 °E C, the delta 18O values of carbonates indicates that calcite were precipitated from high oxygen water (0.3~2.3 permil VSMOW) while aragonite, from significantly low oxygen water (-2.9~-1.8 permil VSMOW). Such isotopically high and low oxygen waters are likely to have been derived from the dissociation and formation of G.H., respectively. U/Th ages of these nodules are around 20-30ky[5]. [1]Matsumoto et al.,2005,2005 AGU Fall Meeting [2]JOGMEC,2005,Kisoshisui Sado Nansei-oki [3]Aoyama et al.,2005,OCEAN'S 04 MTS/IEEE TECNO-OCEAN'04 [4]Tarutani et al.,1969,Geochim.Cosmochim.Acta,Vol.33 pp987- [5]Watanabe,2006,PhD thesis

  20. In situ Raman study of dissolved CaCO3 minerals under subduction zone conditions

    Science.gov (United States)

    Facq, S.; Daniel, I.; Sverjensky, D. A.

    2012-12-01

    The fate and the characteristics of the Earth's deep carbon reservoirs are still not well understood [1]. The connection between the surficial and the deep-Earth carbon cycles occurs at subduction zones where carbon is transported into the mantle and where hydrous silicates and carbonate minerals break down releasing H2O and C-species in fluids associated with mantle metasomatism and the generation of arc volcanism [2]. In order to obtain mass balance between recycling and burial in the deep mantle, the study of the dissolution of CaCO3 minerals in equilibrium with aqueous fluids under mantle conditions is crucial. We report a novel integrated experimental and theoretical study of the equilibration of CaCO3 minerals with aqueous solutions (pure water or NaCl solutions) at high pressures and temperatures (0.5 to 8 GPa and 250 to 500 °C). The fluid speciation was studied using in situ Raman spectroscopy coupled to an externally heated membrane type DAC equipped with 500 μm pure synthetic diamond anvils. In a typical experiment, the aqueous fluid and a calcite crystal [3] were loaded in a rhenium gasket. The pressure was determined from the calibrated shift of the carbonate υ1 symmetric stretching mode of aragonite and the temperature measured with a K-type thermocouple. Raman spectra were recorded using a Labram HR800 Raman spectrometer (Horiba Jobin-Yvon) coupled to a Spectra Physics Ar+ laser. At equilibrium with an aragonite crystal, the Raman data show that bicarbonate is the most abundant species in low-pressure fluids (below 4 GPa) whereas carbonate becomes progressively dominant at higher pressure. After correction from their Raman cross-sections [4], the relative amounts of dissolved carbonate and bicarbonate were estimated from the areas of the Raman bands of the carbonate and bicarbonate ions (υ1 and υ5 symmetric stretching modes, respectively). The presence of sodium chloride influences the speciation by extending the pressure field where the

  1. Current Travertines Precipitation from CO{sub 2}-rich Groundwaters as an alert of CO{sub 2} Leakages from a Natural CO{sub 2} Storage at Ganuelas-Mazarron Tertiary Basin (Murcia, Spain)

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigo-Naharro, J.; Delgado, A.; Herrero, M. J.; Granados, A.; Perez del Villar, L.

    2013-02-01

    Carbon capture and storage technologies (CCS) represent the most suitable solutions related to the high anthropogenic CO{sub 2} emissions to the atmosphere. As a consequence, monitoring of the possible CO{sub 2} leakages from an artificial deep geological CO{sub 2} storage (DGS) is indispensable to guarantee its safety. Fast surficial travertine precipitation related to these CO{sub 2} leakages can be used as an alert for these escapes. Since few studies exist focusing on the long-term behaviour of an artificial CO{sub 2} DGS, natural CO{sub 2} storage affected by natural or artificial escapes must be studied as natural analogues for predicting the long-term behaviour of an artificial CO{sub 2} storage. In this context, a natural CO{sub 2} reservoir affected by artificial CO{sub 2} escapes has been studied in this work. This study has mainly focused on the current travertines precipitation associated with the upwelling CO{sub 2}-rich waters from several hydrogeological wells drilled in the Ganuelas-Mazarron Tertiary basin (SE Spain), and consists of a comprehensive characterisation of parent-waters and their associated carbonates, including elemental and isotopic geochemistry, mineralogy and petrography. Geochemical characterisation of groundwaters has led to recognise 4 hydrofacies from 3 different aquifers. These groundwaters have very high salinity and electrical conductivity; are slightly acid; present high dissolved inorganic carbon (DIC) and free CO{sub 2}; are oversaturated in both aragonite and calcite; and dissolve, mobilize and transport low quantities of heavy and/or toxic elements. Isotopic values indicate that: i) the origin of parent-waters is related to rainfalls from clouds originated in the Mediterranean Sea or continental areas; ii) the origin of C is mainly inorganic; and iii) sulphate anions come mainly from the dissolution of the Messinian gypsum from the Tertiary Basin sediments. Current travertines precipitation seems to be controlled by a

  2. Permeability Reduction in Passively Degassing Seawater-dominated Volcanic-hydrothermal systems: Processes and Perils on Raoul Island, Kermadecs (NZ)

    Science.gov (United States)

    Christenson, B. W.; Reyes, A. G.

    2014-12-01

    The 2006 eruption from Raoul Island occurred apparently in response to local tectonic swarm activity, but without any precursory indication of volcanic unrest within the hydrothermal system on the island. The eruption released some 200 T of SO2, implicating the involvement of a deep magmatic vapor input into the system during/prior to the event. In the absence of any recognized juvenile material in the eruption products, previous explanations for this eruptive event focused on this vapor being a driving force for the eruption. In 2004, at least 80 T/d of CO2 was escaping from the hydrothermal system, but mainly through areas that did not correspond to the 2006 eruption vents. The lack of a pre-eruptive hydrothermal system response related to the seismic event in 2006 can be explained by the presence of a hydrothermal mineralogic seal in the vent area of the volcano. Evidence for the existence of such a seal was found in eruption deposits in the form of massive fracture fillings of aragonite, calcite and anhydrite. Fluid inclusion homogenization temperatures in these phases range from ca. 140 °C to 220 °C which, for pure water indicate boiling point depths of between 40 and 230 m assuming a cold hydrostatic pressure constraint. Elevated pressures behind this seal are consistent with the occurrence of CO2 clathrates in some inclusion fluids, indicating CO2 concentrations approaching 1 molal in the parent fluids. Reactive transport modeling of magmatic volatile inputs into what is effectively a seawater-dominated hydrothermal system provide valuable insights into seal formation. Carbonate mineral phases ultimately come to saturation along this flow path, but we suggest that focused deposition of the observed massive carbonate seal is facilitated by near-surface boiling of these CO2-enriched altered seawaters, leading to large degrees of supersaturation which are required for the formation of aragonite. As the seal grew and permeability declined, pore pressures

  3. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  4. Trace Elements in Calcifying Marine Invertebrates Indicate Diverse Sensitivities to the Seawater Carbonate System

    Science.gov (United States)

    Doss, W. C.

    2015-12-01

    Surface ocean absorption of anthropogenic CO2 emissions resulting in ocean acidification may interfere with the ability of calcifying marine organisms to biomineralize, since the drop in pH is accompanied by reductions in CaCO3 saturation state. However, recent experiments show that net calcification rates of cultured benthic invertebrate taxa exhibit diverse responses to pCO2-induced changes in saturation state (Ries et al., 2009). Advancement of geochemical tools as biomineralization indicators will enable us to better understand these results and therefore help predict the impacts of ongoing and future decrease in seawater pH on marine organisms. Here we build upon previous work on these specimens by measuring the elemental composition of biogenic calcite and aragonite precipitated in four pCO2 treatments (400; 600; 900; and 2850 ppm). Element ratios (including Sr/Ca, Mg/Ca, Li/Ca, B/Ca, U/Ca, Ba/Ca, Cd/Ca, and Zn/Ca) were analyzed in 18 macro-invertebrate species representing seven phyla (crustacea, cnidaria, echinoidea, rhodophyta, chlorophyta, gastropoda, bivalvia, annelida), then compared to growth rate data and experimental seawater carbonate system parameters: [CO32-], [HCO3-], pH, saturation state, and DIC. Correlations between calcite or aragonite composition and seawater carbonate chemistry are highly taxa-specific, but do not resemble trends observed in growth rate for all species. Apparent carbonate system sensitivities vary widely by element, ranging from strongly correlated to no significant response. Interpretation of these results is guided by mounting evidence for the capacity of individual species to modulate pH and/or saturation state at the site of calcification in response to ambient seawater chemistry. Such biomineralization pathways and strategies in turn likely influence elemental fractionation during CaCO3 precipitation. Ries, J.B., A.L. Cohen, A.L., and D.C. McCorkle (2009), Marine calcifiers exhibit mixed responses to CO2-induced ocean

  5. Neodymium isotopes in biogenic carbonates: reliable archives of ɛNd

    Science.gov (United States)

    Montagna, P.; Goldstein, S. L.; Taviani, M.; Frank, N.; McCulloch, M. T.

    2010-12-01

    Neodymium isotope (143Nd/144Nd) compositions from dispersed authigenic ferromanganese oxide fraction in marine sediments, ferromanganese crusts, foraminiferal shells and fossil fish teeth are employed to trace provenance and water mass mixing in the past, having the advantage of not being fractionated by biological processes in the water column. In the modern ocean the different water masses ultimately derive their ɛNd values through continental weathering, erosion and particle-seawater interactions. This geochemical tracer has been only recently applied to scleractinian deep-water coral skeletons sourced from various sites and depths in the Atlantic ocean. Aragonitic corals can be precisely dated by U-series, potentially providing century-long records of intermediate and bathyal zone variability at sub-decadal resolution. Motivated by these recent findings we have investigated the Nd isotopic compositions of living specimens of various calcifying organisms collected in two key locations of the Mediterranean Sea and in the Southern Ocean. In particular, we analyzed several specimens of the aragonitic deep-water corals Desmophyllum dianthus, Lophelia pertusa, Madrepora oculata, Flabellum impensum, the temperate coral Cladocora caespitosa, the calcitic gorgonian coral Corallium rubrum, the bivalves Glans aculeata and Karnekampia bruei and the polychate Serpula vermicularis. Most of the samples were retrieved from the Strait of Sicily and the Southern Adriatic Sea at different water depths. Ten seawater samples from three new profiles in the Mediterranean were also collected at the same locations and depths, offering a unique opportunity to compare the Nd isotopic composition of biogenic carbonates directly with the surrounding ambient seawater. The Mediterranean Sea is particularly suited for this comparison exercise since it is characterized by water masses displaying a large range of ɛNd values, from -10.5 in the Western Mediterranean to -4.8 in the Eastern

  6. Groundtruthing the Neodymium Isotope Proxy in Deep-Sea Corals

    Science.gov (United States)

    van de Flierdt, T.; Robinson, L. F.; Adkins, J. F.

    2007-12-01

    The Nd isotopic composition of marine precipitates is increasingly recognized as a powerful tool in paleoceanography. Unlike nutrient proxies such as δ13C or Cd/Ca, Nd isotopes are not thought to be altered by biological processes, and thus may serve as a quasi-conservative water mass mixing tracer. However, any archive, which is used to extract authigenic Nd isotopes, needs careful examination, to test the integrity of the inferred seawater signal. Here we present first data on cleaning experiments and modern calibration experiments on different species of deep-sea corals. Seven different coral samples ranging in age from modern to ~220ka were selected for experiments designed to remove ferromanganese crusts and / or organic residues that may contain high concentrations of Nd and Th. The aim was to determine whether the rigorous chemical procedure we use to remove Th associated with these crusts is effective at removing Nd, and whether it causes any fractionation in the Nd isotopic composition of the coral aragonite. Crusts were found to contain Th-232 concentrations of up to ~160ppm, with 232Th/230Th ratios dependent on the oceanic location of the coral. Un-cleaned corals had Th-232 concentrations of up to 8ppb and the cleaning procedure reduced these values to less than 0.2ppb in both modern and fossil specimens. Neodymium isotopic compositions reveal that for modern corals, with no visible coating, a pre-cleaning step is sufficient to yield the isotopic composition of ambient seawater. The ferromanganese coating around fossil corals however may have a very different isotopic composition than the coral aragonite since it may be a time-integrated signal biased towards modern values. This bias is observed for intermediate water depth D. dianthus corals from stage 3 in the northwest Atlantic. Modern D. dianthus skeletons from the northwest Atlantic and the Drake Passage reflect the seawater Nd isotopic composition, and we are extending this modern calibration to

  7. Nutrient and carbonate ion proxy calibrations in the deep sea coral D. dianthus (Invited)

    Science.gov (United States)

    Anagnostou, E.; Lavigne, M.; Gagnon, A. C.; Adkins, J. F.; McDonough, W. F.; Sherrell, R. M.

    2009-12-01

    Marine carbonates are among the most successful and reliable substrates for chemical paleoceanographic studies. Deep-sea corals are especially useful because they allow measurement of both 14C and U-Th dates in a single coral. Tracers, however, are needed to derive ventilation rates in the past from the mixing ratio of distinct endmember water masses. Reconstruction of nutrient abundances and carbonate ion distributions, even in regions where deep mixing is sluggish and regeneration is significant, could provide clues about basin-scale variations in export production, changes in whole-ocean nutrient inventory, and carbonate system equilibria on geological timescales. To fill this gap, we present modern calibrations of two paleo-nutrient proxies and a carbonate ion proxy in the deep sea coral D. dianthus. We demonstrate that P/Ca, Ba/Ca and U/Ca are direct proxies for phosphate (remineralized at shallow depths), dissolved barium (a deep-remineralized element with silicate-type distribution) and seawater carbonate ion, respectively. We analyzed 20, globally distributed, D. dianthus specimens using a 193nm excimer laser ablation HR-ICP-MS, along growth axis-oriented septal thick sections, which reveals the internal structure. Using an 80-100 μm spot size, data are collected from within the fibrous aragonite avoiding central band material as well as contamination and altered aragonite on the exterior of the septa. All seawater data used are derived from nearby WOCE/GEOSECS/CLIVAR stations. Plotting the coralline P/Ca against ambient seawater phosphate resulted in a calibration with an apparent partition coefficient (D= Element/Cacoral / Element/Caseawater) of 0.5 ± 0.1 (r=0.8, P<0.05, n=17). Similarly, the Ba/Ca in the coral versus dissolved seawater barium gave a DBa= 1.3 ± 0.3 (r= 0.8, P<0.05, n=15), and coralline U/Ca (µmol/mol) versus seawater carbonate ion (µmol/kg) gave a regression slope of -0.098 ± 0.002 (r=0.8, P<0.05, n=13). We tested potential

  8. Evaluation of boron isotope ratio as a pH proxy in the deep sea coral Desmophyllum dianthus: Evidence of physiological pH adjustment

    Science.gov (United States)

    Anagnostou, E.; Huang, K.-F.; You, C.-F.; Sikes, E. L.; Sherrell, R. M.

    2012-10-01

    The boron isotope ratio (δ11B) of foraminifers and tropical corals has been proposed to record seawater pH. To test the veracity and practicality of this potential paleo-pH proxy in deep sea corals, samples of skeletal material from twelve archived modern Desmophyllum dianthus (D. dianthus) corals from a depth range of 274-1470 m in the Atlantic, Pacific, and Southern Oceans, ambient pH range 7.57-8.05, were analyzed for δ11B. The δ11B values for these corals, spanning a range from 23.56 to 27.88, are found to be related to seawater borate δ11B by the linear regression: δ11Bcoral=(0.76±0.28) δ11Bborate+(14.67±4.19) (1 standard error (SE)). The D. dianthus δ11B values are greater than those measured in tropical corals, and suggest substantial physiological modification of pH in the calcifying space by a value that is an inverse function of seawater pH. This mechanism partially compensates for the range of ocean pH and aragonite saturation at which this species grows, enhancing aragonite precipitation and suggesting an adaptation mechanism to low pH environments in intermediate and deep waters. Consistent with the findings of Trotter et al. (2011) for tropical surface corals, the data suggest an inverse correlation between the magnitude of a biologically driven pH offset recorded in the coral skeleton, and the seawater pH, described by the equation: ΔpH=pH recorded by coral-seawater pH=-(0.75±0.12) pHw+(6.88±0.93) (1 SE). Error analysis based on 95% confidence interval(CI) and the standard deviation of the regression residuals suggests that the uncertainty of seawater pH reconstructed from δ11Bcoral is ±0.07 to 0.12 pH units. This study demonstrates the applicability of δ11B in D. dianthus to record ambient seawater pH and holds promise for reconstructing oceanic pH distribution and history using fossil corals.

  9. The calibration of clumped-isotope thermometry on modern marine mollusk

    Science.gov (United States)

    Canavan, R. R.; Affek, H. P.; Zaarur, S.; Douglas, P. M.; Wang, Z.

    2013-12-01

    Clumped-isotope (Δ47) thermometry is a novel method to reconstruct paleotemperatures that can be applied to studying past coastal and marine environments using marine mollusk shells. Macrofossil mollusk shells are common in the fossil record and provide enough material to satisfy the relatively large-sample requirement for Δ47 analysis, making them ideal for clumped-isotope paleothermometry. If consistent with the clumped isotope thermometer, mollusk Δ47 derived temperatures should record local water temperatures during shell growth season. Recent studies, however, show strong deviations from the empirical Δ47-T calibration derived from synthetic calcite in some modern mollusk shells (cephalopods, gastropods and bivalves; Dennis et al., 2013; Henkes et al., 2013; Eagle et al., 2013) but not in others (bivalves; Douglas et al., submitted; Came et al., 2007). The source of these discrepancies has been hypothesized to be related to 1) different laboratory techniques (including sample preparation and instrument standardization), 2) growth of CaCO3 polymorphs (calcite, aragonite or vaterite) in shells, and 3) variable environmental growth conditions such as salinity and pH. We test the effect of CaCO3 polymorph, taxonomy, and mollusk growth conditions by comparing among Δ47 values of calcitic shells from eastern oysters (Crassostrea virginica), those of clam shells that are mostly aragonitic (collected along the United States' Atlantic coast), and published calibrations of the clumped isotope thermometer. Atlantic oysters were collected from 37°N to 43°N latitude, with temperatures ranging between ~ 10-25°C, and brackish to marine salinities ranging from 14.5 - 34 PSU. Clam genera were similarly collected along the coast between Florida up north to Maine with growth temperatures ranging from ~ 10-22 °C. We further examine whether the deviation from the calibration is related to the relatively low reproducibility observed in modern mollusk Δ47 measurements, and

  10. Crystallization of CaCO3 Induced by Mixed Template of Polymer and Surfactant%聚合物与表面活性剂混合模板调控碳酸钙结晶

    Institute of Scientific and Technical Information of China (English)

    丁红霞; 尹晓爽; 杨文忠

    2011-01-01

    以聚乙烯醇(PVA)和聚苯乙烯磺酸钠(PSSS)分别与十六烷基三甲基溴化铵(CTAB)组成混合模板,在CaCl2、Na2CO3体系中调控合成CaCO3晶体.考察了不同CTAB浓度及结晶温度对碳酸钙晶体的影响.通过扫描电子显微镜(SEM)、红外光谱(FT-IR)及X射线衍射(XRD)等技术对晶体的形貌和结构进行了表征,并对不同形貌碳酸钙的形成机理进行了探讨.结果表明:在PVA和CTAB模板中,5℃为方解石椭球状聚集体,25℃时为菊花状、立方状的方解石和球霰石的混晶,90℃时得到针状文石晶簇.以PSSS和CTAB模板调控下的碳酸钙,5℃时为球状的方解石和球霰石的混晶,25℃为颗粒均匀的球形球霰石,90℃时得到了花朵状文石.不同形貌及晶型碳酸钙的生成源自聚合物与CTAB组成复合物结构的差异.%Calcium carbonate was prepared by the Na2CO3 with CaCl2 in the mixed templates of polymer (PVA/PSSS) and surfactant (CTAB) at different temperatures and concentrations of CTAB. The products were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD). The results showed that in the PVA/CTAB system the ellipsoid aggregates of calcite could be prepared at 5 ℃ and rosette type and cubic aggregates of calcite and vaterite at 25 ℃ while druses of needle-like aragonite crystals were obtained at 90 ℃. In the PSSS/CTAB system, spherical precipitation of calcite and vaterite could be obtained at 5 ℃, uniform size of spherical vaterite were obtained at 25 ℃. At the temperature of 90 ℃, flower-like aragonite was precipitated. The different complex of polymer and CTAB resulted in the different morphology and crystal form of calcium carbonate

  11. Authigenic carbonate crusts and chimneys along the North Anatolian Fault in the Sea of Marmara, Turkey

    Science.gov (United States)

    Yıldız, Güliz; Namık Çaǧatay, M.

    2016-04-01

    The Sea of Marmara is located on the North Anatolian Fault (NAF) fault zone that is a major continental transform plate boundary. It has ca. 1250 m-deep Tekirdag, Central and Cinarcik basins that are separated by two NE-SW trending Central and Western Highs. Extensive cold seeps occur along the active fault segments of the NAF in the deep basins and highs, which are associated with authigenic carbonate crusts, carbonate chimneys and mounds, black sulphidic sediments, and local gas hydrates and oil seepage. The cold seep sites were observed and sampled during the Nautile submersible and Victor 6000 Remotely Operated Vehicle (ROV) dives carried out during MARNAUT and MARSITE cruises in 2007 and 2014, respectively. Here, we report the mineralogical and stable isotopic composition of the authigenic carbonates and discuss their environmental conditions and mechanisms of formation. The carbonate crusts range up to 5 cm in thickness and the chimneys and mounds are up to 2 m high. Some chimneys are active emitting fresh to brackish water at ambient bottom water temperatures (˜ 14° C). The carbonate crusts occur as a pavements, and are commonly covered with black sulphidic sediments and bacterial mats that accommodate a rich chemosynthetic community of bivalves, sea urchins and marine annelid worms (Polychaeta). The authigenic carbonates commonly consist mainly of aragonite, but in a few instances contain subequal amounts of aragonite and calcite. High Mg-calcite is usually a minor to trace component, except in one sample in which it is present as a cement of mudstone. In the active methane emission zones, the sulphate/methane boundary occurs at or close to the seafloor, whereas elsewhere in the Sea of Marmara, the same boundary is located at 2-5 m below the seafloor. This, together with very light stable carbon isotope values (δ13C=-29.8 to - 46.3 ‰ V-PDB), indicates that the anaerobic oxidation of high methane flux emitted from the active faults is the major process

  12. Effect of tartaric acid (C4H6O6) and temperatures on induction time and variation of crystal phases of CaCO3 in a piping system

    Science.gov (United States)

    Putranto, W. A.; Usmany, Y.; Bayuseno, A. P.; Muryanto, S.

    2016-04-01

    Calcium carbonate scale formation is a serious problem found in pipes of many industrial processes, such as chemical, desalination and oil industries. The presence of scale makes the narrowing of the diameter of pipes and reduction of heat transfer performance. This paper presents result of crystallization behavior of CaCO3 in pipes. The crystals forming solutions were made by mixing of equimolar solution to CaCl2 and Na2CO3 with Ca2+ concentration of 3,000 ppm. The parameters studied were the solution flow rates (25, 35, 50 mL/min), temperatures (27, 35, 50°C) and tartaric acid as additives (0.00, 1.00, 10.00 ppm) for the scaling inhibition. The CaCO3 scales formation process was monitored by measuring the change in the solution conductivity. The scale obtained was then characterized by SEM/EDS for morphology and elemental analysis, and XRD for phase composition. It was observed that the conductivity of the solution remained constant after a certain period, and subsequently it dropped sharply. This induction time obtained was varied from 28 min to 46 min depending on the parameters studied. The higher flow rates and temperatures in the solution resulted in more CaCO3 scale mass precipitated, indicating that these two parameters may promote CaCO3 crystallisation. However, the higher tartaric acid concentrations in the solution lead to less mass of the scale produced and could reduce the mass down to 90%. It can be postulated that the tartaric acid may be an effective additive for CaCO3 crystallization. SEM and EDS analysis of the scale indicated that the scale was composed of calcium carbonate. In addition, XRD characterization of the scale confirmed that the scale consisted of vaterite, aragonite and calcite minerals. The scale of aragonite mineral was precipitated under the influence of tartaric acid and temperatures. This indicates that the acid could delay the transformation into stable phase of calcite.

  13. A Holocene speleothem record from Morocco, NW Africa

    Science.gov (United States)

    Wassenburg, Jasper; Fietzke, Jan; Richter, Detlev; Immenhauser, Adrian

    2010-05-01

    A well dated Holocene speleothem (stalagmite) from the Middle Atlas Mountains in Morocco has been investigated for its continental climate record. The aim is to compile an improved understanding of the climatically complex triple point of the North Atlantic, Mediterranean and Saharan / Monsoonal climate realms in NW Africa. At present, only few studies concerning continental climate reconstructions from NW Africa have been published (Lamb et al. 1995, Cheddadi et al. 1998, Genty et al. 2006). Given the significance of this region, this lack of data forms a strong motivation for additional, well dated climate records. The speleothem (GP2) was sampled in the 'Grotte de Piste' (ca 800 m above sea level), mean annual precipitation is about 930 mm (mainly falling in the winter season) and the mean annual temperature is about 13° C. GP2 is 60 cm tall and grew - based on U/Th MC-ICP-MS data - continuously between 11.5 kyr BP (early Holocene) and 2.9 kyr BP (late Holocene). X-Ray Diffraction data indicate a mainly aragonitic mineralogy. 'Hendy tests' suggest that CaCO3 precipitation was close to isotopic equilibrium with respect to oxygen isotopes, however kinetic effects might have influenced carbon isotopes. Carbon and oxygen isotope data have been measured along a transect with increments of approximately 1 mm representing a resolution of about 15 yrs. Highly covariant oscillations in δ13C and δ18O with an average cyclicity of about 410 yrs. are observed. These oscillations coincide with macroscopically visible high density and low density layers, possibly reflecting a higher or lower amount of inclusions and perhaps higher and lower growth rates. Geochemical analysis of speloan aragonite is accompanied by cave monitoring that has started in November 2009. Parameters quantified include: drip water parameters, cave air humidity, pCO2 and cave air temperature. Precipitation experiments using watch glasses will also be performed. References Cheddadi, R., Lamb, H. F

  14. Scleractinian Fossil Corals as Archives of Seawater δ26Mg

    Science.gov (United States)

    Gothmann, A. O.; Higgins, J. A.; Adkins, J. F.; Stolarski, J.; Bender, M. L.

    2014-12-01

    The recovery of environmental signatures from coral skeletons is often made difficult by 'vital effects', which cause skeletal chemistry to deviate from the expected composition of aragonite in equilibrium with seawater. Recent studies show that Mg isotopes in scleractinian corals are subject to vital effects, which appear as a departure of the δ26Mg coral temperature dependence from that of inorganic aragonite [1]. However, different from the case for Mg/Ca or δ44Ca in coral, the magnitude of the observed Mg-isotope vital effect is small (on the order of 0.1 ‰ or less). In addition, measurements of different species of modern coral show similar fractionations, suggesting that coral δ26Mg is not species dependent [2]. Together, these observations indicate that corals should faithfully record the seawater Mg-isotope composition, and that vital effects will not bias reconstructions. We measured Mg isotopes in a set of extremely well-preserved fossil scleractinian corals, ranging in age from Jurassic through Recent, to reconstruct past seawater δ26Mg. Well-preserved fossil corals of similar age show a range in δ26Mg of ~0.2 ‰, pointing to the presence of vital effects. However, our results show little variability in the δ26Mg of fossil corals across different geologic ages, suggesting that seawater δ26Mg has remained relatively constant throughout the Cenozoic and Mesozoic. This pattern has implications for our understanding of the mechanisms driving secular variations in seawater Mg/Ca. In particular, our data imply that dolomitization rates have not changed enough during the Mesozoic and Cenozoic to account for secular variations in seawater Mg/Ca. Our coral δ26Mg record agrees with a Cenozoic record from bulk foraminifera, further supporting the faithfulness of the coral archive. However, both of these records disagree with a third Cenozoic Mg-isotope record, derived from species-specific planktic forams [3]. [1] Saenger, C. et al. (2014) Chem. Geol

  15. Ca and Mg isotope constraints on the origin of Earth's deepest δ13 C excursion

    Science.gov (United States)

    Husson, Jon M.; Higgins, John A.; Maloof, Adam C.; Schoene, Blair

    2015-07-01

    Understanding the extreme carbon isotope excursions found in carbonate rocks of the Ediacaran Period (635-541 Ma), where δ13 C of marine carbonates (δ13 Ccarb) reach their minimum (- 12 ‰) for Earth history, is one of the most vexing problems in Precambrian geology. Known colloquially as the 'Shuram' excursion, the event has been interpreted by many as a product of a profoundly different Ediacaran carbon cycle. More recently, diagenetic processes have been invoked, with the very negative δ13 C values of Ediacaran carbonates explained via meteoric alteration, late-stage burial diagenesis or growth of authigenic carbonates in the sediment column, thus challenging models which rely upon a dramatically changing redox state of the Ediacaran oceans. Here we present 257 δ 44 / 40 Ca and 131 δ26 Mg measurements, along with [Mg], [Mn] and [Sr] data, from carbonates of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia to bring new isotope systems to bear on understanding the 'Shuram' excursion. Data from four measured sections spanning the basin reveal stratigraphically coherent trends, with variability of ∼1.5‰ in δ26 Mg and ∼1.2‰ in δ 44 / 40 Ca. This Ca isotope variability dwarfs the 0.2-0.3 ‰ change seen coeval with the Permian-Triassic mass extinction, the largest recorded in the rock record, and is on par with putative changes in the δ 44 / 40 Ca value of seawater seen over the Phanerozoic Eon. Changes in both isotopic systems are too large to explain with changes in the isotopic composition of Ca and Mg in global seawater given modern budgets and residence times, and thus must be products of alternative processes. Relationships between δ 44 / 40 Ca and [Sr] and δ26 Mg and [Mg] are consistent with mineralogical control (e.g., aragonite vs. calcite, limestone vs. dolostone) on calcium and magnesium isotope variability. The most pristine samples in the Wonoka dataset, preserving Sr concentrations (in the 1000s of ppm range) and δ 44 / 40

  16. Cenozoic Seawater Sr/Ca ratios: Implications for coral reef development through ocean de-acidification

    Science.gov (United States)

    Sosdian, S. M.; Grossman, E. L.; Lear, C. H.; Tao, K.; Rosenthal, Y.

    2010-12-01

    Records of seawater chemistry help constrain the temporal variation in geochemical processes that impact the global carbon cycle and global climate across Earth’s history. To date, various attempts to reconstruct Cenozoic seawater Sr/Ca ratios have produced markedly different results, with estimated Paleogene seawater Sr/Ca ranging from ~50% higher than today to 70% lower. We reconstruct seawater Sr/Ca using Eocene to Pliocene fossil mollusks collected from US Gulf Coast (Mississippi, Alabama, and Florida). We use Conus spp. and Turritella, taxa for which the Sr/Ca distribution coefficients have been determined as a function of temperature in modern specimens [1, 2]. Specimens were serially sampled perpendicular to growth to produce seasonal records of Sr/Ca. Fossil Conus shells show pronounced seasonal Sr/Ca cycles with a strong inverse correlation between Sr/Ca and δ18O, similar to those observed in modern specimens [1]. The fossil Turritella also show similar Sr/Ca cyclicity as modern specimens [2]. We calculate seawater Sr/Ca ratios using our Sr/Ca record, modern Sr/Ca-temperature calibrations for Conus and Turritella [1, 2], and a paleotemperature record based on oxygen isotopes from the same samples [3]. Seawater Sr/Ca increased from ~11.5 to 13.9 mmol/mol between the mid-Eocene (42 Ma) and early Oligocene (33 Ma) and decreased substantially from the mid-Miocene (11 mmol/mol) to the Pliocene (9 mmol/mol) and modern (8.5 mmol/mol). A mass balance model of variations in seawater Sr concentrations suggests a long-term decrease through the Neogene, which we attribute to a significant increase in the proportion of aragonite versus calcite deposition in shallow waters. The largest change is coincident with the proliferation of coral reefs, which occurred after the calcite-aragonite sea transition, and was likely ultimately driven by ocean de-acidification. [1] Sosdian et al. (2006) Geochemistry, Geophysics, Geosystems (G3) 7, Q11023, doi:10.1029/2005GC001233; [2

  17. Mg/Ca and isotopic high resolution record of deep-sea hydrothermal barnacles

    Science.gov (United States)

    Bojar, A.-V.; Bojar, H.-P.; Tufar, W.

    2012-04-01

    Barnacles are crustaceans adapted to a sessile existence and cemented to a substrate by a protein complex. Most of the known species inhabit shallow marine environment, less than 2% of the species are found at depths between 100 and 2500 m. The shell of barnacles has a great adaptive significance, the shell of some barnacle species have been already investigated for microstructure. In this study we investigated the shell microstructure as well as the Mg/Ca and stable isotope distribution of barnacles found at a depth of around 2500m at a black smoker from the Manus Spreading centre, north-east of Papua New Guinea. The shell consists of three substructures: an outer layer with pores and aragonite crystals, a massive interior mass and an inner layer with pores. The shell shows grown lines and the outer layer exhibits longitudinal striation from base to apex. The pores have a medium size of 0.8 microns. The size of the calcitic microcrystals are in the range of 0.2 to 0.5 microns, beside, larger aragonite crystals, with size of c. 10 microns are present. The massive interior mass has a compact structure, no pores or channels could be observed. Oxygen stable isotope data of barnacle shell were performed from the centre to the border of the calcitic shells, along profiles. Within one shell, the isotope values show variations of max. 0.6 ‰. The calculated temperatures from the stable isotope data consistently indicate that the barnacles populate sites with low temperature values, up to a few °C. The calculated temperatures from the isotope data are also in agreement with the reported habitat from the North Fiji and Lau Basins, where temperatures of max. 6°C were measured at sites populated by barnacles. Both calculated and measured temperatures of a few degrees indicate that at the sites where barnacles live, hydrothermal fluid input is present, as ambient temperature is around 1.5°C. Electron-microbeam analyses were done along the interior layer of the shell. The

  18. Characteristics of porosity and permeability layer of fossil Halimeda reef mineral rock of Miocene in the Xisha Islands and its genetic model

    Institute of Scientific and Technical Information of China (English)

    XU Hong; WEI Kai; CUI Ruyong; ZHU Yurui; EBERLI G P; LUO Wei; ZHAO Xinwei; CAI Ying; LIU Xinyu; YAN Guijing; ZHANG Bolin

    2015-01-01

    Halimeda is one of the major reef-building algas in the middle Miocene of Xisha, and one of the significant reef-building algas in the algal reef oil and gas field of the South China Sea. However, there have been few reports regarding the characteristics of mineral rocks, reservoir porosity and permeability layers, and sedimentation-diagenetic-evolution of fossil Halimeda systems. The present paper briefly introduces the relevant studies on chlorophyta Halimeda and the research status of oil and gas exploration. Through the 1 043 m core of the Xichen-1 well, we studied the characteristics of the mineral rocks and porosity and permeability of the middle Miocene Halimeda of the Yongle Atoll, identified and described the segments of fossil Halimeda, and pointed out that most of the segment slides are vertical sections in ovular, irregular or long strips. The overwhelming majority of these fossil Halimeda found and studied are vertical sections instead of cross sections. In this paper, knowledge regarding the cross sections of fossil Halimeda is reported and proven to be similar with the microscopic characteristics of modern living Halimeda;fossil Halimeda are buried in superposition;it is shown that there are different structures present, including typical bio-segment structure, and due to its feature of coexisting with red alga, tying structure, twining structure and encrusting structure are all present;and finally, it is suggested to classify the fossil Halimeda into segment algal reef dolomites. In addition, all of the studied intervals are moderately dolomitized. Secondary microcrystalline-dolosparite dominates the original aragonite raphide zones, and aphanitic-micrite dolomite plays the leading role in the cortexes and medullas;in the aragonite raphide zones between medulla and cysts, secondary dissolved pores and intercrystalline pores are formed inside the segments, and algal frame holes are formed between segments;therefore, a pore space network system

  19. Seasonality and long term trends in dissolved carbon export from large rivers to the Arctic Ocean, and potential effects on coastal ocean acidification (Invited)

    Science.gov (United States)

    Tank, S. E.; Kokelj, S. V.; Raymond, P. A.; Striegl, R. G.; McClelland, J. W.; Holmes, R. M.; Spencer, R. G.

    2013-12-01

    Large Arctic rivers show marked seasonality in constituent flux as a result of variations in flowpath throughout the yearly cycle. Here, we use measurements collected from the mouths of the six largest rivers draining to the Arctic Ocean to explore seasonal variation in dissolved inorganic and dissolved organic carbon (DIC, DOC) flux, and the effect of this flux on nearshore ocean processes. This work uses data from the Yukon and Mackenzie Rivers in North America, and the Kolyma, Lena, Yenisey, and Ob' in Siberia. Mean monthly concentrations of riverine DIC vary synchronously across all rivers, peaking under ice and reaching a low point immediately after the spring freshet. Monthly climatologies for DIC, in addition to similarly constructed climatologies for Ca2+, show that the input of riverwater universally causes aragonite to be undersaturated in riverine-influenced nearshore regions, with an effect that is greater for the Siberian coast than for western North America, and greater in the spring-winter than in the late summer and fall. Because seasonal trends and geographic variation in DOC concentration are opposite to that for DIC in these large rivers, degradation of DOC to CO2 in the nearshore Arctic should accentuate seasonal and spatial patterns in aragonite undersaturation in Arctic coastal regions. Datasets that extend DIC and DOC concentration measurements back to the early 1970's (DIC) and early 1980's (DOC) near the mouth of the Mackenzie River in the western Canadian Arctic indicate that the summertime concentration and flux of these constituents has been increasing over time in this region. While evidence from other regions of the pan-Arctic, and data gathered from smaller sub-catchment studies indicate that this trend is not universal for DOC, there is growing evidence for a consistent increase in summertime DIC flux across both time and gradients of decreasing permafrost extent. These changes, in turn, could have broad implications for both

  20. Review: the effects of secular variation in seawater Mg/Ca on marine biocalcification

    Directory of Open Access Journals (Sweden)

    J. B. Ries

    2009-07-01

    Full Text Available Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO3 precipitates (ooids, marine cements throughout Phanerozoic time is believed to have been caused by tectonically-induced variations in seawater molar Mg/Ca (>2="aragonite seas"; <2="calcite seas". Here, I review a series of experiments in which extant calcifying taxa were reared in experimental seawater formulated over the range of mMg/Ca ratios (1.0 to 5.2 that occurred throughout their geologic history.

    Aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibited higher rates of calcification and growth in the experimental seawaters that favored their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary production increased along with calcification in mineralogically-favorable seawater is consistent with the hypothesis that calcification promotes photosynthesis within autotrophs through the liberation of CO2.

    The Mg/Ca ratio of calcite secreted by the coccolithophores, coralline algae and reef-dwelling animals (crustacea, urchins, calcareous tube worms declined with reductions in seawater Mg/Ca. Calcifying microbial biofilms varied their mineral polymorph with seawater Mg/Ca (mMg/Ca<2=low Mg calc; mMg/Ca>2=arag+high Mg calc, suggesting a nearly abiotic mode of calcification. These results indicate that biomineralogical control can be partially overridden by ambient seawater Mg/Ca and suggests that modern high Mg calcite organisms probably secreted low Mg calcite in calcite seas of the past. Notably, Mg fractionation in autotrophic organisms was more strongly influenced by changes in

  1. Structural characterization of the N-terminal mineral modification domains from the molluscan crystal-modulating biomineralization proteins, AP7 and AP24.

    Science.gov (United States)

    Wustman, Brandon A; Morse, Daniel E; Evans, John Spencer

    2004-08-05

    The AP7 and AP24 proteins represent a class of mineral-interaction polypeptides that are found in the aragonite-containing nacre layer of mollusk shell (H. rufescens). These proteins have been shown to preferentially interfere with calcium carbonate mineral growth in vitro. It is believed that both proteins play an important role in aragonite polymorph selection in the mollusk shell. Previously, we demonstrated the 1-30 amino acid (AA) N-terminal sequences of AP7 and AP24 represent mineral interaction/modification domains in both proteins, as evidenced by their ability to frustrate calcium carbonate crystal growth at step edge regions. In this present report, using free N-terminal, C(alpha)-amide "capped" synthetic polypeptides representing the 1-30 AA regions of AP7 (AP7-1 polypeptide) and AP24 (AP24-1 polypeptide) and NMR spectroscopy, we confirm that both N-terminal sequences possess putative Ca (II) interaction polyanionic sequence regions (2 x -DD- in AP7-1, -DDDED- in AP24-1) that are random coil-like in structure. However, with regard to the remaining sequences regions, each polypeptide features unique structural differences. AP7-1 possesses an extended beta-strand or polyproline type II-like structure within the A11-M10, S12-V13, and S28-I27 sequence regions, with the remaining sequence regions adopting a random-coil-like structure, a trait common to other polyelectrolyte mineral-associated polypeptide sequences. Conversely, AP24-1 possesses random coil-like structure within A1-S9 and Q14-N16 sequence regions, and evidence for turn-like, bend, or loop conformation within the G10-N13, Q17-N24, and M29-F30 sequence regions, similar to the structures identified within the putative elastomeric proteins Lustrin A and sea urchin spicule matrix proteins. The similarities and differences in AP7 and AP24 N-terminal domain structure are discussed with regard to joint AP7-AP24 protein modification of calcium carbonate growth.

  2. Calcium carbonate saturation in the surface water of the Arctic Ocean: undersaturation in freshwater influenced shelves

    Directory of Open Access Journals (Sweden)

    A. Fransson

    2009-11-01

    Full Text Available In the summer of 2005, we sampled surface water and measured pH and total alkalinity (AT underway aboard IB Oden along the Northwest Passage from Cape Farewell (South Greenland to the Chukchi Sea. We investigated the variability of carbonate system parameters, focusing particularly on carbonate concentration [CO32−] and calcium carbonate saturation states, as related to freshwater addition, biological processes and physical upwelling. Measurements on AT, pH at 15°C, salinity (S and sea surface temperature (SST, were used to calculate total dissolved inorganic carbon (CT, [CO32−] and the saturation of aragonite (ΩAr and calcite (ΩCa in the surface water. The same parameters were measured in the water column of the Bering Strait. Some surface waters in the Canadian Arctic Archipelago (CAA and on the Mackenzie shelf (MS were found to be undersaturated with respect to aragonite (ΩAr<1. In these areas, surface water was low in AT and CT (<1500 μmol kg−1 relative to seawater and showed low [CO32−]. The low saturation states were probably due to the likely the effect of dilution due to freshwater addition by sea ice melt (CAA and river runoff (MS. High AT and CT and low pH, corresponded with the lowest [CO32−], ΩAr and ΩCa, observed near Cape Bathurst and along the South Chukchi Peninsula. This was linked to the physical upwelling of subsurface water with elevated CO2. The highest surface ΩAr and ΩCa of 3.0 and 4.5, respectively, were found on the Chukchi Sea shelf and in the cold water north of Wrangel Island, which is heavily influenced by high CO2 drawdown and lower CT from intense biological production. In the western Bering Strait, the cold and saline Anadyr Current carries water that is enriched in AT and

  3. Acidification of the Shallow Arctic Seas as Biogeochemical Consequences of Permafrost Degradation

    Science.gov (United States)

    Semiletov, I. P.; Shakhova, N. E.; Pipko, I.; Repina, I.; Pugach, S.; Dudarev, O.; Charkin, A.

    2013-12-01

    There is increasing concern about consequences of ocean acidification from the increasing atmospheric carbon dioxide driven shifts toward lower seawater pH The largest pH changes in this century are anticipated in the surface waters of the Arctic ocean (Orr et al., 2005; Steinacher et al., 2009). Concurrently, aragonite undersaturation might occur locally and become widespread as atmospheric CO2 increases to more than 450ppm (Olafsson et al., 2009). However, the ocean acidification effects induced by increasing Arctic land-shelf export of fluvial and erosional organic carbon (OC) and its oxidation are unknown. Here we show that massive net redistribution of old OC from thawing permafrost to the East-Siberian Arctic Seas (ESAS) and its consequent remineralization drives acidification over the ESAS which represents the broadest and shallowest shelf of the World Ocean. From top to the bottom the ESAS waters were observed to be undersaturated with respect to aragonite and calcite, and thus potentially corrosive to CaCO3 for the shelf sediments and benthic ecosystems. Our multiyear all-seasonal results (1999-2011) demonstrate how the net ecosystem metabolism of the Siberian shelves, which is the net balance of autotrophic (photosynthesis and net community production) and heterotrophic (respiration and remineralization) processes, is likely to function as the heterotrophic dominated ecosystem. CO2 outgassing from the East Siberian Arctic Shelf (ESAS) is quantified using multi-year eddy-correlation flux measurements. It is shown that the ESAS is currently a source of atmospheric CO2. A continuing warming adds more terrestrial OC to the Arctic Shelf Seas, which increases pCO2, as the same time as decreased transparency lowers primary production, which reduce consumption of CO2 (and increase acidification effects). This effect results in a positive feedback by outgassing CO2 over the Siberian Shelf , which comprises one half of the entire shelf area. This multi-year study

  4. Review: the effects of secular variation in seawater Mg/Ca on marine biocalcification

    Science.gov (United States)

    Ries, J. B.

    2009-07-01

    Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO3 precipitates (ooids, marine cements) throughout Phanerozoic time is believed to have been caused by tectonically-induced variations in seawater molar Mg/Ca (>2="aragonite seas"; experimental seawater formulated over the range of mMg/Ca ratios (1.0 to 5.2) that occurred throughout their geologic history. Aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibited higher rates of calcification and growth in the experimental seawaters that favored their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary production increased along with calcification in mineralogically-favorable seawater is consistent with the hypothesis that calcification promotes photosynthesis within autotrophs through the liberation of CO2. The Mg/Ca ratio of calcite secreted by the coccolithophores, coralline algae and reef-dwelling animals (crustacea, urchins, calcareous tube worms) declined with reductions in seawater Mg/Ca. Calcifying microbial biofilms varied their mineral polymorph with seawater Mg/Ca (mMg/Ca2=arag+high Mg calc), suggesting a nearly abiotic mode of calcification. These results indicate that biomineralogical control can be partially overridden by ambient seawater Mg/Ca and suggests that modern high Mg calcite organisms probably secreted low Mg calcite in calcite seas of the past. Notably, Mg fractionation in autotrophic organisms was more strongly influenced by changes in seawater Mg/Ca, a probable consequence of them inducing a less controlled mode of calcification simply through the removal of CO2 via photosynthesis. This body of work also has implications for thermal

  5. Hydroclimatic variability in the Levant during the early last glacial (∼ 117–75 ka derived from micro-facies analyses of deep Dead Sea sediments

    Directory of Open Access Journals (Sweden)

    I. Neugebauer

    2015-08-01

    Full Text Available The new sediment record from the deep Dead Sea basin (ICDP core 5017-1 provides a unique archive for hydroclimatic variability in the Levant. Here, we present high-resolution sediment facies analysis and elemental composition by μXRF scanning of core 5017-1 to trace lake levels and responses of the regional hydroclimatology during the time interval from ca 117–75 ka, i.e. the transition between the last interglacial and the onset of the last glaciation. We distinguished six major micro-facies types and interpreted these and their alterations in the core in terms of relative lake level changes. The two end-member facies for highest and lowest lake levels are (a up to several meters thick, greenish sediments of alternating aragonite and detrital marl laminae (aad and (b thick halite facies, respectively. Intermediate lake levels are characterised by detrital marls with varying amounts of aragonite, gypsum or halite, reflecting lower-amplitude, shorter-term variability. Two intervals of pronounced lake level drops occurred at ∼110–108 ± 5 and ∼93–87 ± 7 ka. They likely coincide with stadial conditions in the central Mediterranean (Melisey I and II pollen zones in Monticchio and low global sea levels during MIS 5d and 5b. However, our data do not support the current hypothesis of an almost complete desiccation of the Dead Sea during the earlier of these lake level low stands based on a recovered gravel layer. Based on new petrographic analyses, we propose that, although it was a low stand, this well-sorted gravel layer may be a vestige of a thick turbidite that has been washed out during drilling rather than an in-situ beach deposit. Two intervals of higher lake stands at ∼108–93 ± 6 and ∼87–75 ± 7 ka correspond to interstadial conditions in the central Mediterranean, i.e. pollen zones St. Germain I and II in Monticchio, and GI 24 + 23 and 21 in Greenland, as well as to sapropels S4 and S3 in the Mediterranean Sea. These

  6. Coral reefs on the edge? Carbon chemistry on inshore reefs of the great barrier reef.

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    Sven Uthicke

    Full Text Available While increasing atmospheric carbon dioxide (CO2 concentration alters global water chemistry (Ocean Acidification; OA, the degree of changes vary on local and regional spatial scales. Inshore fringing coral reefs of the Great Barrier Reef (GBR are subjected to a variety of local pressures, and some sites may already be marginal habitats for corals. The spatial and temporal variation in directly measured parameters: Total Alkalinity (TA and dissolved inorganic carbon (DIC concentration, and derived parameters: partial pressure of CO2 (pCO2; pH and aragonite saturation state (Ωar were measured at 14 inshore reefs over a two year period in the GBR region. Total Alkalinity varied between 2069 and 2364 µmol kg-1 and DIC concentrations ranged from 1846 to 2099 µmol kg-1. This resulted in pCO2 concentrations from 340 to 554 µatm, with higher values during the wet seasons and pCO2 on inshore reefs distinctly above atmospheric values. However, due to temperature effects, Ωar was not further reduced in the wet season. Aragonite saturation on inshore reefs was consistently lower and pCO2 higher than on GBR reefs further offshore. Thermodynamic effects contribute to this, and anthropogenic runoff may also contribute by altering productivity (P, respiration (R and P/R ratios. Compared to surveys 18 and 30 years ago, pCO2 on GBR mid- and outer-shelf reefs has risen at the same rate as atmospheric values (∼1.7 µatm yr-1 over 30 years. By contrast, values on inshore reefs have increased at 2.5 to 3 times higher rates. Thus, pCO2 levels on inshore reefs have disproportionately increased compared to atmospheric levels. Our study suggests that inshore GBR reefs are more vulnerable to OA and have less buffering capacity compared to offshore reefs. This may be caused by anthropogenically induced trophic changes in the water column and benthos of inshore reefs subjected to land runoff.

  7. Interpreting the effect of CO2-induced ocean acidification on elemental partitioning in biogenic carbonates within the framework of Rayleigh fractionation

    Science.gov (United States)

    Gilmore, R. E.; Eagle, R.; Ries, J. B.; Tripati, A. K.

    2013-05-01

    The elemental composition of calcium carbonate (CaCO3) precipitated by marine invertebrates varies with the physico-chemical properties of seawater, and is thus used for reconstructing past oceanic conditions, including temperature, pH, and seawater composition. Previous studies have used a Rayleigh fractionation model to interpret elemental partitioning within a range of calcitic and aragonitic organisms, including foraminifera and corals. We present elemental ratios for 18 species of calcareous marine invertebrates, including echinoids, corals, bivalves, gastropods, calcifying algae, crustacea, and serpulid worms, which were reared at CO2-induced aragonite saturation states (±SD) of 2.5 (±0.4), 2.0 (±0.4), 1.5 (±0.3), and 0.7 (±0.2). Importantly, specimens were cultured simultaneously at the same temperature and in seawater sourced from the same reservoir, allowing comparison amongst taxa without regard to native water conditions. A combination of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) were used to determine the elemental ratios. We interpret the partitioning of strontium, magnesium, barium, manganese, boron, lithium and uranium within the biogenic carbonates of these 18 invertebrates, along with data from the literature for foraminifera and coccolithophores raised under varying pCO2 and temperature conditions, within a Rayleigh fractionation framework. Application of a Rayleigh model to these systems requires constraints on elemental partitioning into inorganic CaCO3. Our survey of the literature shows that there are limited data for some elements (e.g., Mn) and that, for others (e.g., Sr, Mg), there are a wide range of values reported for a given element. Given this uncertainty, we examine the impact that varying the nominal inorganic partition coefficient has on Rayleigh-derived estimates of calcium-utilization during calcification. The elements examined in this study

  8. Coral reefs on the edge? Carbon chemistry on inshore reefs of the great barrier reef.

    Science.gov (United States)

    Uthicke, Sven; Furnas, Miles; Lønborg, Christian

    2014-01-01

    While increasing atmospheric carbon dioxide (CO2) concentration alters global water chemistry (Ocean Acidification; OA), the degree of changes vary on local and regional spatial scales. Inshore fringing coral reefs of the Great Barrier Reef (GBR) are subjected to a variety of local pressures, and some sites may already be marginal habitats for corals. The spatial and temporal variation in directly measured parameters: Total Alkalinity (TA) and dissolved inorganic carbon (DIC) concentration, and derived parameters: partial pressure of CO2 (pCO2); pH and aragonite saturation state (Ωar) were measured at 14 inshore reefs over a two year period in the GBR region. Total Alkalinity varied between 2069 and 2364 µmol kg-1 and DIC concentrations ranged from 1846 to 2099 µmol kg-1. This resulted in pCO2 concentrations from 340 to 554 µatm, with higher values during the wet seasons and pCO2 on inshore reefs distinctly above atmospheric values. However, due to temperature effects, Ωar was not further reduced in the wet season. Aragonite saturation on inshore reefs was consistently lower and pCO2 higher than on GBR reefs further offshore. Thermodynamic effects contribute to this, and anthropogenic runoff may also contribute by altering productivity (P), respiration (R) and P/R ratios. Compared to surveys 18 and 30 years ago, pCO2 on GBR mid- and outer-shelf reefs has risen at the same rate as atmospheric values (∼1.7 µatm yr-1) over 30 years. By contrast, values on inshore reefs have increased at 2.5 to 3 times higher rates. Thus, pCO2 levels on inshore reefs have disproportionately increased compared to atmospheric levels. Our study suggests that inshore GBR reefs are more vulnerable to OA and have less buffering capacity compared to offshore reefs. This may be caused by anthropogenically induced trophic changes in the water column and benthos of inshore reefs subjected to land runoff.

  9. Late Quaternary changes in surface productivity and oxygen minimum zone (OMZ) in the northwestern Arabian Sea: Micropaleontologic and sedimentary record at ODP site 728A

    Indian Academy of Sciences (India)

    Ajai K Rai; S S Das

    2011-02-01

    Changes in the abundance of selected planktic foraminiferal species and some sedimentological parameters at ODP site 728A were examined to understand the fluctuations in the surface productivity and deep sea oxygenation in the NW Arabian Sea during last ∼540 kyr. The increased relative abundances of high fertility taxa, i.e., Globigerinita glutinata and Globigerina bulloides mainly during interglacial intervals indicate intense upwelling. Strong SW summer monsoon probably increased the upwelling in the western Arabian Sea during interglacial intervals and caused high surface productivities due to the lateral transport of eutrophic waters. Most of the glacial periods (i.e., MIS 2, 4, 6, 8 and 12) are characterized by higher relative abundances of Neogloboquadrina pachyderma and Neogloboquadrina dutertrei associated with Globigerinoides ruber. The more stratified condition and deep mixed layer due to increased NE winter monsoon are mainly responsible for the higher relative abundances of N. pachyderma during glacial periods. Some of the glacial intervals (i.e., MIS 6 and 8) are also characterized by pteropod spikes reflecting deepening of aragonite compensation depth (ACD) and relatively less intense oxygen minimum zone (OMZ) in this region due to deep sea mixing and thermocline ventilation, and relatively less intense surface productivity during winter monsoon. The interglacial periods are largely devoid of pteropod shells indicating more aragonite dissolution due to increased intensity of OMZ in the northwestern Arabian Sea. In general, the interglacial periods are characterized by low sediment accumulation rates than the glacial intervals. On an average, the total biogenic carbonate percentages were higher during interglacial and during periods of higher surface productivity. Most terrigenous material was trapped on shelf during intervals of high sea level stands of interglacial, whereas more erosion of shelf increased the sedimentation rates during glacial

  10. Formation of low-T hydrated silicates in modern microbialites from Mexico and implications for microbial fossilization

    Science.gov (United States)

    Zeyen, Nina; Benzerara, Karim; Li, Jinhua; Groleau, Alexis; Balan, Etienne; Robert, Jean-Louis; Esteve, Imene; Tavera, Rosaluz; Moreira, David; Lopez-Garcia, Purificacion

    2015-10-01

    Microbialites are organo-sedimentary rocks found in abundance throughout the geological record back to ~3.5 Ga. Interpretations of the biological and environmental conditions under which they formed rely on comparisons with modern microbialites. Therefore, a better characterization of diverse modern microbialites is crucial to improve such interpretations. Here, we studied modern microbialites from three Mexican alkaline crater lakes: Quechulac, La Preciosa and Atexcac. The geochemical analyses of water solutions showed that they were supersaturated to varying extents with several mineral phases, including aragonite, calcite, hydromagnesite, as well as hydrated Mg-silicates. Consistently, X-ray diffraction and Fourier transform infrared spectroscopy analyses revealed that microbialites are composed of a diversity of mineral phases including aragonite and sometimes calcite, hydromagnesite, and more interestingly, a poorly-crystalline hydrated silicate phase. Coupling of scanning electron microscopy with energy dispersive X-ray spectrometry microanalyses on polished sections showed that this latter phase is abundant, authigenic, magnesium-rich and sometimes associated with iron and manganese. This mineral phase is similar to kerolite, a hydrated poorly crystalline talc-like phase (Mg3Si4O10(OH)2·nH2O). Diverse microfossils were permineralized by this silicate phase. Some of them were imaged in 3D by FIB-tomography showing that their morphologically was exquisitely preserved down to the few nm-scale. The structural and chemical features of these fossils were further studied using a combination of transmission electron microscopy and scanning transmission X-ray microscopy at the carbon and magnesium K-edges and iron L2,3-edges. These results showed that organic carbon is pervasively associated with kerolite. Overall, it is suggested that the poorly-crystalline hydrated magnesium-rich silicate forms in many alkaline lakes and has a strong potential for fossilization of

  11. Formation of low-T hydrated silicates in modern microbialites from Mexico and implications for microbial fossilization

    Directory of Open Access Journals (Sweden)

    Nina eZeyen

    2015-10-01

    Full Text Available Microbialites are organo-sedimentary rocks found in abundance throughout the geological record back to ~3.5 Ga. Interpretations of the biological and environmental conditions under which they formed rely on comparisons with modern microbialites. Therefore, a better characterization of diverse modern microbialites is crucial to improve such interpretations. Here, we studied modern microbialites from three Mexican alkaline crater lakes: Quechulac, La Preciosa and Atexcac. The geochemical analyses of water solutions showed that they were supersaturated to varying extents with several mineral phases, including aragonite, calcite, hydromagnesite, as well as hydrated Mg-silicates. Consistently, X-ray diffraction and Fourier transform infrared spectroscopy analyses revealed that microbialites are composed of a diversity of mineral phases including aragonite and sometimes calcite, hydromagnesite, and more interestingly, a poorly-crystalline hydrated silicate phase. Coupling of scanning electron microscopy with energy dispersive X-ray spectrometry microanalyses on polished sections showed that this latter phase is abundant, authigenic, magnesium-rich and sometimes associated with iron and manganese. This mineral phase is similar to kerolite, a hydrated poorly crystalline talc-like phase (Mg3Si4O10(OH2·nH2O. Diverse microfossils were permineralized by this silicate phase. Some of them were imaged in 3D by FIB-tomography showing that their morphologically was exquisitely preserved down to the few nm-scale. The structural and chemical features of these fossils were further studied using a combination of transmission electron microscopy and scanning transmission X-ray microscopy at the carbon and magnesium K-edges and iron L2,3-edges. These results showed that organic carbon is pervasively associated with kerolite. Overall, it is suggested that the poorly-crystalline hydrated magnesium-rich silicate forms in many alkaline lakes and has a strong potential

  12. Isotopic constraints of mantle derived carbonatitic melts from Calatrava, Spain

    Science.gov (United States)

    Humphreys, E. R.; Bailey, K.; Hawkesworth, C. J.; Wall, F.; Avanzinelli, R.

    2010-12-01

    Carbonatite volcanism is typically associated both spatially and temporally with alkaline, ultramafic volcanism (Woolley & Church, 2005). Recent discoveries in Calatrava, Spain illustrate the activity of carbonatite in the source melts of leucitite volcanism. Melilitite pyroclastic lapilli tuffs also show a clear association with volcanic carbonate. Carbonatitic activity has been shown to initiate at depths greater than 100km (Humphreys et al., 2010) despite a maximum estimate of lithospheric thickness of 80km. The presence of aragonite and abundant mantle xenoliths in many deposits are clear indication of the rapid emplacement rates of such magmas. Carbonatitic activity in the source of the leucitite melts is indicated by carbonate inclusions within olivine xenocrysts and the presence of occasional carbonatite lenses. The composition of lead and strontium isotope ratios in the bulk rock, and spatially resolved analysis of carbonate from the groundmass and from inclusions demonstrates a genetic affinity between the inclusions and the related bulk rock composition. Lead and strontium isotopic analysis suggest that such melts do not represent the composition of convecting asthenospheric mantle. 87Sr/86Sr (0.7055-0.7068) values are higher than those of MORB and most OIB. Lead isotope ratios show a trend displaced to higher 207Pb/204Pb relative to MORB and OIB. Carbonate inclusions have less radiogenic lead values than the more radiogenic bulk rocks. Our data indicate that carbonatitic activity in the mantle is intrinsic in the generation of the leucitite lava. However, petrographic and isotopic evidence suggest a complex melt history. Olivine xenocrysts are not in equilibrium with the host leucitite, despite inclusions within olivine showing an isotopic affinity to the bulk rock. We suggest that in this example, alkaline magmatism was induced by the presence of CO2 in the mantle source. Isotopic evidence shows that the mantle producing such melts was not

  13. Calcium carbonate saturation in the surface water of the Arctic Ocean: undersaturation in freshwater influenced shelves

    Directory of Open Access Journals (Sweden)

    M. Chierici

    2009-05-01

    Full Text Available In the summer of 2005, we sampled surface water and measured pH and total alkalinity (AT underway aboard IB Oden along the Northwest Passage from Cape Farwell (South Greenland to the Chukchi Sea. We investigated variability of carbonate system parameters, focusing particularly on carbonate concentration [CO32−] and calcium carbonate saturation states, as related to freshwater addition, biological processes and physical upwelling. Measurements on AT, pH at 15°C, salinity (S and sea surface temperature (SST, were used to calculate total dissolved inorganic carbon (DIC, [CO32−] and saturation of aragonite (ΩAr and calcite (ΩCa in the surface water. The same parameters were measured in the water column of the Bering Strait. Some surface waters in the Canadian Arctic Archipelago (CAA and on the Mackenzie shelf (MS were found to be undersaturated with respect to aragonite (ΩAr<1. In these areas, surface water was low in AT and DIC (<1500 μmol kg−1 relative to seawater and showed low [CO32−]. The low saturation states were probably due to the effect of dilution due from freshwater addition by sea ice melt (CAA and river runoff (MS. High AT and DIC and low pH, corresponded with the lowest [CO32−], ΩAr and ΩCa, observed near Cape Bathurst and along the South Chukchi Peninsula. This was linked to physical upwelling of subsurface water with elevated CO2. Highest surface ΩAr and ΩCa of 3.0 and 4.5, respectively, were found on the Chukchi Sea shelf and in the cold water north of Wrangel Island, which is heavily influenced by high CO2 drawdown and lower DIC from intense biological production. In the western Bering Strait, the cold and saline Anadyr Current carries water that is enriched in AT and DIC from enhanced organic matter remineralization, resulting in

  14. Regional variability of acidification in the Arctic: a sea of contrasts

    Directory of Open Access Journals (Sweden)

    E. E. Popova

    2014-01-01

    Full Text Available The Arctic Ocean is a region that is particularly vulnerable to the impact of ocean acidification driven by rising atmospheric CO2, with potentially negative consequences for calcifying organisms such as coccolithophorids and foraminiferans. In this study, we use an ocean-only general circulation model, with embedded biogeochemistry and a comprehensive description of the ocean carbon cycle, to study the response of pH and saturation states of calcite and aragonite to rising atmospheric pCO2 and changing climate in the Arctic Ocean. Particular attention is paid to the strong regional variability within the Arctic, and, for comparison, simulation results are contrasted with those for the global ocean. Simulations were run to year 2099 using the RCP8.5 (an Intergovernmental Panel on Climate Change (IPCC Fifth Assessment Report (AR5 scenario with the highest concentrations of atmospheric CO2. The separate impacts of the direct increase in atmospheric CO2 and indirect effects via impact of climate change (changing temperature, stratification, primary production and freshwater fluxes were examined by undertaking two simulations, one with the full system and the other in which atmospheric CO2 was prevented from increasing beyond its preindustrial level (year 1860. Results indicate that the impact of climate change, and spatial heterogeneity thereof, plays a strong role in the declines in pH and carbonate saturation (Ω seen in the Arctic. The central Arctic, Canadian Arctic Archipelago and Baffin Bay show greatest rates of acidification and Ω decline as a result of melting sea ice. In contrast, areas affected by Atlantic inflow including the Greenland Sea and outer shelves of the Barents, Kara and Laptev seas, had minimal decreases in pH and Ω because diminishing ice cover led to greater vertical mixing and primary production. As a consequence, the projected onset of undersaturation in respect to aragonite is highly variable regionally within the

  15. Effect of ocean acidification on the early life stages of the blue mussel Mytilus edulis

    Science.gov (United States)

    Gazeau, F.; Gattuso, J.-P.; Dawber, C.; Pronker, A. E.; Peene, F.; Peene, J.; Heip, C. H. R.; Middelburg, J. J.

    2010-07-01

    Several experiments have shown a decrease of growth and calcification of organisms at decreased pH levels. There is a growing interest to focus on early life stages that are believed to be more sensitive to environmental disturbances such as hypercapnia. Here, we present experimental data, acquired in a commercial hatchery, demonstrating that the growth of planktonic mussel (Mytilus edulis) larvae is significantly affected by a decrease of pH to a level expected for the end of the century. Even though there was no significant effect of a 0.25-0.34 pH unit decrease on hatching and mortality rates during the first 2 days of development nor during the following 13-day period prior to settlement, final shells were respectively 4.5±1.3 and 6.0±2.3% smaller at pHNBS~7.8 (pCO2~1100-1200 μatm) than at a control pHNBS of ~8.1 (pCO2~460-640 μatm). Moreover, a decrease of 12.0±5.4% of shell thickness was observed after 15d of development. More severe impacts were found with a decrease of ~0.5 pHNBS unit during the first 2 days of development which could be attributed to a decrease of calcification due to a slight undersaturation of seawater with respect to aragonite. Indeed, important effects on both hatching and D-veliger shell growth were found. Hatching rates were 24±4% lower while D-veliger shells were 12.7±0.9% smaller at pHNBS~7.6 (pCO2~1900 μatm) than at a control pHNBS of ~8.1 (pCO2~540 μatm). Although these results show that blue mussel larvae are still able to develop a shell in seawater undersaturated with respect to aragonite, the observed decreases of hatching rates and shell growth could lead to a significant decrease of the settlement success. As the environmental conditions considered in this study do not necessarily reflect the natural conditions experienced by this species at the time of spawning, future studies will need to consider the whole larval cycle (from fertilization to settlement) under environmentally relevant conditions in order to

  16. Comparisons of the ecology and stable isotopic compositions of living (stained) benthic foraminifera from the Sulu and South China Seas

    Science.gov (United States)

    Rathburn, A. E.; Corliss, B. H.; Tappa, K. D.; Lohmann, K. C.

    1996-10-01

    Significant differences are observed between living (Rose Bengal stained) deep-sea benthic foraminifera found in 14 box cores (510-4515 m) from the thermospheric (> 10°C) environments of the Sulu Sea and the psychrospheric ( 2‰ range and are similar to those presented by previous workers, but have no consistent relationship with microhabitat preferences. Vertical distribution patterns and carbon isotope compositions of species, however, reflect microhabitat preferences and are consistent with previous observations from other regions. Epifaunal species (0-1 cm interval) such as Cibicidoides pachyderma, Cibicidoides wuellerstorfi, Hoeglundina elegans and Anomalinoides colligera, have higher δ13C values than taxa which have the ability to live deeper within the sediments. Infaunal taxa that live in the upper 2-3 cm, including Uvigerina peregrina, Uvigerina proboscidea, and Bulimina mexicana, have lower δ13C values than epifaunal species, and the deep infaunal species, Chilostomella oolina, has the lowest δ13C. Cibicidoides bradyi and Oridorsalis umbonatus are found between 0 and ˜ 4 cm and have lower carbon isotope values (by > 1.4‰ in some cores) than epifaunal Cibicidoides species. Exceptions to this pattern include the aragonitic species, Gavelinopsis lobatulus, (0-4 cm) which produces significantly lower δ13C values than deep infaunal taxa, and the shallow infaunal species, Ceratobulimina pacifica (also aragonitic) and Bolivinopsis cubensis (deep infaunal), which yield higher carbon isotopic values than epifaunal taxa. These exceptions are found primarily in only one core, and additional samples are needed to confirm the relationship between their distribution patterns and isotopic compositions. Each of the species examined has a relatively consistent δ13C value throughout its distribution within the sediments that may result from heterogeneity of microhabitats within the intervals sampled. Intrageneric differences in δ13C of Cibicidoides, and possibly

  17. Methane seepage in the Shenhu area of the northern South China Sea: constraints from carbonate chimneys

    Science.gov (United States)

    Guan, Hongxiang; Zhang, Mei; Mao, Shengyi; Wu, Nengyou; Lu, Hongfeng; Chen, Duofu

    2016-06-01

    Two authigenic carbonate chimneys were recovered from the Shenhu area in the northern South China Sea at approximately 400 m water depth. The chimneys' mineralogy, isotopic composition, and lipid biomarkers were studied to examine the biogeochemical process that induced the formation of the chimneys. The two chimneys are composed mostly of dolomite, whereas the internal conduits and semi-consolidated surrounding sediments are dominated by aragonite and calcite. The specific biomarker patterns (distribution of lipids and their depleted δ13C values) indicate the low occurrence of methanotrophic archaea ANME-1 responsible for the chimneys' formation via anaerobic oxidation of methane. A significant input of bacteria/planktonic algae and cyanobacteria to the carbon pool during the precipitation of the carbonate chimneys is suggested by the high contributions of short-chain n-alkanes (69% of total hydrocarbons) and long-chain n-alcohols (on average 56% of total alcohols). The oxygen isotopic compositions of the carbonate mixtures vary from 3.1‰ to 4.4‰ in the dolomite-rich chimneys, and from 2.1‰ to 2.5‰ in the internal conduits, which indicates that they were precipitated from seawater-derived pore waters during a long period covering the last glacial and interglacial cycles. In addition, the mixture of methane and bottom seawater dissolved inorganic carbon could be the carbon sources of the carbonate chimneys.

  18. Microfacies and geochemistry of the Ilam Formation in the Tang-E Rashid area, Izeh, S.W. Iran

    Science.gov (United States)

    Adabi, Mohammad H.; Mehmandosti, Elham Asadi

    2008-07-01

    The Ilam Formation (Santonian-Campanian in age), part of the Bangestan Group, is disconformably overlain by the Sarvak Formation and underlain by the Gurpi Formation in the Tang-E Rashid, Peyon area, Izeh (Zagros), southwest of Iran. Facies analyses indicate that the Ilam carbonates formed in four microfacies belts: tidal flat, lagoon, shoal and open marine, in a platform ramp environment. Major and minor elements and carbon and oxygen isotope values were used to determine the original carbonate mineralogy of the Ilam Formation. Petrographic evidence and elemental and oxygen and carbon isotope values indicate that aragonite was the original carbonate mineralogy in the Ilam Formation. The elemental and isotopic compositions of the Ilam carbonates also illustrate that they have stabilized in the marine phreatic environment. Variations of Sr/Ca and δ 18O values versus Mn suggest that diagenetic alteration occurred in a closed system. Temperature calculation based on the oxygen isotope value of the least-altered sample indicates that the very early shallow burial fluid temperature was around 28 °C. Recognition of the exact boundary between the Ilam and Sarvak Formations is difficult, due to similar lithologies and the absence of the Surgah Formation in the study area. However, elemental and oxygen and carbon isotope analysis were used to determine the boundary between these formations. The δ 18O and δ 13C values, along with elemental results, clearly indicate a subaerial exposure surface, below which meteoric diagenesis affected the sediments.

  19. Community metabolism in shallow coral reef and seagrass ecosystems, lower Florida Keys

    Science.gov (United States)

    Turk, Daniela; Yates, Kimberly K.; Vega-Rodriguez, Maria; Toro-Farmer, Gerardo; L'Esperance, Chris; Melo, Nelson; Ramsewak, Deanesch; Estrada, S. Cerdeira; Muller-Karger, Frank E.; Herwitz, Stan R.; McGillis, Wade

    2016-01-01

    Diurnal variation of net community production (NEP) and net community calcification (NEC) were measured in coral reef and seagrass biomes during October 2012 in the lower Florida Keys using a mesocosm enclosure and the oxygen gradient flux technique. Seagrass and coral reef sites showed diurnal variations of NEP and NEC, with positive values at near-seafloor light levels >100–300 µEinstein m-2 s-1. During daylight hours, we detected an average NEP of 12.3 and 8.6 mmol O2 m-2 h-1 at the seagrass and coral reef site, respectively. At night, NEP at the seagrass site was relatively constant, while on the coral reef, net respiration was highest immediately after dusk and decreased during the rest of the night. At the seagrass site, NEC values ranged from 0.20 g CaCO3 m-2 h-1 during daylight to -0.15 g CaCO3 m-2 h-1 at night, and from 0.17 to -0.10 g CaCO3 m-2 h-1 at the coral reef site. There were no significant differences in pH and aragonite saturation states (Ωar) between the seagrass and coral reef sites. Decrease in light levels during thunderstorms significantly decreased NEP, transforming the system from net autotrophic to net heterotrophic.

  20. A new method to extract matrix proteins directly from the secretion of the mollusk mantle and the role of these proteins in shell biomineralization.

    Science.gov (United States)

    Liu, Xiaojun; Liu, Chang; Chen, Lei; Sun, Juan; Zhou, Yujuan; Li, Qi; Zheng, Guilan; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2011-10-01

    Considering the continuous and substantive secretory ability of the mantle in vitro, we report a new technique to produce shell-matrix proteins by inducing the mantle, after removal from the organism's body, to secrete soluble-matrix proteins into phosphate buffer. By this method, a large amount of matrix proteins could be obtained in 2 h. Experiments involving in vitro calcium carbonate crystallization and organic framework calcium carbonate crystallization indicated that these proteins retain high bioactivity and play key roles in shell biomineralization. Phosphate buffer-soluble proteins secreted by the margin of the mantles (MSPs) were used to reconstruct the stages in the growth of the prismatic layer of the decalcified organic frameworks. The MSPs were observed to aggregate calcites in vitro, and this ability enabled the mollusk to form big calcites in the prismatic layer. During shell biomineralization, an important stage after the self-assembly of the biomacromolecules and the formation of crystals is the assembly of the two parts to form a firm structure. Moreover, a new type of matrix protein, functioning as the binding factor between the crystals and the organic frameworks, was shown to exist in the phosphate buffer-soluble proteins secreted by the central part of mantles (CSPs). Nanoscale-sized bowl-like aragonites, with heights of ∼800 nm, were induced by CSPs in vitro. This method is a successful example of obtaining functional proteins through secretion by animal tissues.

  1. Raman spectroscopic analysis of archaeological specimens from the wreck of HMS Swift, 1770

    Science.gov (United States)

    Edwards, Howell G. M.; Elkin, Dolores; Maier, Marta S.

    2016-12-01

    Specimens from underwater archaeological excavations have rarely been analysed by Raman spectroscopy probably due to the problems associated with the presence of water and the use of alternative techniques. The discovery of the remains of the Royal Navy warship HMS Swift off the coast of Patagonia, South America, which was wrecked in 1770 while undertaking a survey from its base in the Falkland/Malvinas Islands, has afforded the opportunity for a first-pass Raman spectroscopic study of the contents of several glass jars from a wooden chest, some of which had suffered deterioration of their contents owing to leakage through their stoppers. From the Raman spectroscopic data, it was possible to identify organic compounds such as anthraquinone and copal resin, which were empirically used as materia medica in the eighteenth century to treat shipboard diseases; it seems very likely, therefore, that the wooden chest belonged to the barber-surgeon on the ship. Spectra were obtained from the wet and desiccated samples, but several samples from containers that had leaked were found to contain only minerals, such as aragonite and sediment. This article is part of the themed issue "Raman spectroscopy in art