Continental paleothermometry and seasonality using the isotopic composition of aragonitic otoliths of freshwater fishes

Science.gov (United States)

Patterson, William P.; Smith, Gerald R.; Lohmann, Kyger C.

To investigate the applicability of oxygen isotope themometry using fish aragonite, the δ18O values of paired otolith and water samples were analyzed from six large modem temperate lakes. Otoliths are accretionaiy aragonitic structures which are precipitated within the sacculus of fish ears. Deep-water obligate benthic species from the hypolimnion of the Laurentian Great Lakes of North America and Lake Baikal, Siberia, provided cold-water end member values for aragonite δ18O. Warm-water values were obtained from naturally grown warm-water stenothermic species and from fish grown in aquaria under controlled conditions. These two groups, which represent growth over a temperature range of 3.2-30.3°C. were employed to determine the oxygen isotope temperature fractionation relationship for aragonite-water: 103lnα = 18.56 (±0.319)·(103)T-1 K -33.49 (±0.307). Empirical calibration of a fish aragonite thennometry equation allows its direct application to studies of paleoclimate. For example, high-resolution sampling of shallow-water eurythermic species coupled with a knowledge of the isotopic composition of meteoric waters can be used to determine seasonal temperature variation. This approach was tested using a modem shallow-water eurythermic species from Sandusky Bay, Lake Erie. Temperatures calculated from carbonate composition agree with meteorological records from the Sandusky Bay weather station for the same time period.

Calibrating multiple isotopic proxies in a modern aragonite speleothem from northeast India

Science.gov (United States)

Ronay, E.; Oster, J. L.; Sharp, W. D.; Marks, N.; Erhardt, A.; Breitenbach, S. F. M.

2017-12-01

Uranium, strontium, and calcium isotope ratios in calcite speleothems are used as proxies for water-soil-rock interactions and prior calcite precipitation, and thus provide information about effective rainfall amount variations, primarily in semi-arid or highly seasonal regions. However, less is known about how these proxies function in humid regions and in aragonite speleothems. In this study, we use meteorological data to calibrate (234U/238U)i and 87Sr/86Sr in a modern aragonite speleothem from northeast India, the rainiest place on Earth, to determine how these proxies reflect effective monsoon rainfall amount. MAW-0201 is an annually laminated aragonite stalagmite that grew from 1960-2013 in Mawmluh Cave, Meghalaya, India. Rainfall here is extremely seasonal due to the Indian Summer Monsoon (ISM), which brings several meters of rain to the region each summer, but with inter-annual variability in total rainfall. The δ18O in Mawmluh dripwater and speleothems reflects moisture source and transport, rather than rainfall amount. Variations in Mg, U, and Ba concentrations in MAW-0201 show seasonal and multi-annual variability. U and Mg are closely correlated, but multi-year periods show significant anti-correlation. The Mg and U distribution coefficients in calcite and aragonite indicate correlated periods are times of prior calcite precipitation (PCP) and anti-correlated periods are times of prior aragonite precipitation (PAP) in the epikarst. We use δ44/40Ca to test this hypothesis, as Ca isotopes fractionate differently during calcite and aragonite precipitation and speleothem δ44/40Ca will record unique PAP and PCP fingerprints. We propose such shifts from PCP to PAP reflect hydrologic variability and/or flow path changes, which provide a useful tool for understanding epikarst hydrology but may also be a complicating factor in speleothem-based paleoclimate interpretations. Preliminary (234U/238U)i (always <1) and 87Sr/86Sr spanning 1991-2009 each show

Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

Science.gov (United States)

Casella, Laura A.; Griesshaber, Erika; Yin, Xiaofei; Ziegler, Andreas; Mavromatis, Vasileios; Müller, Dirk; Ritter, Ann-Christine; Hippler, Dorothee; Harper, Elizabeth M.; Dietzel, Martin; Immenhauser, Adrian; Schöne, Bernd R.; Angiolini, Lucia; Schmahl, Wolfgang W.

2017-03-01

Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days

Isostructural exclusion of elements between aragonite and calcite layers in the shell of the Pacific oyster Crassostrea gigas

International Nuclear Information System (INIS)

Markwitz, A.; Gauldie, R.W.; Trompetter, W.J.; Pithie, J.; Jamieson, D.N.; Sharma, S.K.

1999-01-01

Sections of the shell of the farmed Pacific oyster 'Crassostrea gigas' that are available commercially in Wellington, New Zealand, showed a distinct alternating pattern in the shell mineral when observed by reflected light. The layers were identified by Raman scattering as alternating bands of the calcite and aragonite mineral forms of calcium carbonate using the micro-Raman facility at the Hawaii Institute of Geophysics and Planetology. The differences in the unit cell structure of calcite and aragonite favour different trace elements in the two minerals. Aragonite is isostructural with Strontianite SrCO 3 , and calcite is isostructural with Smithsonite ZnCO 3 . As a result, Sr deposition should be favoured in the aragonite layer and is excluded from the calcite layer; and, conversely, Zn deposition should be favoured in the calcite layer and is excluded from the aragonite layer. However, up to today, significant differences in the pattern of Sr and Zn in microprobe scans are not discovered. By ion microprobe analysis, it was shown that differences in the unit cell structure of calcite and aragonite favor different trace elements in the two minerals

Triassic aragonite in carbonate source-rock from Ragusa Basin (Sicily): geochemistry, comparison with recent sediments and origin

International Nuclear Information System (INIS)

Loreau, J.P.; Sabbadini, S.; Brosse, E.; Frixa, A.

1995-01-01

Aragonitic muds from the upper Triassic occur in laminites between two laminae rich in clays and/or organic matter. Two types of aragonite are identified. The first shows rod or needle morphology, with Sr content (9,300 ppm), δ 18 O(-1.1 to -1.7) and δ 13 C(+2.1 to +2.8) mostly similar to aragonite of Recent sediments. It is not biodetrital in origin but results from direct precipitation at 22-30 deg C in sea water with a m Sr 2+ / m Ca 2+ ratio very near to Recent values. The second aragonite showing greater prismatic crystals with inclusions of relics of rods and needles, a high content in strontium (15,800 ppm) and a negative δ 13 C(-13.0 to -14.4), is diagenetic. (authors). 23 refs., 6 figs

Growth of aragonite calcium carbonate nanorods in the biomimetic anodic aluminum oxide template

Science.gov (United States)

Lee, Inho; Han, Haksoo; Lee, Sang-Yup

2010-04-01

In this study, a biomimetic template was prepared and applied for growing calcium carbonate (CaCO 3) nanorods whose shape and polymorphism were controlled. A biomimetic template was prepared by adsorbing catalytic dipeptides into the pores of an anodic aluminum oxide (AAO) membrane. Using this peptide-adsorbed template, mineralization and aggregation of CaCO 3 was carried out to form large nanorods in the pores. The nanorods were aragonite and had a structure similar to nanoneedle assembly. This aragonite nanorod formation was driven by both the AAO template and catalytic function of dipeptides. The AAO membrane pores promoted generation of aragonite polymorph and guided nanorod formation by guiding the nanorod growth. The catalytic dipeptides promoted the aggregation and further dehydration of calcium species to form large nanorods. Functions of the AAO template and catalytic dipeptides were verified through several control experiments. This biomimetic approach makes possible the production of functional inorganic materials with controlled shapes and crystalline structures.

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 (Ωar). 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 (Ωar∼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 Ωar levels slightly above 1 and lower at Ωar 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 Ωar 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 Ωar levels close to 1, with net shell growth ceasing at an Ωar 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. PMID:25285916

Reviews and syntheses: Revisiting the boron systematics of aragonite and their application to coral calcification

Science.gov (United States)

DeCarlo, Thomas M.; Holcomb, Michael; McCulloch, Malcolm T.

2018-05-01

The isotopic and elemental systematics of boron in aragonitic coral skeletons have recently been developed as a proxy for the carbonate chemistry of the coral extracellular calcifying fluid. With knowledge of the boron isotopic fractionation in seawater and the B/Ca partition coefficient (KD) between aragonite and seawater, measurements of coral skeleton δ11B and B/Ca can potentially constrain the full carbonate system. Two sets of abiogenic aragonite precipitation experiments designed to quantify KD have recently made possible the application of this proxy system. However, while different KD formulations have been proposed, there has not yet been a comprehensive analysis that considers both experimental datasets and explores the implications for interpreting coral skeletons. Here, we evaluate four potential KD formulations: three previously presented in the literature and one newly developed. We assess how well each formulation reconstructs the known fluid carbonate chemistry from the abiogenic experiments, and we evaluate the implications for deriving the carbonate chemistry of coral calcifying fluid. Three of the KD formulations performed similarly when applied to abiogenic aragonites precipitated from seawater and to coral skeletons. Critically, we find that some uncertainty remains in understanding the mechanism of boron elemental partitioning between aragonite and seawater, and addressing this question should be a target of additional abiogenic precipitation experiments. Despite this, boron systematics can already be applied to quantify the coral calcifying fluid carbonate system, although uncertainties associated with the proxy system should be carefully considered for each application. Finally, we present a user-friendly computer code that calculates coral calcifying fluid carbonate chemistry, including propagation of uncertainties, given inputs of boron systematics measured in coral skeleton.

Seasonal variation in aragonite saturation in surface waters of Puget Sound – a pilot study

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Gregory Pelletier

2018-01-01

Full Text Available A pilot study of sampling, using monthly marine flights over spatially distributed stations, was conducted with the aim to characterize the carbonate system in Puget Sound over a full year-long period. Surface waters of Puget Sound were found to be under-saturated with respect to aragonite during October–March, and super-saturated during April–September. Highest pCO2 and lowest pH occurred during the corrosive October–March period. Lowest pCO2 and highest pH occurred during the super-saturated April–September period. The monthly variations in pCO2 , pH, and aragonite saturation state closely followed the variations in monthly average chlorophyll a. Super-saturated conditions during April–September are likely strongly influenced by photosynthetic uptake of CO2 during the phytoplankton growing season. The relationship between phytoplankton production, the carbonate system, and aragonite saturation state suggests that long-term trends in eutrophication processes may contribute to trends in ocean acidification in Puget Sound

Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

Science.gov (United States)

Waite, A. J.; Swart, P. K.

2011-12-01

As aragonite is the metastable polymorph of calcium carbonate, it lends itself to monotropic inversion to the more stable polymorph, calcite. This inversion is possible through an increase in the temperature and pressure conditions to which the sample is exposed and, although first noted nearly a century ago, has been primarily discussed in the context of sample roasting prior to analyses in paleoclimatological studies. Over the last several decades, however, researchers have found evidence to suggest that the friction associated with the sampling of biogenic carbonates via milling/drilling also induces inversion. Furthermore, this inversion may be associated with a shift in measured oxygen isotopic values and ultimately have significant implications for the interpretation of paleoclimatic reconstructions. Despite this, the isotopic heterogeneity of biogenic aragonite skeletons makes the effects of inversion challenging to test and the subject remains underrepresented in the literature. Here we present a first order study into the effects of milling on both the mineralogy and isotopic compositions measured in sclerosponges, corals, and molluscs. X-Ray diffraction analysis of samples hand ground with a mortar and pestle reveal 100% aragonitic skeletons. Conversely, samples milled with a computerized micromill show measurable inversion to calcite. On average, percent inversion of aragonite to calcite for individual specimens was 15% for sclerosponges, 16% for corals, and 9% for molluscs. Isotopic data from these specimens show that the higher the percentage of aragonite inverted to calcite, the more depleted the measured oxygen isotopic values. In the largest of the datasets (sclerosponges), it is evident that the range of oxygen isotope values from milled samples (-0.02 to +0.84%) exceeds the range in values for those samples which were hand ground and showed no inversion (+0.53 to +0.90%). This, coupled with the strong correlation between the two variables

Synthesis of vaterite and aragonite crystals using biomolecules of tomato and capsicum

Science.gov (United States)

Chen, Long; Xu, Wang-Hua; Zhao, Ying-Guo; Kang, Yan; Liu, Shao-Hua; Zhang, Zai-Yong

2012-12-01

In this paper, biomimetic synthesis of calcium carbonate (CaCO3) in the presence of biomolecules of two vegetables-tomato and capsicum is investigated. Scanning electron microscopy and X-ray powder diffractometry were used to characterize the CaCO3 obtained. The biomolecules in the extracts of two vegetables are determined by UV-vis or FTIR. The results indicate that a mixture of calcite and vaterite spheres constructed from small particles is produced with the extract of tomato, while aragonite rods or ellipsoids are formed in the presence of extract of capsicum. The possible formation mechanism of the CaCO3 crystals with tomato biomolecules can be interpreted by particle-aggregation based non-classical crystallization laws. The proteins and/or other biomolecules in tomato and capsicum may control the formation of vaterite and aragonite crystals by adsorbing onto facets of them.

Effect of carbonation temperature on CO_2 adsorption capacity of CaO derived from micro/nanostructured aragonite CaCO_3

International Nuclear Information System (INIS)

Hlaing, Nwe Ni; Sreekantan, Srimala; Hinode, Hirofumi; Kurniawan, Winarto; Thant, Aye Aye; Othman, Radzali; Mohamed, Abdul Rahman; Salime, Chris

2016-01-01

Recent years, CaO-based synthetic materials have been attracted attention as potential adsorbents for CO_2 capture mainly due to their high CO_2 adsorption capacity. In this study, micro/nanostructured aragonite CaCO_3 was synthesized by a simple hydrothermal method with using polyacrylamide (PAM). The structural, morphological and thermal properties of the synthesized sample were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and thermogravimetry analysis (TG-DTA). The XRD and FESEM results showed that the obtained sample was aragonite CaCO_3 with aggregated nanorods and microspheres composed of nanorods. A TG-DTA apparatus with Thermoplus 2 software was used to investigate the effect of carbonation temperature on the CO_2 adsorption capacity of CaO derived from aragonite CaCO_3 sample. At 300 °C, the sample reached the CO_2 adsorption capacity of 0.098 g-CO_2/g-adsorbent, whereas the sample achieved the highest capacity of 0.682 g-CO_2/g-adsorbent at 700 °C. The results showed that the carbonation temperature significantly influenced on the CO_2 adsorption capacity of the CaO derived from aragonite CaCO_3.

Empirical Algorithms to Predict pH and Aragonite Saturation State on SOCCOM Biogeochemical Argo Floats in the Pacific Sector of the Southern Ocean

Science.gov (United States)

Williams, N. L.; Juranek, L. W.; Feely, R. A.; Johnson, K. S.; Russell, J. L.

2016-02-01

The Southern Ocean plays a major role in the global uptake, transport, and storage of both heat and carbon, yet it remains one of the least-sampled regions of the ocean. The Southern Ocean Carbon and Climate Observations and Modeling (SOCCOM) project aims to fill the observational gaps by deploying over 200 autonomous profiling floats in the Southern Ocean over the next several years. Initial float deployments have greatly expanded our observational capability to include wintertime measurements as well as under-ice measurements, and many of these floats include novel biogeochemical sensors (pH, nitrate, oxygen). Here we present empirical algorithms that can be used to predict pH and ΩAragonite from other float-measured parameters (temperature, salinity, pressure, nitrate, oxygen). These algorithms were trained using bottle measurements from high-quality repeat hydrographic GO-SHIP cruises. We obtained R2 values of 0.98 (pH) and 0.99 (ΩAragonite) and RMS errors of 0.007 (pH) and 0.052 (ΩAragonite) for data between 100-1500 m. These algorithms will allow us to both validate pH data from these sensors, as well as predict ΩAragonite and pH on floats that do not have pH sensors. Here we present estimated pH and ΩAragonite over 20 months of deployment for several SOCCOM floats in the Pacific Sector of the Southern Ocean. The results show seasonal ranges in surface pH and ΩAragonite of 0.05 and 0.1, respectively.

Mg/Ca partitioning between aqueous solution and aragonite mineral: a molecular dynamics study

NARCIS (Netherlands)

Ruiz-Hernandez, S.E.; Grau-Crespo, R.; Almora-Barrios, N.; Wolthers, M.; Ruiz-Salvador, A.R.; Fernandez, N.; Leeuw, N.H. de

2012-01-01

We have calculated the concentrations of Mg in the bulk and surfaces of aragonite CaCO3 in equilibrium with aqueous solution, based on molecular dynamics simulations and grand-canonical statistical mechanics. Mg is incorporated in the surfaces, in particular in the (001) terraces,

In vitro growth of flat aragonite crystals between the layers of the insoluble organic matrix of the abalone Haliotis laevigata

Science.gov (United States)

Gries, Katharina I.; Heinemann, Fabian; Rosenauer, Andreas; Fritz, Monika

2012-11-01

Nacre of abalone shells consists of aragonite platelets and organic material, the so-called organic matrix. During the growth process of the shell the aragonite platelets grow into a scaffold formed by the organic matrix. In this work we tried to mimic this growth process by placing a piece of the insoluble organic matrix (which is a part of the organic matrix) of the abalone Haliotis laevigata in a crystallization device which was flowed through by CaCl2 and NaHCO3 solutions. Using this setup amongst others flat aragonite crystals grow on the insoluble organic matrix. When investigating these crystals in a transmission electron microscope it is possible to recognize similarities to the structure of nacre, like the formation of mineral bridges and growth between layers of the insoluble organic matrix. These similarities are presented in this paper.

Cells containing aragonite crystals mediate responses to gravity in Trichoplax adhaerens (Placozoa), an animal lacking neurons and synapses.

Science.gov (United States)

Mayorova, Tatiana D; Smith, Carolyn L; Hammar, Katherine; Winters, Christine A; Pivovarova, Natalia B; Aronova, Maria A; Leapman, Richard D; Reese, Thomas S

2018-01-01

Trichoplax adhaerens has only six cell types. The function as well as the structure of crystal cells, the least numerous cell type, presented an enigma. Crystal cells are arrayed around the perimeter of the animal and each contains a birefringent crystal. Crystal cells resemble lithocytes in other animals so we looked for evidence they are gravity sensors. Confocal microscopy showed that their cup-shaped nuclei are oriented toward the edge of the animal, and that the crystal shifts downward under the influence of gravity. Some animals spontaneously lack crystal cells and these animals behaved differently upon being tilted vertically than animals with a typical number of crystal cells. EM revealed crystal cell contacts with fiber cells and epithelial cells but these contacts lacked features of synapses. EM spectroscopic analyses showed that crystals consist of the aragonite form of calcium carbonate. We thus provide behavioral evidence that Trichoplax are able to sense gravity, and that crystal cells are likely to be their gravity receptors. Moreover, because placozoans are thought to have evolved during Ediacaran or Cryogenian eras associated with aragonite seas, and their crystals are made of aragonite, they may have acquired gravity sensors during this early era.

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.

Effect of carbonation temperature on CO{sub 2} adsorption capacity of CaO derived from micro/nanostructured aragonite CaCO{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Hlaing, Nwe Ni, E-mail: nwenihlaing76@gmail.com [School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Department of International Development Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo (Japan); Department of Physics, University of Yangon, 11041 Kamayut, Yangon (Myanmar); Sreekantan, Srimala, E-mail: srimala@usm.my [School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Hinode, Hirofumi, E-mail: hinode@ide.titech.ac.jp; Kurniawan, Winarto, E-mail: Kurniawan.w.ab@m.titech.ac.jp [Department of International Development Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo (Japan); Thant, Aye Aye, E-mail: a2thant@gmail.com [Department of Physics, University of Yangon, 11041 Kamayut, Yangon (Myanmar); Othman, Radzali, E-mail: radzali@utem.edu.my [Faculty of Manufacturing Engineering, Universiti Teknikal Malaysia Melaka, Hang Tuah Jaya, 76100 Durian Tunggal, Malacca (Malaysia); Mohamed, Abdul Rahman, E-mail: chrahman@eng.usm.my [Low Carbon Economy (LCE) Research Group, School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Salime, Chris, E-mail: chris.salim@surya.ac.id [Environmental Engineering, Surya University, Tangerang, 15810 Banten (Indonesia)

2016-07-06

Recent years, CaO-based synthetic materials have been attracted attention as potential adsorbents for CO{sub 2} capture mainly due to their high CO{sub 2} adsorption capacity. In this study, micro/nanostructured aragonite CaCO{sub 3} was synthesized by a simple hydrothermal method with using polyacrylamide (PAM). The structural, morphological and thermal properties of the synthesized sample were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and thermogravimetry analysis (TG-DTA). The XRD and FESEM results showed that the obtained sample was aragonite CaCO{sub 3} with aggregated nanorods and microspheres composed of nanorods. A TG-DTA apparatus with Thermoplus 2 software was used to investigate the effect of carbonation temperature on the CO{sub 2} adsorption capacity of CaO derived from aragonite CaCO{sub 3} sample. At 300 °C, the sample reached the CO{sub 2} adsorption capacity of 0.098 g-CO{sub 2}/g-adsorbent, whereas the sample achieved the highest capacity of 0.682 g-CO{sub 2}/g-adsorbent at 700 °C. The results showed that the carbonation temperature significantly influenced on the CO{sub 2} adsorption capacity of the CaO derived from aragonite CaCO{sub 3}.

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

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

2014-01-01

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. PMID:24302723

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.

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. © 2016 Phycological Society of America.

Experimental determination of growth rate effect on U 6+ and Mg 2+ partitioning between aragonite and fluid at elevated U 6+ concentration

Science.gov (United States)

Gabitov, R. I.; Gaetani, G. A.; Watson, E. B.; Cohen, A. L.; Ehrlich, H. L.

2008-08-01

Results are reported from an experimental study in which the partitioning of U and Mg between aragonite and an aqueous solution were determined as a function of crystal growth rate. Crystals, identified as aragonite by X-ray diffractometry and micro-Raman spectroscopy, were grown by diffusion of CO 2 from an ammonium carbonate source into a calcium-bearing solution at temperatures of 22 and 53 °C. Hemispherical bundles (spherulites) of aragonite crystals were produced, the growth rates of which decreased monotonically from the spherulite interiors to the edges and thus provide the opportunity to examine the influence of growth rate on crystal composition. Element concentration ratios were measured using electron microprobe (EMP) and fluid composition was determined by inductively coupled plasma-mass spectrometry (ICP-MS) and atomic absorption (AA). Growth rates were determined directly by addition of a Dy spike to the fluid during the experiment that was subsequently located in an experimentally precipitated spherulite using secondary ion mass spectrometry (SIMS). At 22 °C both U/Ca and Mg/Ca partition coefficients exhibited a strong growth rate dependence when crystal growth rates were low, and became independent of growth rate when crystal growth rates were high. The U/Ca ratios in aragonite increase between 22 and 53 °C; in contrast Mg/Ca ratios show inverse dependence on temperature.

A novel aragonite-based scaffold for osteochondral regeneration: early experience on human implants and technical developments.

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Kon, Elizaveta; Robinson, Dror; Verdonk, Peter; Drobnic, Matej; Patrascu, Jenel Mariano; Dulic, Oliver; Gavrilovic, Gordon; Filardo, Giuseppe

2016-12-01

Chondral and osteochondral lesions represent a debilitating disease. Untreated lesions remain a risk factor for more extensive joint damage. The objective of this clinical study is to evaluate safety and early results of an aragonite-based scaffold used for osteochondral unit repair, by analysing both clinical outcome and MRI results, as well as the benefits of the procedure optimization through novel tapered shaped implants. A crystalline aragonite bi-phasic scaffold was implanted in patients affected by focal chondral-osteochondral knee lesions of the condyle and trochlea. Twenty-one patients (17 men, 4 women with a mean age of 31.0 ± 8.6 years) without severe OA received tapered shaped implants for the treatment of 2.5 ±1.7 cm 2 sized defects. The control group consisted of 76 patients selected according to the same criteria from a database of patients who previously underwent implantation of cylindrical-shaped implants. The clinical outcome of all patients was evaluated with the IKDC subjective score, the Lysholm score, and all 5 KOOS subscales administered preoperatively and at 6 and 12 months after surgery, while MRI evaluation was performed at the 12 month follow-up. A statistically significant improvement in all clinical scores was documented both in the tapered implants and the cylindrical group. No difference could be detected in the comparison between the improvement obtained with the two implant types, neither in the clinical nor in imaging evaluations. A difference could be detected instead in terms of revision rate, which was lower in the tapered implant group with no implant removal - 0% vs 8/76-10.5% failures in the cylindrical implants. This study highlighted both safety and potential of a novel aragonite-based scaffold for the treatment of chondral and osteochondral lesions in humans. A tapered shape relative to the cylindrical shaped implant design, improved the scaffold's safety profile. Tapered scaffolds maintain the clinical improvement

Empirical algorithms to predict aragonite saturation state

Science.gov (United States)

Turk, Daniela; Dowd, Michael

2017-04-01

Novel sensor packages deployed on autonomous platforms (Profiling Floats, Gliders, Moorings, SeaCycler) and biogeochemical models have a potential to increase the coverage of a key water chemistry variable, aragonite saturation state (ΩAr) in time and space, in particular in the under sampled regions of global ocean. However, these do not provide the set of inorganic carbon measurements commonly used to derive ΩAr. There is therefore a need to develop regional predictive models to determine ΩAr from measurements of commonly observed or/and non carbonate oceanic variables. Here, we investigate predictive skill of several commonly observed oceanographic variables (temperature, salinity, oxygen, nitrate, phosphate and silicate) in determining ΩAr using climatology and shipboard data. This will allow us to assess potential for autonomous sensors and biogeochemical models to monitor ΩAr regionally and globally. We apply the regression models to several time series data sets and discuss regional differences and their implications for global estimates of ΩAr.

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

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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.

Theoretical characterization of a model of aragonite crystal orientation in red abalone nacre

International Nuclear Information System (INIS)

Coppersmith, S N; Gilbert, P U P A; Metzler, R A

2009-01-01

Nacre, commonly known as mother-of-pearl, is a remarkable biomineral that in red abalone consists of layers of 400 nm thick aragonite crystalline tablets confined by organic matrix sheets, with the [0 0 1] crystal axes of the aragonite tablets oriented to within ±12 deg. from the normal to the layer planes. Recent experiments demonstrate that greater orientational order develops over a distance of tens of layers from the prismatic boundary at which nacre formation begins. Our previous simulations of a model in which the order develops because of differential tablet growth rates (oriented tablets growing faster than misoriented ones) yield patterns of tablets that agree qualitatively and quantitatively with the experimental measurements. This paper presents an analytical treatment of this model, focusing on how the dynamical development and eventual degree of order depend on model parameters. Dynamical equations for the probability distributions governing tablet orientations are introduced whose form can be determined from symmetry considerations and for which substantial analytic progress can be made. Numerical simulations are performed to relate the parameters used in the analytic theory to those in the microscopic growth model. The analytic theory demonstrates that the dynamical mechanism is able to achieve a much higher degree of order than naive estimates would indicate

Theoretical characterization of a model of aragonite crystal orientation in red abalone nacre

Science.gov (United States)

Coppersmith, S N; Gilbert, P U P A; Metzler, R A

2009-03-01

Nacre, commonly known as mother-of-pearl, is a remarkable biomineral that in red abalone consists of layers of 400 nm thick aragonite crystalline tablets confined by organic matrix sheets, with the [0 0 1] crystal axes of the aragonite tablets oriented to within ±12° from the normal to the layer planes. Recent experiments demonstrate that greater orientational order develops over a distance of tens of layers from the prismatic boundary at which nacre formation begins. Our previous simulations of a model in which the order develops because of differential tablet growth rates (oriented tablets growing faster than misoriented ones) yield patterns of tablets that agree qualitatively and quantitatively with the experimental measurements. This paper presents an analytical treatment of this model, focusing on how the dynamical development and eventual degree of order depend on model parameters. Dynamical equations for the probability distributions governing tablet orientations are introduced whose form can be determined from symmetry considerations and for which substantial analytic progress can be made. Numerical simulations are performed to relate the parameters used in the analytic theory to those in the microscopic growth model. The analytic theory demonstrates that the dynamical mechanism is able to achieve a much higher degree of order than naive estimates would indicate.

Theoretical characterization of a model of aragonite crystal orientation in red abalone nacre

Energy Technology Data Exchange (ETDEWEB)

Coppersmith, S N; Gilbert, P U P A; Metzler, R A [Department of Physics, University of Wisconsin, Madison, WI 53706 (United States)

2009-03-27

Nacre, commonly known as mother-of-pearl, is a remarkable biomineral that in red abalone consists of layers of 400 nm thick aragonite crystalline tablets confined by organic matrix sheets, with the [0 0 1] crystal axes of the aragonite tablets oriented to within {+-}12 deg. from the normal to the layer planes. Recent experiments demonstrate that greater orientational order develops over a distance of tens of layers from the prismatic boundary at which nacre formation begins. Our previous simulations of a model in which the order develops because of differential tablet growth rates (oriented tablets growing faster than misoriented ones) yield patterns of tablets that agree qualitatively and quantitatively with the experimental measurements. This paper presents an analytical treatment of this model, focusing on how the dynamical development and eventual degree of order depend on model parameters. Dynamical equations for the probability distributions governing tablet orientations are introduced whose form can be determined from symmetry considerations and for which substantial analytic progress can be made. Numerical simulations are performed to relate the parameters used in the analytic theory to those in the microscopic growth model. The analytic theory demonstrates that the dynamical mechanism is able to achieve a much higher degree of order than naive estimates would indicate.

Accelerator mass spectrometry 14C determination in CO2 produced from laser decomposition of aragonite.

Science.gov (United States)

Rosenheim, Brad E; Thorrold, Simon R; Roberts, Mark L

2008-11-01

The determination of (14)C in aragonite (CaCO(3)) decomposed thermally to CO(2) using an yttrium-aluminum-garnet doped neodymium laser is reported. Laser decomposition accelerator mass spectrometry (LD-AMS) measurements reproduce AMS determinations of (14)C from the conventional reaction of aragonite with concentrated phosphoric acid. The lack of significant differences between these sets of measurements indicates that LD-AMS radiocarbon dating can overcome the significant fractionation that has been observed during stable isotope (C and O) laser decomposition analysis of different carbonate minerals. The laser regularly converted nearly 30% of material removed into CO(2) despite it being optimized for ablation, where laser energy breaks material apart rather than chemically altering it. These results illustrate promise for using laser decomposition on the front-end of AMS systems that directly measure CO(2) gas. The feasibility of such measurements depends on (1) the improvement of material removal and/or CO(2) generation efficiency of the laser decomposition system and (2) the ionization efficiency of AMS systems measuring continuously flowing CO(2).

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.

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.

Safety assessments of subcutaneous doses of aragonite calcium carbonate nanocrystals in rats

Science.gov (United States)

Jaji, Alhaji Zubair; Zakaria, Zuki Abu Bakar; Mahmud, Rozi; Loqman, Mohamad Yusof; Hezmee, Mohamad Noor Mohamad; Abba, Yusuf; Isa, Tijani; Mahmood, Saffanah Khuder

2017-05-01

Calcium carbonate nanoparticles have shown promising potentials in the delivery of drugs and metabolites. There is however, a paucity of information on the safety of their intentional or accidental over exposures to biological systems and general health safety. To this end, this study aims at documenting information on the safety of subcutaneous doses of biogenic nanocrystals of aragonite polymorph of calcium carbonate derived from cockle shells (ANC) in Sprague-Dawley (SD) rats. ANC was synthesized using the top-down method, characterized using the transmission electron microscopy and field emission scanning electron microscope and its acute and repeated dose 28-day trial toxicities were evaluated in SD rats. The results showed that the homogenous 30 ± 5 nm-sized spherical pure aragonite nanocrystals were not associated with mortality in the rats. Severe clinical signs and gross and histopathological lesions, indicating organ toxicities, were recorded in the acute toxicity (29,500 mg/m2) group and the high dose (5900 mg/m2) group of the repeated dose 28-day trial. However, the medium- (590 mg/m2 body weight) and low (59 mg/m2)-dose groups showed moderate to mild lesions. The relatively mild lesions observed in the low toxicity dosage group marked the safety margin of ANC in SD rats. It was concluded from this study that the toxicity of CaCO3 was dependent on the particulate size (30 ± 5 nm) and concentration and the route of administration used.

Decadal changes in the aragonite and calcite saturation state of the Pacific Ocean

Science.gov (United States)

Feely, Richard A.; Sabine, Christopher L.; Byrne, Robert H.; Millero, Frank J.; Dickson, Andrew G.; Wanninkhof, Rik; Murata, Akihiko; Miller, Lisa A.; Greeley, Dana

2012-09-01

Based on measurements from the WOCE/JGOFS global CO2 survey, the CLIVAR/CO2 Repeat Hydrography Program and the Canadian Line P survey, we have observed an average decrease of 0.34% yr-1 in the saturation state of surface seawater in the Pacific Ocean with respect to aragonite and calcite. The upward migrations of the aragonite and calcite saturation horizons, averaging about 1 to 2 m yr-1, are the direct result of the uptake of anthropogenic CO2 by the oceans and regional changes in circulation and biogeochemical processes. The shoaling of the saturation horizon is regionally variable, with more rapid shoaling in the South Pacific where there is a larger uptake of anthropogenic CO2. In some locations, particularly in the North Pacific Subtropical Gyre and in the California Current, the decadal changes in circulation can be the dominant factor in controlling the migration of the saturation horizon. If CO2 emissions continue as projected over the rest of this century, the resulting changes in the marine carbonate system would mean that many coral reef systems in the Pacific would no longer be able to sustain a sufficiently high rate of calcification to maintain the viability of these ecosystems as a whole, and these changes perhaps could seriously impact the thousands of marine species that depend on them for survival.

Review of aragonite and calcite crystal morphogenesis in thermal spring systems

Science.gov (United States)

Jones, Brian

2017-06-01

Aragonite and calcite crystals are the fundamental building blocks of calcareous thermal spring deposits. The diverse array of crystal morphologies found in these deposits, which includes monocrystals, mesocrystals, skeletal crystals, dendrites, and spherulites, are commonly precipitated under far-from-equilibrium conditions. Such crystals form through both abiotic and biotic processes. Many crystals develop through non-classical crystal growth models that involve the arrangement of nanocrystals in a precisely controlled crystallographic register. Calcite crystal morphogenesis has commonly been linked to a ;driving force;, which is a conceptual measure of the distance of the growth conditions from equilibrium conditions. Essentially, this scheme indicates that increasing levels of supersaturation and various other parameters that produce a progressive change from monocrystals and mesocrystals to skeletal crystals to crystallographic and non-crystallographic dendrites, to dumbbells, to spherulites. Despite the vast amount of information available from laboratory experiments and natural spring systems, the precise factors that control the driving force are open to debate. The fact that calcite crystal morphogenesis is still poorly understood is largely a reflection of the complexity of the factors that influence aragonite and calcite precipitation. Available information indicates that variations in calcite crystal morphogenesis can be attributed to physical and chemical parameters of the parent water, the presence of impurities, the addition of organic or inorganic additives to the water, the rate of crystal growth, and/or the presence of microbes and their associated biofilms. The problems in trying to relate crystal morphogenesis to specific environmental parameters arise because it is generally impossible to disentangle the controlling factor(s) from the vast array of potential parameters that may act alone or in unison with each other.

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

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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

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.

Coral calcifying fluid aragonite saturation states derived from Raman spectroscopy

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T. M. DeCarlo

2017-11-01

Full Text Available Quantifying the saturation state of aragonite (ΩAr within the calcifying fluid of corals is critical for understanding their biomineralization process and sensitivity to environmental changes including ocean acidification. Recent advances in microscopy, microprobes, and isotope geochemistry enable the determination of calcifying fluid pH and [CO32−], but direct quantification of ΩAr (where ΩAr =  [CO32−][Ca2+]∕Ksp has proved elusive. Here we test a new technique for deriving ΩAr based on Raman spectroscopy. First, we analysed abiogenic aragonite crystals precipitated under a range of ΩAr from 10 to 34, and we found a strong dependence of Raman peak width on ΩAr with no significant effects of other factors including pH, Mg∕Ca partitioning, and temperature. Validation of our Raman technique for corals is difficult because there are presently no direct measurements of calcifying fluid ΩAr available for comparison. However, Raman analysis of the international coral standard JCp-1 produced ΩAr of 12.3 ± 0.3, which we demonstrate is consistent with published skeletal Mg∕Ca, Sr∕Ca, B∕Ca, δ11B, and δ44Ca data. Raman measurements are rapid ( ≤  1 s, high-resolution ( ≤  1 µm, precise (derived ΩAr ± 1 to 2 per spectrum depending on instrument configuration, accurate ( ±2 if ΩAr < 20, and require minimal sample preparation, making the technique well suited for testing the sensitivity of coral calcifying fluid ΩAr to ocean acidification and warming using samples from natural and laboratory settings. To demonstrate this, we also show a high-resolution time series of ΩAr over multiple years of growth in a Porites skeleton from the Great Barrier Reef, and we evaluate the response of ΩAr in juvenile Acropora cultured under elevated CO2 and temperature.

Lithium in the aragonite skeletons of massive Porites corals: A new tool to reconstruct tropical sea surface temperatures

Science.gov (United States)

Hathorne, Ed C.; Felis, Thomas; Suzuki, Atsushi; Kawahata, Hodaka; Cabioch, Guy

2013-01-01

Previous studies have demonstrated the potential for the Li content of coral aragonite to record information about environmental conditions, but no detailed study of tropical corals exists. Here we present the Li and Mg to Ca ratios at a bimonthly to monthly resolution over 25 years in two modern Porites corals, the genus most often used for paleoclimate reconstructions in the tropical Indo-Pacific. A strong relationship exists between coral Li/Ca and locally measured SST, indicating that coral Li/Ca can be used to reconstruct tropical SST variations. However, Li/Ca ratios of the skeleton deposited during 1979-1980 do not track local SST well and are anomalously high in places. The Mg/Ca ratios of this interval are also anomalously high, and we suggest Li/Ca can be used to reconstruct tropical SST only when Mg/Ca data are used to carefully screen for relatively rare biological effects. Mg/Li or Li/Mg ratios provide little advantage over Li/Ca ratios, except that the slope of the Li/Mg temperature relationship is more similar between the two corals. The Mg/Li temperature relationship for the coral that experienced a large temperature range is similar to that found for cold water corals and aragonitic benthic foraminifera in previous studies. The comparison with data from other biogenic aragonites suggests the relationship between Li/Mg and water temperature can be described by a single exponential relationship. Despite this hint at an overarching control, it is clear that biological processes strongly influence coral Li/Ca, and more calibration work is required before widely applying the proxy.

Quantifying the influence of CO2 seasonality on future aragonite undersaturation onset

Science.gov (United States)

Sasse, T. P.; McNeil, B. I.; Matear, R. J.; Lenton, A.

2015-10-01

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 of the food chain 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 (representative concentration pathways; RCPs 2.6, 4.5 and 8.5) to provide new insights into future aragonite undersaturation onset. Under a high emissions scenario (RCP 8.5), our results suggest accounting for seasonality will bring forward the initial onset of month-long undersaturation by 17 ± 10 years compared to annual-mean estimates, with differences extending up to 35 ± 16 years in the North Pacific due to strong regional seasonality. This earlier onset will result in large-scale undersaturation once atmospheric CO2 reaches 496 ppm in the North Pacific and 511 ppm in the Southern Ocean, independent of emission scenario. This work suggests accounting for seasonality is critical to projecting the future impacts of ocean acidification on the marine environment.

Dating of aragonite and dolomite from Devil's cave - SP, by dosimetric thermoluminescent method (DTL) and ESR

International Nuclear Information System (INIS)

Tatumi, S.H.

1987-01-01

We have investigated TL (Thermoluminescence) and ESR (electron spin resonance) properties of aragonite and dolomite found at ''Caverna do Diabo (Devil's cave)'' in the state of Sao Paulo to determine the ages of these geological materials. The aragonite, which is not a thermoluminescent material, shows one ESR signal whit g = 2.003. We obtained the age of 1.1 x 10 5 years and the growth rate of 1 μ m/year by the sample calibration with additional Y irradiation. The dolomite gives a TL glow curve with three distinct peaks at 261, 334 and 395 0 C. We found that the fit for the TL glow curve to second-order kinetics can be considerered as very acceptable. Using the second TL peak we obtained the age of 9.4 x 10 5 years and the compatible values of the activation energy (1.90 ± 0,07 eV) by the following methods: Hyperbolic heating, isothermal decay and fractional glow technique. We observed many ESR absorption signals in the dolomite. Three principal signal com g = 2.002, 2.003 and 2.005 were studied. We found that the first and second ESR signals were atributed to the CO 2 - and/or CO 3 3- centers and the last to the CO 3 - centers, and observed that the first ESR signal might related with the second TL peak and the TL sensitivity were associated with the concentration of Mn 2+ [pt

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

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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

Geochemistry of recent aragonite-rich sediments in Mediterranean karstic marine lakes: Trace elements as pollution and palaeoredox proxies and indicators of authigenic mineral formation.

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Sondi, Ivan; Mikac, Nevenka; Vdović, Neda; Ivanić, Maja; Furdek, Martina; Škapin, Srečo D

2017-02-01

This study investigates the geochemical characteristics of recent shallow-water aragonite-rich sediments from the karstic marine lakes located in the pristine environment on the island of Mljet (Adriatic Sea). Different trace elements were used as authigenic mineral formation, palaeoredox and pollution indicators. The distribution and the historical record of trace elements deposition mostly depended on the sedimentological processes associated with the formation of aragonite, early diagenetic processes governed by the prevailing physico-chemical conditions and on the recent anthropogenic activity. This study demonstrated that Sr could be used as a proxy indicating authigenic formation of aragonite in a marine carbonate sedimentological environment. Distribution of the redox sensitive elements Mo, Tl, U and Cd was used to identify changes in redox conditions in the investigated lake system and to determine the geochemical cycle of these elements through environmental changes over the last 100 years. The significant enrichment of these elements and the presence of early formed nanostructured authigenic framboidal pyrite in laminated deeper parts of sediment in Malo Jezero, indicate sporadic events of oxygen-depleted euxinic conditions in the recent past. Concentrations of trace elements were in the range characteristic for non-contaminated marine carbonates. However, the increase in the concentrations of Zn, Cu, Pb, Sn, Bi in the upper-most sediment strata of Veliko Jezero indicates a low level of trace element pollution, resulting from anthropogenic inputs over the last 40 years. The presence of butyltin compounds (BuTs) in the surface sediment of Veliko Jezero additionally indicates the anthropogenic influence in the recent past. Copyright © 2016 Elsevier Ltd. All rights reserved.

Probe microanalysis of aragonitic structures in marine organisms as a means of measuring population structure and mobility

International Nuclear Information System (INIS)

Thresher, R.E.; Sie, S.H.

1991-01-01

Experiments began in 1987 with a view to using ontogenetic variation in the chemical composition of fish otoliths ('ear bones' - the first calcified tissue to develop in embryonic fishes) as an indicator of movement/migration patterns. Acquiring such data dictated the use of a probe microanalyzer, which could be scanned along the growth axis of an otolith and provide discrete information on otolith composition at different stages in the life of the animal. The suitability of electron and proton probe analyzers is examined and the optimal operating parameters determined for both, when dealing with biogenic aragonite matrices. 1 refs

Seasonal pH and aragonite saturation horizons in the Gulf of Alaska during the North Pacific Survey, 1956–1957

OpenAIRE

McKinnell, S.; Christian, J. R.

2009-01-01

The extent of global change in carbon system parameters can only be evaluated by comparing present with past measurements. In the northern North Pacific, where aragonite saturation horizons are among the shallowest in the world, historical measurements of carbonate parameters vary from rare to nonexistent. However, during the summer of 1956 and winter of 1957, an extensive survey of the oceanography of the Northeast Pacific, under the auspices of the Canadian Committee on Oceanography, was co...

Distortions of the calcite and aragonite atomic structures from interstitial water

Energy Technology Data Exchange (ETDEWEB)

Sinha, S.; Rez, P., E-mail: Peter.Rez@asu.edu

2015-05-01

Amorphous calcium carbonate (ACC), as observed by diffraction or infra-red spectroscopy, is especially significant as a precursor in biomineralization. The atomic structure and mechanisms for transformation to the crystalline phases are still unknown. It is conceivable that insertion of water molecules could give rise to distortions that result in the observed diffraction patterns and infrared spectra. We use the VASP density functional theory code to relax model supercells with 24 formula units of CaCO{sub 3} where we have inserted up to 5 water molecules, corresponding to 3.75 wt%. The main effect is tilting of the carbonate planes, which can be as high as 50°. This leads to a range of Ca–O distances that are consistent with the observed changes in the IR spectra in ACC. The spread in cation–cation distances is not enough to destroy coherent diffraction from regions 70 nm across, and so does not explain amorphous diffraction profiles. - Highlights: • Low concentrations of water in the calcite or aragonite structures lead to tilting of the carbonate planes. • This is consistent with IR observations from amorphous calcium carbonate. • It does not explain amorphous diffraction patterns.

Trace elements records from vermetids aragonite as millennial paleo-oceanographic archives in the South-East Mediterranean

Science.gov (United States)

Jacobson, Yitzhak; Yam, Ruth; Shemesh, Aldo

2017-04-01

The Mediterranean Sea is a region under high anthropogenic stress, thus a hotspot for climate change studies. Natural conditions, such as SST, productivity, precipitation and dust fluxes along with human induced activity affect seawater chemistry. We study millennial variability of trace elements in East Mediterranean Sea high-resolution records, in attempt to connect them to environmental factors. The Mediterranean reef builder Vermetid, D. petraeum is a sessile gastropod, secreting its aragonite shells in tidal zones. Cores of Vermetid reefs from the South Eastern Mediterranean (Israel) were previously analyzed by Sisma?Ventura et al. (2014) to reconstruct seawater surface temperature (SST) and δ13C of dissolved inorganic carbon (DIC). In this study we analyzed trace elements of these vermetid cores, and reconstructed millennial records of elements to calcium (el/Ca) molar ratios. Vermetid trace element contents from recent decades are mostly in agreement with known values for marine biogenic aragonites from corals and mollusk. We divide vermetid trace element records into three element groups: 1) Sr and U are related to SST and DIC. These elements correlate with major climatic events of the last millennium, such as the Medieval Warm Period (900-1300 AD) and the Little Ice Age (1450-1850 AD). 2) Pb and Cd are related to anthropogenic pollution and demonstrate industrial sourced trends throughout the anthropocene (since 1750 AD). 3) Terrogenous elements, including Fe, Al, Mn and V. Al in seawater and sediments has been used to trace water masses and land derived sediment source. We observe a major change in average vermetid Al/Fe ratios from 0.5 to 2.5 over the recorded period (n=72). This vermetid Al/Fe change points at a possible shift from Nilotic sediments (0.1-0.5 Al/Fe molar ratio) to Saharan dust ratio (2-4 Al/Fe molar ratio). Mn and V show a similar variability to Fe. Understanding the variability of vermetid TE can help us interpret the relative

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...

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.

Calcite/aragonite-biocoated artificial coral reefs for marine parks

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Volodymyr Ivanov

2017-08-01

Full Text Available Natural formation of the coral reefs is complicated by slow biomediated precipitation of calcium carbonate from seawater. Therefore, manufactured artificial coral reefs can be used for the formation of “underwater gardens” in marine parks for the recreational fishing and diving that will protect natural coral reefs from negative anthropogenic effects. Additionally, the coating of the concrete, plastic or wooden surfaces of artificial coral reef with calcium carbonate layer could promote attachment and growth of coral larvae and photosynthetic epibiota on these surfaces. Three methods of biotechnological coating of the artificial coral reefs have been tested: (1 microbially induced calcium carbonate precipitation from concentrated calcium chloride solution using live bacterial culture of Bacillus sp. VS1 or dead but urease-active cells of Yaniella sp. VS8; (2 precipitation from calcium bicarbonate solution; (3 precipitation using aerobic oxidation of calcium acetate by bacteria Bacillus ginsengi strain VSA1. The thickness of biotechnologically produced calcium carbonate coating layer was from 0.3 to 3 mm. Biocoating using calcium salt and urea produced calcite in fresh water and aragonite in seawater. The calcium carbonate-coated surfaces were colonized in aquarium with seawater and hard corals as inoculum or in aquarium with fresh water using cyanobacteria Chlorella sorokiana as inoculum. The biofilm on the light-exposed side of calcium carbonate-coated surfaces was formed after six weeks of incubation and developed up to the average thickness of 250 µm in seawater and about 150 µm in fresh water after six weeks of incubation. The biotechnological manufacturing of calcium carbonate-coated concrete, plastic, or wooden surfaces of the structures imitating natural coral reef is technologically feasible. It could be commercially attractive solution for the introduction of aesthetically pleasant artificial coral reefs in marine parks and

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

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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

Aragonite saturation state in a tropical coastal embayment dominated by phytoplankton blooms (Guanabara Bay - Brazil).

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Cotovicz, Luiz C; Knoppers, Bastiaan A; Brandini, Nilva; Poirier, Dominique; Costa Santos, Suzan J; Abril, Gwenaël

2018-04-01

The dynamics of the aragonite saturation state (Ω arag ) were investigated in the eutrophic coastal waters of Guanabara Bay (RJ-Brazil). Large phytoplankton blooms stimulated by a high nutrient enrichment promoted the production of organic matter with strong uptake of dissolved inorganic carbon (DIC) in surface waters, lowering the concentrations of dissolved carbon dioxide (CO 2aq ), and increasing the pH, Ω arag and carbonate ion (CO 3 2- ), especially during summer. The increase of Ω arag related to biological activity was also evident comparing the negative relationship between the Ω arag and the apparent utilization of oxygen (AOU), with a very close behavior between the slopes of the linear regression and the Redfield ratio. The lowest values of Ω arag were found at low-buffered waters in regions that receive direct discharges from domestic effluents and polluted rivers, with episodic evidences of corrosive waters (Ω arag <1). This study showed that the eutrophication controlled the variations of Ω arag in Guanabara Bay. Copyright © 2017 Elsevier Ltd. All rights reserved.

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite, and the effect of ion (de)solvation.

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Böttcher, Michael E; Neubert, Nadja; von Allmen, Katja; Samankassou, Elias; Nägler, Thomas F

2018-06-01

In this study, we present the experimental results for stable barium (Ba) isotope fractionation ( 137 Ba/ 134 Ba) during the transformation of aragonite (CaCO 3 ) and gypsum (CaSO 4 ·2H 2 O) in Ba-bearing aqueous solution to witherite (BaCO 3 ) and barite (BaSO 4 ), respectively. The process was studied at three temperatures between 4 and 60 °C. In all cases, the transformation leads to a relative enrichment of the lighter 134 Ba isotope in the solid compared to the aqueous solution, with 137/134 Ba enrichment factors between -0.11 and -0.17 ‰ for BaCO 3 , and -0.21 and -0.26 ‰ for BaSO 4 . The corresponding mass-dependent 138/134 Ba enrichment factors are -0.15 to -0.23 ‰ for BaCO 3 , and -0.28 to -0.35 ‰ for BaSO 4 . The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80 °C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO 4 and BaCO 3 using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.

Metabolic Energy Demand Is Not Increased during Initial Shell Formation of Bivalves Exposed to Aragonite Undersaturation

Science.gov (United States)

Pan, F.; Frieder, C.; Applebaum, S.; Manahan, D. T.

2016-02-01

The Pacific oyster, Crassostrea gigas, is a major commercial species in global aquaculture. Ocean acidification is having a negative effect on larval production of this species, so the mechanisms of this impact are of considerable interest. Formation of new shell in C. gigas during the first 2-days post-fertilization results in a rapid six-fold increase in total mass. This period of early development has high sensitivity to changes in carbonate chemistry, in particular aragonite saturation state (Ω). An elevated energy cost for calcification at low Ω is often invoked as a mechanism. In this study, we characterized the developmental progression of first shell formation, total metabolic expenditure, and underlying biochemical processes of energy allocation during early development of C. gigas, under control (Ω >> 1) and undersaturated conditions (Ω pump activity (Na+, K+-ATPase) between the two treatments. We conclude that early development to the shelled-veliger larval stage does not require more energy at undersaturation. This finding helps constrain potential mechanisms of larval sensitivity to ocean acidification and narrows the focus for possible mitigation strategies for oyster aquaculture production.

Seasonal variations in the aragonite saturation state in the upper open-ocean waters of the North Pacific Ocean

Science.gov (United States)

Kim, Tae-Wook; Park, Geun-Ha; Kim, Dongseon; Lee, Kitack; Feely, Richard A.; Millero, Frank J.

2015-06-01

Seasonal variability of the aragonite saturation state (ΩAR) in the upper (50 m and 100 m depths) North Pacific Ocean (NPO) was investigated using multiple linear regression (MLR). The MLR algorithm derived from a high-quality carbon data set accurately predicted the ΩAR of evaluation data sets (three time series stations and P02 section) with acceptable uncertainty (<0.1 ΩAR). The algorithm was combined with seasonal climatology data, and the estimated ΩAR varied in the range of 0.4-0.6 in the midlatitude western NPO, with the largest variation found for the tropical eastern NPO. These marked variations were largely controlled by seasonal changes in vertical mixing and thermocline depth, both of which determine the degree of entrainment of CO2-rich corrosive waters from deeper depths. Our MLR-based subsurface ΩAR climatology is complementary to surface climatology based on pCO2 measurements.

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite-dolomite marbles from the Greek Rhodope massif in the system CaO-MgO-Al 2O 3-SiO 2-CO 2 and indications of prior aragonite

Science.gov (United States)

Proyer, A.; Mposkos, E.; Baziotis, I.; Hoinkes, G.

2008-08-01

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti-)clinohumite and phlogopite were observed in calcite-dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO-MgO-Al 2O 3-SiO 2-CO 2 (CMAS-CO 2) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite-calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and aCO 2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO 2, garnet has to be present in aluminous calcite-dolomite-marble at UHP conditions.

Electrothermal atomic absorption spectrometric determination of cobalt, copper, lead and nickel traces in aragonite following flotation and extraction separation.

Science.gov (United States)

Zendelovska, D; Pavlovska, G; Cundeva, K; Stafilov, T

2001-03-30

A method of determination of Co, Cu, Pb and Ni in nanogram quantities from aragonite is presented. Flotation and extraction of Co, Cu, Pb and Ni is suggested as methods for elimination matrix interferences of calcium. The method of flotation is performed by iron(III) hexamethylenedithiocarbamate, Fe(HMDTC)(3), as a colloid precipitate collector. The liquid-liquid extraction of Co, Cu, Pb and Ni is carried out by sodium diethyldithiocarbamate, NaDDTC, as complexing reagent into methylisobutyl ketone, MIBK. The electrothermal atomic absorption spectrometry (ETAAS) is used for determination of analytes. The detection limits of ETAAS followed by flotation are: 7.8 ng.g(-1) for Co, 17.1 ng.g(-1) for Cu, 7.2 ng.g(-1) for Pb and 9.0 mug.g(-1) for Ni. The detection limits of ETAAS followed by extraction are found to be: 12.0 ng.g(-1) for Co, 51.0 ng.g(-1) for Cu, 24.0 ng.g(-1) for Pb and 21.0 ng.g(-1) for Ni.

The combined effects of acidification and hypoxia on pH and aragonite saturation in the coastal waters of the California current ecosystem and the northern Gulf of Mexico

Science.gov (United States)

Feely, Richard A.; Okazaki, Remy R.; Cai, Wei-Jun; Bednaršek, Nina; Alin, Simone R.; Byrne, Robert H.; Fassbender, Andrea

2018-01-01

Inorganic carbon chemistry data from the surface and subsurface waters of the West Coast of North America have been compared with similar data from the northern Gulf of Mexico to demonstrate how future changes in CO2 emissions will affect chemical changes in coastal waters affected by respiration-induced hypoxia ([O2] ≤ 60 μmol kg-1). In surface waters, the percentage change in the carbon parameters due to increasing CO2 emissions are very similar for both regions even though the absolute decrease in aragonite saturation is much higher in the warmer waters of the Gulf of Mexico. However, in subsurface waters the changes are enhanced due to differences in the initial oxygen concentration and the changes in the buffer capacity (i.e., increasing Revelle Factor) with increasing respiration from the oxidation of organic matter, with the largest impacts on pH and CO2 partial pressure (pCO2) occurring in the colder West Coast waters. As anthropogenic CO2 concentrations begin to build up in subsurface waters, increased atmospheric CO2 will expose organisms to hypercapnic conditions (pCO2 >1000 μatm) within subsurface depths. Since the maintenance of the extracellular pH appears as the first line of defense against external stresses, many biological response studies have been focused on pCO2-induced hypercapnia. The extent of subsurface exposure will occur sooner and be more widespread in colder waters due to their capacity to hold more dissolved oxygen and the accompanying weaker acid-base buffer capacity. Under present conditions, organisms in the West Coast are exposed to hypercapnic conditions when oxygen concentrations are near 100 μmol kg-1 but will experience hypercapnia at oxygen concentrations of 260 μmol kg-1 by year 2100 under the highest elevated-CO2 conditions. Hypercapnia does not occur at present in the Gulf of Mexico but will occur at oxygen concentrations of 170 μmol kg-1 by the end of the century under similar conditions. The aragonite saturation

Attempt of absolute dating and reconstitutions of climate changes in the Caribbean Sea: multi-proxy approaches to planktonic foraminifera and fine aragonitic fraction

International Nuclear Information System (INIS)

Sepulcre, S.

2008-06-01

Absolute dating of climate archives is essential to better understand climate mechanisms. A marine sediment core from the Caribbean Sea enriched in fine-grained aragonite (suitable to U/Th dating) has been studied for both planktonic foraminifera tests (≥150 μm) and fine fraction (≤63 μm) over the last one million years using mineralogical and geochemical approaches. This study aims at i) examining lead/lag of δ 18 O and radiometric ages of the different-size fractions and ii) reconstructing paleo-environment in the area. The fine fraction mineralogy is strongly influenced by glacial-interglacial sea level changes. The offset of δ 18 O and 14 C ages between the fine and foraminifera fractions during Termination I is partly explained by a bioturbation model. Attempt of U/Th dating to Termination II and V reveals that the fine fraction contains non-radiogenic Th, which needs further analytical development. Reconstructed surface water δ 18 O changes suggest a decrease in surface water salinity at the end of Mid-Pleistocene Transition related to ITCZ position over the Caribbean Sea. (author)

Can Empirical Algorithms Successfully Estimate Aragonite Saturation State in the Subpolar North Atlantic?

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Daniela Turk

2017-12-01

Full Text Available The aragonite saturation state (ΩAr in the subpolar North Atlantic was derived using new regional empirical algorithms. These multiple regression algorithms were developed using the bin-averaged GLODAPv2 data of commonly observed oceanographic variables [temperature (T, salinity (S, pressure (P, oxygen (O2, nitrate (NO3-, phosphate (PO43-, silicate (Si(OH4, and pH]. Five of these variables are also frequently observed using autonomous platforms, which means they are widely available. The algorithms were validated against independent shipboard data from the OVIDE2012 cruise. It was also applied to time series observations of T, S, P, and O2 from the K1 mooring (56.5°N, 52.6°W to reconstruct for the first time the seasonal variability of ΩAr. Our study suggests: (i linear regression algorithms based on bin-averaged carbonate system data can successfully estimate ΩAr in our study domain over the 0–3,500 m depth range (R2 = 0.985, RMSE = 0.044; (ii that ΩAr also can be adequately estimated from solely non-carbonate observations (R2 = 0.969, RMSE = 0.063 and autonomous sensor variables (R2 = 0.978, RMSE = 0.053. Validation with independent OVIDE2012 data further suggests that; (iii both algorithms, non-carbonate (MEF = 0.929 and autonomous sensors (MEF = 0.995 have excellent predictive skill over the 0–3,500 depth range; (iv that in deep waters (>500 m observations of T, S, and O2 may be sufficient predictors of ΩAr (MEF = 0.913; and (iv the importance of adding pH sensors on autonomous platforms in the euphotic and remineralization zone (<500 m. Reconstructed ΩAr at Irminger Sea site, and the K1 mooring in Labrador Sea show high seasonal variability at the surface due to biological drawdown of inorganic carbon during the summer, and fairly uniform ΩAr values in the water column during winter convection. Application to time series sites shows the potential for regionally tuned algorithms, but they need to be further compared against �

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

Preparation and characterization of cockle shell aragonite nanocomposite porous 3D scaffolds for bone repair

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Saffanah Khuder Mahmood

2017-07-01

Full Text Available The demands for applicable tissue-engineered scaffolds that can be used to repair load-bearing segmental bone defects (SBDs is vital and in increasing demand. In this study, seven different combinations of 3 dimensional (3D novel nanocomposite porous structured scaffolds were fabricated to rebuild SBDs using an extraordinary blend of cockle shells (CaCo3 nanoparticles (CCN, gelatin, dextran and dextrin to structure an ideal bone scaffold with adequate degradation rate using the Freeze Drying Method (FDM and labeled as 5211, 5400, 6211, 6300, 7101, 7200 and 8100. The micron sized cockle shells powder obtained (75 µm was made into nanoparticles using mechano-chemical, top-down method of nanoparticles synthesis with the presence of the surfactant BS-12 (dodecyl dimethyl bataine. The phase purity and crystallographic structures, the chemical functionality and the thermal characterization of the scaffolds’ powder were recognized using X-Ray Diffractometer (XRD, Fourier transform infrared (FTIR spectrophotometer and Differential Scanning Calorimetry (DSC respectively. Characterizations of the scaffolds were assessed by Scanning Electron Microscopy (SEM, Degradation Manner, Water Absorption Test, Swelling Test, Mechanical Test and Porosity Test. Top-down method produced cockle shell nanoparticles having averagely range 37.8±3–55.2±9 nm in size, which were determined using Transmission Electron Microscope (TEM. A mainly aragonite form of calcium carbonate was identified in both XRD and FTIR for all scaffolds, while the melting (Tm and transition (Tg temperatures were identified using DSC with the range of Tm 62.4–75.5 °C and of Tg 230.6–232.5 °C. The newly prepared scaffolds were with the following characteristics: (i good biocompatibility and biodegradability, (ii appropriate surface chemistry and (iii highly porous, with interconnected pore network. Engineering analyses showed that scaffold 5211 possessed 3D interconnected homogenous

Minute co-variations of Sr/Ca ratios and microstructures in the aragonitic shell of Cerastoderma edule (Bivalvia) - Are geochemical variations at the ultra-scale masking potential environmental signals?

Science.gov (United States)

Füllenbach, Christoph S.; Schöne, Bernd R.; Shirai, Kotaro; Takahata, Naoto; Ishida, Akizumi; Sano, Yuji

2017-05-01

It remains a challenging task to reconstruct water temperatures from Sr/Ca ratios of bivalve shells. Although in many aragonitic species, Sr/Ca is negatively correlated to temperature - which is expected based on abiogenic precipitation experiments, the incorporation of Sr into the shell of bivalves is strongly controlled by physiological processes and occurs away from the predicted thermodynamic equilibrium. Strontium-to-calcium ratios of aragonitic shells remain far below that of the ambient water. Moreover, Sr concentrations vary considerably among shell portions consisting of different microstructures and/or organic content. Values observed at annual growth lines and within the intervening shell portions (= annual growth increments) deviate much stronger from each other than expected from a change in temperature or Sr/Cawater. As demonstrated here by ultra-high-resolution chemical analysis (EPMA, NanoSIMS) of a Cerastoderma edule shell, Sr concentrations are also heterogeneously distributed at approximately micrometer resolution. For example, in the outer portion of the outer shell layer, Sr/Ca ratios were statistically significantly (t-, u-tests) higher at circatidal growth lines (irregular simple prismatic structure; arithmetic mean ± 1 standard deviation = 2.86 ± 0.38 mmol/mol; n = 53) than within circatidal increments (nondenticular prismatic structure; 2.42 ± 0.25 mmol/mol; n = 51). S/Cashell, a representative of the concentration of organics, showed the opposite pattern, i.e., significantly higher values in circatidal increments (2.37 ± 0.29 mmol/mol; n = 51) than at circatidal growth lines (2.13 ± 0.47 mmol/mol; n = 53). Overall highest values of Sr/Cashell (3.47 ± 0.65 mmol/mol; n = 3) and S/Cashell (3.98 ± 0.65 mmol/mol; n = 3), however, were typically associated with annual growth lines and larger biomineral units. The intimate link between Sr/Cashell, S/Cashell and shell architecture may indicate that microstructures or the processes

Seasonal Variability of Aragonite Saturation State in the North Pacific Ocean Predicted by Multiple Linear Regression

Science.gov (United States)

Kim, T. W.; Park, G. H.

2014-12-01

Seasonal variation of aragonite saturation state (Ωarag) in the North Pacific Ocean (NPO) was investigated, using multiple linear regression (MLR) models produced from the PACIFICA (Pacific Ocean interior carbon) dataset. Data within depth ranges of 50-1200m were used to derive MLR models, and three parameters (potential temperature, nitrate, and apparent oxygen utilization (AOU)) were chosen as predictor variables because these parameters are associated with vertical mixing, DIC (dissolved inorganic carbon) removal and release which all affect Ωarag in water column directly or indirectly. The PACIFICA dataset was divided into 5° × 5° grids, and a MLR model was produced in each grid, giving total 145 independent MLR models over the NPO. Mean RMSE (root mean square error) and r2 (coefficient of determination) of all derived MLR models were approximately 0.09 and 0.96, respectively. Then the obtained MLR coefficients for each of predictor variables and an intercept were interpolated over the study area, thereby making possible to allocate MLR coefficients to data-sparse ocean regions. Predictability from the interpolated coefficients was evaluated using Hawaiian time-series data, and as a result mean residual between measured and predicted Ωarag values was approximately 0.08, which is less than the mean RMSE of our MLR models. The interpolated MLR coefficients were combined with seasonal climatology of World Ocean Atlas 2013 (1° × 1°) to produce seasonal Ωarag distributions over various depths. Large seasonal variability in Ωarag was manifested in the mid-latitude Western NPO (24-40°N, 130-180°E) and low-latitude Eastern NPO (0-12°N, 115-150°W). In the Western NPO, seasonal fluctuations of water column stratification appeared to be responsible for the seasonal variation in Ωarag (~ 0.5 at 50 m) because it closely followed temperature variations in a layer of 0-75 m. In contrast, remineralization of organic matter was the main cause for the seasonal

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

Signatures of geochemical changes at methane-seeps as recorded by seep carbonates

OpenAIRE

Himmler, Tobias

2011-01-01

This thesis compiles three manuscripts: (1) The first manuscript (chapter 2.1) contains petrographic and geochemical data of aragonitic seep carbonates from the Makran accretionary prism. High-resolution rare earth element (REE) analysis yield distinct total REE[aragonite] concentrations and shale-normalised REE[aragonite] patterns. The REE variations are ascribed to different pore fluid compositions and accompanied redox changes during aragonite precipitation. (2) The second manuscript (chap...

Hierarchical assembly strategy and multiscale structural origin of exceptional mechanical performance in nacre

Science.gov (United States)

Huang, Zaiwang

Nacre (mother of pearl) is a self-assembled hierarchical nanocomposite in possession of exquisite multiscale architecture and exceptional mechanical properties. Previous work has shown that the highly-ordered brick-mortar-like structure in nacre is assembled via epitaxial growth and the aragonite platelets are pure single-crystals. Our results challenge this conclusion and propose that nacre's individual aragonite platelets are constructed with highly-aligned aragonite nanoparticles mediated by screw dislocation and amorphous aggregation. The underlying physics mechanism why the aragonite nanoparticles choose highly-oriented attachment as its crystallization pathway is rationalized in terms of thermodynamics. The aragonite nanoparticle order-disorder transformation can be triggered by high temperature and mechanical deformation, which in turn confirms that the aragonite nanoparticles are basic building blocks for aragonite platelets. Particularly fascinating is the fracture toughness enhancement of nacre through exquisitely collecting mechanically inferior calcium carbonate (CaCO3) and biomolecules. The sandwich-like microarchitecture with a geometrically staggered arrangement can induce crack deflection along its biopolymer interface, thus significantly enhancing nacre's fracture toughness. Our new findings ambiguously demonstrate that, aside from crack deflection, the advancing crack can invade aragonite platelet, leaving a zigzag crack propagation pathway. These unexpected experimental observations disclose, for the first time, the inevitable structural role of aragonite platelets in enhancing nacre's fracture toughness. Simultaneously, the findings that the crack propagates in a zigzag manner within individual aragonite platelets overturn the previously well-established wisdom that considers aragonite platelets as brittle single-crystals. Moreover, we investigated the dynamical mechanical response of nacre under unixial compression. Our results show that the

New aragonite 87Sr/86Sr records of Mesozoic ammonoids and approach to the problem of N, O, C and Sr isotope cycles in the evolution of the Earth

Science.gov (United States)

Zakharov, Yuri D.; Dril, Sergei I.; Shigeta, Yasunari; Popov, Alexander M.; Baraboshkin, Eugenij Y.; Michailova, Irina A.; Safronov, Peter P.

2018-02-01

New Sr isotope data from well-preserved aragonite ammonoid shell material from the Mesozoic are compared with that from a living Nautilus shell. The prominent negative Sr isotope excursions known from the Middle Permian, Jurassic and Cretaceous probably have their origins in intensive plate tectonic activity, followed by enhanced hydrothermal activity at the mid-ocean ridges (mantle volcanism) which supplied low radiogenic Sr to seawater. The maximum positive (radiogenic) shift in the lower Mesozoic Sr isotope curve (Lower Triassic peak) was likely caused by a significant expansion of dry land surfaces (Dabie-Sulu Triassic orogeny) and their intensive silicate weathering in conditions of extreme warming and aridity in the very end of the Smithian, followed by warm and humid conditions in the late Spathian, which apparently resulted in a significant oceanic input of radiogenic Sr through riverine flux. The comparatively high 87Sr/86Sr ratio obtained from the living Nautilus shell is probably a function of both the Alpine orogeny, which was accompanied by significant continental weathering and input of radiogenic Sr to the oceans, and the weakening of mantle volcanism.

Os polimorfos de carbonato de cálcio: uma síntese fácil de aragonita

OpenAIRE

Bessler,Karl E.; Rodrigues,Laécio C.

2008-01-01

Aragonite is a metastable polymorph of calcium carbonate. The calcareous exoskeletons of some organisms like corals or molluscs consist essentially of aragonite. The questions of how, and why these organisms prefer the thermodynamically unstable aragonite for the construction of their hard shells are discussed. The importance of the biomineralization process for the development of new materials is outlined. In the experimental part, a very simple synthesis of polycrystalline aragonite is perf...

Combination of FTIR and SEM for Identifying Freshwater-Cultured Pearls from Different Quality

Science.gov (United States)

Satitkune, Somruedee; Monarumit, Natthapong; Boonmee, Chakkrich; Phlayrahan, Aumaparn; Promdee, Kittiphop; Won-in, Krit

2016-03-01

The freshwater-cultured pearl ( Chamberlainia hainesiana species) is an organic gemstone mainly composed of calcium carbonate mineral including calcite, aragonite and vaterite phases. Generally, the quality of freshwater-cultured pearl is based on its luster. The high luster pearl is full of the aragonite phase without vaterite phase. On the other hand, the low luster pearl consists of aragonite and vaterite phases. These data could be proved by the Fourier Transform Infrared (FTIR) spectroscopy combined with the scanning electron microscopy (SEM). As the results, the high luster pearl similarly shows the FTIR spectrum of aragonite phase, and also, it shows the hexagonal shape of aragonite for the SEM image. On the other hand, the FTIR spectrum of low luster pearl has been pointed to the mixture component among aragonite and vaterite phases, and based on the SEM image; the irregular form is also interpreted to the mixture of aragonite and vaterite phases. This research concludes that the quality of freshwater-cultured pearls can be identified by the combination data of FTIR spectra and SEM images. These techniques are suitable for applied gemology.

Diagenesis of a drapery speleothem from Castañar Cave: from dissolution to dolomitization

Directory of Open Access Journals (Sweden)

Martín-Pérez A.

2012-07-01

Full Text Available A drapery speleothem (DRA-1 from Castañar Cave in Spain was subjected to a detailed petrographical study in order to identify its primary and diagenetic features. The drapery’s present day characteristics are the result of the combined effects of the primary and diagenetic processes that DRA-1 underwent. Its primary minerals are calcite, aragonite and huntite. Calcite is the main constituent of the speleothem, whereas aragonite forms as frostwork over the calcite. Huntite is the main mineral of moonmilk which covers the tips of aragonite. These primary minerals have undergone a set of diagenetic processes, which include: 1 partial dissolution or corrosion that produces the formation of powdery matt-white coatings on the surface of the speleothem. These are seen under the microscope as dark and highly porous microcrystalline aggregates; 2 total dissolution produces pores of few cm2 in size; 3 calcitization and dolomitization of aragonite result in the thickening and lost of shine of the aragonite fibres. Microscopically, calcitization is seen as rhombohedral crystals which cover and replace aragonite forming mosaics that preserve relics of aragonite precursor. Dolomitization results in the formation of microcrystalline rounded aggregates over aragonite fibres. These aggregates are formed by dolomite crystals of around 1 μm size. The sequence of diagenetic processes follows two main pathways. Pathway 1 is driven by the increase of saturation degree and Mg/Ca ratio of the karstic waters and is visible in the NW side of the drapery. This sequence of processes includes: 1 aragonite and huntite primary precipitation and 2 dolomitization. Pathway 2 is driven by a decrease in the degree of saturation of calcite and aragonite and Mg/Ca ratio of the cave waters, and it is observed in the SE side of the drapery. The diagenetic processes of the second pathway include: 1 calcitization of aragonite; 2 incomplete dissolution (micritization of both

Environmental controls on the boron and strontium isotopic composition of aragonite shell material of cultured Arctica islandica

Directory of Open Access Journals (Sweden)

Y.-W. Liu

2015-06-01

Full Text Available Ocean acidification, the decrease in ocean pH associated with increasing atmospheric CO2, is likely to impact marine organisms, particularly those that produce carbonate skeletons or shells. Therefore, it is important to investigate how environmental factors (seawater pH, temperature and salinity influence the chemical compositions in biogenic carbonates. In this study we report the first high-resolution strontium (87Sr / 86Sr and δ88 / 86Sr and boron (δ11B isotopic values in the aragonite shell of cultured Arctica islandica (A. islandica. The 87Sr / 86Sr ratios from both tank water and shell samples show ratios nearly identical to the open ocean, which suggests that the shell material reflects ambient ocean chemistry without terrestrial influence. The 84Sr–87Sr double-spike-resolved shell δ88 / 86Sr and Sr concentration data show no resolvable change throughout the culture period and reflect no theoretical kinetic mass fractionation throughout the experiment despite a temperature change of more than 15 °C. The δ11B records from the experiment show at least a 5‰ increase through the 29-week culture season (January 2010–August 2010, with low values from the beginning to week 19 and higher values thereafter. The larger range in δ11B in this experiment compared to predictions based on other carbonate organisms (2–3‰ suggests that a species-specific fractionation factor may be required. A significant correlation between the ΔpH (pHshell − pHsw and seawater pH (pHsw was observed (R2 = 0.35, where the pHshell is the calcification pH of the shell calculated from boron isotopic composition. This negative correlation suggests that A. islandica partly regulates the pH of the extrapallial fluid. However, this proposed mechanism only explains approximately 35% of the variance in the δ11B data. Instead, a rapid rise in δ11B of the shell material after week 19, during the summer, suggests that the boron uptake changes when a thermal

Late Quaternary sea level and environmental changes from relic ...

Indian Academy of Sciences (India)

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 ...

The impact of low pH, low aragonite saturation state on calcifying corals: an in-situ study of ocean acidification from the "ojos" of Puerto Morelos, Mexico

Science.gov (United States)

Crook, E. D.; Paytan, A.; Potts, D. C.; Hernandez Terrones, L.; Rebolledo-Vieyra, M.

2010-12-01

Recent increases in atmospheric carbon dioxide have resulted in rising aqueous CO2 concentrations that lower the pH of the oceans (Caldeira and Wickett 2003, 2005, Doney et al., 2009). It is estimated that over the next 100 years, the pH of the surface oceans will decrease by ~0.4 pH units (Orr et al., 2005), which is expected to hinder the calcifying capabilities of numerous marine organisms. Previous field work (Hall-Spencer et al., 2008) indicates that ocean acidification will negatively impact calcifying species; however, to date, very little is known about the long-term impacts of ocean acidification from the in-situ study of coral reef ecosystems. The Yucatán Peninsula of Quintana Roo, Mexico, represents an ecosystem where naturally low pH groundwater (7.14-8.07) has been discharging offshore at highly localized points (called ojos) for millennia. We present preliminary chemical and biological data on a selection of ojos from lagoon sites in Puerto Morelos, Mexico. Our findings indicate a decrease in species richness and size with proximity to the low pH waters. We address the potential long-term implications of low pH, low aragonite saturation state on coral reef ecosystems.

Subsurface pH and carbonate saturation state of aragonite on the Chinese side of the North Yellow Sea: seasonal variations and controls

Science.gov (United States)

Zhai, W.-D.; Zheng, N.; Huo, C.; Xu, Y.; Zhao, H.-D.; Li, Y.-W.; Zang, K.-P.; Wang, J.-Y.; Xu, X.-M.

2014-02-01

Based upon eight field surveys conducted between May 2011 and May 2012, we investigated seasonal variations in pH, carbonate saturation state of aragonite (Ωarag), and ancillary data on the Chinese side of the North Yellow Sea, a western North Pacific continental margin of major economic importance. Subsurface waters were CO2-undersaturated in May and nearly in equilibrium with atmospheric CO2 in June. From July to October, the fugacity of CO2 (fCO2) of bottom water gradually increased from 438 ± 44 μatm to 630 ± 84 μatm, and pHT decreased from 8.02 ± 0.04 to 7.88 ± 0.06 due to local aerobic remineralization of primary-production-induced biogenic particles. The subsurface community respiration rates in summer and autumn were estimated to be from 0.80 to 1.08 μmol-O2 kg-1 d-1 within a relatively high salinity range of 31.63 to 32.25. From November to May in the next year, however, subsurface fCO2 gradually decreased and pH increased due to cooling and water column ventilation. The corresponding bottom water Ωarag was 1.85 ± 0.21 (May), 1.79 ± 0.24 (June), 1.75 ± 0.27 (July), 1.76 ± 0.29 (August), 1.45 ± 0.31 (October), 1.52 ± 0.25 (November), and 1.41 ± 0.12 (January). Extremely low Ωarag values (from 1.13 to 1.40) were observed mainly in subsurface waters within the high salinity range of 31.63 to 32.25, which covered a major fraction of the study area in October and November. Of the China seas, the North Yellow Sea represents one of the systems most vulnerable to the potential negative effects of ocean acidification.

Coprecipitation of alkali metal ions with calcium carbonate

International Nuclear Information System (INIS)

Okumura, Minoru; Kitano, Yasushi

1986-01-01

The coprecipitation of alkali metal ions Li + , Na + , K + and Rb + with calcium carbonate has been studied experimentally and the following results have been obtained: (1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite. (2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na + which has approximately the same ionic radius as Ca 2+ . (3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals. (4) Our results support the hypothesis that (a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca 2+ in the lattice, but (b) in aragonite, alkali metals substitute for Ca 2+ in the crystal structure. (5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li + , Na + , K + and Rb + ) coprecipitated with calcite but decrease those with aragonite. (6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li + , K + and Rb + ) into the aragonite. (author)

Vertically oriented structure and its fracture behavior of the Indonesia white-pearl oyster.

Science.gov (United States)

Chen, Guowei; Luo, Hongyun; Luo, Shunfei; Lin, Zhenying; Ma, Yue

2017-02-01

Structural calcites, aragonites, and the bonding organic network decide the growth, structure and mechanical properties of the mollusk bivalvia shell. Here, it was found out that the calcite prisms together with the coated organics construct another kind of 'brick and mortar' structure similar to the aragonite tablets. The calcite layer can be divided into three sublayers and direct evidences show that the calcite prisms are produced by two methods: nucleation and growing in the first sublayer; or fusing from the aragonites, which is quite different from some previous reports. The crystallographic orientation, micro hardness and crack propagations were tested and observed by XRD, micro harness tester, SEM and TEM. Submicron twin crystals were observed in the immature aragonite tablets. The fracture processes and the micro deformation of the aragonite tablets are detected by acoustic emission (AE) in the tensile tests, which gave the interpretation of the dynamical fracture processes: plastic deformation and fracture of the organics, and friction of the minerals at the first two stages; wear and fracture of the minerals at the third stage. Calcites and aragonites are combined and working together, like two layers of vertical 'brick and mortar's, ensuring the stable mechanical properties of the whole shell. Copyright © 2016 Elsevier Ltd. All rights reserved.

Abrupt climate-induced changes in carbonate burial in the Arabian Sea: Causes and consequences.

Digital Repository Service at National Institute of Oceanography (India)

Naidu, P.D.; Singh, A.D.; Ganeshram, R.S.; Bharti, S.K.

glacial and particularly during stadials (Heinrich Events). Using aragonite content, pteropods abundance, organic carbon percentage, and abundance of fertile (eutrophic) species of planktonic foraminifer, we demonstrate that aragonite contents...

Relic carbonate deposits along the western margin of India: Sea level and environmental changes during the Late Quaternary

Digital Repository Service at National Institute of Oceanography (India)

Rao, V.P.

sands (pelletal/oolitic sediments) and aragonite-cemented limestones, oyster shells, corals, coralline-algal and foraminiferal-dominated nodules. The petrology and mineralogy of the deposits indicate that except for aragonite sands and foraminiferal... pellets while others are ooilte- dominated. The age of the sands ranges between 14.3 ka to 7.6 cal kaBP. The limestones associated with the platform exhibit acicular aragonite cements and their ages lie between 11 ka and 13.3 kaBP. Large oyster shells...

X-ray diffraction, XAFS and scanning electron microscopy study of otolith of a crevalle jack fish (caranx hippos)

Energy Technology Data Exchange (ETDEWEB)

Pattanaik, Sidhartha [Bailey Hall 703, Illinois Institute of Technology, 3101 S. Wabash Avenue, Chicago, IL 60616 (United States)]. E-mail: sidpattanaik@yahoo.com

2005-04-01

The otolith of a crevalle jack fish (caranx hippos) has been investigated by means of X-ray diffraction, X-ray absorption fine structure spectroscopy and scanning electron microscopy techniques. The results suggest that the biomineralization of otolith occurs predominantly in the aragonite phase. A detailed X-ray Rietveld analysis showed that the first shell Ca-O distances in otolith lay in the range 2.371-2.652 A, with each calcium atom coordinated to 9 oxygen atoms. While the average Ca-O distance remains same in both otolith and aragonite, certain Ca-O distances in otolith differ markedly from those in aragonite. Such difference reflects the remarkable degree of control that the protein matrix exercised over packing of calcium and carbonate ions to promote growth of rarer aragonite otolith. In view of the complex coordination chemistry of calcium in otoliths, the EXAFS analysis was limited to obtaining local atomic environment about calcium up to the first Ca-O shell. EXAFS data showed an asymmetric distribution of Ca-O bond distances with the centroid of distribution at 2.48 A, which is closer to the average Ca-O distance in aragonite than in calcite. The asymmetry in the Ca-O peak is consistent with an apparent departure of Ca-O distances from a near regular distribution, as expected of an aragonite otolith.

X-ray diffraction, XAFS and scanning electron microscopy study of otolith of a crevalle jack fish (caranx hippos)

International Nuclear Information System (INIS)

Pattanaik, Sidhartha

2005-01-01

The otolith of a crevalle jack fish (caranx hippos) has been investigated by means of X-ray diffraction, X-ray absorption fine structure spectroscopy and scanning electron microscopy techniques. The results suggest that the biomineralization of otolith occurs predominantly in the aragonite phase. A detailed X-ray Rietveld analysis showed that the first shell Ca-O distances in otolith lay in the range 2.371-2.652 A, with each calcium atom coordinated to 9 oxygen atoms. While the average Ca-O distance remains same in both otolith and aragonite, certain Ca-O distances in otolith differ markedly from those in aragonite. Such difference reflects the remarkable degree of control that the protein matrix exercised over packing of calcium and carbonate ions to promote growth of rarer aragonite otolith. In view of the complex coordination chemistry of calcium in otoliths, the EXAFS analysis was limited to obtaining local atomic environment about calcium up to the first Ca-O shell. EXAFS data showed an asymmetric distribution of Ca-O bond distances with the centroid of distribution at 2.48 A, which is closer to the average Ca-O distance in aragonite than in calcite. The asymmetry in the Ca-O peak is consistent with an apparent departure of Ca-O distances from a near regular distribution, as expected of an aragonite otolith

The exposure of the Great Barrier Reef to ocean acidification

KAUST Repository

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

Contrasting biogeochemical responses of ENSO induced upwelling variability in the Humboldt Current System

Science.gov (United States)

Franco, Ana C.; Gruber, Nicolas; Münnich, Matthias

2017-04-01

The Humboldt Current System (HCS) is one of the most productive ecosystems in the world. This high productivity is supported by a large input of nutrients from the subsurface layers to the surface due to year-round upwelling. However, upwelling also supplies waters with low pH and low aragonite saturation state potentially affecting many organisms, especially those that calcify. The influence, extent and source of upwelled water vary substantially on interannual timescales in association with the El Niño/Southern Oscillation (ENSO) phenomenon, generating natural contrasting responses on the biogeochemistry of this system. Here we analyze these responses using an eddy resolving, basin-scale ocean model that covers the whole Pacific Ocean with high resolution (4 km) on the west coast of South America. We performed a simulation of the last 30 years (hindcast simulation) that allows us to investigate the influence of at least eight El Niño episodes and eight La Niña episodes on productivity variations and changes in oxygen concentration and aragonite saturation state. An absolute change in surface omega aragonite of almost 2 units, as well as an absolute change of the aragonite saturation depth of 200 m result from the change of an El Niño phase to a La Niña phase. This variability is on the same order of magnitude as the projected change in the aragonite saturation state in a centennial timescale. During La Niña events, a lower aragonite saturation state values and reduced oxygen concentration in the surface layer are a direct consequence of enhanced upwelling and increased net primary productivity. The opposite is true during El Niño events, where high values of omega aragonite occur in concordance with extraordinarily low net primary productivity values.

Amorphous calcium carbonate associated with biofilms in hot spring deposits

Science.gov (United States)

Jones, Brian; Peng, Xiaotong

2012-08-01

Calcium carbonate nanoparticles are intimately associated with crystalline calcite and aragonite in the Eryuan, Gongxiaoshe, and Zhuyuan hot springs (water temperature > 75 °C), which are located in Yunnan Province, China. The nanoparticles, springs, the ACC is always found under, in, or on top of biofilms, commonly in close proximity to crystalline calcite and/or aragonite. Textural evidence indicates that the ACC probably developed in microdomains that develop in the complex biofilm hydrogels. Critically, there is no evidence to support the notion that the nanoparticles are calcified nannobacteria. In the Chinese springs, ACC appears to play a formative role in the development of wheat-sheaf arrays of aragonite crystals and some of the calcite crystals. Hollow cores in some of the aragonite bundles probably formed as ACC was dissolved and many of the aragonite crystals appear to have developed as ACC recrystallized. Similarly, layers of ACC that coat the surfaces of some calcite crystals could be diagenetically transformed into calcite. The development of ACC in hot spring systems may be widespread and may play a critical but transitory role in the development of crystalline CaCO3 in these high temperature environments.

Variation in the Asian monsoon intensity and dry-wet condition since the Little Ice Age in central China revealed by an aragonite stalagmite

Science.gov (United States)

Yin, J.-J.; Yuan, D.-X.; Li, H.-C.; Cheng, H.; Li, T.-Y.; Edwards, R. L.; Lin, Y.-S.; Qin, J.-M.; Tang, W.; Zhao, Z.-Y.; Mii, H.-S.

2014-04-01

Highlight: this paper focuses on the climate variability in central China since 1300 AD, involving: 1. A well-dated, 1.5 year resolution stalagmite δ18O record from Lianhua Cave, central China; 2. Links of the δ18O record with regional dry-wet condition, monsoon intensity, and temperature over eastern China; 3. Correlations among drought events in the Lianhua record, solar irradiation, and ENSO index. We present a highly precisely 230Th/U dated, 1.5 year resolution δ18O record of an aragonite stalagmite (LHD1) collected from Lianhua Cave in Wuling mountain area of central China. The comparison of the δ18O record with the local instrumental record and historical documents exhibits at least 15 drought events in the Wuling mountain and adjacent areas during the Little Ice Age, in which some of them were corresponding to megadrought events in the broad Asian monsoonal region of China. Thus, the stalagmite δ18O record reveals variations in the summer monsoon precipitation and dry-wet condition in Wuling mountain area. The eastern China temperature varied with the solar activity, showing higher temperature under stronger solar irradiation which produces stronger summer monsoon. During Maunder, Dalton and 1900 sunspot minima, more severe drought events occurred, indicating weakening of the summer monsoon when solar activity decreased on decadal time scales. On interannual time scale, dry conditions in the studying area were prevailing under El Niño condition, which is also supported by the spectrum analysis. Hence, our record illustrates the linkage of Asian summer monsoon precipitation to solar irradiation and ENSO: wetter condition under stronger summer monsoon during warm periods and vice versa; During cold periods, the Walker circulation will shift toward central Pacific under El Niño condition, resulting further weakening of Asian summer monsoon. However, the δ18O of LHD1 record is positively correlated with temperature after ~1940 AD which is opposite to the

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

NARCIS (Netherlands)

Wall-Palmer, D.; Burridge, A.K.; Peijnenburg, K.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

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

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

International Nuclear Information System (INIS)

Chateigner, D.; Ouhenia, S.; Krauss, C.; Hedegaard, C.; Gil, O.; Morales, M.; Lutterotti, L.; Rousseau, M.; Lopez, E.

2010-01-01

Research highlights: → Nacre could be a non ancestral form of calcium carbonate in molluscs. → Texture terms as useful links to ancestors in classification. → X-ray diffraction useful for biomineralisation, phylogeny, cladistic and implantology. → Farming conditions do not influence much shell growth. → 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.

Endogenic carbonate sedimentation in Bear Lake, Utah and Idaho, over the last two glacial-interglacial cycles

Science.gov (United States)

Dean, W.E.

2009-01-01

Sediments deposited over the past 220,000 years in Bear Lake, Utah and Idaho, are predominantly calcareous silty clay, with calcite as the dominant carbonate mineral. The abundance of siliciclastic sediment indicates that the Bear River usually was connected to Bear Lake. However, three marl intervals containing more than 50% CaCO3 were deposited during the Holocene and the last two interglacial intervals, equivalent to marine oxygen isotope stages (MIS) 5 and 7, indicating times when the Bear River was not connected to the lake. Aragonite is the dominant mineral in two of these three high-carbonate intervals. The high-carbonate, aragonitic intervals coincide with warm interglacial continental climates and warm Pacific sea-surface temperatures. Aragonite also is the dominant mineral in a carbonate-cemented microbialite mound that formed in the southwestern part of the lake over the last several thousand years. The history of carbonate sedimentation in Bear Lake is documented through the study of isotopic ratios of oxygen, carbon, and strontium, organic carbon content, CaCO3 content, X-ray diffraction mineralogy, and HCl-leach chemistry on samples from sediment traps, gravity cores, piston cores, drill cores, and microbialites. Sediment-trap studies show that the carbonate mineral that precipitates in the surface waters of the lake today is high-Mg calcite. The lake began to precipitate high-Mg calcite sometime in the mid-twentieth century after the artificial diversion of Bear River into Bear Lake that began in 1911. This diversion drastically reduced the salinity and Mg2+:Ca2+ of the lake water and changed the primary carbonate precipitate from aragonite to high-Mg calcite. However, sediment-trap and core studies show that aragonite is the dominant mineral accumulating on the lake floor today, even though it is not precipitating in surface waters. The isotopic studies show that this aragonite is derived from reworking and redistribution of shallow-water sediment

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. © 2011 Blackwell Publishing Ltd.

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 aragonite (Ωaragonite 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.

The carbonate mineralogy and distribution of habitat-forming deep-sea corals in the southwest pacific region

Science.gov (United States)

Bostock, Helen C.; Tracey, Dianne M.; Currie, Kim I.; Dunbar, Gavin B.; Handler, Monica R.; Mikaloff Fletcher, Sara E.; Smith, Abigail M.; Williams, Michael J. M.

2015-06-01

Habitat-forming deep-sea scleractinian and alcyonacean corals from around the southwest Pacific were analysed for their calcium carbonate mineralogy. Scleractinian coral species Solenosmilia variabilis, Enallopsammia rostrata, Goniocorella dumosa, Madrepora oculata and Oculina virgosa were all found to be 100% aragonitic, while some members of the alcyonacean taxa Keratoisis spp., Lepidisis spp., and Paragorgia spp. were determined to be high magnesium (Mg) calcite (with 8-11 mol% MgCO3) and Primnoa sp. is bimineralic with both aragonite and Mg calcite. The majority of these habitat-forming deep-sea corals are found at intermediate depths (800-1200 m) in the Antarctic Intermediate Waters (AAIW) with low salinities (~34.5), temperatures of 4-8 °C and high oxygen concentrations (>180 μmol/kg) and currently sitting above the aragonite saturation horizon (ASH). However, habitat-forming corals have been recorded from greater depths, in cooler waters (2-4 °C) that are undersaturated with respect to aragonite (Ωaragonite160 μmol/kg. To address the sampling depth bias the coral records were normalised by the number of benthic stations (sampling effort) in the same depth range. This shows that the highest number of corals per sampling effort is between 1000 and 1400 m with corals present in over 5% of the stations at these depths. The normalised records and Boot Strap analyses suggests that scleractinian corals, especially S. variabilis should be present in >1% of stations down to 1800 m water depth, with E. rostrata, M. oculata and G. dumosa slightly shallower. While alcyonacean corals are found in >1% down to 2600 m, with Keratoisis spp. the deepest down to 2600 m, while Lepidisis spp. and Paragorgia spp. found down to 1800 m. This suggests that most species can probably tolerate some undersaturation of aragonite (Ωaragonite=0.8-0.9), with several species/genera (S. variabilis; Keratoisis spp.) even more tolerant of lower carbonate concentrations ([CO3 2 -]), down

Variation in the Asian monsoon intensity and dry-wet conditions since the Little Ice Age in central China revealed by an aragonite stalagmite

Science.gov (United States)

Yin, J.-J.; Yuan, D.-X.; Li, H.-C.; Cheng, H.; Li, T.-Y.; Edwards, R. L.; Lin, Y.-S.; Qin, J.-M.; Tang, W.; Zhao, Z.-Y.; Mii, H.-S.

2014-10-01

This paper focuses on the climate variability in central China since AD 1300, involving: (1) a well-dated, 1.5-year resolution stalagmite δ18O record from Lianhua Cave, central China (2) links of the δ18O record with regional dry-wet conditions, monsoon intensity, and temperature over eastern China (3) correlations among drought events in the Lianhua record, solar irradiation, and ENSO (El Niño-Southern Oscillation) variation. We present a highly precise, 230Th / U-dated, 1.5-year resolution δ18O record of an aragonite stalagmite (LHD1) collected from Lianhua Cave in the Wuling Mountain area of central China. The comparison of the δ18O record with the local instrumental record and historical documents indicates that (1) the stalagmite δ18O record reveals variations in the summer monsoon intensity and dry-wet conditions in the Wuling Mountain area. (2) A stronger East Asian summer monsoon (EASM) enhances the tropical monsoon trough controlled by ITCZ (Intertropical Convergence Zone), which produces higher spring quarter rainfall and isotopically light monsoonal moisture in the central China. (3) The summer quarter/spring quarter rainfall ratio in central China can be a potential indicator of the EASM strength: a lower ratio corresponds to stronger EASM and higher spring rainfall. The ratio changed from 1 after 1950, reflecting that the summer quarter rainfall of the study area became dominant under stronger influence of the Northwestern Pacific High. Eastern China temperatures varied with the solar activity, showing higher temperatures under stronger solar irradiation, which produced stronger summer monsoons. During Maunder, Dalton and 1900 sunspot minima, more severe drought events occurred, indicating a weakening of the summer monsoon when solar activity decreased on decadal timescales. On an interannual timescale, dry conditions in the study area prevailed under El Niño conditions, which is also supported by the spectrum analysis. Hence, our record

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

Directory of Open Access Journals (Sweden)

M. Yamamoto-Kawai

2016-11-01

Full Text Available 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.

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

In-vitro study on calcium carbonate crystal growth mediated by organic matrix extracted from fresh water pearls

International Nuclear Information System (INIS)

Ma Yufei; Qiao Li; Feng Qingling

2012-01-01

For the purpose of studying the mediation of organic matrix on the crystallization of calcium carbonate, water soluble matrix (WSM), acid soluble matrix (ASM) and acid insoluble matrix (AIM) were extracted from aragonite pearls and vaterite pearls respectively. Then, in-vitro calcium carbonate crystallization experiments under the control of these six organic matrices were carried out in the present study. Scanning electron microscopy (SEM) was utilized to observe the morphology of CaCO 3 and Raman spectroscopy as a powerful technique was used to distinguish the crystal polymorph. Influences of the six kinds of organic matrices on the calcium carbonate crystal growth are proposed. ASM of vaterite pearls can induce vaterite to crystallize and WSM of aragonite pearls mediates to produce aragonite crystals. The single AIM membranes of the two pearls have no pronounced effect on the CaCO 3 crystallization. Additionally, the crystal size obtained with the additive of WSM of the two kinds of pearls is smaller than that with the additive of ASM. Moreover, self-assembly phenomenon in the biomineralization process and the distorted morphology calcite are observed. Current results demonstrate important aspects of matrix protein-controlled crystallization, which is beneficial to the understanding of nacre biomineralization mechanism. Further study of the precise control of these matrix proteins on CaCO 3 crystal growth is being processed. - Highlights: ► WSM, ASM and AIM are extracted from aragonite pearls and vaterite pearls. ► ASM of vaterite pearl induces vaterite. ► WSM of aragonite pearl mediates to produce aragonite. ► WSM can fine control crystal size smaller than that with the additive of ASM. ► Self-assembly and the distorted calcite existed in the mineralization process.

Meridional overturning circulation conveys fast acidification to the deep Atlantic Ocean

Science.gov (United States)

Perez, Fiz F.; Fontela, Marcos; García-Ibáñez, Maribel I.; Mercier, Herlé; Velo, Anton; Lherminier, Pascale; Zunino, Patricia; de La Paz, Mercedes; Alonso-Pérez, Fernando; Guallart, Elisa F.; Padin, Xose A.

2018-02-01

Since the Industrial Revolution, the North Atlantic Ocean has been accumulating anthropogenic carbon dioxide (CO2) and experiencing ocean acidification, that is, an increase in the concentration of hydrogen ions (a reduction in pH) and a reduction in the concentration of carbonate ions. The latter causes the ‘aragonite saturation horizon’—below which waters are undersaturated with respect to a particular calcium carbonate, aragonite—to move to shallower depths (to shoal), exposing corals to corrosive waters. Here we use a database analysis to show that the present rate of supply of acidified waters to the deep Atlantic could cause the aragonite saturation horizon to shoal by 1,000-1,700 metres in the subpolar North Atlantic within the next three decades. We find that, during 1991-2016, a decrease in the concentration of carbonate ions in the Irminger Sea caused the aragonite saturation horizon to shoal by about 10-15 metres per year, and the volume of aragonite-saturated waters to reduce concomitantly. Our determination of the transport of the excess of carbonate over aragonite saturation (xc[CO32-])—an indicator of the availability of aragonite to organisms—by the Atlantic meridional overturning circulation shows that the present-day transport of carbonate ions towards the deep ocean is about 44 per cent lower than it was in preindustrial times. We infer that a doubling of atmospheric anthropogenic CO2 levels—which could occur within three decades according to a ‘business-as-usual scenario’ for climate change—could reduce the transport of xc[CO32-] by 64-79 per cent of that in preindustrial times, which could severely endanger cold-water coral habitats. The Atlantic meridional overturning circulation would also export this acidified deep water southwards, spreading corrosive waters to the world ocean.

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)

Thermally induced phase transformation of pearl powder

International Nuclear Information System (INIS)

Zhang, Guoqing; Guo, Yili; Ao, Ju; Yang, Jing; Lv, Guanglie; Shih, Kaimin

2013-01-01

The polymorphic phase transformation of thermally treated pearl powder was investigated by X-ray diffraction and thermoanalytical techniques. The phase transformation was based on quantification of the calcite content at various temperatures using Rietveld refinement analysis. The results show that the phase transformation of pearl aragonite occurred within a temperature range of 360–410 °C, which is 50–100 °C lower than the range for non-biomineralized aragonite. These thermoanalytical results suggest that the phase transformation of pearl aragonite may occur immediately after the thermal decomposition of the organic matrix in the pearl powder. An important finding is that decomposition of the organic matrix may greatly facilitate such transformation by releasing additional space for an easier structural reconstruction during the phase transformation process. - Highlights: ► Providing a new method to describe the polymorphic transition of pearl powder ► The phase transition sketch was exhibited by XRD phase quantitative analysis. ► There are dozens of degrees in advance comparing to natural aragonite. ► The phase transition occurs following the thermal decomposition of organism

Characterization of Carbonate Crust from Deep-sea Methane Seeps on the Northern US Atlantic Margin.

Science.gov (United States)

Gabitov, R. I.; Borrelli, C.; Buettner, J.; Testa, M.; Garner, B.; Weremeichik, J.; Thomas, J. B.; Wahidi, M.; Thirumalai, R. V. K. G.; Kirkland, B. L.; Skarke, A. D.

2017-12-01

Authigenic carbonate minerals widely occur at the seafloor as carbonate crusts and are often directly linked to microbial activity, about which promotion of carbonate crystal growth and geochemistry are not entirely understood. To evaluate a potential metabolic contribution, studies were conducted on carbonate crust collected from a methane seep and on precipitation experiments which produced inorganic aragonite crystallized at high pressure. Among the samples collected during a NSF sponsored cruise to the North Atlantic Continental Margin of the United States (off of New England) in July-August 2016, we analyzed one carbonate crust sample (AD4835 BB-4522) collected at 39.805860; -69.592593 and at a depth of 1419.6 m. In this crust sample, two textural types of aragonite were identified: 1) groundmass consisting of fine grey crystals (100 µm, 24.9 wt%), feldspar (5.6 wt%), and dolomite (3.6 wt%), and trace amount of troilite were identified using XRD, SEM, and optical microscopy. The sample was cut into slabs parallel to crust growth assuming the crust grew in a downward direction. Concentrations of Na, Mg, Al, Si, S, K, Ca, Mn, Fe, Sr, Zr, Ba, and U were measured in the direction parallel to growth of the crust using LA-ICP-MS. Proportions of Si, Al, (Na+K), Mg, S, and Fe in the groundmass suggest the occurrence of sub-micron inclusions of alkali feldspar, and potentially pyroxene, Fe oxide, and Fe sulfide, which were impossible to avoid with the instrument's spatial resolution. The occurrence of micro non-carbonate inclusions causes high elemental concentrations compared to the values expected for aragonite crystallized from seawater. White aragonite acicular crystals were free of silicate and sulfide inclusions, and therefore, yielded lower concentrations of all measured elements except Sr compared to the groundmass. Analyzed Mg and Sr are consistent with published data for deep-sea corals. Also, Sr is similar to experimental data on inorganic aragonite. Mg

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

International Nuclear Information System (INIS)

Merschel, Gila; Bau, Michael

2015-01-01

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

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

Studies of biominerals relevant to the search for life on Mars.

Science.gov (United States)

Blanco, Armando; D'Elia, Marcella; Licchelli, Domenico; Orofino, Vincenzo; Fonti, Sergio

2006-12-01

The evidence of the water erosion on Mars is particularly interesting since present climatic conditions are such that liquid water cannot exist at the surface. But, if water was present on the planet in the past, there may have been life, too. Since the discovery of carbonates on Mars also may have very important implications on the possibility that life developed there, we are studying minerals that can have biotic or abiotic origin: calcite (CaCO(3)) and aragonite, a metastable state of calcite.We have analysed biomineral aragonite, in the form of recent sea shells, as well as crystals of mineral aragonite. Infrared spectroscopy in the 2-25 mum wavelength range reveals that, after thermal processing, the biotic samples have a different spectral behaviour from the abiotic ones. As a result, it is possible to distinguish abiotic mineral aragonite from aragonite of recent biological origin.Obviously, if life existed in the past on the Red Planet, we could expect to find "ancient" biotic carbonates, which should therefore be investigated, in order to search for a way of discriminating them from abiotic minerals. For this reason, at the beginning we have considered samples of crushed fossil shells of aragonite composition. Afterwards, in order to take into account that fossilization processes almost always produce a transformation of metastable form (aragonite) into more stable form (calcite), we also studied samples of mineral calcite and different types of fossils completely transformed into calcite. All these biotic fossil samples show the same spectral behaviour as the fresh biotic material after thermal annealing at 485 degrees C. Instead, the calcite behaves like abiotic aragonite.Furthermore, it is known that seashells and other biominerals are formed through an intimate association of inorganic materials with organic macromolecules. The macromolecules control the nucleation, structure, morphology, crystal orientation and spatial confinement of the inorganic

Characterization of organic matrix extracted from fresh water pearls

International Nuclear Information System (INIS)

Ma Yufei; Gao Yonghua; Feng Qingling

2011-01-01

Aragonite pearl and vaterite pearl from cultured Hyriopsis cumingii in Zhuji (Zhejiang province, China) were chosen for the study. The matrix proteins were extracted using water and weak acid, and classified as water soluble matrix (WSM), acid soluble matrix (ASM) and acid insoluble matrix (AIM). The proteins from both pearls were characterized by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE), X-ray diffraction (XRD) and Fourier transformation infrared spectra (FTIR). The results showed that, AIM of aragonite pearl and vaterite pearl had an ordered structure of α-helix. ASM conformations of these two pearls were different from each other. WSM differed the most between these two pearls. - Research Highlights: → We use a specific method for extracting matrix proteins from aragonite pearl and vaterite pearl respectively. → The matrix proteins are extracted by water and weak acid, and classified as water soluble matrix (WSM), acid soluble matrix (ASM) and acid insoluble matrix (AIM). → AIM of aragonite pearl and vaterite pearl have an ordered structure. ASM conformations of the two pearls are different from each other. WSM differ the most between these two pearls.

Effect of Interannual Variability on the Ocean Acidification-induced Habitat Restriction of the Humboldt Current System.

Science.gov (United States)

Franco, A. C.; Gruber, N.; Munnich, M.

2016-02-01

The Humboldt Current System (HCS) is one of the most productive ecosystems in the world. This high productivity is supported by a large input of nutrients from the subsurface layers to the surface due to year-round upwelling. However, upwelling also supplies waters with low pH and low aragonite saturation state potentially affecting many organisms, especially those that calcify. The influence, extent and source of upwelled water varies substantially on interannual timescales in association with the El Niño/Southern Oscillation (ENSO) phenomenon, accentuating productivity during La Niña events and dampening it during El Niño, altering the dynamics of the whole ecosystem. On top of this natural variability, the continuing acidification of the upper ocean in response to raising atmospheric CO2 may decrease pH further and increase the volume of water corrosive to aragonite in this region, leading to a progressively smaller suitable habitat for sensitive organisms. Here we use an eddy-resolving basin-scale ocean model that covers the whole Pacific Ocean with higher resolution near the coast off South America ( 6 km) to investigate the role of ENSO events on low aragonite saturation episodes and productivity variations. We compare 2 simulations: a hindcast simulation that spans the last 30 years and a future scenario that represents year 2090 (following IPCC's "business-as-usual" scenario). We found that in the region off Peru, the sole effect of increasing atmospheric CO2 to 840 matm shoals the annual average aragonite saturation depth to 30 m, creating a year round presence of aragonite undersaturated water in the euphotic zone. We then contrast the effect on primary productivity and the aragonite saturation state of at least eight El Niño and eight La Niña episodes that have been reported for the past 30 years, in an attempt to answer the question: does habitat availability under future ocean acidification will resemble a pervasive La Niña-like state?

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

Science.gov (United States)

Bookman, Revital; Lopez-Merino, Lourdes; Belmaker, Reuven; Eshel, Amram; Epshtein Epshtein, Valentina; Leroy, Suzanne

2017-04-01

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; detritus deposition during the winter and aragonite in the summer. These sequences were used for varve counting and chronology, however this assumption has never been robustly validated. Here, we report an examination of the seasonal deposition of detrital and 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 pollen 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. The conclusions suggest that detrital and aragonite couplets in the Dead Sea laminated sediments are most likely not varves and that the laminae deposition is related to the occurrence of flash-flood events. Consequently, at least for the Holocene sequences, laminated sediments cannot be considered as varves and Quaternary laminated sequences should be re-evaluated. The Dead Sea Basin laminated sequences (as the ICDP Dead Sea Deep Drilling Project record) should be used for the reconstruction of

Geochemical gradients within modern and fossil shells of Concholepas concholepas from northern Chile: an insight into U-Th systematics and diagenetic/authigenic isotopic imprints in mollusk shells

Science.gov (United States)

Labonne, Maylis; Hillaire-Marcel, Claude

2000-05-01

Seriate geochemical measurements through shells of one modern, one Holocene, and two Sangamonian Concholepas concholepas, from marine terraces of Northern Chile, were performed to document diagenetic vs. authigenic geochemical signatures, and to better interpret U-series ages on such material. Subsamples were recovered by drilling from the outer calcitic layer to the inner aragonitic layer of each of the studied shells. Unfortunately, this sampling procedure induces artifacts, notably the convertion of up to ˜20% of calcite into aragonite, and of up to ˜6% of aragonite into calcite, as well as in the epimerization of a few percent of isoleucine into D-alloisoleucine/ L-isoleucine. Negligible sampling artifacts were noticed for stable isotope and total amino acid contents. Diagenetic effects on the geochemical properties of the shells are particularly pronounced in the inner aragonitic layer and more discrete in the outer calcitic layer. The time-dependent decay of the organic matrix of the shell is illustrated by a one order of magnitude lower total amino acid content in the Sangamonian specimens by comparison with the modern shell. Conversely, the Sangamonian shells U contents increase by a similar factor and 13C- 18O enrichments as high as 2 to 3‰ seem also to occur through the same time interval possibly due to partial replacement of aragonite by gypsum. The decay of the organic matrix of the aragonitic layer of the shell is thought to play a major role with respect to U-uptake processes and stable isotope shifts. Nevertheless, asymptotic 230Th-ages (˜100 ka) in the inner U-rich layers of the Sangamonian shells, and 234U/ 238U ratios compatible with a marine origin for U, suggest U-uptake within a short diagenetic interval, when marine waters were still bathing the embedding sediment. Thus, U-series ages on fossil mollusks from such a hyper-arid environment should not differ much from the age of the corresponding marine unit deposition. However, the

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

Science.gov (United States)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

Depositional facies and aqueous-solid geochemistry of travertine-depositing hot springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, USA)

Energy Technology Data Exchange (ETDEWEB)

Fouke, B.W.; Farmer, J.D.; Des Marais, D.J.; Pratt, L.; Sturchio, N.C.; Burns, P.C.; Discipulo, M.K.

2000-05-01

Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73 C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43--72 C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30--62 C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite ice sheets, calcified bubbles, and aggregates of aragonite needles (fuzzy dumbbells) precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28--54 C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28--30 C) is composed of calcite spherules and calcite feather crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO{sub 2} degassing causes a +2 unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding {delta}{sup 13}C. Travertine {delta}{sup 13}C and {delta}{sup 18}O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature ({approximately}50--73 C) depositional facies. Conversely, travertine precipitating in the lower-temperature (<{approximately}50 C) depositional facies exhibits {delta}{sup 13}C and {delta}{sup 18}O values that are as

Skeleton microstructure of Porites lutea in Kondang Merak, Malang, East Java

Science.gov (United States)

Luthfi, Oktiyas Muzaky; Sontodipoero, R. M. Agung M. Rizqon; Isdianto, Andik; Setyohadi, Daduk; Jauhari, Alfan; Januarsa, I. Nyoman

2017-11-01

Research on coral microstructure in Indonesia, especially in East Java is rarely done. Therefore, this study aims to examine the shape of Aragonite Crystal coral Porites lutea in Pantai Kondak Merak, East Java, especially in 1998 which is the time of El Nino and has a global impact on coral growth. The shape of the aragonite crystal on the reef can be seen using the Scanning Electron Microscopy-Energy Dispersion X-Ray (SEM - EDX). Based on the coral aragonite crystal form, the increasing temperature in 1998 was not proven to have a devastating effect on the growth of corals of Pantai Kondang Merak. In contrast, the temperature at this site should support corals in order to grow rapidly, but there are other environmental factors that ultimately inhibit the growth of the coral.

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. Copyright © 2014 Elsevier Inc. All rights reserved.

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.

Surface Modification and Planar Defects of Calcium Carbonates by Magnetic Water Treatment

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Yeh MS

2010-01-01

Full Text Available Abstract Powdery calcium carbonates, predominantly calcite and aragonite, with planar defects and cation–anion mixed surfaces as deposited on low-carbon steel by magnetic water treatment (MWT were characterized by X-ray diffraction, electron microscopy, and vibration spectroscopy. Calcite were found to form faceted nanoparticles having 3x ( commensurate superstructure and with well-developed { } and { } surfaces to exhibit preferred orientations. Aragonite occurred as laths having 3x ( commensurate superstructure and with well-developed ( surface extending along [100] direction up to micrometers in length. The (hkil-specific coalescence of calcite and rapid lath growth of aragonite under the combined effects of Lorentz force and a precondensation event account for a beneficial larger particulate/colony size for the removal of the carbonate scale from the steel substrate. The coexisting magnetite particles have well-developed {011} surfaces regardless of MWT.

Final report for grant number DE-FG02-06ER64244 to the University of Idaho (RW Smith)-coupling between flow and precipitation in heterogeneous subsurface environments and effects on contaminant fate and transport

Energy Technology Data Exchange (ETDEWEB)

Smith, Robert W. [Univ. of Idaho, Idaho Falls, ID (United States); Beig, Mikala S. [Univ. of Idaho, Idaho Falls, ID (United States); Gebrehiwet, Tsigabu [Univ. of Idaho, Idaho Falls, ID (United States); Corriveau, Catherine E. [Univ. of Idaho, Idaho Falls, ID (United States); Redden, George [Idaho National Lab. (INL), Idaho Falls, ID (United States); Fujita, Yoshiko [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2010-06-18

Engineered remediation strategies for inducing mineral precipitation in the subsurface typically involve the introduction of at least one reactant either by direct injection or by in situ generation. The localization of reactant sources means a wide range of saturation states and ion ratios will be created as reactants are mixed: These conditions together can result in a wide range of precipitation rates, as well as impact which mineral phase precipitates. This is potentially important for the capacity of the precipitates to take up of trace metal contaminants, for their long term stability. Aragonite, for example, is able to sequester a larger amount of Sr than calcite. However, aragonite is less stable under typical groundwater conditions, and so may release sequestered Sr over time as the aragonite transforms to a more stable phase. In addition, previous experimental studies have indicated that other system constituents may influence calcium carbonate precipitation and consequently the Sr uptake potential of a system. For example, dissolved organic carbon (at levels typical of groundwaters) can suppress crystal growth. As a result, the continuous nucleation of small crystals, rather than growth of existing crystals, may be the dominant mode of precipitation. This has the potential for greater uptake of Sr because the smaller crystal sizes associated with nucleated calcite may more readily accommodate the distortion resulting from substitution of the larger Sr ion for Ca ions than can larger crystals. However, these smaller crystals may also be less stable and over the long term release Sr as a result of Ostwald ripening. To better understand the formation and composition of relevant calcium carbonate mineral phases two related series of mineral precipitation experiments were conducted. The first series of experiments, conducted using a Continuously Stirred Tank Reactor (CSTR) operated at steady state rates of precipitation was focused on understanding the

Sub-Milankovitch cycles in periplatform carbonates from the early Pliocene Great Bahama Bank

OpenAIRE

Reuning, Lars; Reijmer, John; Betzler, C.; Timmermann, A.; Steph, Silke

2006-01-01

High-resolution bulk sediment (magnetic susceptibility and aragonite content) and δ18O records from two different planktonic foraminifera species were analyzed in an early Pliocene core interval from the Straits of Florida (Ocean Drilling Program site 1006). The δ18O record of the shallow-dwelling foraminifera G. sacculifer and the aragonite content are dominated by sub-Milankovitch variability. In contrast, magnetic susceptibility and the δ18O record of the deeper-dwelling foraminifera G. me...

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

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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.

Precipitation diagram of calcium carbonate polymorphs: its construction and significance

International Nuclear Information System (INIS)

Kawano, Jun; Shimobayashi, Norimasa; Miyake, Akira; Kitamura, Masao

2009-01-01

In order to interpret the formation mechanism of calcium carbonate polymorphs, we propose and construct a new 'precipitation diagram', which has two variables: the driving force for nucleation and temperature. The precipitation experiments were carried out by mixing calcium chloride and sodium carbonate aqueous solutions. As a result, a calcite-vaterite co-precipitation zone, a vaterite precipitation zone, a vaterite-aragonite co-precipitation zone and an aragonite precipitation zone can be defined. Theoretical considerations suggest that the steady state nucleation theory can explain well the appearance of these four zones, and the first-order importance of the temperature dependency of surface free energy in the nucleation of aragonite. Furthermore, the addition of an impurity will likely result in the change of these energies, and this precipitation diagram gives a new basis for interpreting the nature of the polymorphs precipitated in both inorganic and biological environments.

Direct contribution of the seagrass Thalassia testudinum to lime mud production

Science.gov (United States)

Enríquez, Susana; Schubert, Nadine

2014-01-01

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. PMID:24848374

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

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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.

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

Science.gov (United States)

Busch, D Shallin; Maher, Michael; Thibodeau, Patricia; McElhany, Paul

2014-01-01

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.

Polycrystalline apatite synthesized by hydrothermal replacement of calcium carbonates

Science.gov (United States)

Kasioptas, Argyrios; Geisler, Thorsten; Perdikouri, Christina; Trepmann, Claudia; Gussone, Nikolaus; Putnis, Andrew

2011-06-01

Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH 4) 2HPO 4 solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product. Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in 18O (97%) further revealed that the 18O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of 18O with Raman spectroscopy was possible because the incorporation of 18O in the PO 4 group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm -1, in addition to the ν1(PO 4) symmetric stretching band of apatite located at 962 cm -1, which can be assigned to four 18O-bearing PO 4 species. The relative intensities of these bands reflect the 18O content in the PO 4 group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the 18O distribution between aqueous phosphate and water, we could show that the concentration of 18O in the apatite product is linked to the degree of 18O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.

Threshold of carbonate saturation state determined by CO2 control experiment

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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.

The co-effect of collagen and magnesium ions on calcium carbonate biomineralization

International Nuclear Information System (INIS)

Jiao Yunfeng; Feng Qingling; Li Xiaoming

2006-01-01

The process of calcium carbonate biomineralization in the solution containing collagen and magnesium ions was studied in this paper. The results were characterized by using powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect rules were obtained by the cooperation of collagen and magnesium ions in different concentration. The experiment results showed that in the presence of both collagen and magnesium ions, aragonite and vaterite were precipitated at low Mg/Ca ion concentration ratio, while only aragonite with regular spherical morphology was precipitated at high Mg/Ca ion concentration ratio. It indicated that collagen has a promotional effect on magnesium ions in controlling the polymorph of calcium carbonate crystal. A much wider range of calcium carbonate morphologies was observed in the presence of both collagen and magnesium ions. The experiments suggested that collagen acts in combination with magnesium ions to inhibit calcite crystal growth, while favoring the formation of aragonite crystals

An interatomic potential model for carbonates allowing for polarization effects

International Nuclear Information System (INIS)

Birse, S.E.A.; Archer, T.D.; Dove, Martin T.; Cygan, Randall Timothy; Gale, Julian D.; Redern, Simon A.T.

2003-01-01

An empirical model for investigating the behavior of CaCO 3 polymorphs incorporating a shell model for oxygen has been created. The model was constructed by fitting to: the structure of aragonite and calcite; their elastic, static and high-frequency dielectric constants; phonon frequencies at the wave vectors (1/2 0 2) and (0 0 0) of calcite; and vibrational frequencies of the carbonate deformation modes of calcite. The high-pressure phase transition between calcite I and II is observed. The potentials for the CO 3 group were transferred to other carbonates, by refitting the interaction between CO 3 and the cation to both the experimental structures and their bulk modulus, creating a set of potentials for calculating the properties of a wide range of carbonate materials. Defect energies of substitutional cation defects were analyzed for calcite and aragonite phases. The results were rationalized by studying the structure of calcite and aragonite in greater detail.

Nuclear microprobe and Raman investigation of the chemistry of the shell of the pacific oyster, Crassostrea gigas

International Nuclear Information System (INIS)

Markwitz, A.; Gauldie, R.W.; Pithie, J.; Sharma, S.K.; Jamieson, D.J.

1999-01-01

High-resolution nuclear microscopy was used to study the layered structure in the shell of the pacific oyster, Crassostrea gigas. In cross section, the layers appear as opaque white zones and clearer translucent zones. Raman spectroscopy indicates that the zones consist of alternating layers of the aragonite and calcite morphs of calcium carbonate, the mineral constituent of the shell. The chemistry of the shell varies from individual to individual but generally the predominant metal ion is Ca, with varying amounts of Si, Cl, Cr, Mn, Fe, Zn, Sb, Ni, Fe, As and Sr. Two dimensional maps of these major, minor and trace elements were measured in many shells with nuclear microscopy to identify the patterns of Zn and Sr deposition reflecting the calcite and aragonite layers. The significant difference in the patterns identified by ion beam analyses are possibly a result of isostructural exclusion of these metal ions between the different aragonite and calcite polymorphic forms of calcium carbonate. (author)

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

Reconstruction of pH and partial pressure of carbon dioxide during the Mesozoic era period using boron and oxygen isotopic compositions of fresh ammonoids & nautiloids

Science.gov (United States)

Kawahata, Hodaka; Fukushima, Ayaka; Moriya, Kazuyori; Ishikawa, Tsuyoshi; Suzuki, Atsushi; Tanabe, Kazushige

2013-04-01

The increase of partial pressure of carbon dioxide (pCO2) in the atmosphere induces global warming and ocean acidification at the modern condition. The reconstruction of pCO2 during the geological time is required together with proxy calibration by laboratory experiments to predict the future environments. Boron isotopic ratio is an excellent proxy for pH and the relevant partial pressure of carbon dioxide in the seawater (PCO2). This study is the first to quantify pH dependence of delta 11B of the ammonoids and nautiloids mainly in the Cretaceous and in Jurassic (70-162 Ma), which are expected to be much warmer due to higher PCO2. However, no reliable reconstruction data using foraminiferal delta 11B before Cenozoic era has been reported. We used the very fresh aragonite shells of ammonoids and nautiloids by big advantages. Since aragonite changes into secondary calcite by diagenesis, it is easy and effective to identify the degree of alteration at each sample by measuring calcite/aragonite ratio. Also we carefully conducted the assessment of secondary alteration from three perspectives: 1) Determination of calcite/aragonite ratio by X-ray diffraction (XRD), 2) Observation of microstructures of the nacreous layers by scanning electron microscope (SEM), and 3) Measurement of trace element contents and stable isotope ratios. We conducted high precision boron isotope analysis of biogenic carbonates with +/- 0.1 per mil reproducibility by adopting positive thermal ionization mass spectrometry (P-TIMS) methods. Also we analyzed delta 18O to estimate paleo-temperature, at which biogenic aragonite was formed. Combination of delta 11B and delta 18O of biogenic aragonite in 80 Ma and 86 Ma revealed that deeper dwellers showed lower delta 11B values, which corresponded to lower pH. This feature is consistent with those observed in the modern vertical water column. The respective shallow water temperature was 19.7 and 19.1 centigrade. Based on these results, the

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

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.

Hot spring deposits on a cliff face: A case study from Jifei, Yunnan Province, China

Science.gov (United States)

Jones, Brian; Peng, Xiaotong

2014-04-01

A cliff face in the Jifei karst area, southwest China, is covered by a spectacular succession of precipitates that formed from the hot spring water that once flowed down its surface. This layered succession is formed of aragonite layers that are formed largely of “fountain dendrites”, calcite layers that are formed mostly of “cone dendrites”, and microlaminated layers that contain numerous microbes and extracellular polymeric substances (EPS). Many of the aragonite crystals are hollow due to preferential dissolution of their cores. The calcite cone dendrites are commonly covered with biofilms, reticulate Si-Mg coatings, and other precipitates. The microbial layers include dodecahedral calcite crystals and accessory minerals that include opal-A, amorphous Si-Mg coatings, trona, barite, potassium sulfate crystals, mirabillite, and gaylussite. Interpretation of the δ18O(calcite) and δ18O(aragonite) indicates precipitation from water with a temperature of 54 to 66 °C. The active hot spring at the top of the cliff presently ejects water at a temperature of 65 °C. Layers, 1 mm to 6 cm thick, record temporal changes in the fluids from which the precipitates formed. This succession is not, however, formed of recurring cycles that can be linked to diurnal or seasonal changes in the local climate. Indeed, it appears that the climatic contrast between the wet season and the dry season had little impact on precipitation from the spring waters that flowed down the cliff face. Integration of currently available evidence suggests that the primary driving force was aperiodic changes in the CO2 content of the spring waters because that seems to be the prime control on the saturation levels that underpinned precipitation of the calcite and aragonite as well as the dissolution of the aragonite. Such variations in the CO2 content of the spring water were probably due to changes that took place in the subterranean plumbing system of the spring.

Monohydrocalcite: a promising remediation material for hazardous anions

International Nuclear Information System (INIS)

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-01-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO 3 ·H 2 O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO 4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO 4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO 4 than calcite and aragonite. The modes of PO 4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple

Monohydrocalcite: a promising remediation material for hazardous anions

Science.gov (United States)

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption

Monohydrocalcite: a promising remediation material for hazardous anions

Directory of Open Access Journals (Sweden)

Keisuke Fukushi, Takashi Munemoto, Minoru Sakai and Shintaro Yagi

2011-01-01

Full Text Available The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3centerdotH2O, as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly

Monohydrocalcite: a promising remediation material for hazardous anions

Energy Technology Data Exchange (ETDEWEB)

Fukushi, Keisuke [Institute of Nature and Environmental Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Munemoto, Takashi [Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Sakai, Minoru [Department of Earth and Planetary Sciences, Faculty of Science, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan); Yagi, Shintaro [Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192 (Japan)

2011-12-15

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO{sub 3}{center_dot}H{sub 2}O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO{sub 4} and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO{sub 4} in solution (>30 {mu}M) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO{sub 4} than calcite and aragonite. The modes of PO{sub 4} uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC

Magnesian calcite and the problem of the origin of carbonates in the deep-sea Old Black Sea sediments

Energy Technology Data Exchange (ETDEWEB)

Georgiev, V M

1988-04-01

The Old Black Sea (Lower-Middle Holocene) deep-sea sediments in the Black Sea basin contain carbonate laminae with a fixed position in the section - in the base of the typical sapropelic muds. The areal distribution of these laminae covers the whole continental slope and rise. They are usually lacking in the sediments of the abyssal plain. XRD, SEM and EDS studies show that the laminae comprise mainly authigenic carbonates - aragonite and magnesian calcite. Aragonite occurs as elongated rice-shaped monocrystals or as diverse aggregates of elongated crystal platelets. The magnesian calcite (6-14 mol % MgCO/sub 3/) forms aggregates of isometric grains with submicritic dimensions between the aragonite grains or individual laminae consisting of idiomorphic rhombohedral and/or skeleton crystals. Low-magnesian calcite is also found sometimes. Usually it is related to Holocene coccoliths without traces of recrystallization. The laminae do not show traces of lithification. A hemogenic-synsedimentary genesis of the carbonate laminae is suggested; their mineral composition witnesses marine chemical composition of the initial solutions with a high Mg/Ca ratio.

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.

Palaeoclimate significance of speleothems in crystalline rocks: a test case from the Late Glacial and early Holocene (Vinschgau, northern Italy)

Science.gov (United States)

Koltai, Gabriella; Cheng, Hai; Spötl, Christoph

2018-03-01

Partly coeval flowstones formed in fractured gneiss and schist were studied to test the palaeoclimate significance of this new type of speleothem archive on a decadal-to-millennial timescale. The samples encompass a few hundred to a few thousand years of the Late Glacial and the early Holocene. The speleothem fabric is primarily comprised of columnar fascicular optic calcite and acicular aragonite, both indicative of elevated Mg / Ca ratios in the groundwater. Stable isotopes suggest that aragonite is more prone to disequilibrium isotope fractionation driven by evaporation and prior calcite/aragonite precipitation than calcite. Changes in mineralogy are therefore attributed to these two internal fracture processes rather than to palaeoclimate. Flowstones formed in the same fracture show similar δ18O changes on centennial scales, which broadly correspond to regional lacustrine δ18O records, suggesting that such speleothems may provide an opportunity to investigate past climate conditions in non-karstic areas. The shortness of overlapping periods in flowstone growth and the complexity of in-aquifer processes, however, render the establishment of a robust stacked δ18O record challenging.

Comparative study on nano-mechanics and thermodynamics of fish otoliths

Energy Technology Data Exchange (ETDEWEB)

Dongni, Ren; Yonghua, Gao [State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China); Qingling, Feng, E-mail: biomater@mail.tsinghua.edu.cn [Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084 (China)

2013-01-01

Fish otolith is a kind of typical natural biomineral, which is composed of calcium carbonate and organic matrix. In fresh water carp otolith, the inorganic phase of lapillus is pure aragonite, and for asteriscus it is pure vaterite. In this research, the phase composition, phase transformation, mechanical property and solubility of lapillus and asteriscus were studied. And results showed that, the organic content of lapillus was higher than that of asteriscus; the phase-transition temperature of lapillus (aragonite-calcite) and asteriscus (vaterite-calcite) both happened between 520 and 640 Degree-Sign C; the nano-mechanical property of lapillus was better than that of asteriscus; the solubility of asteriscus powder was higher than that of lapillus powder. - Highlights: Black-Right-Pointing-Pointer The nano-mechanical property of lapillus (aragonite) was better than that of asteriscus (vaterite). Black-Right-Pointing-Pointer The phase-transition temperature of lapillus and asteriscus were both between 520 and 640 Degree-Sign C. Black-Right-Pointing-Pointer The solubility property of asteriscus powder was better than that of lapillus powder.

Relict ooids off northwestern India: Inferences on their genesis and late Quaternary sea level

Science.gov (United States)

Purnachandra Rao, V.; Milliman, John D.

2017-08-01

Relict carbonate sands dominated by ooids and faecal pellets are common on the continental shelf, between 60 and 110 m, off northwestern India. The shiny tan/white aragonitic ooids closely resemble modern Bahamian ooids, with cortex thicknesses varying from stacked tubules, similar in appearance to algal or microbial filaments. Bacteria associated with the decaying organic sheath of the laminae may have played an important role in subsequent aragonite precipitation. Bladed or radial aragonite microstructures are secondary features in the cortex, apparently formed during early diagenesis by mineralization of organic matter associated with the tangential laminae. Calibrated ages of the ooids range between 9.8 and > 23 ka BP, and δ18O values suggest that these relict ooids formed during cooler and drier post-LGM conditions and later during the re-intensified Holocene monsoon climate. An age vs. depth plot suggests that most of the ooids formed at water depths between 10 and - 40 m, thereby calling into question whether relict shelf ooids are reliable indicators of past sea level.

Ionising radiation effect on the luminescence emission of inorganic and biogenic calcium carbonates

Energy Technology Data Exchange (ETDEWEB)

Boronat, C. [CIEMAT, Av. Complutense 40, Madrid 28040 (Spain); Correcher, V., E-mail: v.correcher@ciemat.es [CIEMAT, Av. Complutense 40, Madrid 28040 (Spain); Virgos, M.D. [CIEMAT, Av. Complutense 40, Madrid 28040 (Spain); Garcia-Guinea, J. [CSIC, Museo Nacional Ciencias Naturales, José Gutiérrez Abascal 2, Madrid 28006 (Spain)

2017-06-15

Highlights: • Aragonite and biogenic Ca-carbonates could be used as a TL dosimeters. • TL can be employed for retrospective dosimetry purposes. • Calcium carbonates show an acceptable ionizing radiation sensitivity. • The stability of the radiation–induced TL remains, at least, till 700 h. - Abstract: As known, the luminescence emission of mineral phases could be potentially employed for dosimetric purposes in the case of radiological terrorism or radiation accident where conventional monitoring is not available. In this sense, this paper reports on the thermo- (TL) and cathodoluminescence (CL) emission of both biogenic (common periwinkle – littorina littorera – shell made of calcite 90% and aragonite 10%) and inorganic (aragonite 100%) Ca-rich carbonates previously characterized by X-ray diffraction and Raman spectroscopy. Whereas the aragonite sample displays the main CL waveband peaked in the red region (linked to point defects), the more intense emission obtained from the common periwinkle shell appears at higher energies (mainly associated with structural defects). The UV-blue TL emission of the samples, regardless of the origin, displays (i) an acceptable ionizing radiation sensitivity, (ii) linear dose response in the range of interest (up to 8 Gy), (iii) reasonable stability of the TL signal after 700 h of storage with an initial decay of ca. 88% for the mineral sample and 60% for the biogenic sample and maintaining the stability from 150 h onwards. (iv) The tests of thermal stability of the TL emission performed in the range of 180–320 °C confirm a continuum in the trap system.

Ionising radiation effect on the luminescence emission of inorganic and biogenic calcium carbonates

International Nuclear Information System (INIS)

Boronat, C.; Correcher, V.; Virgos, M.D.; Garcia-Guinea, J.

2017-01-01

Highlights: • Aragonite and biogenic Ca-carbonates could be used as a TL dosimeters. • TL can be employed for retrospective dosimetry purposes. • Calcium carbonates show an acceptable ionizing radiation sensitivity. • The stability of the radiation–induced TL remains, at least, till 700 h. - Abstract: As known, the luminescence emission of mineral phases could be potentially employed for dosimetric purposes in the case of radiological terrorism or radiation accident where conventional monitoring is not available. In this sense, this paper reports on the thermo- (TL) and cathodoluminescence (CL) emission of both biogenic (common periwinkle – littorina littorera – shell made of calcite 90% and aragonite 10%) and inorganic (aragonite 100%) Ca-rich carbonates previously characterized by X-ray diffraction and Raman spectroscopy. Whereas the aragonite sample displays the main CL waveband peaked in the red region (linked to point defects), the more intense emission obtained from the common periwinkle shell appears at higher energies (mainly associated with structural defects). The UV-blue TL emission of the samples, regardless of the origin, displays (i) an acceptable ionizing radiation sensitivity, (ii) linear dose response in the range of interest (up to 8 Gy), (iii) reasonable stability of the TL signal after 700 h of storage with an initial decay of ca. 88% for the mineral sample and 60% for the biogenic sample and maintaining the stability from 150 h onwards. (iv) The tests of thermal stability of the TL emission performed in the range of 180–320 °C confirm a continuum in the trap system.

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

Science.gov (United States)

Gazeau, Frédéric; Gattuso, Jean-Pierre; Greaves, Mervyn; Elderfield, Henry; Peene, Jan; Heip, Carlo H R; Middelburg, Jack J

2011-01-01

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.

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.

Nanoasperity: structure origin of nacre-inspired nanocomposites.

Science.gov (United States)

Xia, Shuang; Wang, Zuoning; Chen, Hong; Fu, Wenxin; Wang, Jianfeng; Li, Zhibo; Jiang, Lei

2015-02-24

Natural nacre with superior mechanical property is generally attributed to the layered "brick-and-mortar" nanostructure. However, the role of nanograins on the hard aragonite platelets, which is so-called nanoasperity, is rarely addressed. Herein, we prepared silica platelets with aragonite-like nanoasperities via biomineralization strategy and investigated the effects of nanoasperity on the mechanical properties of resulting layered nanocomposites composed of roughened silica platelets and poly(vinyl alcohol). The tensile deformation behavior of the nanocomposites demonstrates that nanograins on silica platelets are responsive for strain hardening, improved strength, and toughness. The structure origin is attributed to the nanoasperity-controlled platelet sliding.

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

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Zhai, W.-D.; Zheng, N.; Huo, C.; Xu, Y.; Zhao, H.-D.; Li, Y.-W.; Zang, K.-P.; Wang, J.-Y.; Xu, X.-M.

2013-02-01

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.

The influence of diet on the δ 13C of shell carbon in the pulmonate snail Helix aspersa

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Stott, Lowell D.

2002-02-01

The influence of diet and atmospheric CO 2 on the carbon isotope composition of shell aragonite and shell-bound organic carbon in the pulmonate snail Helix aspersa raised in the laboratory was investigated. Three separate groups of snails were raised on romaine lettuce (C3 plant, δ 13C=-25.8‰), corn (C4 plant, δ 13C=-10.5‰), and sour orange ( 12C-enriched C3 plant, δ 13C=-39.1‰). The isotopic composition of body tissues closely tracked the isotopic composition of the snail diet as demonstrated previously. However, the isotopic composition of the acid insoluble organic matrix extracted from the aragonite shells does not track diet in all groups. In snails that were fed corn the isotopic composition of the organic matrix was more negative than the body by as much as 5‰ whereas the matrix was approximately 1‰ heavier than the body tissues in snails fed a diet of C3 plant material. These results indicate that isotopic composition of the organic matrix carbon cannot be used as an isotopic substrate for paleodietary reconstructions without first determining the source of the carbon and any associated fractionations. The isotopic composition of the shell aragonite is offset from the body tissues by 12.3‰ in each of the culture groups. This offset was not influenced by the consumption of carbonate and is not attributable to the diffusion of atmospheric CO 2 into the hemolymph. The carbon isotopic composition of shell aragonite is best explained in terms of equilibrium fractionations associated with exchange between metabolic CO 2 and HCO 3 in the hemolymph and the fractionation associated with carbonate precipitation. These results differ from previous studies, based primarily on samples collected in the field, that have suggested atmospheric carbon dioxide contributes significantly to the shell δ 13C. The culture results indicate that the δ 13C of aragonite is a good recorder of the isotopic composition of the snail body tissue, and therefore a better

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

International Nuclear Information System (INIS)

Romana, L.; Thomas, P.; Bilas, P.; Mansot, J.L.; Merrifiels, M.; Bercion, Y.; Aranda, D. Aldana

2013-01-01

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

Skeletal mineralogy of coral recruits under high temperature and pCO2

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Foster, T.; Clode, P. L.

2016-03-01

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 may leave 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 Ma. 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 1-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 the investigation of the combined impact of high pCO2 and reduced Mg / Ca ratio on coral skeletal mineralogy.

Response of ocean acidification to a gradual increase and decrease of atmospheric CO2

International Nuclear Information System (INIS)

Cao, Long; Zhang, Han; Zheng, Meidi; Wang, Shuangjing

2014-01-01

We perform coupled climate–carbon cycle model simulations to examine changes in ocean acidity in response to idealized change of atmospheric CO 2 . Atmospheric CO 2 increases at a rate of 1% per year to four times its pre-industrial level of 280 ppm and then decreases at the same rate to the pre-industrial level. Our simulations show that changes in surface ocean chemistry largely follow changes in atmospheric CO 2 . However, changes in deep ocean chemistry in general lag behind the change in atmospheric CO 2 because of the long time scale associated with the penetration of excess CO 2 into the deep ocean. In our simulations with the effect of climate change, when atmospheric CO 2 reaches four times its pre-industrial level, global mean aragonite saturation horizon (ASH) shoals from the pre-industrial value of 1288 to 143 m. When atmospheric CO 2 returns from the peak value of 1120 ppm to pre-industrial level, ASH is 630 m, which is approximately the value of ASH when atmospheric CO 2 first increases to 719 ppm. At pre-industrial CO 2 9% deep-sea cold-water corals are surrounded by seawater that is undersaturated with aragonite. When atmospheric CO 2 reaches 1120 ppm, 73% cold-water coral locations are surrounded by seawater with aragonite undersaturation, and when atmospheric CO 2 returns to the pre-industrial level, 18% cold-water coral locations are surrounded by seawater with aragonite undersaturation. Our analysis indicates the difficulty for some marine ecosystems to recover to their natural chemical habitats even if atmospheric CO 2 content can be lowered in the future. (paper)

Effect of Hydraulic Activity on Crystallization of Precipitated Calcium Carbonate (PCC) for Eco-Friendly Paper

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Kim, Jung-Ah; Han, Gi-Chun; Lim, Mihee; You, Kwang-Suk; Ryu, Miyoung; Ahn, Ji-Whan; Fujita, Toyohisa; Kim, Hwan

2009-01-01

Wt% of aragonite, a CaCO3 polymorph, increased with higher hydraulic activity (°C) of limestone in precipitated calcium carbonate (PCC) from the lime-soda process (Ca(OH)2-NaOH-Na2CO3). Only calcite, the most stable polymorph, was crystallized at hydraulic activity under 10 °C, whereas aragonite also started to crystallize over 10 °C. The crystallization of PCC is more dependent on the hydraulic activity of limestone than CaO content, a factor commonly used to classify limestone ores according to quality. The results could be effectively applied to the determination of polymorphs in synthetic PCC for eco-friendly paper manufacture. PMID:20087470

An investigation of green iridescence on the mollusc Patella granatina

Energy Technology Data Exchange (ETDEWEB)

Brink, D J; Berg, N G van der [Department of Physics, University of Pretoria, Pretoria 0002 (South Africa)

2005-01-21

In this paper we investigate the relatively rare phenomenon of iridescence on the outer surface of seashells (not the well known pearly inner surfaces). Using reflection spectroscopy and scanning electron microscopy we show that rows of iridescent green spots on the mollusc Patella granatina are caused by a thin-film stack buried about 100 {mu}m below the rough outer surface of the shell. The high-density layers in the stack seem to be made of crystalline aragonite, but according to Raman spectroscopy and ellipsometry measurements the low-density layers as well as the bulk of the shell wall are a mixture of porous aragonite and organic materials such as carotenoids.

Natural variability in the surface ocean carbonate ion concentration

Science.gov (United States)

Lovenduski, N. S.; Long, M. C.; Lindsay, K.

2015-11-01

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 aragonite (Ωaragonite) 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 will aid the interpretation of trends

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.

Key Role of Alphaproteobacteria and Cyanobacteria in the Formation of Stromatolites of Lake Dziani Dzaha (Mayotte, Western Indian Ocean

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Emmanuelle Gérard

2018-05-01

Full Text Available Lake Dziani Dzaha is a thalassohaline tropical crater lake located on the “Petite Terre” Island of Mayotte (Comoros archipelago, Western Indian Ocean. Stromatolites are actively growing in the shallow waters of the lake shores. These stromatolites are mainly composed of aragonite with lesser proportions of hydromagnesite, calcite, dolomite, and phyllosilicates. They are morphologically and texturally diverse ranging from tabular covered by a cauliflower-like crust to columnar ones with a smooth surface. High-throughput sequencing of bacterial and archaeal 16S rRNA genes combined with confocal laser scanning microscopy (CLSM analysis revealed that the microbial composition of the mats associated with the stromatolites was clearly distinct from that of the Arthrospira-dominated lake water. Unicellular-colonial Cyanobacteria belonging to the Xenococcus genus of the Pleurocapsales order were detected in the cauliflower crust mats, whereas filamentous Cyanobacteria belonging to the Leptolyngbya genus were found in the smooth surface mats. Observations using CLSM, scanning electron microscopy (SEM and Raman spectroscopy indicated that the cauliflower texture consists of laminations of aragonite, magnesium-silicate phase and hydromagnesite. The associated microbial mat, as confirmed by laser microdissection and whole-genome amplification (WGA, is composed of Pleurocapsales coated by abundant filamentous and coccoid Alphaproteobacteria. These phototrophic Alphaproteobacteria promote the precipitation of aragonite in which they become incrusted. In contrast, the Pleurocapsales are not calcifying but instead accumulate silicon and magnesium in their sheaths, which may be responsible for the formation of the Mg-silicate phase found in the cauliflower crust. We therefore propose that Pleurocapsales and Alphaproteobacteria are involved in the formation of two distinct mineral phases present in the cauliflower texture: Mg-silicate and aragonite

Ionising radiation effect on the luminescence emission of inorganic and biogenic calcium carbonates

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Boronat, C.; Correcher, V.; Virgos, M. D.; Garcia-Guinea, J.

2017-06-01

As known, the luminescence emission of mineral phases could be potentially employed for dosimetric purposes in the case of radiological terrorism or radiation accident where conventional monitoring is not available. In this sense, this paper reports on the thermo- (TL) and cathodoluminescence (CL) emission of both biogenic (common periwinkle - littorina littorera - shell made of calcite 90% and aragonite 10%) and inorganic (aragonite 100%) Ca-rich carbonates previously characterized by X-ray diffraction and Raman spectroscopy. Whereas the aragonite sample displays the main CL waveband peaked in the red region (linked to point defects), the more intense emission obtained from the common periwinkle shell appears at higher energies (mainly associated with structural defects). The UV-blue TL emission of the samples, regardless of the origin, displays (i) an acceptable ionizing radiation sensitivity, (ii) linear dose response in the range of interest (up to 8 Gy), (iii) reasonable stability of the TL signal after 700 h of storage with an initial decay of ca. 88% for the mineral sample and 60% for the biogenic sample and maintaining the stability from 150 h onwards. (iv) The tests of thermal stability of the TL emission performed in the range of 180-320 °C confirm a continuum in the trap system.

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

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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,Ωaragonite 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.

Calcification rates of crustose coralline algae (CCA) derived from Calcification Accretion Units (CAUs) deployed at coral reef sites in Batangas, Philippines in 2012 and recovered in 2015 (NCEI Accession 0162831)

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

Calcification Rates of Crustose Coralline Algae derived from Calcification Accretion Units (CAUs) deployed across American Samoa and the Pacific Remote Island Areas in 2010 and recovered in 2012 (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...

Water Chemistry and Conductivity-Temperature-Depth (CTD) profiles at coral reef sites in Batangas, Philippines from discrete surface and bottom water samples collected between 2012-03-12 and 2015-06-03 (NCEI Accession 0162832)

Data.gov (United States)

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

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...

Calcium Carbonate Polymorphs Growing in the Presence of Sericin: A New Composite Mimicking the Hierarchic Structure of Nacre

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Linda Pastero

2018-06-01

Full Text Available Bioinspired self-assembled composite materials are appealing both for their industrial applications and importance in natural sciences, and represent a stimulating topic in the area of materials science, biology, and medicine. The function of the organic matrix has been studied from the biological, chemical, crystallographic, and engineering point of view. Little attention has been paid to the effect of one of the two main components of the organic matrix, the sericin fraction, on the growth morphology of calcium carbonate polymorphs. In the present work, we address this issue experimentally, emphasizing the morphological effects of sericin on calcite and aragonite crystals, and on the formation of a sericin-aragonite-calcite self-assembled composite with a hierarchic structure comparable to that of natural nacre.

Radium isotopes, alkaline earth diagenesis, and age determination of travertine from Mammoth Hot Springs, Wyoming, U.S.A

International Nuclear Information System (INIS)

Sturchio, N.C.

1990-01-01

Travertine from active springs, former vents, and drill core was analyzed for Ra isotopes, other alkaline earth elements, and mineralogical composition. Thermal water also was analyzed. Travertine, presently being deposited, contains 3.0-15.3 pCi/g 226 Ra, and has a 228 Ra/ 226 Ra ratio identical to that in thermal water. Travertine precipitates mostly as aragonite and experiences a complete diagenetic transformation to calcite within 9 a. Systematic compositional changes associated with this diagenetic transformation are enrichment of Mg and depletion of Sr, Ba and Ra. Apparent mineral-water distribution coefficients for Mg, Sr and Ba in aragonite and calcite are within the range of those determined experimentally, implying near-equilibrium conditions and high water-rock ratios during diagenesis. Impure travertine from near the base of a section in the Y-10 drill hole (at 72.9 m depth) has a 230 Th/ 234 U isochron age of 7700±440 a. The content of 226 Ra in the normal, subhorizontally layered, porous travertine decreases with depth. The observed 226 Ra vs depth relation is consistent with continuous deposition of travertine at the site from 7700 a BP to near present at a mean rate of ∼1.0 cm/a, and indicates minimal exchange of Ra between travertine and pore water after the early diagenetic transformation of aragonite to calcite. (author)

Rearing conditions and habitat use of white seabass (Atractoscion nobilis) in the northeastern Pacific based on otolith isotopic composition

Science.gov (United States)

Romo-Curiel, Alfonsina E.; Herzka, Sharon Z.; Sepulveda, Chugey A.; Pérez-Brunius, Paula; Aalbers, Scott A.

2016-03-01

White seabass, Atractoscion nobilis, is an important coastal resource throughout both California and Baja California, but whether this species comprises a single or multiple subpopulations in the northeastern Pacific is not known. The aim of this study was to infer larval rearing habitats and population structure of white seabass by sampling adults from three regions spanning a latitudinal temperature gradient and a distance of over 1000 km, and analyzing the isotopic composition (δ18O and δ13C) of otolith aragonite corresponding to the larval, juvenile and adult stages. Otolith cores revealed high isotopic variability and no significant differences among regions, suggesting overlapping rearing conditions during the larval stage, the potential for long distance dispersal or migration or selective mortality of larvae at higher temperatures. Back-calculated temperatures of aragonite precipitation derived using regional salinity-δw relationships and local salinity estimates also did not differ significantly. However, there were significant differences between the δ18O values of the first seasonal growth ring of age 0 fish as well as back-calculated aragonite precipitation temperatures, suggesting the presence of two potentially discrete subpopulations divided by Punta Eugenia (27°N) along the central Baja California peninsula. These findings are consistent with regional oceanographic patterns and are critical for understanding white seabass population structure, and provide information needed for the implementation of appropriate management strategies.

Neoproterozoic marine carbonates and their paleoceanographic significance

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Hood, Ashleigh van Smeerdijk; Wallace, Malcolm William

2018-01-01

The primary mineralogy of marine carbonate precipitates has been a crucial factor in constraining the major element composition of ancient oceans. Secular changes in Phanerozoic marine chemistry, including Mg/Ca, have been well-documented using the original carbonate mineralogy of ooids, marine cements and biominerals. However, the history of Precambrian seawater chemistry is not as well constrained, partially due to the prevalence of dolomitisation in the Precambrian geological record. The Neoproterozoic ( 1000 Ma to 541 Ma) record of primary carbonate mineralogy is documented here using a combination of literature data and new analysis of marine carbonate precipitates from the Otavi Fold Belt, Namibia, the Death Valley succession, USA and the Adelaide Fold Belt, Australia. These data suggest that the last 460 million years of the Proterozoic were dominated by aragonite and high-Mg calcite precipitation in shallow marine settings. In contrast, low-Mg calcite has only been recognised in a small number of formations. In addition to aragonite and calcite precipitation, marine dolomite precipitation was widespread in Neoproterozoic oceans, including mimetic (syn-sedimentary) dolomitisation and primary dolomite marine cementation. The combination of marine aragonite, high Mg-calcite and dolomite precipitation during the Neoproterozoic suggests extremely high seawater Mg/Ca conditions relative to Phanerozoic oceans. Marine dolomite precipitation may also be linked to widespread marine anoxia during this time.

Photoacoustic FTIR spectroscopic study of undisturbed nacre from red abalone

Science.gov (United States)

Verma, Devendra; Katti, Kalpana; Katti, Dinesh

2006-07-01

In this work, photoacoustic Fourier transform infrared (PA-FTIR) spectroscopy has been utilized to study interfacial interactions of undisturbed nacre and nacre powder from red abalone shell. The spectra of both undisturbed nacre and nacre powder showed characteristic bands of aragonite and proteins. Although nacre powder and undisturbed nacre are chemically identical, PA-FTIR spectrum of undisturbed nacre is found to be significantly different from that of nacre powder. A broad and strong band is observed at around 1485 cm -1 in nacre powder. The intensity of this band is notably reduced in undisturbed nacre. This result is explained on the basis of interfacial interactions between aragonite platelets and acidic proteins. It is also observed that band at around 1788 cm -1 originates from three overlapping bands 1797, 1787 and 1778 cm -1. The band at around 1787 cm -1 is assigned to C dbnd O stretching of carboxylate groups of acidic proteins. The other two bands at 1797 and 1778 cm -1, originate from aragonite and have been assigned to combination bands, ν 3 + ν 4a and ν 3 + ν 4b, respectively. For the study of stratification in undisturbed nacre, PA-FTIR spectra have been collected in step scan mode. The variation in spectra with depth can be attributed to changes in conformation of proteins as well as interfacial interactions.

EPR study of sagitta otoliths of Sciaenidae fish

International Nuclear Information System (INIS)

Beneditto, Ana Paula Madeira di; Franco, Roberto Weider de Assis

2011-01-01

Full text. Otoliths are crystalline structures of calcium carbonate (CaCO 3 ) located in the inner ear of bone fish that are responsible for balance maintenance in the water column and sense of direction. The bio mineralization of these structures occurs during the fish development; when the otolith growth layers are formed. In this work, electron paramagnetic resonance (EPR) spectroscopy is applied to study the sagitta otoliths via manganese (Mn 2+ ) spectra, since in calcium carbonates the Mn 2+ ion is a natural substitutional impurity at Ca 2+ sites. The sagitta otoliths of the Sciaenidae fish Paralonchurus brasiliensis, commonly known as cabeca dura (47 samples), and Stellifer rastrifer, known as cangoa (22 samples), were obtained from specimens captured in coastal areas of Rio de Janeiro State, southeastern Brazil: Atafona (21 deg 37'S), Farol de Sao Tome (22 deg 05'S) and Rio das Ostras (22 deg 30'S). EPR spectra of sagitta otoliths were obtained in X-band (9GHz) at room temperature. The EPR spectra are typical of Mn 2+ in aragonite powder, associated to an occupation of Ca 2+ site with nine nearest neighbor oxygen atoms. It is well established in the literature that the otolith core is constituted by calcite, which is covered by aragonite during the fish growth. However, otoliths of younger fishes showed similar EPR spectra when compared to the older ones, indicating that aragonite is the main bio mineral structure in both maturity stages. In a previous work, these two Sciaenidae species presented significant differences in sagitta otoliths shape, which were related to environmental differences (e.g. water temperature, nutrients, depth) among the sampling sites (Atafona, Farol de Sao Tome and Rio das Ostras). Meanwhile, we do not observed differences in the EPR spectra, indicating that the aragonite crystallization process and the occupation of manganese are not related with the environment where these fish species are living. Then, we can infer that the

Natural variability in the surface ocean carbonate ion concentration

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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 aragonite (Ωaragonite 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

Factors Influencing the Formation of Corrosive Conditions in Puget Sound and the Extreme Conditions Observed During Summer 2015 Associated with the NE Pacific Warm Anomaly (a.k.a. The Blob)

Science.gov (United States)

Alin, S. R.; Curry, B.; Newton, J.; Feely, R. A.; Sutton, A.

2016-02-01

Puget Sound is a complex glacial estuarine system that receives input from many rivers and streams, in addition to runoff from the urban and agricultural environments surrounding the southern part of the Salish Sea ecosystem. A series of glacial sills restrict estuarine circulation such that intrusions of seawater only occur episodically, resulting in long residence times in some parts of the basin. Through survey cruises and stationary time-series, we have observed the dynamic biogeochemical cycles in various sub-basins of Puget Sound since 2008. Areas of Puget Sound with restricted circulation may experience conditions of high pCO2, low pH, and low aragonite saturation state throughout the year. Historically, the highest pCO2 and lowest pH and aragonite saturation states have been observed in early fall in Hood Canal. Upwelling of dense, nutrient- and CO2-rich but oxygen-poor water along the coast provides the marine source water for Puget Sound's deep waters. We estimate that marine waters entering Puget Sound via the Strait of Juan de Fuca are now corrosive 95% of the time, representing a 26% increase in frequency since the preindustrial era. Both river inputs and intense primary production in surface waters drive remineralization in deep waters of Puget Sound basins, contributing to the formation of corrosive conditions in waters below the productive surface. In addition, we estimate that regionally enhanced atmospheric CO2 content may result in an increase in CO2 uptake in the region. In 2015 many features of the seasonal carbon cycle were accelerated relative to earlier years, as a result of the influence of the NE Pacific warm anomaly. In southern Hood Canal, the surface spring bloom began weeks earlier than usual, and in July, we saw the lowest estimated pH and aragonite saturation values in deep waters observed to date in Washington marine environments, which was about two months earlier than historical seasonal minima in pH and aragonite saturation.

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

Holocene millennial to centennial scale carbonate cycles (leeward margin, Great Bahama Bank)

Science.gov (United States)

Roth, S.; Reijmer, J. J. G.

2003-04-01

The main research topic of this project is the evaluation of Holocene to Recent climatic variability and the impact on shallow-water sediment production of carbonate platforms. A 38m long sediment core (MD992201) was analyzed, obtained from 290m water depth on the leeward margin of Great Bahama Bank. Fourteen Accelerator Mass Spectrometry (AMS) dates determined a core bottom age of 7,230 years BP and permitted the construction of a precise time frame. With a sampling interval of 5cm, a decadal time resolution could be achieved. Sedimentation rates varied between 3 to 14m/kyr. Carbonate content ranges from 96 to almost 100wt%, most of which is aragonite (83-92wt%). High Magnesium Calcite (HMC) makes up the second major fraction with 2-9wt%, while Low Magnesium Calcite occurs with minor percentages (0.5-4wt%). Singular Spectrum Analysis (SSA) of the aragonitic carbonate phase showed two different trends and two primary oscillatory signals. Aragonite production on Great Bahama Bank started at 7,230yr BP when the Holocene sea-level rise flooded the shallow platform top. The first eigenvector captures this long-term trend extending over the entire Mid to Late Holocene succession displaying the Holocene sea-level fluctuations. The second trend indicates millennial scale variations, which can be attributed to a combination of geomagnetic shielding and solar parameters. The two quasi-periodic signals show wavelengths of 400-600 years and approx. 210 years. These oscillations are interpreted in terms of instabilities of the thermohaline circulation and solar parameters, respectively. The oscillatory aragonite signals and oxygen isotope derived temperatures (planktonic foraminifers) agree with northern hemisphere temperature changes (e.g. Medieval Warm Period and Little Ice Age) and the delta-14C record of tree rings (e.g. Oort to Dalton solar minima). This study shows that carbonate platform systems not only respond to sea-level variations but also are precise recorders of

Effects of ocean acidification with pCO2 diurnal fluctuations on survival and larval shell formation of Ezo abalone, Haliotis discus hannai.

Science.gov (United States)

Onitsuka, Toshihiro; Takami, Hideki; Muraoka, Daisuke; Matsumoto, Yukio; Nakatsubo, Ayumi; Kimura, Ryo; Ono, Tsuneo; Nojiri, Yukihiro

2018-03-01

This study assessed the effects of constant and diurnally fluctuating pCO 2 on development and shell formation of larval abalone Haliotis discus hannai. The larvae was exposed to different pCO 2 conditions; constant [450, 800, or 1200 μatm in the first experiment (Exp. I), 450 or 780 μatm in the second experiment (Exp. II)] or diurnally fluctuating pCO 2 (800 ± 400 or 1200 ± 400 μatm in Exp. I, 450 ± 80, 780 ± 200 or 780 ± 400 μatm in Exp. II). Mortality, malformation rates or shell length of larval abalone were not significantly different among the 450, 800, and 800 ± 400 μatm pCO 2 treatments. Meanwhile, significantly higher malformation rates and smaller shells were detected in the 1200 and 1200 ± 400 μatm pCO 2 treatments than in the 450 μatm pCO 2 treatment. The negative impacts were greater in the 1200 ± 400 μatm than in the 1200 μatm. Shell length and malformation rate of larval abalone were related with aragonite saturation state (Ω-aragonite) in experimental seawater, and greatly changed around 1.1 of Ω-aragonite which corresponded to 1000-1300 μatm pCO 2 . These results indicate that there is a pCO 2 threshold associated with Ω-aragonite in the seawater, and that pCO 2 fluctuations produce additional negative impacts on abalone when above the threshold. Clear relationships were detected between abalone fitness and the integrated pCO 2 value over the threshold, indicating that the effects of OA on development and shell formation of larval abalone can be determined by intensity and time of exposure to pCO 2 over the threshold. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

Mechanism of unusual polymorph transformations in calcium carbonate: Dissolution-recrystallization vs additive-mediated nucleation. Arpita Sarkar Samiran Mahapatra. Volume 124 Issue 6 ... Keywords. Polymorph transformation; calcium carbonate; calcite; vaterite; aragonite; dissolution-recrystallization; additive-mediated.

Study of Factors Related to Magnetic Treatment of Calcium Carbonate Saturated Water

National Research Council Canada - National Science Library

Lambert, Kevin

1998-01-01

..., calcium carbonate concentration and number of magnetic device attached. XRD of crystals gave relative proportions of calcite and aragonite present and XRF measured transition metals and elements known to substitute for calcium in scale...

Carbonate mineralogy and faunal relationship in tropical shallow water marine sediments: Cape Comorin, India

Digital Repository Service at National Institute of Oceanography (India)

Hashimi, N.H.; Nair, R.R.; Kidwai, R.M.; Rao, V.P.

molluscs exceed other components, as on the eastern shelf between 10 and 40 m, the most abundant mineral is aragonite. Low-magnesium calcite does not appear to be related to depth or carbonate components...

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 Pacific Winter Water transport, driven by an anomalous circulation pattern and sea-ice retreat, is primarily responsible for the expansion, although local carbon recycling and anthropogenic CO2 uptake have also contributed. These results indicate more rapid acidification is occurring in the 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.

Deep-Sea Corals: A New Oceanic Archive

National Research Council Canada - National Science Library

Adkins, Jess

1998-01-01

Deep-sea corals are an extraordinary new archive of deep ocean behavior. The species Desmophyllum cristagalli is a solitary coral composed of uranium rich, density banded aragonite that I have calibrated for several paleoclimate tracers...

Transformation and Crystallization Energetics of Synthetic and Biogenic Amorphous Calcium Carbonate

Energy Technology Data Exchange (ETDEWEB)

Radha, A. V. [Peter A. Rock Thermochemistry Lab. and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Univ. of California, Davis, CA (United States); Forbes, Tori Z. [Peter A. Rock Thermochemistry Lab. and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Univ. of California, Davis, CA (United States); Killian, Christopher E. [Univ. of Wisconsin, Madison, WI (United States); Gilbert, P.U.P.A [Univ. of Wisconsin, Madison, WI (United States); Navrotsky, Alexandra [Peter A. Rock Thermochemistry Lab. and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Univ. of California, Davis, CA (United States)

2010-01-01

Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC→anhydrous ACC ~ biogenic anhydrous ACC→vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO₂ sequestration.

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. Copyright © 2015 Elsevier Inc. All rights reserved.

Radon health hazards of some rocks of Iranian origin, frequently used as building stones

International Nuclear Information System (INIS)

Noori, H.; Ranjbar, A.H.

2011-01-01

Radon exhalation rate from various types of stones, used inside the living buildings, is a major factor for evaluation of the environmental radon level. To verify the significance and lethal impacts of this unknown and obscure source of radiation upon the people around the world, the exhaled radon gas concentrations from the rocks, granodiorite, granite, limestone and aragonite, and the effect of their block sizes on the exhalation rate, have been studied. The block samples, collected from their ores, were transferred to plastic containers in which the CR-39 detectors could properly be placed and air tightened, for concentration measurements. The results show the radon concentration of 7.4 ± 0.8, 6.6 ± 0.6, 0.08 ± 0.02 and 0.09 ± 0.02 kBq m -3 for granodiorite, granite, limestone and aragonite, respectively. The corresponding annual dose values in a closed environment are: 186 ± 20, 166 ± 15, 2.5 ± 1 and 2 ± 1 mSv y -1 . These absorbed dose values indicate that granodiorite and granite when used inside the buildings could increase the risk of various cancers while aragonite and limestone have much lower risks and are recommended for use inside the buildings. The former ones when used in the closure areas remedial action should be implemented. The results do not show obvious dependence between the rock size of the samples and their radon exhalation rate. (author)

Mineralogy of the carbonate sediments - western continental shelf of India

Digital Repository Service at National Institute of Oceanography (India)

Nair, R.R.; Hashimi, N.H.

An X-ray diffraction study of forty-six sediment samples and three oolitic limestone samples from the western continental shelf of India shows that aragonite is the dominant carbonate mineral (99% maximum), followed by low-magnesium calcite (77...

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

Digital Repository Service at National Institute of Oceanography (India)

Rao, V.P.; Rajagopalan, G.; Vora, K.H.; Almeida, F.

. 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...

Environmental controls on daytime net community calcification on a Red Sea reef flat

KAUST Repository

Bernstein, W. N.; Hughen, K. A.; Langdon, C.; McCorkle, D. C.; Lentz, S. J.

2016-01-01

in the near future. Controlled laboratory studies demonstrate that calcification by corals and coralline algae is sensitive to changes in aragonite saturation state (Ωa), as well as temperature, light, and nutrition. Studies also show that the dissolution rate

Effect of organic matrices on the determination of the trace element chemistry (Mg, Sr, Mg/Ca, Sr/Ca) of aragonitic bivalve shells (Arctica islandica). Comparison of ICP-OES and LA-ICP-MS data

International Nuclear Information System (INIS)

Schoene, Bernd R.; Zhang, Zengjie; Jacob, Dorrit; Soldate, Analia; Gillikin, David P.; Tuetken, Thomas; Garbe-Shoenberg, Dieter; McConnaughey, Ted

2010-01-01

The element chemistry of biogenic carbonates can provide important data on past environments. However, the Sr/Ca and Mg/Ca ratios as well as the Mg and Sr concentrations of biological carbonates, especially aragonitic bivalves often depart from apparent thermodynamic equilibrium. When measured in situ by means of LA-ICP-MS, the Mg concentration is often substantially enriched (two- to threefold) near the organic-rich, annual growth lines. To test the hypothesis that some organic components exert a major influence on the skeletal metal content, the element chemistry of different shell components (insoluble organic matrix, IOM; dissolved CaCO 3 and soluble organics, SOM) of Arctica islandica was measured by means of ICP-OES and LA-ICP-MS. The ICP-OES data indicate that the IOM is strongly enriched in Mg (130 ppm) and depleted in Sr and Ca (10 ppm and 0.22 wt%, respectively) when compared to the whole biomineral (Mg: 68 to 99 ppm, Sr: 860 to 1,060 ppm, Ca: ∼35.72 wt%). Although the average relative abundance of the IOM barely exceeds 0.46 wt%, its chemical composition in combination with its heterogeneous distribution across the shell can significantly increase estimates of the Mg concentration if measured in situ by LA-ICP-MS. Depending on the distribution of the IOM, the Ca concentration may be significantly lower locally than the average Ca concentration of the whole shell (35.72 wt%). If this remains undetected, the Mg concentration of shell portions with higher than average IOM content is overestimated by LA-ICP-MS and, conversely, the Mg concentration is underestimated in shell portions with lower than average IOM content. Removal of the IOM prior to the chemical analysis by LA-ICP-MS or mathematical correction for the IOM-derived magnesium concentrations is therefore strongly advised. The different chemistry of the IOM may also exert a major control on the trace element to calcium ratios. Shell portions enriched in IOM will show up to 200 times higher Mg

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.

cements occur as isopachous crusts. Dissolution and clotting of aragonite needles and drusy calcite in the interstices indicate cementation of the limestones at inter-tidal conditions. The age of the limestones is 11,900 years BP. These imply that the 130...

Holocene phosphorites of the western continental margin of India

Digital Repository Service at National Institute of Oceanography (India)

Nair, R.R.

, francolite (carbonate flourapatite), quartz, feldspar and aragonite. P2 O5 concentration varies between 0.8% and 10.8% indicating a wide variation in chemical composition with the area. Age determined by the radiocarbon method is 11,040 years. It appears...

Amorphous Ca-phosphate precursors for Ca-carbonate biominerals mediated by Chromohalobacter marismortui

NARCIS (Netherlands)

Rivadeneyra, María Angustias; Martín-Algarra, Agustín; Sánchez-Román, Mónica; Sánchez-Navas, Antonio; Martín-Ramos, José Daniel

Although diverse microbial metabolisms are known to induce the precipitation of carbonate minerals, the mechanisms involved in the bacterial mediation, in particular nucleation, are still debated. The study of aragonite precipitation by Chromohalobacter marismortui during the early stages (3-7 days)

Study of Raman Spectroscopy on Phase Relations of CaCO3 at High Temperature and High Pressure

Science.gov (United States)

Li, M.; Zheng, H.; Duan, T.

2006-05-01

Laser Raman Spectroscopy was used to study phase relations between calcite I, calcite II and aragonite at high pressure and high temperature. The experiment was performed in an externally heated Basselt type diamond anvil cell (DAC). Natural calcite (calcite I) was used as starting mineral. The sample and a small chip of quartz were loaded in a cavity (300 μm in diameter and 250 μm in depth) in a rhenium gasket. The Na2CO3 aqueous solution of 1mol/L was also loaded as a pressure medium to yield hydrostatic pressure. The whole assembly was pressurized first and then heated stepwise to 400°C. Pressure and temperature in the chamber were determined by the shift of Raman band at 464 cm-1 of quartz and by NiCr-NiSi thermocouple, respectively. The Raman spectra were measured by a Renishaw 1000 spetrometer with 50 mW of 514.5nm argon-ion laser as the excitation light source. The slit width was 50 μm and the corresponding resolution was ±1 cm-1. From the experiments, we observed the phase transitions between calcite I and calcite II, calcite I and aragonite, calcite II and aragonite, respectively. Our data showed a negative slope for the boundary between calcite I and calcite II, which was similar to Bridgman's result, although Hess et al. gave a positive slope. The boundary with a negative slope for calcite II and aragonite was also defined, which had never been done before. And all these data can yield a more complete phase diagram of CaCO3 than the studies of Hess et al. and Suito et al.Reference:Bridgeman P. W.(1939) Journal: American Journal of Science, Vol. 237, p. 7-18Bassett W. A. et al. (1993) Journal: Review of Scientific Instruments, Vol. 64, p. 2340-2345Suito K. et al. (2001) Journal: American Mineralogist, Vol. 86, p. 997- 1002Hess N. J. et al. (1991) In A. K. Singh, Ed., Recent Trends in High Pressure Research; Proc. X IIIth AIRAPT International Conference on High Pressure Science and Technology, p. 236-241. Oxford & IBH Publishing Co. Pvt, Ltd., New

EPR study of sagitta otoliths of Sciaenidae fish

Energy Technology Data Exchange (ETDEWEB)

Beneditto, Ana Paula Madeira di; Franco, Roberto Weider de Assis [Universidade Estadual do Norte Fluminense (UENF), RJ (Brazil)

2011-07-01

Full text. Otoliths are crystalline structures of calcium carbonate (CaCO{sub 3}) located in the inner ear of bone fish that are responsible for balance maintenance in the water column and sense of direction. The bio mineralization of these structures occurs during the fish development; when the otolith growth layers are formed. In this work, electron paramagnetic resonance (EPR) spectroscopy is applied to study the sagitta otoliths via manganese (Mn{sup 2+}) spectra, since in calcium carbonates the Mn{sup 2+} ion is a natural substitutional impurity at Ca{sup 2+} sites. The sagitta otoliths of the Sciaenidae fish Paralonchurus brasiliensis, commonly known as cabeca dura (47 samples), and Stellifer rastrifer, known as cangoa (22 samples), were obtained from specimens captured in coastal areas of Rio de Janeiro State, southeastern Brazil: Atafona (21 deg 37'S), Farol de Sao Tome (22 deg 05'S) and Rio das Ostras (22 deg 30'S). EPR spectra of sagitta otoliths were obtained in X-band (9GHz) at room temperature. The EPR spectra are typical of Mn{sup 2+} in aragonite powder, associated to an occupation of Ca{sup 2+} site with nine nearest neighbor oxygen atoms. It is well established in the literature that the otolith core is constituted by calcite, which is covered by aragonite during the fish growth. However, otoliths of younger fishes showed similar EPR spectra when compared to the older ones, indicating that aragonite is the main bio mineral structure in both maturity stages. In a previous work, these two Sciaenidae species presented significant differences in sagitta otoliths shape, which were related to environmental differences (e.g. water temperature, nutrients, depth) among the sampling sites (Atafona, Farol de Sao Tome and Rio das Ostras). Meanwhile, we do not observed differences in the EPR spectra, indicating that the aragonite crystallization process and the occupation of manganese are not related with the environment where these fish species

Speleothem microstructure/speleothem ontogeny: a review of Western contributions

Directory of Open Access Journals (Sweden)

White William B.

2012-07-01

Full Text Available Mineral ontogeny is the study of the growth and development of mineral deposits in general and, in the present context, speleothems in particular. Previous researchers, mainly in Russia, have developed a nomenclatural hierarchy based on the forms and habits of individual crystals and the assembly of individual crystals into both monomineralic and polymineralic aggegates (i.e. speleothems. Although investigations of the growth processes of speleothems are sparse, there is a large literature on growth processes of speleothem minerals and related crystals in the geochemical and materials science literature. The purpose of the present paper is to sort through the various concepts of crystal growth and attempt to relate these to observations on speleothems and to the Russian conceptual framework of mineral ontogeny. For calcite, the most common mineral in speleothems, the activation energy for two dimensional nucleation (required for the growth of large single crystals is almost the same as the activation energy for three- dimensional nucleation (which would result in the growth of many small crystals. Calcite growth is highly sensitive to minor impurities that may poison growth in certain crystallographic directions or may poison growth altogether. Extensive recent research using the atomic force microscope (AFM provides many details of calcite growth including the transition from growth on screw dislocations to growth by two-dimensional nucleation. The deposition of aragonite speleothems requires metastable supersaturation curve and is usually ascribed to the impurities Mg2+ and Sr2+. AFM studies reveal that Mg2+ poisons calcite growth by blocking deposition sites on dislocations, thus allowing supersaturation to build up past the aragonite solubility curve. Sr2+ precipitates as a Sr-rich nucleus with the aragonite structure which acts as a template for aragonite growth. The different morphology of gypsum speleothems can be explained by the

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...

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

Bathymetry and sediments on the carbonate platform off western ...

Indian Academy of Sciences (India)

64

tropical, shallow marine environments (Hillis-Colinvaux 1980). ... aragonite saturation state but the magnitude of these effects is species-specific. Some ... specific conditions (climate and environmental change) responsible for their favored growth .... Finally, three profiles were extracted along the north-south orientation from.

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,

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.

Effects of seawater pCO2 and temperature on calcification and productivity in the coral genus Porites spp.: an exploration of potential interaction mechanisms

Science.gov (United States)

Cole, C.; Finch, A. A.; Hintz, C.; Hintz, K.; Allison, N.

2018-06-01

Understanding how rising seawater pCO2 and temperatures impact coral aragonite accretion is essential for predicting the future of reef ecosystems. Here, we report 2 long-term (10-11 month) studies assessing the effects of temperature (25 and 28 °C) and both high and low seawater pCO2 (180-750 μatm) on the calcification, photosynthesis and respiration of individual massive Porites spp. genotypes. Calcification rates were highly variable between genotypes, but high seawater pCO2 reduced calcification significantly in 4 of 7 genotypes cultured at 25 °C but in only 1 of 4 genotypes cultured at 28 °C. Increasing seawater temperature enhanced calcification in almost all corals, but the magnitude of this effect was seawater pCO2 dependent. The 3 °C temperature increase enhanced calcification rate on average by 3% at 180 μatm, by 35% at 260 μatm and by > 300% at 750 μatm. The rate increase at high seawater pCO2 exceeds that observed in inorganic aragonites. Responses of gross/net photosynthesis and respiration to temperature and seawater pCO2 varied between genotypes, but rates of all these processes were reduced at the higher seawater temperature. Increases in seawater temperature, below the thermal stress threshold, may mitigate against ocean acidification in this coral genus, but this moderation is not mediated by an increase in net photosynthesis. The response of coral calcification to temperature cannot be explained by symbiont productivity or by thermodynamic and kinetic influences on aragonite formation.

Groundwater geochemistry of Isla de Mona, Puerto Rico

Science.gov (United States)

Wicks, C.M.; Troester, J.W.

1998-01-01

In this study, we explore the differences between the hydrogeochemical processes observed in a setting that is open to input from the land surface and in a setting that is closed with respect to input from the land surface. The closed setting was a water-filled passage in a cave. Samples of groundwater and of a solid that appeared to be suspended in the relatively fresh region of saline-freshwater mixing zone were collected. The solid was determined to be aragonite. Based on the analyses of the composition and saturation state of the groundwater, the mixing of fresh and saline water and precipitation of aragonite are the controlling geochemical processes in this mixing zone. We found no evidence of sulfate reduction. Thus, this mixing zone is similar to that observed in Caleta Xel Ha, Quintana Roo, also a system that is closed with respect to input from the land surface. The open setting was an unconfined aquifer underlying the coastal plain along which four hand-dug wells are located. Two wells are at the downgradient ends of inferred flowpaths and one is along a flowpath. The composition of the groundwater in the downgradient wells is sulfide-rich and brackish. In contrast, at the well located along a flow line, the groundwater is oxygenated and brackish. All groundwater is oversaturated with respect to calcite, aragonite, and dolomite. The composition is attributed to mixing of fresh and saline groundwater, CO2 outgassing, and sulfate reduction. This mixing zone is geochemically similar to that observed in blue holes and cenotes.

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.

Unique morphology and gradient arrangement of nacre's platelets in green mussel shells

Energy Technology Data Exchange (ETDEWEB)

Xu, Jun; Zhang, Gangsheng, E-mail: zhanggs@gxu.edu.cn

2015-07-01

Nacre has long served as a classic model in biomineralization and the synthesis of biomimetic materials. However, the morphology and arrangement of its basic building blocks, the aragonite platelets, are still under hot debate. In this study, using a field emission scanning electron microscope (SEM), a high-resolution transmission electron microscope (HRTEM), and an X-ray diffractometer (XRD), we investigate the platelets at the edges and centers of green mussel shells. We find that 1) flat and curved platelets coexist in green mussel shells; 2) the immature platelets at the shell edge are aggregates of aragonite nanoparticles, whereas the immature ones at the shell center are single crystals; and 3) the morphology and thickness of the platelets exhibit a gradient arrangement. Based on these findings, we hypothesize that the gradient in the thickness and curvature of the platelets may probably result from the difference in growth rate between the edge and the center of the shell and from the gradient in compressive stress imposed by the closing of the shells by the adductor muscles or the withdrawal of the periostracum by the mantle. We expect that the presented results will shed new light on the formation mechanisms of natural composite materials. - Highlights: • Flat and curved platelets coexist in green mussel shells. • The immature platelets at the shell edge consist of aragonite nanoparticles. • The immature platelets at the shell center are single crystals. • The morphology and thickness of platelets exhibit a gradient arrangement. • The gradient arrangement of platelets may result from the stress gradient.

Příspěvek k poznání petrografie, mineralogie a fluidních inkluzí jeskynních sintrů první generace z Koněpruských jeskyní a z některých lokalit v jejich okolí

Czech Academy of Sciences Publication Activity Database

Suchý, V.; Dobeš, P.; Zeman, Antonín

2014-01-01

Roč. 47, č. 1 (2014), s. 140-143 ISSN 0514-8057 Institutional support: RVO:68378297 Keywords : Bohemian Karst * speleothems * aragonite * gothic -arch calcite * fluid inclusions Subject RIV: AL - Art, Architecture, Cultural Heritage http://www.geology.cz/img/zpravyvyzkum/fulltext/Zpr2013D-11.pdf

Adsorption Properties of Chalk Reservoir Materials

DEFF Research Database (Denmark)

Okhrimenko, Denis

/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...

Lipids from the nacreous and prismatic layers of two Pteriomorpha Mollusc shells

Science.gov (United States)

Farre, B.; Dauphin, Y.

2009-04-01

Mollusc shells are the best-known Ca-carbonate biominerals. They are commonly described as a mineralized two layered structure: an outer layer composed of calcite prismatic units, and an internal layer composed of tablets of aragonite: the nacreous layer. An external organic layer (periostracum) is present in most taxa. However, the most common structure in the Mollusc shell is the aragonite crossed lamellar layer, but aragonite prisms, calcite foliated layers and homogeneous layers have been also described by Boggild (1930) in all the Mollusc orders. Since, more detailed descriptions of Bivalve shells have been done (Taylor et al., 1969, 1973). Despite the nacroprismatic arrangement is rare, calcite prismatic and aragonite nacreous layers are the best studied because of their simple 3D structure and large units. Among these Molluscs, some Bivalve species composed of these two layers are of commercial interest, such as the pearl oyster, Pinctada margaritifera, cultivated in French Polynesia to produce black pearls. It is well established that Mollusc shells are composite structures of organic and inorganic components (Hatchett, 1799; Grégoire et al., 1955; Beedham, 1958; Simkiss, 1965; Mutvei, 1969; Cuif et al., 1980; Berman et al., 1993; Kobayashi and Samata, 2006). Numerous studies are concerned with the organic matrix of the shell. Organic components are commonly obtained after a strong or mild decalcification process. They are said to consist of both a soluble and insoluble fraction. The main part of studies is dedicated to the soluble components, and among them, proteins (Grégoire et al., 1955; Grégoire, 1961; Krampitz et al., 1976; Samata et al., 1980, 2004; Weiner, 1983; Miyamoto et al., 2006). Despite the pioneering work of Wada (1980) sugars are usually neglected despite their role in biomineralization. The third component of the organic matrix of calcareous biominerals is lipids. To date, there is a paucity of information concerning the presence

Whiting–related sediment export along the Middle Miocene carbonate ramp of Great Bahama Bank.

NARCIS (Netherlands)

Turpin, M.; Emmanuel, L.; Reijmer, J.J.G.; Renard, M.

2011-01-01

Modern aragonite needles are present all along the modern leeward margin of Great Bahama Bank (ODP Leg 166), while Middle Miocene sediments contain needles only in more distal areas (Sites 1006 and 1007). In contrast to the rimmed, flat-topped platform topography during the Plio-Pleistocene, the

Reef coral δ18O thermometer in Hainan island waters, south China sea

International Nuclear Information System (INIS)

He Xuexian; Peng Zicheng; Wang Zhaorong; Huo Weiguo; Tan Jun; Nie Baofu; Chen Tegu; Zhong Jinliang

2000-01-01

An 18-year-long (1981-1998) study was conducted in Hainan Island waters (22 degree 22'N, 110 degree 39'E) to determine the relationship between δ 18 O in skeletal aragonite carbonate and sea surface temperature (SST) in porites lutea of reef-building corals. δ 18 O values in skeletal aragonite carbonate were measured by means of mass spectrometry. Coral samples grew at 5 m depth at Longwan Bay. Monthly measurements of the SST from 1960 to 1998 were taken at Qinglan Bay adjacent to the place of the collected samples. The thermometer shows that SST = -4.16 δ 18 O PDB + 4.9 (r = 0.80) and dδ 18 O/dT = -0.24 per mil/degree C. The δ 18 O thermometer is strongly influenced by the rainfall and runoff. Using the thermometer, the SST in the past hundred years with monthly resolution will be reconstructed and the climatic change in the northern area of South China Sea will be hind cast

Growth history of cultured pearl oysters based on stable oxygen isotope analysis

Science.gov (United States)

Nakashima, R.; Furuta, N.; Suzuki, A.; Kawahata, H.; Shikazono, N.

2007-12-01

We investigated the oxygen isotopic ratio in shells of the pearl oyster Pinctada martensii cultivated in embayments in Mie Prefecture, central Japan, to evaluate the biomineralization of shell structures of the species and its pearls in response to environmental change. Microsamples for oxygen isotope analysis were collected from the surfaces of shells (outer, middle, and inner shell layers) and pearls. Water temperature variations were estimated from the oxygen isotope values of the carbonate. Oxygen isotope profiles of the prismatic calcite of the outer shell layer reflected seasonal variations of water temperature, whereas those of nacreous aragonites of the middle and inner shell layers and pearls recorded temperatures from April to November, June to September, and July to September, respectively. Lower temperatures in autumn and winter might slow the growth of nacreous aragonites. The oxygen isotope values are controlled by both variations of water temperature and shell structures; the prismatic calcite of this species is useful for reconstructing seasonal changes of calcification temperature.

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

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.

Comparative study on nano-mechanics and thermodynamics of fish otoliths

International Nuclear Information System (INIS)

Dongni, Ren; Yonghua, Gao; Qingling, Feng

2013-01-01

Fish otolith is a kind of typical natural biomineral, which is composed of calcium carbonate and organic matrix. In fresh water carp otolith, the inorganic phase of lapillus is pure aragonite, and for asteriscus it is pure vaterite. In this research, the phase composition, phase transformation, mechanical property and solubility of lapillus and asteriscus were studied. And results showed that, the organic content of lapillus was higher than that of asteriscus; the phase-transition temperature of lapillus (aragonite–calcite) and asteriscus (vaterite–calcite) both happened between 520 and 640 °C; the nano-mechanical property of lapillus was better than that of asteriscus; the solubility of asteriscus powder was higher than that of lapillus powder. - Highlights: ► The nano-mechanical property of lapillus (aragonite) was better than that of asteriscus (vaterite). ► The phase-transition temperature of lapillus and asteriscus were both between 520 and 640 °C. ► The solubility property of asteriscus powder was better than that of lapillus powder.

Carbon isotopic fractionation in live benthic foraminifera -comparison with inorganic precipitate studies

Energy Technology Data Exchange (ETDEWEB)

Grossmann, E L [University of Southern California, Los Angeles (USA). Dept. of Geological Sciences

1984-07-01

Carbon and oxygen isotopic analyses have been performed on live-stained aragonitic and calcitic benthic foraminifera and dissolved inorganic carbon from the Southern California Borderland to examine carbon isotopic fractionation in foraminifera. Temperature, salinity and pH data have also been collected to permit accurate determination of the delta/sup 13/C of bicarbonate ion and thus aragonite-HCO/sub 3//sup -/ and calcite-HCO/sub 3//sup -/ isotopic enrichment factors (epsilonsub(ar-b) and epsilonsub(cl-b), respectively). Only species which precipitate in /sup 18/O equilibrium have been considered. epsilonsub (ar-b) values based on Hoeglundina elegans range from 1.9 per mille at 2.7 deg C to 1.1 per mille at 9.5 deg C. The temperature dependence of epsilonsub(ar-b) is considerably greater than the equilibrium equation would predict and may be due to a vital effect. The calcitic foraminifera Cassidulina tortuosa, Cassidulina braziliensis, and Cassidulina limbata, Bank and Terrace dwellers, have s

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

Localized quantification of anhydrous calcium carbonate polymorphs using micro-Raman spectroscopy

Czech Academy of Sciences Publication Activity Database

Ševčík, Radek; Mácová, Petra

2018-01-01

Roč. 95, March (2018), s. 1-6 ISSN 0924-2031 R&D Projects: GA MŠk(CZ) LO1219 Keywords : micro-Raman * quantification * calcite * vaterite * aragonite * nanolime Subject RIV: CA - Inorganic Chemistry Impact factor: 1.740, year: 2016 http://www.sciencedirect.com/science/article/pii/S0924203117302886

Frictional behaviour and transport properties of simulated fault gouges derived from a natural CO2 reservoir

NARCIS (Netherlands)

Bakker, E.; Hangx, S.J.T.|info:eu-repo/dai/nl/30483579X; Niemeijer, A.R.|info:eu-repo/dai/nl/370832132; Spiers, C.J.|info:eu-repo/dai/nl/304829323

2016-01-01

We investigated the effects of long-term CO2-brine-rock interactions on the frictional and transport properties of reservoir-derived fault gouges, prepared from both unexposed and CO2-exposed sandstone, and from aragonite-cemented fault rock of an active CO2-leaking conduit, obtained from a natural

Comparison of authigenic carbonates formation at mud volcanoes and pockmarks in the Portuguese Margin vs. at the Yinazao serpentinite mud volcano in the Marianas forearc

Science.gov (United States)

Magalhaes, V. H.; Freitas, M.; Azevedo, M. R.; Pinheiro, L. M.; Salgueiro, E.; Abrantes, F. F. G.

2017-12-01

On the Portuguese passive continental margin, active and past seepage processes form mud volcanoes and pockmarks at the seafloor. Often associated with these structures are extensive methane-derived authigenic carbonates that form from deep-sourced methane-rich fluids that ascend from deep to the upper sedimentary column and often discharge at the seafloor. These carbonates form within the sediments and are either dominated by dolomite and high-Mg calcites, when formed under a restricted seawater circulation environment, anoxic and low sulphate conditions; or by aragonite and calcite when formed close to or at the seafloor in a high sulphate system. The δ13C values (-56.2‰ VPDB) found on the carbonate-cemented material clearly indicates methane as the major carbon source. On the Yinazao serpentinite mud volcano at an active, non-accretionary, convergent margin, sediment samples from IODP Sites U1491 and U1492 (Exp. 366) contain authigenic minerals such as aragonite, calcite, brucite, gypsum among others. Authigenic aragonite occurs predominantly within the top meters of the cores where both oxidation and seawater circulation in the sedimentary column are higher. In this system, initial results indicate that the major carbon source is most probably not methane but seawater related. This work discusses and compares the major carbon sources in both systems: sedimentary mud volcanoes and pockmarks of a passive margin vs. a serpentinite mud volcano of an active, non-accretionary, convergent margin. We acknowledge the support from the PES project - Pockmarks and fluid seepage in the Estremadura Spur: implications for regional geology, biology, and petroleum systems (PTDC/GEOFIQ/5162/2014) financed by the Portuguese Foundation for Science and Technology (FCT).

The temperature dependent strontium isotope fractionation (δ88/86Sr) during calcium carbonate precipitation

International Nuclear Information System (INIS)

Fietzke, J.; Eisenhauer, A.

2006-01-01

Full text: In order to study the influence of stable isotope fractionation during inorganic and biologically controlled CaCO 3 precipitation we have developed the analytical principles for the measurement of strontium (Sr) isotope fractionation. We have established a measurement protocol for the application on a MC-ICP-MS (AXIOM) using the common bracketing standard technique. The Sr-standard CRM NBS987 was used as reference material for all measurements and to calculate the Sr fractionation. Latter value is expressed by the δ-notation defined as: δ 88/86 Sr = [( 88 Sr/ 86 Sr)sample / ( 88 Sr/ 86 Sr)standard ] * 1000 -1. A first set of experiments focused on the temperature dependency of Sr-isotope fractionation. For this purpose inorganically precipitated aragonite and calcite was prepared under controlled conditions in a temperature range from 10 to 50 o C. In addition, cultured and naturally grown corals were analyzed for their δ 88/86 Sr values. Repeated measurements of IAPSO seawater standard showed a mean δ 88/86 Sr value of 0.383 ± 0.008 (2 SEM) being the isotopically heaviest material measured so far. The first results of the inorganically precipitated aragonite and the natural corals revealed a clear temperature dependency of the δ 88/86 Sr values. For inorganic aragonite the slope of this correlation is about 0.0055 permil/ o C. However, for naturally grown corals (Pavona clavus) a 6 fold steeper slope of 0.033 permil/ o C was determined. This strong temperature dependency implies the potential to use stable Sr isotopes as a new marine (paleo)temperature proxy. (author)

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 pH_T,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 (C_T and total alkalinity (A_T offered minima values in the Antarctic Intermediate Water and UCDW layers. These coefficients suggest that a small increase in C_T will sharply decrease the status of pH and carbonate saturation

Effect of temperature on the reaction pathway of calcium carbonate formation via precursor phases

Science.gov (United States)

Purgstaller, Bettina; Mavromatis, Vasileios; Konrad, Florian; Dietzel, Martin

2016-04-01

It has been earlier postulated that some biogenic and sedimentary calcium carbonate (CaCO3) minerals (e.g. calcite and aragonite) are secondary in origin and have originally formed via a metastable calcium carbonate precursor phase (e.g. amorphous CaCO3, [1-2]). Such formation pathways are likely affected by various physicochemical parameters including aqueous Mg and temperature. In an effort to improve our understanding on the formation mechanism of CaCO3 minerals, precipitation experiments were carried out by the addition of a 0.6 M (Ca,Mg)Cl2 solution at distinct Mg/Ca ratios (1/4 and 1/8) into a 1 M NaHCO3 solution under constant pH conditions(8.3 ±0.1). The formation of CaCO3 was systematically examined as a function of temperature (6, 12, 18 and 25 ±0.3° C). During the experimental runs mineral precipitation was monitored by in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. The results revealed two pathways of CaCO3 formation depending on the initial Mg/Ca ratio and temperature: (i) In experiments with a Mg/Ca ratio of 1/4 at ≤ 12° C as well as in experiments with a Mg/Ca ratio of 1/8 at ≤ 18° C, ikaite (CaCO3 6H2O) acts as a precursor phase for aragonite formation. (ii) In contrast higher temperatures induced the formation of Mg-rich amorphous CaCO3 (Mg-ACC) which was subsequently transformed to Mg-rich calcite. In situ Raman spectra showed that the transformation of Mg-ACC to Mg-calcite occurs at a higher rate (˜ 8 min) compared to that of ikaite to aragonite (> 2 h). Thus, the formation of aragonite rather than of Mg-calcite occurs due to the slower release of Ca2+and CO32- ions into the Mg-rich reactive solution during retarded ikaite dissolution. This behavior is generally consistent with the observation that calcite precipitation is inhibited at elevated aqueous Mg/Ca ratios. [1] Addadi L., Raz S. and Weiner S. (2003) Advanced Materials 15, 959-970. [2] Rodriguez-Blanco J. D

Structural and functional biological materials: Abalone nacre, sharp materials, and abalone foot adhesion

Science.gov (United States)

Lin, Albert Yu-Min

A three-part study of lessons from nature is presented through the examination of various biological materials, with an emphasis on materials from the mollusk Haliotis rufescens, commonly referred to as the red abalone. The three categories presented are: structural hierarchy, self-assembly, and functionality. Ocean mollusk shells are composed of aragonite/calcite crystals interleaved with layers of a visco-elastic protein, having dense, tailored structures with excellent mechanical properties. The complex nano-laminate structure of this bio-composite material is characterized and related to its mechanical properties. Three levels of structural hierarchy are identified: macroscale mesolayers separating larger regions of tiled aragonite, microscale organization of 0.5 mum by 10 mum aragonite bricks; nanoscale mineral bridges passing through 30 nm layers of organic matrix separating individual aragonite tiles. Composition and growth mechanisms of this nanostructure were observed through close examination of laboratory-grown samples using scanning electron microscopy (SEM), Raman spectroscopy, and transmission electron microscopy (TEM). Glass slides and nacre pucks were implanted onto the growth surface of living abalone and removed periodically to observe trends in nacre deposition. Various deproteinization and demineralization experiments are used to explore the inorganic and organic components of the nacre's structure. The organic component of the shell is characterized by atomic force microscopy (AFM). The functionality of various biological materials is described and investigated. Two specific types of functionality are characterized, the ability of some materials to cut and puncture through sharp designs, and the ability for some materials to be used as attachment devices. Aspects of cutting materials employed by a broad range of animals were characterized and compared. In respect to the attachment mechanisms the foot of the abalone and the tree frog were

Groundwater circulation and hydrogeochemical evolution in ...

Indian Academy of Sciences (India)

water and interaction with minerals and sediments ... naturally recharged by lateral flow in the edge of ... K. Na. Ca. Mg. Cl. SO. 4. HCO. 3. NO. 3 δ. 18. O δ. D. (TU). (pMC). Alluvial. F a n. R1 ..... state (SI>0) with respect to calcite, aragonite and.

CaCO3-III and CaCO3-VI, high-pressure polymorphs of calcite: Possible host structures for carbon in the Earth's mantle

Science.gov (United States)

Merlini, M.; Hanfland, M.; Crichton, W. A.

2012-06-01

Calcite, CaCO3, undergoes several high pressure phase transitions. We report here the crystal structure determination of the CaCO3-III and CaCO3-VI high-pressure polymorphs obtained by single-crystal synchrotron X-ray diffraction. This new technical development at synchrotron beamlines currently affords the possibility of collecting single-crystal data suitable for structure determination in-situ at non-ambient conditions, even after multiphase transitions. CaCO3-III, observed in the pressure range 2.5-15 GPa, is triclinic, and it presents two closely related structural modifications, one, CaCO3-III, with 50 atoms in the unit cell [a=6.281(1) Å, b=7.507(2) Å, c=12.516(3) Å, α=93.76(2)°, β=98.95(2)°, γ=106.49(2)°, V=555.26(20) Å3 at 2.8 GPa], the second, CaCO3-IIIb, with 20 atoms [a=6.144(3) Å, b=6.3715(14) Å, c=6.3759(15) Å, α= 93.84(2)°, β=107.34(3)°, γ=107.16(3)°, V=224.33(13) Å3 at 3.1 GPa]. Different pressure-time experimental paths can stabilise one or the other polymorph. Both structures are characterised by the presence of non-coplanar CO3 groups. The densities of CaCO3-III (2.99 g/cm3 at 2.8 GPa) and CaCO3-IIIb (2.96 g/cm3 at 3.1 GPa) are lower than aragonite, in agreement with the currently accepted view of aragonite as the thermodynamically stable Ca-carbonate phase at these pressures. The presence of different cation sites, with variable volume and coordination number (7-9), suggests however that these structures have the potential to accommodate cations with different sizes without introducing major structural strain. Indeed, this structure can be adopted by natural Ca-rich carbonates, which often exhibit compositions deviating from pure calcite. Mg-calcites are found both in nature (Frezzotti et al., 2011) and in experimental syntheses at conditions corresponding to deep subduction environments (Poli et al., 2009). At these conditions, the low pressure rhombohedral calcite structure is most unlikely to be stable, and, at the same

Diagenesis of polymineralic temperate limestones in a cyclothemic sedimentary succession, eastern North Island, New Zealand

International Nuclear Information System (INIS)

Haywick, D.W.

2004-01-01

Temperate carbonate petrofacies (calcarenite and coquina) in the Pliocene-Pleistocene Petane Group of eastern North Island, New Zealand, are dominated by aragonite faunas consisting primarily of bivalves and gastropods. Unlike calcite-dominated temperate limestones, these polymineralic carbonates have undergone extensive early diagenetic alteration including extensive calcite cementation induced by aragonite dissolution. Marine cementation (type 1: pore-lining, bladed calcite) was isolated to biogenic pores. It predated glauconite and may have been precipitated as low-magnesium calcite, possibly in marine phreatic environments during sea-level transgressions. Four phases of calcite cement with varying but definitive degrees of meteoric influence occur in the Petane Group. Type 2 (ferroan scalenohedral calcite) was the initial pore-filling cement and precipitated from reduced pore fluids in a phreatic environment, possibly during or soon after the transition from marine to meteoric diagenesis. Type 3 (moderately ferroan drusy) calcite and type 4 (non-ferroan drusy) calcite were sequentially precipitated during meteoric conditions from pore waters that changed from reducing to oxidising. Type 5 (sinter) cements comprise several forms precipitated during vadose meteoric diagenesis, the final meteoric phase of alteration in the Petane Group. Ferroan calcite cementation of silt matrix in coquina limestones overlain by terrigenous silt (type 6: matrix cement) probably occurred simultaneously with type 2/3 pore-filling phases. A similar ferroan to moderately ferroan to non-ferroan suite of drusy calcite cements also lithified concretions in non-carbonate (siliciclastic sand) facies in the Petane Group, but only after the onset of compaction. Extensive skeletal diagenesis (stabilisation of magnesium calcite allochems, dissolution/recrystallisation of aragonite) occurred during type 3 and 4 cementation phases. Diagenesis in the Petane Group was stratigraphically influenced

Investigation of fish otoliths by combined ion beam analysis

International Nuclear Information System (INIS)

Huszank, R.; Simon, A.; Keresztessy, K.

2008-01-01

Complete text of publication follows. This work was implemented within the framework of the Hungarian Ion beam Physics Platform (http://hipp.atomki.hu/). Otoliths are small structures, 'the ear stones' of a fish, and are used to detect acceleration and orientation. They are composed of a combination of protein matrix and calcium carbonate (CaCO 3 ) forming aragonite micro crystals. They have an annually deposited layered conformation with a microstructure corresponding to the seasonal and daily increments. Trace elements, such as Sr, Zn, Fe etc., are also incorporated into the otolith from the environment and the nutrition. The elemental distribution of the otolith of fresh water fish burbot (Lota lota L.) collected in Hungary was measured with Elastic Recoil Detection Analysis (ERDA), Rutherford backscattering spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) at the Nuclear Microprobe Facility of HAS ATOMKI. The spatial 3D structure of the otolith could be observed with a sub-micrometer resolution. It is confirmed that the aragonite micro-crystals are covered by an organic layer and there are some protein rich regions in the otolith, too. By applying the RBSMAST code developed for RBS on macroscopic structure, it was proven that the orientation of the needle shaped aragonite crystals is considerably different at adjacent locations in the otolith. The organic and inorganic component of the otolith could be set apart in the depth selective hydrogen and calcium maps derived by micro- ERDA and micro-RBS. Similar structural analysis could be done near the surface by combining the C, O and Ca elemental maps determined by micro-PIXE measurements. It was observed that the trace metal Zn is bound to the protein component. Acknowledgements This work was partially supported by the Hungarian OTKA Grant No. T046238 and the EU cofunded Economic Competitiveness Operative Programme (GVOP-3.2.1.-2004-04-0402/3.0)

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

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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.

Barium isotopes in cold-water corals

Science.gov (United States)

Hemsing, Freya; Hsieh, Yu-Te; Bridgestock, Luke; Spooner, Peter T.; Robinson, Laura F.; Frank, Norbert; Henderson, Gideon M.

2018-06-01

Recent studies have introduced stable Ba isotopes (δ 138 / 134Ba) as a novel tracer for ocean processes. Ba isotopes could potentially provide insight into the oceanic Ba cycle, the ocean's biological pump, water-mass provenance in the deep ocean, changes in activity of hydrothermal vents, and land-sea interactions including tracing riverine inputs. Here, we show that aragonite skeletons of various colonial and solitary cold-water coral (CWC) taxa record the seawater (SW) Ba isotope composition. Thirty-six corals of eight different taxa from three oceanic regions were analysed and compared to δ 138 / 134Ba measurements of co-located seawater samples. Sites were chosen to cover a wide range of temperature, salinity, Ba concentrations and Ba isotope compositions. Seawater samples at the three sites exhibit the well-established anti-correlation between Ba concentration and δ 138 / 134Ba. Furthermore, our data set suggests that Ba/Ca values in CWCs are linearly correlated with dissolved [Ba] in ambient seawater, with an average partition coefficient of DCWC/SW = 1.8 ± 0.4 (2SD). The mean isotope fractionation of Ba between seawater and CWCs Δ138/134BaCWC-SW is -0.21 ± 0.08‰ (2SD), indicating that CWC aragonite preferentially incorporates the lighter isotopes. This fractionation likely does not depend on temperature or other environmental variables, suggesting that aragonite CWCs could be used to trace the Ba isotope composition in ambient seawater. Coupled [Ba] and δ 138 / 134Ba analysis on fossil CWCs has the potential to provide new information about past changes in the local and global relationship between [Ba] and δ 138 / 134Ba and hence about the operation of the past global oceanic Ba cycle in different climate regimes.

The smallest Gliders in the Ocean- Temperature Recordings from Pteropods using SIMS

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Keul, N.; Orland, I. J.; Valley, J. W.; Kozdon, R.; deMenocal, P. B.

2016-02-01

During the last few decades, the development, refinement and application of geochemical methods have lead to the establishment of new proxies to estimate global change. The oxygen isotope composition of carbonate shells formed by marine organisms is a widely used proxy for past ocean temperatures. Secondary ion mass spectrometry (SIMS) is a high spatial-resolution in situ technique, allowing oxygen isotope measurements on very small samples (down to 3 μm spot size). Pteropods are pelagic mollusks, producing shells made out of aragonite, which is more soluble than calcite in seawater, making them one of the first responders to climate change. They calcify closely at the aragonite- seawater equilibrium and are therefor ideal candidates to reconstruct temperatures based on their d18O. The oxygen isotopic composition of pteropod shells from sediment traps, net tows and a culture study from the Fram Strait will be presented. Specimens travelled in the Westspitsbergen Current prior to sinking into the sediment. During this transport specimens continue to grow, sequentially adding aragonite to the shell. We show that when using traditional (whole shell) δ18O measurements, the isotopic signatures of whole shells reflect the latitudinal gradient. Combining this with SIMS-derived δ18O measurements on individual shell parts, however, reveals that this is only half the story: Comparing δ18O of earlier (produced further South) and later shell parts (produced further North) shows that pteropods calcify in sequentially shallower water depths, overriding the latitudinal South to North temperature gradient. Combining traditional and novel δ18O measurements can potentially not only allow the reconstruction of temperature/ global warming, but also to assess ecological key parameters, such as habitat depth, at the same time.

Removal of phosphate from solution by adsorption and precipitation of calcium phosphate onto monohydrocalcite.

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Yagi, Shintaro; Fukushi, Keisuke

2012-10-15

The sorption behavior and mechanism of phosphate on monohydrocalcite (CaCO(3)·H(2)O: MHC) were examined using batch sorption experiments as a function of phosphate concentrations, ionic strengths, temperatures, and reaction times. The mode of PO(4) sorption is divisible into three processes depending on the phosphate loading. At low phosphate concentrations, phosphate is removed by coprecipitation of phosphate during the transformation of MHC to calcite. The sorption mode at the low-to-moderate phosphate concentrations is most likely an adsorption process because the sorption isotherm at the conditions can be fitted reasonably with the Langmuir equation. The rapid sorption kinetics at the conditions is also consistent with the adsorption reaction. The adsorption of phosphate on MHC depends strongly on ionic strength, but slightly on temperature. The maximum adsorption capacities of MHC obtained from the regression of the experimental data to the Langmuir equation are higher than those reported for stable calcium carbonate (calcite or aragonite) in any conditions. At high phosphate concentrations, the amount of sorption deviates from the Langmuir isotherm, which can fit the low-to-moderate phosphate concentrations. Speciation-saturation analyses of the reacted solutions at the conditions indicated that the solution compositions which deviate from the Langmuir equation are supersaturated with respect to a certain calcium phosphate. The obtained calcium phosphate is most likely amorphous calcium phosphate (Ca(3)(PO(4))(2)·xH(2)O). The formation of the calcium phosphate depends strongly on ionic strength, temperature, and reaction times. The solubility of MHC is higher than calcite and aragonite because of its metastability. Therefore, the higher solubility of MHC facilitates the formation of the calcium phosphates more than with calcite and aragonite. Copyright © 2012 Elsevier Inc. All rights reserved.

Hierarchical structure of the otolith of adult wild carp

International Nuclear Information System (INIS)

Li Zhuo; Gao Yonghua; Feng Qingling

2009-01-01

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.

Isotope analysis of water trapped in fluid inclusions in deep sea corals

Science.gov (United States)

Vonhof, Hubert; Reijmer, John; Feenstra, Eline; Mienis, Furu

2015-04-01

Extant Lophelia pertusa deep sea coral specimens from the Loachev mound region in the North Atlantic Ocean contain water filled fluid inclusions in their skeleton. This fluid inclusion water was extracted with a crushing device, and its hydrogen and oxygen isotope ratios analysed. The resulting data span a wide range of isotope values which are remarkably different from the seawater isotope composition of the sites studied. Comparison with food source isotope signatures suggests that coral inclusion water contains a high, but variable proportion of metabolic water. The isotope composition of the inclusion water appears to vary with the position on the deep see coral reef, and shows a correlation with the stable isotope composition of the coral aragonite. This correlation seems to suggest that growth rate and other ecological factors play an important role in determining the isotope composition of fluids trapped in the coral skeleton, which can potentially be developed as a proxy for non-equilibrium isotope fractionation observed in the aragonite skeleton of many of the common deep sea coral species.

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.

Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms.

Science.gov (United States)

Orr, James C; Fabry, Victoria J; Aumont, Olivier; Bopp, Laurent; Doney, Scott C; Feely, Richard A; Gnanadesikan, Anand; Gruber, Nicolas; Ishida, Akio; Joos, Fortunat; Key, Robert M; Lindsay, Keith; Maier-Reimer, Ernst; Matear, Richard; Monfray, Patrick; Mouchet, Anne; Najjar, Raymond G; Plattner, Gian-Kasper; Rodgers, Keith B; Sabine, Christopher L; Sarmiento, Jorge L; Schlitzer, Reiner; Slater, Richard D; Totterdell, Ian J; Weirig, Marie-France; Yamanaka, Yasuhiro; Yool, Andrew

2005-09-29

Today's surface ocean is saturated with respect to calcium carbonate, but increasing atmospheric carbon dioxide concentrations are reducing ocean pH and carbonate ion concentrations, and thus the level of calcium carbonate saturation. Experimental evidence suggests that if these trends continue, key marine organisms--such as corals and some plankton--will have difficulty maintaining their external calcium carbonate skeletons. Here we use 13 models of the ocean-carbon cycle to assess calcium carbonate saturation under the IS92a 'business-as-usual' scenario for future emissions of anthropogenic carbon dioxide. In our projections, Southern Ocean surface waters will begin to become undersaturated with respect to aragonite, a metastable form of calcium carbonate, by the year 2050. By 2100, this undersaturation could extend throughout the entire Southern Ocean and into the subarctic Pacific Ocean. When live pteropods were exposed to our predicted level of undersaturation during a two-day shipboard experiment, their aragonite shells showed notable dissolution. Our findings indicate that conditions detrimental to high-latitude ecosystems could develop within decades, not centuries as suggested previously.

Discrete element modeling of microstructure of nacre

Science.gov (United States)

Chandler, Mei Qiang; Cheng, Jing-Ru C.

2018-04-01

The microstructure of nacre consists of polygon-shaped aragonite mineral tablets bonded by very thin layers of organic materials and is organized in a brick-mortar morphology. In this research, the discrete element method was utilized to model this structure. The aragonite mineral tablets were modeled with three-dimensional polygon particles generated by the Voronoi tessellation method to represent the Voronoi-like patterns of mineral tablets assembly observed in experiments. The organic matrix was modeled with a group of spring elements. The constitutive relations of the spring elements were inspired from the experimental results of organic molecules from the literature. The mineral bridges were modeled with simple elastic bonds with the parameters based on experimental data from the literature. The bulk stress-strain responses from the models agreed well with experimental results. The model results show that the mineral bridges play important roles in providing the stiffness and yield strength for the nacre, while the organic matrix in providing the ductility for the nacre. This work demonstrated the suitability of particle methods for modeling microstructures of nacre.

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.

The stability and Raman spectra of ikaite, CaCO3·6H2O, at high pressure and temperature

Science.gov (United States)

Shahar, Anat; Bassett, William A.; Mao, Ho-kwang; Chou, I-Ming; Mao, Wendy

2005-01-01

Raman analyses of single crystals of ikaite, CaCO3·6H2O, synthesized in a diamond-anvil cell at ambient temperature yield spectra from 0.14 to 4.08 GPa; the most intense peaks are at 228 and 1081 cm−1 corresponding to Eg(external) and A1g (internal) modes of vibrations in CO2− 3 ions, respectively. These are in good agreement with Raman spectra previously published for ikaite in powder form at ambient temperature and pressure. Visual observations of a sample consisting initially of a mixture of calcite + water in a hydrothermal diamond-anvil cell yielded a P-T phase diagram up to 2 GPa and 120 °C; the boundary for the reaction ikaite ↔ aragonite + water has a positive slope and is curved convexly toward the aragonite + water field similar to typical melt curves. This curvature can be explained in terms of the Clapeyron equation for a boundary between a solid phase and a more compressible liquid phase or largely liquid phase assemblage.

Ochtinská Aragonitová jaskyňa – špecifický typ hypogénnej jaskyne?

Czech Academy of Sciences Publication Activity Database

Bella, P.; Bosák, Pavel; Gaál, Ľ.; Pruner, Petr; Haviarová, D.

2017-01-01

Roč. 22, č. 2 (2017), s. 65-66 ISSN 1335-213X. [Vedecká konferencia „Výskum, využívanie a ochrana jaskýň“ /11./. 25.09.2017-26.09.2017, Liptovský Mikuláš] Institutional support: RVO:67985831 Keywords : caves * Ochtinská Aragonite Cave * karsology Subject RIV: DB - Geology ; Mineralogy

Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

Science.gov (United States)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

2015-12-01

Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in

Freshwater on the route of hominids "out of Africa" during the last interglacial revealed by U-Th in northern Red Sea fossil reefs

Science.gov (United States)

Lazar, B.; Stein, M.; Agnon, A.; Shaked, Y.

2012-04-01

The migration of Anatomically Modern Hominids (AMH) "out of Africa" is a fundamental problem in the study of human culture concerning that the route passed through the presently hyperarid deserts surrounding the Red Sea. Here, we outline the evidence for significant presence of freshwater in a well developed phreatic coastal aquifer along the Red Sea shores during the last interglacial period. The fringing coral reefs were tectonically uplifted through the freshwater lens resulting in extensive recrystallization of reef framework from the primary aragonite into calcite. We developed a novel open-system U-Th dating methodology that enabled us estimating two ages for the calcitic reef terrace: 1. The original age of the reef terrace, deposited at ~190 ka BP; and 2. the time of freshwater recrystallization (from the primary aragonite into calcite) at ~140 ka BP. The age of freshwater recrystallization is consistent with other geological lines of evidence placing the time of AMH migration "out of Africa" at the onset of the last interglacial. It is likely therefore that during that time the hyperarid Red Sea area was wetter than today facilitating the migration of AMH to Europe and Asia.

The influence of the magnetic field on the crystallisation form of calcium carbonate and the testing of a magnetic water-treatment device

Energy Technology Data Exchange (ETDEWEB)

Kobe, S. E-mail: spomenka.kobe@ijs.si; Drazic, G.; McGuiness, P.J.; Strazisar, J

2001-10-01

By using X-ray analysis and a TEM equipped with a link AN-10000 EDXS analysing system and an ultra-thin-window Si(Li) detector, different crystal forms of CaCO{sub 3} crystals were characterised. These crystals were grown from tap water and model water both with and without a magnetic field. Separate aragonite crystals were formed in the treated water and clusters of calcite in the untreated water. We observed that under the influence of a magnetic field higher than 500 mT, the nucleation and subsequent growth of aragonite could be successfully used as a way of preventing scale. The prototype of a magnetic water-treatment device (MWTD) was constructed for testing in a pilot plant that treats tap water. It has been in use for more than 2 years and the results look very promising for reducing the need for chemically treated water. The weight gains of the heat exchangers, which were used in the three parallel pipelines equipped with three different devices against scaling, were followed. The MWTD designed and built in the IJS laboratory, showed only a slightly higher weight gain than that achieved with the use of chemicals.

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.

Influence of the Mg-content on ESR-signals in synthetic calcium carbonate

International Nuclear Information System (INIS)

Barabas, M.; Bach, A.; Mudelsee, M.; Mangini, A.

1989-01-01

Carbonate crystals doped with various concentrations of Mg 2+ -ions have been grown by a gel-diffusion method. An increase of the Mg/Ca-ratio to more than about 1 caused a phase change in the crystal lattice from calcite to aragonite. The properties of the ESR-signals of the synthetic carbonates were studied and compared with natural marine carbonates. The following results were derived: (a) In the presence of Mg 2+ -ions the synthetic carbonates display the same ESR-signals as natural calcites of marine origin with similar properties (thermal stability, radiation sensitivity). (b) The saturation value of the signal at g=2.0006 in synthetic calcites was found to be strongly related with the Mg-content in the crystals. (c) The signal at g=2.0036 (axial symmetry) which is present in calcite was not influenced by the Mg-concentration. Its saturation value decreases when the crystal phase changed from calcite to aragonite and in complement the signal at g=2.0031 appeared. (d) The signals at g=2.0057 and g=2.0031 are most probably not of organic origin. (author)

Drivers of the Seasonal Carbon Cycle in the Coastal Gulf of Alaska

Science.gov (United States)

Pilcher, D.; Siedlecki, S. A.; Hermann, A. J.; Coyle, K. O.; Mathis, J. T.

2016-02-01

The Coastal Gulf of Alaska serves as a significant carbon sink annually, but varies seasonally from net carbon efflux in winter, to net carbon uptake from spring through fall. This significant uptake of anthropogenic CO2 combined with the naturally cold, low calcium carbonate surface waters is expected to accelerate ocean acidification. Observational evidence has already detected subsurface aragonite undersaturation, likely resulting from carbon remineralization of sinking organic matter. Other processes such as storm-induced vertical mixing, glacial runoff, temperature change, and nutrient supply can further modify the carbon cycle. Improving knowledge of these seasonal processes is critical for the region's fisheries that provide substantial ecosystem services and can be adversely impacted by sub-optimal aragonite saturation conditions. We use a regional model of the Coastal Gulf of Alaska coupled to an ecosystem model with full carbonate chemistry to investigate the physical and biogeochemical mechanisms that drive the seasonal carbon cycle. Boundary conditions are set from the coarser Northeast Pacific model, with alkalinity and carbon concentrations determined from empirical relationships with salinity. Model output from a 2009 hindcast simulation is compared to observations of alkalinity and dissolved inorganic carbon concentrations for model verification and to elucidate seasonal mechanisms.

Characterization of powdered fish heads for bone graft biomaterial applications.

Science.gov (United States)

Oteyaka, Mustafa Ozgür; Unal, Hasan Hüseyin; Bilici, Namık; Taşçı, Eda

2013-01-01

The aim of this study was to define the chemical composition, morphology and crystallography of powdered fish heads of the species Argyrosomus regius for bone graft biomaterial applications. Two sizes of powder were prepared by different grinding methods; Powder A (coarse, d50=68.5 µm) and Powder B (fine, d50=19.1 µm). Samples were analyzed using X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), thermogravimetry (TG), and energy dispersive X-ray spectroscopy (EDS). The powder was mainly composed of aragonite (CaCO3) and calcite (CaCO3). The XRD pattern of Powder A and B matched standard aragonite and calcite patterns. In addition, the calcium oxide (CaO) phase was found after the calcination of Powder A. Thermogravimetry analysis confirmed total mass losses of 43.6% and 47.3% in Powders A and B, respectively. The microstructure of Powder A was mainly composed of different sizes and tubular shape, whereas Powder B showed agglomerated particles. The high quantity of CaO and other oxides resemble the chemical composition of bone. In general, the powder can be considered as bone graft after transformation to hydroxyapatite phase.

The influence of the magnetic field on the crystallisation form of calcium carbonate and the testing of a magnetic water-treatment device

International Nuclear Information System (INIS)

Kobe, S.; Drazic, G.; McGuiness, P.J.; Strazisar, J.

2001-01-01

By using X-ray analysis and a TEM equipped with a link AN-10000 EDXS analysing system and an ultra-thin-window Si(Li) detector, different crystal forms of CaCO 3 crystals were characterised. These crystals were grown from tap water and model water both with and without a magnetic field. Separate aragonite crystals were formed in the treated water and clusters of calcite in the untreated water. We observed that under the influence of a magnetic field higher than 500 mT, the nucleation and subsequent growth of aragonite could be successfully used as a way of preventing scale. The prototype of a magnetic water-treatment device (MWTD) was constructed for testing in a pilot plant that treats tap water. It has been in use for more than 2 years and the results look very promising for reducing the need for chemically treated water. The weight gains of the heat exchangers, which were used in the three parallel pipelines equipped with three different devices against scaling, were followed. The MWTD designed and built in the IJS laboratory, showed only a slightly higher weight gain than that achieved with the use of chemicals

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.

Biomineral repair of abalone shell apertures.

Science.gov (United States)

Cusack, Maggie; Guo, Dujiao; Chung, Peter; Kamenos, Nicholas A

2013-08-01

The shell of the gastropod mollusc, abalone, is comprised of nacre with an outer prismatic layer that is composed of either calcite or aragonite or both, depending on the species. A striking characteristic of the abalone shell is the row of apertures along the dorsal margin. As the organism and shell grow, new apertures are formed and the preceding ones are filled in. Detailed investigations, using electron backscatter diffraction, of the infill in three species of abalone: Haliotis asinina, Haliotis gigantea and Haliotis rufescens reveals that, like the shell, the infill is composed mainly of nacre with an outer prismatic layer. The infill prismatic layer has identical mineralogy as the original shell prismatic layer. In H. asinina and H. gigantea, the prismatic layer of the shell and infill are made of aragonite while in H. rufescens both are composed of calcite. Abalone builds the infill material with the same high level of biological control, replicating the structure, mineralogy and crystallographic orientation as for the shell. The infill of abalone apertures presents us with insight into what is, effectively, shell repair. Copyright © 2013 Elsevier Inc. All rights reserved.

Contribution to origin of the reefs in northeastern

International Nuclear Information System (INIS)

Nobrega Coutinho, P. da; Farias, C.C.

1979-01-01

Several reef lines parallel to the seashore are encountered on the heaches of north east Brazil, composing one of the most characteristic morphological phenomena of the region. The textural and mineralogical composition of the reefs is very similar to the sediments met in the submarine beach. The initial comentation seems to take place beach. X-ray diffraction analyses showed that the cement of the first reef line of the intertidal zone is constituited of 60% aragonite and of 40% magnesium calcite with approximately 15-18 mol. %MgCO 3 in the calcite. The cement of the second reef line in the submarine beach is made up of solely calcite with only 3 mol. %MgCO 3 . This proportion becomes even smaller in the cement in the reefs beneath the sand bank. The cement of these reefs is a result of the dissolution and precipitation of organic fragments present in the submarine beach sediments, especial Halimeda. The composition of these fragments appeared to be identical to the reefs of the intertidal zone. The magnesium calcite is mainly a result to the alteration of the aragonite, being the marine inorganic precipitation as a secondary process. (author) [pt

Detecting the progression of ocean acidification from the saturation state of CaCO3 in the subtropical South Pacific

Science.gov (United States)

Murata, Akihiko; Hayashi, Kazuhiko; Kumamoto, Yuichiro; Sasaki, Ken-ichi

2015-04-01

Progression of ocean acidification in the subtropical South Pacific was investigated by using high-quality data from trans-Pacific zonal section at 17°S (World Ocean Circulation Experiment section P21) collected in 1994 and 2009. During this 15 year period, the CaCO3 saturation state of seawater with respect to calcite (Ωcal) and aragonite (Ωarg) in the upper water column (Pacific Ocean.

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, John

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

A comparison of growth rate of late Holocene stalagmites with atmospheric precipitation and temperature, and its implications for paleoclimatology

Science.gov (United States)

Railsback, L. Bruce

2018-05-01

Growth rate of stalagmites can vary with many factors of physical environment, ecology, and karst hydrogeology, to the extent that growth rates calculated from a carefully selected set of data from 80 stalagmites from around the world vary by a factor of 400 from smallest to largest. Growth rates of those 80 stalagmites nonetheless collectively show correlations to atmospheric precipitation and temperature that are non-trivial (r2 = 0.12 and 0.20, respectively) and unlikely to have arisen randomly (p = 0.002 and 0.00002). Those global relationships are also supported by previously published studies of individual drip sites. The general trend of growth rates is not a monotonic increase with precipitation; instead, it reaches a maximum at annual precipitation rates between 700 and 2300 mm/year, which both counters many model predictions that growth rates should increase monotonically with drip rate and complicates use of growth rate as a proxy for past precipitation. The general trend of growth rates among the 80 stalagmites is a monotonic increase with temperature. However, the low values of r2 in both of these general trends indicate that growth rate can be at best a qualitative rather than quantitative proxy of past conditions. Growth rate shows no statistically significant relationship to effective precipitation, seemingly because of the confounding effect of temperature. Growth rates of aragonite-bearing stalagmites are commonly greater than rates in stalagmites in which calcite is the only carbonate mineral, suggesting both the need for careful identification of mineralogy and the special applicability of aragonitic stalagmites in high-resolution studies. Aragonite has exceptionally great frequency in settings with low effective atmospheric precipitation, supporting previous linkages of that mineral to warm dry environments. Closely-spaced sampling used in recent paleoclimatological studies suggests that unexploited long-term low-resolution records of past

Ocean Acidification in the Surface Waters of the Pacific-Arctic Boundary Regions

Science.gov (United States)

Mathis, J. T.; Cross, J. N.; Evans, W.; Doney, S. C.

2016-02-01

The continental shelves of the Pacific-Arctic Region (PAR) are especially vulnerable to the effects of ocean acidification (OA) because the intrusion of anthropogenic CO2 is not the only process that can reduce pH and carbonate mineral saturation states for aragonite (ΩArag). Enhanced sea-ice melt, respiration of organic matter, upwelling and riverine inputs have been shown to exacerbate CO2-driven ocean acidification in high-latitude regions. Additionally, the indirect effect of changing sea-ice coverage is providing a positive feedback to OA as more open water will allow for greater uptake of atmospheric CO2. Here, we compare model-based outputs from the Community Earth System Model with a subset of recent ship-based observations, and take an initial look at future model projections of surface water ΩArag in the Bering, Chukchi and Beaufort Seas. We then use the model outputs to define benchmark years when biological impacts are likely to result from reduced ΩArag. Each of the three continental shelf seas in the PAR will become undersaturated with respect to aragonite at approximately 30-year intervals, indicating that aragonite undersaturations gradually progress upstream along the flow path of the waters as they move north from the Pacific Ocean. However, naturally high variability in ΩArag may indicate higher resilience of the Bering Sea ecosystem to these low-ΩArag conditions than the Chukchi and the Beaufort Seas. Based on our initial results, we have determined that the annual mean for ΩArag will pass below the current range of natural variability in 2025 for the Beaufort Sea and 2027 for the Chukchi Sea. Because of the higher range of natural variability, the annual mean for ΩArag for the Bering Sea does not pass out of the natural variability range until 2044. As ΩArag in these shelf seas slips below the present-day range of large seasonal variability by midcentury, it could put tremendous pressure on the diverse ecosystems that support some of

Benthic metabolic feedbacks to carbonate chemistry on coral reefs:implications for ocean acidification

Science.gov (United States)

Price, N.; Rohwer, F. L.; Stuart, S. A.; Andersson, A.; Smith, J.

2012-12-01

The metabolic activity of resident organisms can cause spatio-temporal variability in carbonate chemistry within the benthic boundary layer, and thus potentially buffer the global impacts of ocean acidification. But, little is known about the capacity for particular species assemblages to contribute to natural daily variability in carbonate chemistry. We encapsulated replicate areas (~3m2) of reef across six Northern Line Islands in the central Pacific for 24 hrs to quantify feedbacks to carbonate chemistry within the benthic boundary layer from community metabolism. Underneath each 'tent', we quantified relative abundance and biomass of each species of corals and algae. We coupled high temporal resolution time series data on the natural diurnal variability in pH, dissolved oxygen, salinity, and temperature (using autonomous sensors) with resident organisms' net community calcification and productivity rates (using change in total dissolved carbon and total alkalinity over time) to examine feedbacks from reef metabolism to boundary layer carbonate chemistry. These reefs experienced large ranges in pH (> 0.2 amplitude) each day, similar to the magnitude of 'acidification' expected over the next century. Daily benthic pH, pCO2, and aragonite saturation state (Ωaragonite) were contrasted with seasonal threshold values estimated from open ocean climatological data extrapolated at each island to determine relative inter-island feedbacks. Diurnal amplitude in pH, pCO2, and Ωaragonite at each island was dependent upon the resident species assemblage of the benthos and was particularly reliant upon the biomass, productivity, and calcification rate of Halimeda. Net primary productivity of fleshy algae (algal turfs and Lobophora spp.) predominated on degraded, inhabited islands where net community calcification was negligible. In contrast, the chemistry over reefs on 'pristine', uninhabited islands was driven largely by net calcification of calcareous algae and stony

A comparative study of modern carbonate mud in reefs and carbonate platforms: Mostly biogenic, some precipitated

Science.gov (United States)

Gischler, Eberhard; Dietrich, Sarah; Harris, Daniel; Webster, Jody M.; Ginsburg, Robert N.

2013-06-01

Carbonate mud from reefs and carbonate platforms in six locations of the Atlantic, Indian, and Pacific Oceans (Belize, Bahamas, Florida, the Maldives, French Polynesia, Great Barrier Reef) was systematically and quantitatively analyzed with regard to texture, composition, mineralogy, and geochemistry. Mud composition shows considerable variability, however, the data supports the contention that these muds are largely derived from the breakdown of skeletal grains and codiacean algae. Only mud from the Bahamas and northern Belize, areas which are characterized by common whitings, is interpreted to be mainly inorganically precipitated. Three grain-size fractions (63-20 μm, 20-4 μm, aragonite needles, nanograins, and coccoliths. Coccoliths are common in deeper lagoonal settings of the open ocean settings (Maldives, French Polynesia). The geochemistry of the aragonite contents and strontium concentrations, suggesting physico-chemical precipitation. The northern Belize and Great Barrier Reef samples show the highest magnesium calcite values and, accordingly, produced the lowest aragonite and strontium measurements. The high-magnesium calcite portion of the northern Belize mud is either precipitated or due to abundant micritized skeletal grains (e.g., foraminifera): more studies are needed to verify the origin. In the case of the Great Barrier Reef sample, coralline algae appear to be the source of abundant high-magnesium calcite. This study emphasizes that from a global perspective, modern muds in reefs and carbonate platforms exhibit different compositions but are in many cases biologically derived. Even though the composition of modern carbonate muds varies among the six locations investigated, they may serve as analogs for the formation of muds in Cenozoic and Mesozoic reefs and carbonate platforms. Limitations of the interpretation of carbonate-mud origin include the difficulty of identifying, quantifying, and analyzing small grains, the ease with which small

Nacre biomineralisation: A review on the mechanisms of crystal nucleation.

Science.gov (United States)

Nudelman, Fabio

2015-10-01

The wide diversity of biogenic minerals that is found in nature, each with its own morphology, mechanical properties and composition, is remarkable. In order to produce minerals that are optimally adapted for their function, biomineralisation usually occurs under strict cellular control. This control is exerted by specialised proteins and polysaccharides that assemble into a 3-dimensional organic matrix framework, forming a microenvironment where mineral deposition takes place. Molluscs are unique in that they use a striking variety of structural motifs to build their shells, each made of crystals with different morphologies and different calcium carbonate polymorphs. Much of want is known about mollusc shell formation comes from studies on the nacreous layer, or mother-of-pearl. In this review, we discuss two existing models on the nucleation of aragonite crystals during nacre formation: heteroepitaxial nucleation and mineral bridges. The heteroepitaxial nucleation model is based on the identification of chemical functional groups and aragonite-nucleating proteins at the centre of crystal imprints. It proposes that during nacre formation, each aragonite tablet nucleates independently on a nucleation site that is formed by acidic proteins and/or glycoproteins adsorbed on the chitin scaffold. The mineral bridges model is based on the identification of physical connections between the crystals in a stack, which results in a large number of crystals across several layers sharing the same crystallographic orientation. These observations suggest that there is one nucleation event per stack of tablets. Once the first crystal nucleates and reaches the top interlamellar matrix, it continues growing through pores, giving rise to the next layer of nacre, subsequently propagating into a stack. We compare both models and propose that they work in concert to control crystal nucleation in nacre. De novo crystal nucleation has to occur at least once per stack of aligned crystals

High-pressure phase transitions of strontianite

Science.gov (United States)

Speziale, S.; Biedermann, N.; Reichmann, H. J.; Koch-Mueller, M.; Heide, G.

2015-12-01

Strontianite (SrCO3) is isostructural to aragonite, a major high-pressure polymorph of calcite. Thus it is a material of interest to investigate the high-pressure phase behavior of aragonite-group minerals. SrCO3 is a common component of natural carbonates and knowing its physical properties at high pressures is necessary to properly model the thermodynamic properties of complex carbonates, which are major crustal minerals but are also present in the deep Earth [Brenker et al., 2007] and control carbon cycling in the Earth's mantle. The few available high-pressure studies of SrCO3 disagree regarding both pressure stability and structure of the post-aragonite phase [Lin & Liu, 1997; Ono et al., 2005; Wang et al. 2015]. To clarify such controversies we investigated the high-pressure behavior of synthetic SrCO3 by Raman spectroscopy. Using a diamond anvil cell we compressed single-crystals or powder of strontianite (synthesized at 4 GPa and 1273 K for 24h in a multi anvil apparatus), and measured Raman scattering up to 78 GPa. SrCO3 presents a complex high-pressure behavior. We observe mode softening above 20 GPa and a phase transition at 25 - 26.9 GPa, which we interpret due to the CO3 groups rotation, in agreement with Lin & Liu [1997]. The lattice modes in the high-pressure phase show dramatic changes which may indicate a change from 9-fold coordinated Sr to a 12-fold-coordination [Ono, 2007]. Our results confirm that the high-pressure phase of strontianite is compatible with Pmmn symmetry. References Brenker, F.E. et al. (2007) Earth and Planet. Sci. Lett., 260, 1; Lin, C.-C. & Liu, L.-G. (1997) J. Phys. Chem. Solids, 58, 977; Ono, S. et al. (2005) Phys. Chem. Minerals, 32, 8; Ono, S. (2007) Phys. Chem. Minerals, 34, 215; Wang, M. et al. (2015) Phys Chem Minerals 42, 517.

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

Directory of Open Access Journals (Sweden)

Sarah Hamylton

Full Text Available 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

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

Micro-X-ray fluorescence-based comparison of skeletal structure and P, Mg, Sr, O and Fe in a fossil of the cold-water coral Desmophyllum sp., NW Pacific

Science.gov (United States)

Yoshimura, Toshihiro; Suzuki, Atsushi; Tamenori, Yusuke; Kawahata, Hodaka

2014-02-01

Micro-scale distributions of trace and minor elements in, for example, coral skeletons are crucial as geochemical tracers of past environmental conditions, because they have the inherent advantage of accounting for confounding diagenetic and physiological effects. To extract reproducible paleoceanographic records from coral skeletons, a selective measurement of specific ultrastructures at high spatial resolution is required. Compared to warm-water reef-building corals, such data are limited in cold-water corals and, to the best of the authors' knowledge, the latter have to date not been examined by means of micro-X-ray fluorescence. This technique was used for micrometer-scale imaging of P, Mg, Sr, O, and Fe intensities (counts per unit time) in a fossil specimen (as yet unknown age) of the cold-water coral Desmophyllum sp. from surface sediments of the NW Pacific. Cross plots confirmed that the micro-XRF signals were associated with corresponding trends in elemental concentration (ppm). Two major structural components of the septum—centers of calcification (COCs) and the surrounding fibrous aragonite portion—differed in composition. The COCs were characterized by higher intensities of P and Mg (650 and 220 counts per 5 s, respectively), and lower intensities of Sr (2,800) and O (580; corresponding values for the fibrous aragonite are 370, 180, 3,300 and 620 counts per 5 s, respectively). Oxygen intensity values were mostly homogeneous, but slightly lower in COCs and substantially higher in a well-defined patch in the fibrous aragonite. The mostly homogeneous P signals in the fibrous aragonite confirm the utility of this structural component and of coral septa in general for tracer studies of oceanic P. Nevertheless, spot occurrences of elevated P (>950 counts per 5 s) spanning tens of micrometers in specific parts of the fibrous region of the septum would cause overestimates of oceanic P, and should evidently not be overlooked in future research. The

Antarctic urchin Ctenocidaris speciosa spines: lessons from the deep

OpenAIRE

Catarino, A.I.; Guibourt, V.; Moureaux, C.; De Ridder, C.; Compère, P.; Dubois, P.

2013-01-01

Ocean acidification is leading to changes in the oceanic carbonate system. As a result, calcium carbonate saturation horizon is shallowing, especially at high latitudes. Biogenic high magnesium-calcites could be particularly vulnerable, since their solubility is either similar or greater than that of aragonite. Cidaroid urchins have magnesium-calcite spines covered by a polycrystalline cortex which becomes exposed to seawater when mature (not covered by an epidermis). However, deep species li...

Frontiers of Karst Research: Proceedings and recommendations of the workshop held in San Antonio, Texas on 3-5 May 2007. Karst Waters Institute Special Publication 13

Science.gov (United States)

2009-01-08

L., Gon- zalez, I., and Saiz-Jimenez, C., 1999, Microbial communities associated with hydromagnesite and needle- fiber aragonite de- posits in a...Gonzalez, J.M., and Saiz-Jimenez, C., 2006, On the origin of fiber calcite crystals in moonmilk deposits: Naturwissen- schaften, v. 93, p. 27-32...Geomi- crobiology of carbonate-silicate microbalites from Hawaiian basaltic sea caves: Chemical Geology, v. 169, p. 339-355. Macalady, J.L., Jones, D.S

Spectral luminescence and geochemistry of coral aragonite: Effects of whole-core treatment

NARCIS (Netherlands)

Nagtegaal, R.; Grove, C.A.; Kasper, S.; Zinke, J.; Brummer, G.J.A.

2012-01-01

Luminescent and geochemical properties of coral skeletons are increasingly used for time-series analysis to resolve past and ongoing changes in environmental and climatic conditions. Corals also contain non-skeletal matter which not only quenches luminescence but is also reported to compromise

Sm-Nd in marine carbonates and phosphates: implications for Nd isotopes in seawater and crustal ages

International Nuclear Information System (INIS)

Shaw, H.F.; Wasserburg, G.J.

1985-01-01

This study explores the possibility of establishing Nd isotopic variations in seawater over geologic time. Calcite, aragonite and apatite are examined as possible phases recording seawater values of epsilonsubNd. Modern, biogenic and inorganically precipitated calcite and aragonite from marine environments were found to have Nd concentrations of from 0.2 to 70 ppb, showing that primary marine CaCO 3 contains little REE and that Nd/Ca is not greatly enhanced relative to seawater during carbonate precipitation. Very young marine limestone and dolomite containing no continental detritus have approx. 200 ppb Nd. All the carbonates are LREE enriched. Modern and very young Atlantic and Pacific carbonates have epsilonsub(Nd) in the range of shallow Atlantic and Pacific seawater respectively, implying that they derive their REE from local seawater. The Nd in well preserved carbonate fossils is 4 ppb, much greater than in their modern counterparts but like the high values found for carbonates in other studies. Results are also reported for apatite. They suggest that sedimentary apatite can be used to determine epsilonsub(Nd)(T) in ancient seawater. The seawater values so inferred range between -1.7 and -8.9 over the last 700 my and lie in the range of modern seawater, showing no evidence for drastic changes. (U.K.)

Carbon isotopic fractionation in live benthic foraminifera -comparison with inorganic precipitate studies

International Nuclear Information System (INIS)

Grossmann, E.L.

1984-01-01

Carbon and oxygen isotopic analyses have been performed on live-stained aragonitic and calcitic benthic foraminifera and dissolved inorganic carbon from the Southern California Borderland to examine carbon isotopic fractionation in foraminifera. Temperature, salinity and pH data have also been collected to permit accurate determination of the delta 13 C of bicarbonate ion and thus aragonite-HCO 3 - and calcite-HCO 3 - isotopic enrichment factors (epsilonsub(ar-b) and epsilonsub(cl-b), respectively). Only species which precipitate in 18 O equilibrium have been considered. epsilonsub (ar-b) values based on Hoeglundina elegans range from 1.9 per mille at 2.7 deg C to 1.1 per mille at 9.5 deg C. The temperature dependence of epsilonsub(ar-b) is considerably greater than the equilibrium equation would predict and may be due to a vital effect. The calcitic foraminifera Cassidulina tortuosa, Cassidulina braziliensis, and Cassidulina limbata, Bank and Terrace dwellers, have similar delta 13 C values and yield an average epsilonsub(cl-b) value of -0.2 +- 0.1 per mille between 8 deg and 10 deg C. Calcitic Uvigerina curticosta, Uvigerina peregrina, and megalospheric B, argentea, Slope and Basin dwellers, are -0.7 +- 0.1 per mille enriched relative to ambient bicarbonate for 3 to 9 deg C. (author)

Future coral reef habitat marginality: Temporal and spatial effects of climate change in the Pacific basin

Science.gov (United States)

Guinotte, J.M.; Buddemeier, R.W.; Kleypas, J.A.

2003-01-01

Marginal reef habitats are regarded as regions where coral reefs and coral communities reflect the effects of steady-state or long-term average environmental limitations. We used classifications based on this concept with predicted time-variant conditions of future climate to develop a scenario for the evolution of future marginality. Model results based on a conservative scenario of atmospheric CO2 increase were used to examine changes in sea surface temperature and aragonite saturation state over the Pacific Ocean basin until 2069. Results of the projections indicated that essentially all reef locations are likely to become marginal with respect to aragonite saturation state. Significant areas, including some with the highest biodiversity, are expected to experience high-temperature regimes that may be marginal, and additional areas will enter the borderline high temperature range that have experienced significant ENSO-related bleaching in the recent past. The positive effects of warming in areas that are presently marginal in terms of low temperature were limited. Conditions of the late 21st century do not lie outside the ranges in which present-day marginal reef systems occur. Adaptive and acclimative capabilities of organisms and communities will be critical in determining the future of coral reef ecosystems.

Defying Dissolution: Discovery of Deep-Sea Scleractinian Coral Reefs in the North Pacific.

Science.gov (United States)

Baco, Amy R; Morgan, Nicole; Roark, E Brendan; Silva, Mauricio; Shamberger, Kathryn E F; Miller, Kelci

2017-07-14

Deep-sea scleractinian coral reefs are protected ecologically and biologically significant areas that support global fisheries. The absence of observations of deep-sea scleractinian reefs in the Central and Northeast Pacific, combined with the shallow aragonite saturation horizon (ASH) and high carbonate dissolution rates there, fueled the hypothesis that reef formation in the North Pacific was improbable. Despite this, we report the discovery of live scleractinian reefs on six seamounts of the Northwestern Hawaiian Islands and Emperor Seamount Chain at depths of 535-732 m and aragonite saturation state (Ω arag ) values of 0.71-1.33. Although the ASH becomes deeper moving northwest along the chains, the depth distribution of the reefs becomes shallower, suggesting the ASH is having little influence on their distribution. Higher chlorophyll moving to the northwest may partially explain the geographic distribution of the reefs. Principle Components Analysis suggests that currents are also an important factor in their distribution, but neither chlorophyll nor the available current data can explain the unexpected depth distribution. Further environmental data is needed to elucidate the reason for the distribution of these reefs. The discovery of reef-forming scleractinians in this region is of concern because a number of the sites occur on seamounts with active trawl fisheries.

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. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

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

Experimental Evidence that Abrasion of Carbonate Sand is a Significant Source of Carbonate Mud

Science.gov (United States)

Trower, L.; Kivrak, L.; Lamb, M. P.; Fischer, W. W.

2017-12-01

Carbonate mud is a major sedimentary component of modern and ancient tropical carbonate environments, yet its enigmatic origin remains debated. Early views on the origin of carbonate mud considered the abrasion of carbonate sand during sediment transport as a possible mechanism. In recent decades, however, prevailing thought has generally settled on a binary explanation: 1) precipitation of aragonite needles within the water column, and 2) post-mortem dispersal of biological aragonite, in particular from algae, and perhaps aided by fish. To test these different hypotheses, we designed a model and a set of laboratory experiments to quantify the rates of mud production associated with sediment transport. We adapted a recent model of ooid abrasion rate to predict the rate of mud production by abrasion of carbonate sand as a function of grain size and sediment transport mode. This model predicts large mud production rates, ranging from 103 to 104 g CaCO3/m2/yr for typical grain sizes and transport conditions. These rate estimates are at least one order of magnitude more rapid than the 102 g CaCO3/m2/yr estimates for other mechanisms like algal biomineralization, indicating that abrasion could produce much larger mud fluxes per area as other mechanisms. We tested these estimates using wet abrasion mill experiments; these experiments generated mud through mechanical abrasion of both ooid and skeletal carbonate sand for grain sizes ranging from 250 µm to >1000 µm over a range of sediment transport modes. Experiments were run in artificial seawater, including a series of controls demonstrating that no mud was produced via homogenous nucleation and precipitation in the absence of sand. Our experimental rates match the model predictions well, although we observed small systematic differences in rates between abrasion ooid sand and skeletal carbonate sand that likely stems from innate differences in grain angularity. Electron microscopy of the experimental products revealed

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

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

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.

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

OpenAIRE

N. R. Bates; M. I. Orchowska; R. Garley; J. T. Mathis

2013-01-01

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...

Qualitative analysis of the crystalline and chemical content of the Teredo sp. (Turu)

International Nuclear Information System (INIS)

Matos, E.; Matos, M.; Matos, P.

1990-01-01

A qualitative analysis of the crystalline and elementary content of the Teredo sp. (Turu) is realised by diffraction and fluorescence Phillips equipment. A diffractogram and X-ray spectra are studied. The head constitution is almost exclusively formed by aragonite and calcite, visceral mass and coat, formed by Ca, K, S, P, Cl, Si, Fe and Ti. The relative amount of these chemical elements is the difference between each part of the Teredo sp. (Turu). (M.A.C.)

Climate change feedbacks on future oceanic acidification

OpenAIRE

McNeil, Ben I.; Matear, Richard J.

2011-01-01

Oceanic anthropogenic CO2 uptake will decrease both the pH and the aragonite saturation state (Ωarag) of seawater leading to an oceanic acidification. However, the factors controlling future changes in pH and Ωarag are independent and will respond differently to oceanic climate change feedbacks such as ocean warming, circulation and biological changes. We examine the sensitivity of these two CO2-related parameters to climate change feedbacks within a coupled atmosphere-ocean model. The ocean ...

Comparative genomics explains the evolutionary success of reef-forming corals

OpenAIRE

Bhattacharya, Debashish; Agrawal, Shobhit; Aranda, Manuel; Baumgarten, Sebastian; Belcaid, Mahdi; Drake, Jeana L; Erwin, Douglas; Foret, Sylvian; Gates, Ruth D; Gruber, David F; Kamel, Bishoy; Lesser, Michael P; Levy, Oren; Liew, Yi Jin; MacManes, Matthew

2016-01-01

eLife digest For millions of years, reef-building stony corals have created extensive habitats for numerous marine plants and animals in shallow tropical seas. Stony corals consist of many small, tentacled animals called polyps. These polyps secrete a mineral called aragonite to create the reef ? an external ?skeleton? that supports and protects the corals. Photosynthesizing algae live inside the cells of stony corals, and each species depends on the other to survive. The algae produce the co...

Carbon dioxide addition to coral reef waters suppresses net community calcification

Science.gov (United States)

Albright, Rebecca; Takeshita, Yuichiro; Koweek, David A.; Ninokawa, Aaron; Wolfe, Kennedy; Rivlin, Tanya; Nebuchina, Yana; Young, Jordan; Caldeira, Ken

2018-03-01

Coral reefs feed millions of people worldwide, provide coastal protection and generate billions of dollars annually in tourism revenue. The underlying architecture of a reef is a biogenic carbonate structure that accretes over many years of active biomineralization by calcifying organisms, including corals and algae. Ocean acidification poses a chronic threat to coral reefs by reducing the saturation state of the aragonite mineral of which coral skeletons are primarily composed, and lowering the concentration of carbonate ions required to maintain the carbonate reef. Reduced calcification, coupled with increased bioerosion and dissolution, may drive reefs into a state of net loss this century. Our ability to predict changes in ecosystem function and associated services ultimately hinges on our understanding of community- and ecosystem-scale responses. Past research has primarily focused on the responses of individual species rather than evaluating more complex, community-level responses. Here we use an in situ carbon dioxide enrichment experiment to quantify the net calcification response of a coral reef flat to acidification. We present an estimate of community-scale calcification sensitivity to ocean acidification that is, to our knowledge, the first to be based on a controlled experiment in the natural environment. This estimate provides evidence that near-future reductions in the aragonite saturation state will compromise the ecosystem function of coral reefs.

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.

Calcium dynamics in microbialite-forming exopolymer-rich mats on the atoll of Kiritimati, Republic of Kiribati, Central Pacific.

Science.gov (United States)

Ionescu, D; Spitzer, S; Reimer, A; Schneider, D; Daniel, R; Reitner, J; de Beer, D; Arp, G

2015-03-01

Microbialite-forming microbial mats in a hypersaline lake on the atoll of Kiritimati were investigated with respect to microgradients, bulk water chemistry, and microbial community composition. O2, H2S, and pH microgradients show patterns as commonly observed for phototrophic mats with cyanobacteria-dominated primary production in upper layers, an intermediate purple layer with sulfide oxidation, and anaerobic bottom layers with sulfate reduction. Ca(2+) profiles, however, measured in daylight showed an increase of Ca(2+) with depth in the oxic zone, followed by a sharp decline and low concentrations in anaerobic mat layers. In contrast, dark measurements show a constant Ca(2+) concentration throughout the entire measured depth. This is explained by an oxygen-dependent heterotrophic decomposition of Ca(2+)-binding exopolymers. Strikingly, the daylight maximum in Ca(2+) and subsequent drop coincides with a major zone of aragonite and gypsum precipitation at the transition from the cyanobacterial layer to the purple sulfur bacterial layer. Therefore, we suggest that Ca(2+) binding exopolymers function as Ca(2+) shuttle by their passive downward transport through compression, triggering aragonite precipitation in the mats upon their aerobic microbial decomposition and secondary Ca(2+) release. This precipitation is mediated by phototrophic sulfide oxidizers whose action additionally leads to the precipitation of part of the available Ca(2+) as gypsum. © 2014 John Wiley & Sons Ltd.

Amorphous calcium carbonate particles form coral skeletons

Science.gov (United States)

Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu; Stifler, Cayla A.; Frazier, Matthew J.; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V.; Marcus, Matthew A.; Gilbert, Pupa U. P. A.

2017-09-01

Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.

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.

Phase transitions of natural corals monitored by ESR spectroscopy

International Nuclear Information System (INIS)

Vongsavat, V.; Winotai, P.; Meejoo, S.

2006-01-01

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 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 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 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

Model-Based Assessment of the CO2 Sequestration Potential of Coastal Ocean Alkalinization

Science.gov (United States)

Feng, E. Y.; Koeve, W.; Keller, D. P.; Oschlies, A.

2017-12-01

The potential of coastal ocean alkalinization (COA), a carbon dioxide removal (CDR) climate engineering strategy that chemically increases ocean carbon uptake and storage, is investigated with an Earth system model of intermediate complexity. The CDR potential and possible environmental side effects are estimated for various COA deployment scenarios, assuming olivine as the alkalinity source in ice-free coastal waters (about 8.6% of the global ocean's surface area), with dissolution rates being a function of grain size, ambient seawater temperature, and pH. Our results indicate that for a large-enough olivine deployment of small-enough grain sizes (10 µm), atmospheric CO2 could be reduced by more than 800 GtC by the year 2100. However, COA with coarse olivine grains (1000 µm) has little CO2 sequestration potential on this time scale. Ambitious CDR with fine olivine grains would increase coastal aragonite saturation Ω to levels well beyond those that are currently observed. When imposing upper limits for aragonite saturation levels (Ωlim) in the grid boxes subject to COA (Ωlim = 3.4 and 9 chosen as examples), COA still has the potential to reduce atmospheric CO2 by 265 GtC (Ωlim = 3.4) to 790 GtC (Ωlim = 9) and increase ocean carbon storage by 290 Gt (Ωlim = 3.4) to 913 Gt (Ωlim = 9) by year 2100.

Cementing mussels to oysters in the pteriomorphian tree: a phylogenomic approach

Science.gov (United States)

González, Vanessa L.; Bieler, Rüdiger; Giribet, Gonzalo

2016-01-01

Mussels (Mytilida) are a group of bivalves with ancient origins and some of the most important commercial shellfish worldwide. Mytilida consists of approximately 400 species found in various littoral and deep-sea environments, and are part of the higher clade Pteriomorphia, but their exact position within the group has been unstable. The multiple adaptive radiations that occurred within Pteriomorphia have rendered phylogenetic classifications difficult and uncertainty remains regarding the relationships among most families. To address this phylogenetic uncertainty, novel transcriptomic data were generated to include all five orders of Pteriomorphia. Our results, derived from complex analyses of large datasets from 41 transcriptomes and evaluating possible pitfalls affecting phylogenetic reconstruction (matrix occupancy, heterogeneity, evolutionary rates, evolutionary models), consistently recover a well-supported phylogeny of Pteriomorphia, with the only exception of the most complete but smallest data matrix (Matrix 3: 51 genes, 90% gene occupancy). Maximum-likelihood and Bayesian mixture model analyses retrieve strong support for: (i) the monophyly of Pteriomorphia, (ii) Mytilida as a sister group to Ostreida, and (iii) Arcida as sister group to all other pteriomorphians. The basal position of Arcida is congruent with its shell microstructure (solely composed of aragonitic crystals), whereas Mytilida and Ostreida display a combination of a calcitic outer layer with an aragonitic inner layer composed of nacre tablets, the latter being secondarily lost in Ostreoidea. PMID:27358369

Origins of carbonate spherulites: Implications for Brazilian Aptian pre-salt reservoir

Science.gov (United States)

Chafetz, Henry; Barth, Jennifer; Cook, Megan; Guo, Xuan; Zhou, Jie

2018-03-01

Spherulites, spherical to elliptical allochems composed of crystals radiating from a common core, investigated from a variety of depositional settings, e.g., hot springs, ambient water temperature geyser, tufa, and caliche, are all composed of a fine-grained nucleus made-up of carbonate encrusted bacterial bodies, biofilms, and/or EPS and surrounded by a cortex of radiating crystals of either aragonite or calcite. The microbes and their by-products in the nucleus induced the precipitation of carbonate, overcoming the inhibition to initiate crystal formation. The enveloping radiating crystals comprising aragonitic cortices tended to grow abiotically producing well-formed euhedral crystals with a paucity of included bacterial fossils. Whereas those cortical crystals made-up of calcite commonly contained bacterial fossils, indicating that the bacterial colonies contributed to the calcitic cortical crystal precipitation. Similar spherulites form a thick, widespread accumulation in the Aptian Pre-Salt lacustrine deposits in the Campos Basin, offshore Brazil. As with the travertine, tufa, and caliche spherulites, the Pre-Salt spherulites most likely initiated carbonate precipitation around bacterial colonies and/or their bioproducts, probably while afloat in a lacustrine water column before settling to the water-sediment interface. Absence of inter-spherulite sediment and the spherulite-to-spherulite compaction indicate that cortical crystal growth continued while the spherulites were at the sediment-water interface rather than displacively within a sediment.

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.

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.

Impacts of Near-Future Ocean Acidification and Warming on the Shell Mechanical and Geochemical Properties of Gastropods from Intertidal to Subtidal Zones.

Science.gov (United States)

Leung, Jonathan Y S; Connell, Sean D; Nagelkerken, Ivan; Russell, Bayden D

2017-11-07

Many marine organisms produce calcareous shells as the key structure for defense, but the functionality of shells may be compromised by ocean acidification and warming. Nevertheless, calcifying organisms may adaptively modify their shell properties in response to these impacts. Here, we examined how reduced pH and elevated temperature affect shell mechanical and geochemical properties of common grazing gastropods from intertidal to subtidal zones. Given the greater environmental fluctuations in the intertidal zone, we hypothesized that intertidal gastropods would exhibit more plastic responses in shell properties than subtidal gastropods. Overall, three out of five subtidal gastropods produced softer shells at elevated temperature, while intertidal gastropods maintained their shell hardness at both elevated pCO 2 (i.e., reduced pH) and temperature. Regardless of pH and temperature, degree of crystallization was maintained (except one subtidal gastropod) and carbonate polymorph remained unchanged in all tested species. One intertidal gastropod produced less soluble shells (e.g., higher calcite/aragonite) in response to reduced pH. In contrast, subtidal gastropods produced only aragonite which has higher solubility than calcite. Overall, subtidal gastropods are expected to be more susceptible than intertidal gastropods to shell dissolution and physical damage under future seawater conditions. The increased vulnerability to shell dissolution and predation could have serious repercussions for their survival and ecological contributions in the future subtidal environment.

A comparative study of mud-like and coralliform calcium carbonate gallbladder stones.

Science.gov (United States)

Ma, Rui-Hong; Luo, Xiao-Bing; Wang, Xiao-Feng; Qiao, Tie; Huang, Hai-Yi; Zhong, Hai-Qiang

2017-07-01

To gain insight to underlying mechanism of the formation of calcium carbonate (CaCO 3 ) gallbladder stones, we did comparative study of stones with mud appearance and those with coralliform appearance. A total of 93 gallbladder stones with mud appearance and 50 stones with coralliform appearance were analyzed. The appearance, color, texture, and the detection of Clonorchis sinensis eggs by microscopic examination were compared between the two groups. Then, the material compositions of stones were analyzed using Fourier Transform Infrared spectroscopy and the spectrogram characteristics were compared. Moreover, microstructure characteristics of the two kinds of stones were observed and compared with Scanning Electron Microscopy. Mud-like gallbladder stones were mainly earthy yellow or brown with brittle or soft texture, while coralliform stones were mainly black with extremely hard texture, the differences between the two groups was significant (p mud-like gallbladder stones were CaCO 3 stones, and mainly aragonite; while all of the coralliform stones were CaCO 3 stones, and mainly calcite (p mud-like CaCO 3 stones was lower than that in coralliform CaCO 3 stones (p Mud-like CaCO 3 stones mainly happened to patients with cystic duct obstruction. Clonorchis sinensis infection was mainly associated with coralliform (calcite) CaCO 3 stones. Cystic duct obstruction was mainly associated with mud-like (aragonite) CaCO 3 stones. © 2017 Wiley Periodicals, Inc.

Gradual Ordering in Red Abalone Nacre

International Nuclear Information System (INIS)

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

2008-01-01

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

Suitability of the thermoluminescence method for detection of irradiated foods

International Nuclear Information System (INIS)

Pinnioja, S.

1993-01-01

Irradiated foods can be detected by thermoluminescence (TL) of contaminating minerals. Altogether about 300 lots of herbs, spices, berries, mushrooms and seafood were studied by the TL method. Irradiated herbs and spices were easily differentiated from unirradiated ones two years after irradiation of a 10 kGy dose. The mineral composition of seafood was variable; and while calcite was suitable for the TL analysis, aragonite and smectite gave unreliable results. Control analyses during two years confirmed the reliability of TL method. (author)

Electron microscopy of the Bikini ash which covered the fishing boat, fifth Fukuryu Maru

Energy Technology Data Exchange (ETDEWEB)

Suito, E; Takiyama, K

1955-01-01

The electron microscopy diffraction study of the ash produced by the H-bomb experiment revealed that the fine white powder had a nearly uniform diameter of particles (about 0.3 mm) and was identified as calcite crystals. A coral reef of aragonite might have been decomposed into CaO or into an atonic state owing to the bomb explosion and then recrystallized into calcite by the action of H/sub 2/O and CO/sub 2/ in the air occluding radioactive elements.

Colloid morphological and crystalline studies in Bikini dust from the No. 5 Fukuryu Maru by electron microscopy and diffraction methods

Energy Technology Data Exchange (ETDEWEB)

Suito, E; Takiyama, K; Uyeda, N

1954-01-01

Dust was collected from the deck, fishes, and other parts of the ship. The dust was white granules, approximately 0.3 mm. in size and sp. gr. 2.42. These granules were composed of unit particles which were cubic or spindle of 0.1 to 3. ..mu.. in size. The Bikini dust was calcite as determined by electron microdiffraction and x-ray diffraction studies. The coral reef is aragonite. It is suggested that coral reef was evapd. by the H-bomb explosion.

Carbonate deposition on tail feathers of ruddy ducks using evaporation ponds

Science.gov (United States)

Euliss, N.H.; Jarvis, R.L.; Gilmer, D.S.

1989-01-01

Substantial carbonate deposits were observed on rectrices of Ruddy Ducks (Oxyura jamaicensis) collected during 1982-1984 on evaporation ponds in the San Joaquin Valley, California. Carbonate deposits were composed of about 75% aragonite and 25% calcite, both polymorphous forms of CaCO3. Significantly more carbonate deposits were observed on Ruddy Ducks as length of exposure to agricultural drain water increased, during the 1983-1984 field season when salt concentrations in the ponds were higher, and in certain evaporation-pond systems.

Spectroscopic characterisation of biological vaterite: relations to synthetic and geological vaterites

Science.gov (United States)

Jacob, D. E.; Wehrmeister, U.; Soldati, A. L.; Hofmeister, W.

2009-04-01

The pair aragonite and calcite are some of the most intensively studied polymorphous minerals. These CaCO3 polymorphs are most commonly observed in biological minerals produced by marine molluscs, whereas in freshwater molluscs mostly aragonite and vaterite, the third CaCO3 polymorph is identified (e.g. Wehrmeister et al., 2007). Vaterite is the thermodynamically most unstable CaCO3 polymorph and is often discussed as a precursor phase in the mineralization of aragonite or calcite by organisms. Apart from these biological parageneses, vaterite is also known as rare small polycrystalline aggregates from geological occurrences. In laboratory crystallisation experiments, vaterite can be stabilized either kinetically or with the help of organic macromolecules (e.g. Falini et al., 2005). Despite considerable research on vaterite, it is less well known that the crystal structure of vaterite is not unobjectionably determined. Due to the overall small crystal sizes, single crystal XRD analysis of vaterite is very difficult and this could be one of the reasons for the lack of a conclusive determination of the crystal structure. At least four different crystal structure proposals have to be considered: One proposed vaterite to be pseudo hexagonal and to crystallise in the orthorhombic space group Pnma (Meyer 1959). In addition, three crystal structures with hexagonal unit cells are proposed: Kamhi (1963) and Meyer (1969) proposed the same crystal space group: P63/mmc, whereas the site symmetry of the carbonate ion is proposed to be different with 2mm and m, respectively. Lastly, Lippmann (1973) proposed a structure based on the high-temperature modification of YbBO3 with space group 6322. Here, we present new and complete Raman spectra for biological, geological and synthetic vaterite. The spectroscopic results are evaluated in light of all published crystal structures for vaterite and are aimed at gaining more detailed information about the crystallographic features of

Lead concentration and isotopic composition in the Pacific sclerosponge (Acanthochaetetes wellsi) reflects environmental lead pollution

OpenAIRE

Ohmori, Kazuto; Watanabe, Tsuyoshi; Tanimizu, Masaharu; Shirai, Kotaro

2014-01-01

We measured Pb/Ca and Pb isotopes with high resolution in the high-Mg calcite skeleton of a Pacific sclerosponge (Acanthochaetetes wellsi) collected from the reef edge off the western coast of Kume Island (East China Sea), to investigate its potential to he used as a proxy for lead contamination in the environment, and atmospheric transportation and fallout over the last few decades. Skeletal Pb/Ca ranged from 58 to 1642 nmol/mol, 10x higher than that of the aragonite skeleton of Pacific cora...

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 (Ω_arag, 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 Ω_arag (~ 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 Ω_arag 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 Ω_arag, 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 Ω_arag, 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

Formation of secondary minerals and uptake of various anions under naturally-occurring hyper-alkaline conditions in Oman - 16344

International Nuclear Information System (INIS)

Anraku, Sohtaro; Sato, Tsutomu; Yoneda, Tetsuro; Morimoto, Kazuya

2009-01-01

In Japanese transuranic (TRU) waste disposal facilities, 129 I is the most important key nuclide for the long-term safety assessment. Thus, the K d values of I to natural minerals are important factor in the safety assessment. However, the degradation of cement materials in the repositories can produce high pH pore fluid which can affect the anion transport behavior. Therefore, it is necessary to understand the behavior of anions such as I- under the hyper-alkaline conditions. The natural hyper-alkaline spring water (pH>11) in the Oman ophiolite is known to be generated from the partly serpentinized peridotites. The spring water is characteristically hyper-alkaline, reducing, low-Mg, Si and HCO 3 - , and high-Ca, while the river water is moderately alkaline, oxidizing, high-Mg and HCO 3 - . The mixing of these spring and river water resulted in the formation of secondary minerals. In the present study, the naturally occurring hyper-alkaline conditions near the springs in Oman were used as natural analogue for the interaction between cement pore fluid and natural Mg-HCO 3 - groundwater. The present aim of this paper is to examine the conditions of secondary mineral formation and the anion uptake capacity of these mineral in this system. Water and precipitate samples were collected from the different locations around the spring vent to identify the effect of mixing ratios between spring and river water on mineral composition and water-mineral distribution coefficient of various anions. On-site synthesis was also carried out to support these data quantitatively. Aragonite was observed in all precipitates, while calcite, brucite and Mg-Al hydrotalcite-like compounds (HTlc) were also determined in some samples. Calcite was observed only closed to the springs. At locations far from the springs, calcite formation was inhibited due to high-Mg fluid from river water. Brucite was observed from the springs with relatively low-Al concentration and HTlc was the opposite. During

Mineral textures in Serpentine-hosted Alkaline Springs from the Oman ophiolite

Science.gov (United States)

Giampouras, Manolis; Garcia-Ruiz, Juan Manuel; Bach, Wolfgang; Garrido, Carlos J.; Los, Karin; Fussmann, Dario; Monien, Monien

2017-04-01

Meteoric water infiltration in ultramafic rocks leads to serpentinization and the formation of subaerial, low temperature, hydrothermal alkaline springs. Here, we present a detailed investigation of the mineral precipitation mechanisms and textural features of mineral precipitates, along as the geochemical and hydrological characterization, of two alkaline spring systems in the Semail ophiolite (Nasif and Khafifah sites, Wadi Tayin massif). The main aim of the study is to provide new insights into mineral and textural variations in active, on-land, alkaline vents of the Oman ophiolite. Discharge of circulating fluids forms small-scale, localized hydrological catchments consisting in unevenly interconnected ponds. Three different types of waters can be distinguished within the pond systems: i) Mg-type; alkaline (7.9 11.6), Ca-OH-rich waters; and iii) Mix-type waters arising from the mixing of Mg-type and Ca-type waters (9.6 ponds were carried out by X-ray diffraction (XRD), Raman spectroscopy and field-emission scanning electron microscopy coupled to dispersive energy spectroscopy (FE-SEM-EDS). Aragonite and calcite are the dominant minerals (95 vol.%) of the total mineralogical index in all sites. Mg-type waters host hydrated magnesium carbonates (nesquehonite) and magnesium hydroxycarbonate hydrates (artinite) due to evaporation. Brucite, hydromagnesite and dypingite presence in Mix-type waters is spatially controlled by the hydrology of the system and is localized around mixing zones between Ca-type with Mg-type waters. Residence time of discharging waters in the ponds before mixing has an impact on fluid chemistry as it influences the equilibration time with the atmosphere. Acicular aragonite is the main textural type in hyper-alkaline Ca-type waters, acting as a substratum for the growth of calcite and brucite crystals. Low crystallinity, dumbbell shaped and double pyramid aragonite dominates in Mix-type water precipitates. Rate of supersaturation is essential

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.

Estimates of ikaite export from sea ice to the underlying seawater in a sea ice–seawater mesocosm

Directory of Open Access Journals (Sweden)

N.-X. Geilfus

2016-09-01

seawater can potentially hamper 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.

Mechanical properties of crossed-lamellar structures in biological shells: A review.

Science.gov (United States)

Li, X W; Ji, H M; Yang, W; Zhang, G P; Chen, D L

2017-10-01

The self-fabrication of materials in nature offers an alternate and powerful solution towards the grand challenge of designing advanced structural materials, where strength and toughness are always mutually exclusive. Crossed-lamellar structures are the most common microstructures in mollusks that are composed of aragonites and a small amount of organic materials. Such a distinctive composite structure has a fracture toughness being much higher than that of pure carbonate mineral. These structures exhibiting complex hierarchical microarchitectures that span several sub-level lamellae from microscale down to nanoscale, can be grouped into two types, i.e., platelet-like and fiber-like crossed-lamellar structures based on the shapes of basic building blocks. It has been demonstrated that these structures have a great potential to strengthen themselves during deformation. The observed underlying toughening mechanisms include microcracking, channel cracking, interlocking, uncracked-ligament bridging, aragonite fiber bridging, crack deflection and zig-zag, etc., which play vital roles in enhancing the fracture resistance of shells with the crossed-lamellar structures. The exploration and utilization of these important toughening mechanisms have attracted keen interests of materials scientists since they pave the way for the development of bio-inspired advanced composite materials for load-bearing structural applications. This article is aimed to review the characteristics of hierarchical structures and the mechanical properties of two kinds of crossed-lamellar structures, and further summarize the latest advances and biomimetic applications based on the unique crossed-lamellar structures. Copyright © 2017 Elsevier Ltd. All rights reserved.

16,000 Years of Tropical Eastern Ocean Climate Variability Recorded in a Speleothem From Sumatra, Indonesia

Science.gov (United States)

Wurtzel, J. B.; Abram, N.; Hantoro, W. S.; Rifai, H.; Hellstrom, J. C.; Heslop, D.; Troitzsch, U.; Eggins, S.

2015-12-01

Holocene climate variability in the Indo-Pacific has largely been inferred from sediment cores primarily from the central and eastern Warm Pool region. A limited number of speleothem oxygen-isotope records have provided decadally-resolved time-series of past rainfall variability over the central Indo-Pacific Warm Pool region, however no records currently exist for the Indian Ocean sector of the IPWP. Here we present the first continuous, high-resolution (~15year) speleothem record from the eastern tropical Indian Ocean, collected from central western Sumatra, Indonesia. Petrographic and geochemical analysis reveals that the sample is primarily composed of aragonite but is punctuated by intervals of primary calcite growth. In addition to Raman spectroscopy, trace element analysis by laser ablation ICP-MS reveals strongly antiphased behaviour between magnesium and strontium, attributed to the strong preference of those elements for the calcite and aragonite lattices, respectively. This relationship is utilized to develop a quantitative correction for the stable isotope fractionation offset between the two calcium carbonate polymorphs identified in the speleothem. The corrected oxygen isotope record shows a rapid transition from drier conditions during the Younger Dryas (YD) into a wetter Holocene, similar in timing and pattern to that recorded in Dongge Cave, China. This is strikingly different from other IPWP speleothem records, which show no YD or a wetter YD, suggesting that different mechanisms may be controlling rainfall amount in the eastern tropical Indian Ocean. These disparate responses are further explored through proxy-model comparison.

Decadal variability of Subtropical Mode Water subduction and its impact on biogeochemistry

Science.gov (United States)

Oka, E.; Qiu, B.; Takatani, Y.; Enyo, K.; Sasano, D.; Kosugi, N.; Ishii, M.; Nakano, T.; Suga, T.

2016-02-01

Temperature and salinity data from Argo profiling floats during 2005-2014 were analyzed to examine the decadal variability of the North Pacific Subtropical Mode Water (STMW) in relation to that of the Kuroshio Extension (KE) system. The formation volume of STMW in the southern recirculation gyre of KE in the cooling season was larger during the stable KE period after 2010 than the unstable KE period of 2006-2009 by 50%. As a result, the volume and spatial extent of STMW increased (decreased) in the formation region during the stable (unstable) KE period, as well as in the southern, downstream region with a time lag of 1-2 years. The decadal expansion and contraction of STMW were also detected by shipboard observations conducted routinely in the most downstream region near the western boundary, in terms of not only physical but also biogeochemical parameters. After 2010, enhanced subduction of STMW consistently increased dissolved oxygen, pH, and aragonite saturation state and decreased potential vorticity, apparent oxygen utilization, nitrate, and dissolved inorganic carbon, among which changes of dissolved inorganic carbon, pH, and aragonite saturation state were against their long-term trends. These results indicate a new mechanism consisting of westward sea surface height anomaly propagation, the KE state transition, and the STMW formation and subduction, by which the climate variability affects physical and biogeochemical structures in the ocean's interior and potentially impacts the surface ocean acidification trend and biological production.

A regression modeling approach for studying carbonate system variability in the northern Gulf of Alaska

Science.gov (United States)

Evans, Wiley; Mathis, Jeremy T.; Winsor, Peter; Statscewich, Hank; Whitledge, Terry E.

2013-01-01

northern Gulf of Alaska (GOA) shelf experiences carbonate system variability on seasonal and annual time scales, but little information exists to resolve higher frequency variability in this region. To resolve this variability using platforms-of-opportunity, we present multiple linear regression (MLR) models constructed from hydrographic data collected along the Northeast Pacific Global Ocean Ecosystems Dynamics (GLOBEC) Seward Line. The empirical algorithms predict dissolved inorganic carbon (DIC) and total alkalinity (TA) using observations of nitrate (NO3-), temperature, salinity and pressure from the surface to 500 m, with R2s > 0.97 and RMSE values of 11 µmol kg-1 for DIC and 9 µmol kg-1 for TA. We applied these relationships to high-resolution NO3- data sets collected during a novel 20 h glider flight and a GLOBEC mesoscale SeaSoar survey. Results from the glider flight demonstrated time/space along-isopycnal variability of aragonite saturations (Ωarag) associated with a dicothermal layer (a cold near-surface layer found in high latitude oceans) that rivaled changes seen vertically through the thermocline. The SeaSoar survey captured the uplift to aragonite saturation horizon (depth where Ωarag = 1) shoaled to a previously unseen depth in the northern GOA. This work is similar to recent studies aimed at predicting the carbonate system in continental margin settings, albeit demonstrates that a NO3--based approach can be applied to high-latitude data collected from platforms capable of high-frequency measurements.

Plastic deformation in nano-scale multilayer materials — A biomimetic approach based on nacre

Energy Technology Data Exchange (ETDEWEB)

Lackner, Juergen M., E-mail: juergen.lackner@joanneum.at [JOANNEUM RESEARCH Forschungsges.m.b.H., Institute for Surface Technologies and Photonics, Functional Surfaces, Leobner Strasse 94, A-8712 Niklasdorf (Austria); Waldhauser, Wolfgang [JOANNEUM RESEARCH Forschungsges.m.b.H., Institute for Surface Technologies and Photonics, Functional Surfaces, Leobner Strasse 94, A-8712 Niklasdorf (Austria); Major, Boguslaw; Major, Lukasz [Polish Academy of Sciences, Institute of Metallurgy and Materials Sciences, IMIM-PAN, ul. Reymonta 25, PL-30059 Krakow (Poland); Kot, Marcin [University of Science and Technology, AGH, Aleja Adama Mickiewicza 30, 30-059 Krakow (Poland)

2013-05-01

The paper reports about a biomimetic based comparison of deformation in magnetron sputtered multilayer coatings based on titanium (Ti), titanium nitride (TiN) and diamond-like carbon (DLC) layers and the deformation mechanisms in nacre of mollusc shells. Nacre as highly mineralized tissue combines high stiffness and hardness with high toughness, enabling resistance to fracture and crack propagation during tensile loading. Such behaviour is based on a combination of load transmission by tensile stressed aragonite tablets and shearing in layers between the tablets. Shearing in these polysaccharide and protein interlayers demands hydrated conditions. Otherwise, nacre has similar brittle behaviour to aragonite. To prevent shear failure, shear hardening occurs by progressive tablet locking due to wavy dovetail-like surface geometry of the tablets. Similar effects by shearing and strain hardening mechanisms were found for Ti interlayers between TiN and DLC layers in high-resolution transmission electron microscopy studies, performed in deformed zones beneath spherical indentations. 7 nm thin Ti films are sufficient for strong toughening of the whole multi-layered coating structure, providing a barrier for propagation of cracks, starting from tensile-stressed, hard, brittle TiN or DLC layers. - Highlights: • Biomimetic approach to TiN-diamond-like carbon (DLC) multilayers by sputtering • Investigation of deformation in/around hardness indents by HR-TEM • Plastic deformation with shearing in 7-nm thick Ti interlayers in TiN–DLC multilayers • Biomimetically comparable to nacre deformation.

Identification of carbonates as additives in pressure-sensitive adhesive tape substrate with Fourier transform infrared spectroscopy (FTIR) and its application in three explosive cases.

Science.gov (United States)

Lv, Jungang; Feng, Jimin; Zhang, Wen; Shi, Rongguang; Liu, Yong; Wang, Zhaohong; Zhao, Meng

2013-01-01

Pressure-sensitive tape is often used to bind explosive devices. It can become important trace evidence in many cases. Three types of calcium carbonate (heavy, light, and active CaCO(3)), which were widely used as additives in pressure-sensitive tape substrate, were analyzed with Fourier transform infrared spectroscopy (FTIR) in this study. A Spectrum GX 2000 system with a diamond anvil cell and a deuterated triglycine sulfate detector was employed for IR observation. Background was subtracted for every measurement, and triplicate tests were performed. Differences in positions of main peaks and the corresponding functional groups were investigated. Heavy CaCO(3) could be identified from the two absorptions near 873 and 855/cm, while light CaCO(3) only has one peak near 873/cm because of the low content of aragonite. Active CaCO(3) could be identified from the absorptions in the 2800-2900/cm region because of the existence of organic compounds. Tiny but indicative changes in the 878-853/cm region were found in the spectra of CaCO(3) with different content of aragonite and calcite. CaCO(3) in pressure-sensitive tape, which cannot be differentiated by scanning electron microscope/energy dispersive X-ray spectrometer and thermal analysis, can be easily identified using FTIR. The findings were successfully applied to three specific explosive cases and would be helpful in finding the possible source of explosive devices in future cases. © 2012 American Academy of Forensic Sciences.

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.

Mineralogical assemblages forming at hyperalkaline warm springs hosted on ultramafic rocks: A case study of Oman and Ligurian ophiolites

Science.gov (United States)

Chavagnac, Valérie; Ceuleneer, Georges; Monnin, Christophe; Lansac, Benjamin; Hoareau, Guilhem; Boulart, Cédric

2013-07-01

We report on the mineralogical assemblages found in the hyperalkaline springs hosted on Liguria and Oman ophiolites based on exhaustive X-ray diffraction and scanning electron microprobe analyses. In Liguria, hyperalkaline springs produce a thin brownish calcite precipitate that covers the bedrock due to the concomitant atmospheric CO2 uptake and neutralization of the hyperalkaline waters. No brucite and portlandite minerals are observed. The discharge of alkaline waters in Oman ophiolite forms white-orange precipitates. Calcium carbonate minerals (calcite and/or aragonite) are the most abundant and ubiquitous precipitates and are produced by the same mechanism as in Liguria. This process is observed as a thin surface crust made of rhombohedral calcite. Morphological features of aragonite vary from needle-, bouquet-, dumbbell-, spheroidal-like habitus according to the origin of carbon, temperature, and ionic composition of the hyperalkaline springs, and the biochemical and organic compounds. Brucite is observed both at hyperalkaline springs located at the thrust plane and at the paleo-Moho. The varying mixing proportions between the surface runoff waters and the hyperalkaline ones control brucite precipitation. The layered double hydroxide minerals occur solely in the vicinity of hyperalkaline springs emerging within the bedded gabbros. Finally, the dominant mineralogical associations we found in Oman (Ca-bearing carbonates and brucite) in a serpentinizing environment driven by the meteoric waters are surprisingly the same as those observed at the Lost City hydrothermal site in a totally marine environment.

Mixed oceanic and freshwater depositional conditions for beach rocks of NE Brazil: Evidence from C and O isotopes

International Nuclear Information System (INIS)

Chaves, Nubia S.; Kiang, Chang H.

1998-01-01

Full text: Beach rocks, a common feature of northeastern coastline of Brazil are formed in the inter tidal zone, considered as ancient coastal line, cemented by CaCO 3 which have variable extension. They occur parallel to the coastline as linear ridges. Beach rocks are sub horizontally disposed and surfaces are irregular, displacing potholes due to differential erosion, perforations by organisms, diaclasis, cross stratification and rare laminations. The dominant detrital components are quartz and minor fractions of feldspars and rock fragments. Zircon, epi dote, hornblende, garnet, muscovite, rutile, opaque and sillimanite are present in trace quantity. Bivalves, mollusks, gastropods, halimeda, corals, pelecipods and equinoids, constitute the biotic components. Beach rocks cement vary from aragonite to Mg-calcite. The dominant micro facies, consists of isopach crystals of aragonite, enclosing bioclastic and/or clastic grains forming uniform fringe formed in the marine phreatic zone. The second is represented by cryptocrystalline inter-granulate cement like micritic envelop formed in meteoric phreatic environment (Moore 1971). The third is formed by inter granulate cryptocrystalline cement, filling the pores. Beach rock samples locate in the coastal zone show an interval with depleted C and O ratios (average δ 13 C = -1.3%0, δ 18 O = -2.1%0) and an interval of enriched isotopic ratios (average δ 13 C = +3.5%0, δ 18 O +1.2%0). Depleted oxygen isotope values considered to be indicative of meteoric diagenesis with minor freshwater influx (Allan and Mattew 1982). (author)

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...... fields. In order to fulfill their roles in organisms, biominerals have strictly controlled physical and chemical properties. Transmission electron microscopy (TEM) is ideally suited for the study of the structures, arrangements, compositions, morphologies, crystallographic orientations, crystallographic...... minerals that form in the cells of magnetotactic bacteria....

Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs)

DEFF Research Database (Denmark)

Muchitsch, Nanna; Nooten, Thomas Van; Bastiaens, Leen

2011-01-01

An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important...... performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples...

Lyoluminescence of calcium carbonate and possible applications in the dating of loess and soils

International Nuclear Information System (INIS)

Copty-Wergles, K.; Nowotny, R.; Hille, P.

1990-01-01

Lyoluminescence (LL) during the dissolution in HCl of calcite and aragonite snail shells irradiated with 60 Co γ rays was investigated. In the dose range of 100 to 3000 Gy the LL response of analytical grade calcite powder samples is sub-linear but shows no saturation. The influence of solvent concentration, temperature and of dissolved nitrogen on LL yield was studied. The traps responsible for LL are not stable under illumination. Annealing experiments indicate the existence of several different traps and the possibility of electron transfer between them. (author)

Fish age validation by radiometric analysis of otoliths

International Nuclear Information System (INIS)

Fenton, G.E.

1992-01-01

Radiochemical analysis of aragonitic fish otoliths provides a useful approach to validating ages obtained by more common methods. The history of applications of radiometry using short-lived natural isotopes to clams, Nautilus, living corals and fish otoliths is briefly reviewed. The biogeochemical assumptions required for successful use of these techniques are discussed, and the appropriate mathematical treatments required for data analysis are outlined. Novel normalization techniques designed to widen the validity of this approach are proposed. Desirable lines of further research are also briefly discussed. 38 refs., 1 tab

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.

On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy.

Science.gov (United States)

Nebel, Holger; Neumann, Markus; Mayer, Christian; Epple, Matthias

2008-09-01

The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.

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.

Comparisons of multiple isotope systems in the aragonitic shells of cultured Arctica islandica clams

Science.gov (United States)

Liu, Y. W.; Aciego, S.; Wanamaker, A. D.

2014-12-01

Previous work using oxygen and stable carbon isotopes from Arctica islandica shells has shown that this archive can provide information on past seawater temperatures, carbon cycling and ocean circulation. However, relatively less attention has been devoted to other "non-traditional" isotope systems within this proxy archive. In this study, we report the boron (δ11B) and strontium isotopic values (87Sr/86Sr and δ88/86Sr) from A. islandicashells collected and cultured from the Gulf of Maine. The long-lived ocean quahog, A. islandica was collected and cultured in the Gulf of Maine for 8 months. Our high-resolution δ11B records from the experiment show 5-7‰ of increase through the culture, with low values from January to May and higher values after May. The 87Sr/86Sr ratios from both tank water and shell samples suggest that the shell material reflects ambient ocean chemistry without interferences from terrestrial sources. Although It has been suggested that stable Sr isotopic ratios (δ88/86Sr) in biogenic carbonates are influenced by the temperature of the precipitating fluid, our nearly identical δ88/86Sr data do not support this hypothesis despite a 15 °C temperature change during the experiment. Based on the in-situ measurements of culture seawater temperature, salinity and pH, and two commonly used fractionation factors (α3-4) for corals and forams, we predicted the range in shell δ11B values for the experiment. Our boron results are at the extreme ends of the two prediction lines suggesting the potential usage of the bivalve shells as seawater pH indicator. However, the wider range in δ11B in this experiment than the predictions based on other carbonate organisms (only 2 to 3‰) suggests that a species-specific fractionation factor may be required. Recent work from an additional constant temperature experiment (10 and 15 °C) in the Gulf of Maine will allow us to further evaluate temperature influences and potential vital effects on the shell boron isotope values.

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 carbonates. Furthermore, the severity of the temperature effects on gross dissolution rates also varied with respect to carbonate polymorph solubility, with warming (10-25 °C) exerting the greatest effect on biogenic high-Mg calcite, an intermediate effect on biogenic aragonite, and the least effect on biogenic low-Mg calcite. These results indicate that both ocean acidification and warming will lead to increased dissolution of biogenic carbonates in future oceans, with shells/skeletons composed of the more

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

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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.

Fishnet model for failure probability tail of nacre-like imbricated lamellar materials

Science.gov (United States)

Luo, Wen; Bažant, Zdeněk P.

2017-12-01

Nacre, the iridescent material of the shells of pearl oysters and abalone, consists mostly of aragonite (a form of CaCO3), a brittle constituent of relatively low strength (≈10 MPa). Yet it has astonishing mean tensile strength (≈150 MPa) and fracture energy (≈350 to 1,240 J/m2). The reasons have recently become well understood: (i) the nanoscale thickness (≈300 nm) of nacre's building blocks, the aragonite lamellae (or platelets), and (ii) the imbricated, or staggered, arrangement of these lamellea, bound by biopolymer layers only ≈25 nm thick, occupying engineering applications, however, the failure probability of ≤10-6 is generally required. To guarantee it, the type of probability density function (pdf) of strength, including its tail, must be determined. This objective, not pursued previously, is hardly achievable by experiments alone, since >10^8 tests of specimens would be needed. Here we outline a statistical model of strength that resembles a fishnet pulled diagonally, captures the tail of pdf of strength and, importantly, allows analytical safety assessments of nacreous materials. The analysis shows that, in terms of safety, the imbricated lamellar structure provides a major additional advantage—˜10% strength increase at tail failure probability 10^-6 and a 1 to 2 orders of magnitude tail probability decrease at fixed stress. Another advantage is that a high scatter of microstructure properties diminishes the strength difference between the mean and the probability tail, compared with the weakest link model. These advantages of nacre-like materials are here justified analytically and supported by millions of Monte Carlo simulations.

Low coral cover in a high-CO2 world

Science.gov (United States)

Hoegh-Guldberg, Ove

2005-09-01

Coral reefs generally exist within a relatively narrow band of temperatures, light, and seawater aragonite saturation states. The growth of coral reefs is minimal or nonexistent outside this envelope. Climate change, through its effect on ocean temperature, has already had an impact on the world's coral reefs, with almost 30% of corals having disappeared since the beginning of the 1980s. Abnormally warm temperatures cause corals to bleach (lose their brown dinoflagellate symbionts) and, if elevated for long enough, to die. Increasing atmospheric CO2 is also potentially affecting coral reefs by lowering the aragonite saturation state of seawater, making carbonate ions less available for calcification. The synergistic interaction of elevated temperature and CO2 is likely to produce major changes to coral reefs over the next few decades and centuries. Known tolerances of corals to projected changes to sea temperatures indicate that corals are unlikely to remain abundant on reefs and could be rare by the middle of this century if the atmospheric CO2 concentration doubles or triples. The combination of changes to sea temperature and carbonate ion availability could trigger large-scale changes in the biodiversity and function of coral reefs. The ramifications of these changes for the hundred of millions of coral reef-dependent people and industries living in a high-CO2 world have yet to be properly defined. The weight of evidence suggests, however, that projected changes will cause major shifts in the prospects for industries and societies that depend on having healthy coral reefs along their coastlines.

Estimating carbonate parameters from hydrographic data for the intermediate and deep waters of the Southern Hemisphere oceans

Science.gov (United States)

Bostock, H. C.; Mikaloff Fletcher, S. E.; Williams, M. J. M.

2013-10-01

Using ocean carbon data from global datasets, we have developed several multiple linear regression (MLR) algorithms to estimate alkalinity and dissolved inorganic carbon (DIC) in the intermediate and deep waters of the Southern Hemisphere (south of 25° S) from only hydrographic data (temperature, salinity and dissolved oxygen). A Monte Carlo experiment was used to identify a potential density (σθ) of 27.5 as an optimal break point between the two regimes with different MLR algorithms. The algorithms provide a good estimate of DIC (R2=0.98) and alkalinity (R2=0.91), and excellent agreement for aragonite and calcite saturation states (R2=0.99). Combining the algorithms with the CSIRO Atlas of Regional Seas (CARS), we have mapped the calcite saturation horizon (CSH) and aragonite saturation horizon (ASH) for the Southern Ocean at a spatial resolution of 0.5°. These maps are more detailed and more consistent with the oceanography than the previously gridded GLODAP data. The high-resolution ASH map reveals a dramatic circumpolar shoaling at the polar front. North of 40° S the CSH is deepest in the Atlantic (~ 4000 m) and shallower in the Pacific Ocean (~ 2750 m), while the CSH sits between 3200 and 3400 m in the Indian Ocean. The uptake of anthropogenic carbon by the ocean will alter the relationships between DIC and hydrographic data in the intermediate and deep waters over time. Thus continued sampling will be required, and the MLR algorithms will need to be adjusted in the future to account for these changes.

Estimating carbonate parameters from hydrographic data for the intermediate and deep waters of the Southern Hemisphere oceans

Directory of Open Access Journals (Sweden)

H. C. Bostock

2013-10-01

Full Text Available Using ocean carbon data from global datasets, we have developed several multiple linear regression (MLR algorithms to estimate alkalinity and dissolved inorganic carbon (DIC in the intermediate and deep waters of the Southern Hemisphere (south of 25° S from only hydrographic data (temperature, salinity and dissolved oxygen. A Monte Carlo experiment was used to identify a potential density (σθ of 27.5 as an optimal break point between the two regimes with different MLR algorithms. The algorithms provide a good estimate of DIC (R2=0.98 and alkalinity (R2=0.91, and excellent agreement for aragonite and calcite saturation states (R2=0.99. Combining the algorithms with the CSIRO Atlas of Regional Seas (CARS, we have mapped the calcite saturation horizon (CSH and aragonite saturation horizon (ASH for the Southern Ocean at a spatial resolution of 0.5°. These maps are more detailed and more consistent with the oceanography than the previously gridded GLODAP data. The high-resolution ASH map reveals a dramatic circumpolar shoaling at the polar front. North of 40° S the CSH is deepest in the Atlantic (~ 4000 m and shallower in the Pacific Ocean (~ 2750 m, while the CSH sits between 3200 and 3400 m in the Indian Ocean. The uptake of anthropogenic carbon by the ocean will alter the relationships between DIC and hydrographic data in the intermediate and deep waters over time. Thus continued sampling will be required, and the MLR algorithms will need to be adjusted in the future to account for these changes.

Direct dating of fossils by the helium-uranium method

International Nuclear Information System (INIS)

Schaeffer, O.A.

1967-01-01

The He-U method has been found to be applicable to the dating of fossil carbonates. This method furnishes a new dating technique particularly applicable to the Pleistocene and the Tertiary periods, especially the Late Tertiary, for which other methods of age dating either fail or are difficult to correlate with the fossil record. The method has been checked for possible losses of helium and uranium from or to the surroundings. It has been found that, while a calcite lattice does not appear to retain helium, if the lattice is aragonite there is good evidence that helium leakage is not a problem. This is true at least for times up to 20 m. y. For corals where the uranium is apparently uniformly distributed within the lattice as a trace element, the uranium does not exchange or undergo concentration changes. As a result aragonite corals yield reliable He-U ages. On the other hand, the uranium in mollusc fossils is apparently mainly in the grain boundaries and is not always a tight system as far as uranium exchange or concentration changes are concerned. To obtain a reliable age for a mollusc one needs additional evidence to ensure lack of changes in uranium concentration. If the measurement of U and He is combined with 238 U, 234 U and 230 Th determinations, it appears that many mollusc shells will also be datable by the method. The resulting evidence for secular equilibrium in the 238 U chain is good evidence for a closed system as far as U concentration changes are concerned. (author)

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.

Skeletal carbonate mineralogy of Scottish bryozoans

Science.gov (United States)

Spencer Jones, Mary; Najorka, Jens; Smith, Abigail M.

2018-01-01

This paper describes the skeletal carbonate mineralogy of 156 bryozoan species collected from Scotland (sourced both from museum collections and from waters around Scotland) and collated from literature. This collection represents 79% of the species which inhabit Scottish waters and is a greater number and proportion of extant species than any previous regional study. The study is also of significance globally where the data augment the growing database of mineralogical analyses and offers first analyses for 26 genera and four families. Specimens were collated through a combination of field sampling and existing collections and were analysed by X-ray diffraction (XRD) and micro-XRD to determine wt% MgCO3 in calcite and wt% aragonite. Species distribution data and phylogenetic organisation were applied to understand distributional, taxonomic and phylo-mineralogical patterns. Analysis of the skeletal composition of Scottish bryozoans shows that the group is statistically different from neighbouring Arctic fauna but features a range of mineralogy comparable to other temperate regions. As has been previously reported, cyclostomes feature low Mg in calcite and very little aragonite, whereas cheilostomes show much more variability, including bimineralic species. Scotland is a highly variable region, open to biological and environmental influx from all directions, and bryozoans exhibit this in the wide range of within-species mineralogical variability they present. This plasticity in skeletal composition may be driven by a combination of environmentally-induced phenotypic variation, or physiological factors. A flexible response to environment, as manifested in a wide range of skeletal mineralogy within a species, may be one characteristic of successful invasive bryozoans. PMID:29897916

Preparation and Characterization of Microfiltration Ceramic Membranes Based on Natural Quartz Sand

Directory of Open Access Journals (Sweden)

Andrei Ivanets

2017-06-01

Full Text Available The effect of phase and chemical composition of natural quartz sand, binder and burnable additives was studied. The conditions of application of the membrane and biocide layers on the formation of porous ceramic and microfiltration membranes were investigated. It is shown that a crystalline oxide of Si(IV is determinant for obtaining the ceramic materials. The presence of carbonates (calcite, dolomite, aragonite, etc. and crystalline aluminosilicates (microcline, albite, phlogopit, etc. leads to a decrease in mechanical strength of ceramics. The biocide coating designed to protect the ceramic membrane surfaces from biofouling was applied and its anti-bacterial activity was shown.

Gas dusulfurization

International Nuclear Information System (INIS)

Powell, B.E.; Bakhshi, V.S.; Randolph, D.A.

1984-01-01

A process for adsorbing sulfur dioxide from a gas comprising contacting a gas containing SO 2 , such as a flue gas, with about stoichiometric amounts of a specially prepared calcium oxide so that substantially all of the sulfur dioxide content is reacted throughout the calcium oxide particle to form a calcium sulfate reaction product. The useful calcium oxide particles comprise a highly voided skeletal structure of very large surface area and large pore volume with numerous macro pores. Such particles are obtained by flash calcining sand-size grains of calcium carbonate, such as aragonite, calcite or dolomite

Mg and Ca isotope fractionation during CaCO3 biomineralisation

International Nuclear Information System (INIS)

Chang, Veronica T.-C.; Williams, R.J.P.; Makishima, Akio; Belshawl, Nick S.; O'Nions, R. Keith

2004-01-01

The natural variation of Mg and Ca stable isotopes of carbonates has been determined in carbonate skeletons of perforate foraminifera and reef coral together with Mg/Ca ratios to assess the influence of biomineralisation processes. The results for coral aragonite suggest its formation, in terms of stable isotope behaviour, approximates to inorganic precipitation from a seawater reservoir. In contrast, results for foraminifera calcite suggest a marked biological control on Mg isotope ratios presumably related to its low Mg content compared with seawater. The bearing of these observations on the use of Mg and Ca isotopes as proxies in paleoceanography is considered

Morphology and Kinetics of Growth of CaCO3 Precipitates Formed in Saline Water at 30°C

Science.gov (United States)

Sui, Xin; Wang, Baohui; Wu, Haiming

2018-02-01

The crystallization kinetics and morphology of CaCO3 crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO3 crystal lattice. The morphology of CaCO3 precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).

Comparison of 230Th/234U Dating Results Obtained on Fossil Mollusk Shell from Morocco and Fossil Coral Samples from Egypt. Research of Methodological Criteria to Valid the Measured Age

International Nuclear Information System (INIS)

Choukri, A.; Hakam, O.K.; Reyss, J.L.

2013-01-01

Radiochemical ages of 126 unrecrystallized coral samples from the Egyptian shoreline and 125 fossil mollusk shell samples from the Atlantic coast of Moroccan High Atlas are discussed.For corals, the obtained ages are in good agreement with the ages reported previously on urecristallized corals except in some sites where some samples are affected by a cementation of younger aragonite.For mollusk shells, the obtained ages are in the most of cases, rejuvenated.This rejuvenation is due eventually to a post-incorporation of secondary uranium that is responsible of the wide dispersion of apparent ages of mollusk shells.

Contrasting Impact of Future CO2 Emission Scenarios on the Extent of CaCO3 Mineral Undersaturation in the Humboldt Current System

Science.gov (United States)

Franco, A. C.; Gruber, N.; Frölicher, T. L.; Kropuenske Artman, L.

2018-03-01

The eastern boundary upwelling systems are among those regions that are most vulnerable to an ocean acidification-induced transition toward undersaturated conditions with respect to mineral CaCO3, but no assessment exists yet for the Humboldt Current System. Here we use a high-resolution (˜7.5 km) regional ocean model to investigate past and future changes in ocean pH and CaCO3 saturation state in this system. We find that within the next few decades, the nearshore waters off Peru are projected to become corrosive year round with regard to aragonite, the more soluble form of CaCO3. The volume of aragonite undersaturated water off Peru will continue to increase in the future irrespective of the amount of CO2 emitted to the atmosphere. In contrast, the development of the saturation state with regard to calcite, a less soluble form of carbonate, depends strongly on the scenario followed. By 2050, calcite undersaturation appears in the nearshore waters off Peru occasionally, but by 2090 in a high-emission scenario (RCP8.5), ˜60% of the water in the euphotic zone will become permanently calcite undersaturated. Most of this calcite undersaturation off Peru can likely be avoided if a low emission scenario (RCP2.6) consistent with the Paris Agreement is followed. The progression of ocean acidification off Chile follows a similar pattern, except that the saturation states are overall higher. But also here, calcite undersaturated waters will become common in the subsurface waters under the RCP8.5 scenario by the end of this century, while this can be avoided under the RCP2.6 scenario.

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, Robert 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.

Quantifying the influence of CO2 seasonality on future ocean acidification

Science.gov (United States)

Sasse, T. P.; McNeil, B. I.; Matear, R. J.; Lenton, A.

2015-04-01

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.

CO2-driven compromises to marine life along the Chilean coast

Science.gov (United States)

Mayol, E.; Ruiz-Halpern, S.; Duarte, C. M.; Castilla, J. C.; Pelegrí, J. L.

2010-12-01

CO2-driven compromises to marine life were examined along the Chilean sector of the Humboldt Current System, a particularly vulnerable hypoxic and upwelling area, applying the Respiration index (RI = log10 pO2) and the pH-dependent aragonite saturation (Ω) to delineate the water masses where aerobic and calcifying organisms are stressed. There was a remarkable negative relationship between oxygen concentration and pH or pCO2 in the studied area, with the subsurface hypoxic Equatorial Subsurface Waters extending from 100 m to about 300 m depth and supporting elevated pCO2 values. The RI reached a minimum at about 200 m depth and decreased towards the Equator. Increased pCO2 in the hypoxic water layer reduced the RI values by as much as 0.59 RI units, with the upper water layer that presents conditions suitable for aerobic life (RI>0.7) declining by half between 42° S and 28° S. The intermediate waters hardly reached those stations closer to the equator so that the increased pCO2 lowered pH and the saturation of aragonite. A significant fraction of the water column along the Chilean sector of the Humboldt Current System suffers from CO2-driven compromises to biota, including waters corrosive to calcifying organisms, stress to aerobic organisms or both. The habitat free of CO2-driven stresses was restricted to the upper mixed layer and to small water parcels at about 1000 m depth. pCO2 acts as a hinge connecting respiratory and calcification challenges expected to increase in the future, resulting in a spread of the challenges to aerobic organisms.

A biomineralization study of the Indo-Pacific giant clam Tridacna gigas

Science.gov (United States)

Gannon, M. E.; Pérez-Huerta, A.; Aharon, P.; Street, S. C.

2017-06-01

The giant clam, Tridacna gigas, is an important faunal component of reef ecosystems of the Indo-Pacific region. In addition to its ecological role, shells of this bivalve species are useful bioarchives for past climate and environmental reconstructions. However, the biomineralization processes involved in shell aragonite deposition are insufficiently understood. Here, we present a study of the shell microstructure of modern specimens from Palm Island, Great Barrier Reef (GBR), Australia, and Huon Peninsula, Papua New Guinea (PNG), using a combination of petrography, scanning electron microscopy, electron backscatter diffraction, Raman spectroscopy and stable carbon isotope ratios. Daily growth increments were recognizable in all specimens through ontogeny, and counting these growth lines provides a robust specimen age estimate. For the internal layers, paired increments of organized aragonitic needles and compact, oblong crystals were recognized in a specimen from PNG, whereas specimens from GBR were composed of shield-like crystals that were not definable at the microscale. The combination of nutrient availability, rainfall and solar irradiance are likely to be the most significant factors controlling shell growth and may explain the observed differences in microstructure. The external layer, identical in all specimens, was composed of dendritic microstructure that is significantly enriched in 13C compared to the internal layer, suggesting different metabolic controls on layer deposition. We propose that the mineralization of the internal and external layers is independent from each other and associated with the activity of specific mantles. Future studies using T. gigas shells as bioarchives should consider the microstructure as it reflects the environment in which the individual lived and the differences in mineralization pathways of internal and external layers.

Earth system commitments due to delayed mitigation

International Nuclear Information System (INIS)

Pfister, Patrik L; Stocker, Thomas F

2016-01-01

As long as global CO 2 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. (letter)

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

Desiccator Volume: A Vital Yet Ignored Parameter in CaCO3 Crystallization by the Ammonium Carbonate Diffusion Method

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Joe Harris

2017-07-01

Full Text Available Employing the widely used ammonium carbonate diffusion method, we demonstrate that altering an extrinsic parameter—desiccator size—which is rarely detailed in publications, can alter the route of crystallization. Hexagonally packed assemblies of spherical magnesium-calcium carbonate particles or spherulitic aragonitic particles can be selectively prepared from the same initial reaction solution by simply changing the internal volume of the desiccator, thereby changing the rate of carbonate addition and consequently precursor formation. This demonstrates that it is not merely the quantity of an additive which can control particle morphogenesis and phase selectivity, but control of other often ignored parameters are vital to ensure adequate reproducibility.

Study by X-ray diffraction of the crystalline structure versus time of a radioactive implanted coral and of a non radioactive implanted coral

International Nuclear Information System (INIS)

Irigaray, J.L.; Oudadesse, H.; Sauvage, T.; El Fadl, H.

1993-01-01

The corals used as biomaterials in bone surgery consist of 98% calcium carbonate in the form of aragonite and have orthorhombic crystalline structure. This structure changes progressively into a bone structure in an hexagonal form when the coral is implanted in cortical or spongy surroundings. For this experiment, a radioactive and a non radioactive coral have been implanted in the metaphysics of the ovine femur. The transformation of the orthorhombic structure into the hexagonal bone structure has been studied for the two types of implant. This makes it possible to verify if radioactivity modifies the process of transformation of the implanted biocoral. (K.A.) 3 refs.; 7 figs

Synthesis of Eu3+-doped calcium and strontium carbonate phosphors at room temperature

International Nuclear Information System (INIS)

Pan Yuexiao; Wu Mingmei; Su Qiang

2003-01-01

Red phosphors CaCO 3 :Eu 3+ and SrCO 3 :Eu 3+ have been prepared by co-precipitation with ammonium bicarbonate (NH 4 HCO 3 ) at room temperature. Pure calcite CaCO 3 can be obtained by prolonging the reaction time at 220 deg. C and it decomposes to cubic CaO at 1000 deg. C. Trivalent Eu 3+ acts as a luminescent probe to determine both the calcite and the mixed phase of calcite and vaterite phase of CaCO 3 host and to analyze its decomposition process. High temperature sintering improved both the crystallization and luminescence of SrCO 3 :Eu 3+ in aragonite phase

Study by X-ray diffraction of the crystalline structure versus time of a radioactive implanted coral and of a non radioactive implanted coral

Energy Technology Data Exchange (ETDEWEB)

Irigaray, J.L.; Oudadesse, H.; Sauvage, T.; El Fadl, H. [Clermont-Ferrand-2 Univ., 63 - Aubiere (France). Lab. de Physique Corpusculaire; Lefevre, J.; Barlet, J.P. [Institut National de Recherches Agronomiques, 63 -Saint-Genes-Champanelle (France)

1993-12-31

The corals used as biomaterials in bone surgery consist of 98% calcium carbonate in the form of aragonite and have orthorhombic crystalline structure. This structure changes progressively into a bone structure in an hexagonal form when the coral is implanted in cortical or spongy surroundings. For this experiment, a radioactive and a non radioactive coral have been implanted in the metaphysics of the ovine femur. The transformation of the orthorhombic structure into the hexagonal bone structure has been studied for the two types of implant. This makes it possible to verify if radioactivity modifies the process of transformation of the implanted biocoral. (K.A.) 3 refs.; 7 figs.

Evaluating Zeta Potential and the Calcite/Aragonite Ratio as Potential Success Indicators for Magnetic Water Treatment

National Research Council Canada - National Science Library

Lambert, Kevin

1999-01-01

The potential benefits of anti-scale magnetic treatment (AMT) are not realized or reliably predicted because the factors measuring performance of magnetic treatment have either not been identified or are poorly defined...

Effect of permethrin, anthracene and mixture exposure on shell components, enzymatic activities and proteins status in the Mediterranean clam Venerupis decussata

International Nuclear Information System (INIS)

Sellami, Badreddine; Khazri, Abdelhafidh; Mezni, Amine; Louati, Héla; Dellali, Mohamed; Aissa, Patricia; Mahmoudi, Ezzeddine; Beyrem, Hamouda; Sheehan, David

2015-01-01

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

Diagenetic pathways in deposits of cool- and cold-water carbonate factories

Science.gov (United States)

Frank, T. D.; James, N. P.

2017-12-01

This investigation integrates sedimentological, petrographic, and geochemical observations from modern and ancient heterozoan carbonate deposits that formed at temperate to polar latitudes with the aim of evaluating diagenetic pathways characteristic of these systems. These factories operate under conditions distinct from those of photozoan counterparts. Lower temperatures, higher trophic resources, lower carbonate saturation states, and strong seasonality govern not only the nature of carbonate communities, but also how deposits translate into the rock record. In these settings, carbonate production is entirely biogenic, assemblages are of low diversity, and there are no significant calcareous phototrophs. Aragonitic taxa may be present in living communities, but allochems rapidly disappear via dissolution. Carbonate producers are not capable of building rigid frameworks, so their deposits accumulate as sands and gravels and are prone to winnowing and reworking. Low production rates lead to long seafloor residence times (1000s of years) for grains, which undergo physical reworking, dissolution, and repeated infestation by endolithic borers. Microborings remain empty, increasing grain susceptibility to disintegration. Intergranular cementation on the seafloor is rare and restricted to hardgrounds. Periods of subaerial exposure do not leave traces of meteoric alteration. Results show that the deposits of heterozoan carbonate factories tend enter the geologic record as taphonomic remnants, namely reworked, unconsolidated sands and gravels with low diagenetic potential. During burial, physical and chemical compaction produce limestones with tightly packed, grain-supported fabrics, often with grains in sutured contact. Significant cementation is associated with the deep burial realm. Results reveal a dramatically different diagenetic pathway than is typical for deposits of tropical photozoan factories, in which significant recrystallization and lithification occur on

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.

Directory of Open Access Journals (Sweden)

Ella L Howes

Full Text Available 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

Carbon–climate feedbacks accelerate ocean acidification

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R. J. Matear

2018-03-01

Full Text Available Carbon–climate feedbacks have the potential to significantly impact the future climate by altering atmospheric CO2 concentrations (Zaehle et al. 2010. By modifying the future atmospheric CO2 concentrations, the carbon–climate feedbacks will also influence the future ocean acidification trajectory. Here, we use the CO2 emissions scenarios from four representative concentration pathways (RCPs with an Earth system model to project the future trajectories of ocean acidification with the inclusion of carbon–climate feedbacks. We show that simulated carbon–climate feedbacks can significantly impact the onset of undersaturated aragonite conditions in the Southern and Arctic oceans, the suitable habitat for tropical coral and the deepwater saturation states. Under the high-emissions scenarios (RCP8.5 and RCP6, the carbon–climate feedbacks advance the onset of surface water under saturation and the decline in suitable coral reef habitat by a decade or more. The impacts of the carbon–climate feedbacks are most significant for the medium- (RCP4.5 and low-emissions (RCP2.6 scenarios. For the RCP4.5 scenario, by 2100 the carbon–climate feedbacks nearly double the area of surface water undersaturated with respect to aragonite and reduce by 50 % the surface water suitable for coral reefs. For the RCP2.6 scenario, by 2100 the carbon–climate feedbacks reduce the area suitable for coral reefs by 40 % and increase the area of undersaturated surface water by 20 %. The sensitivity of ocean acidification to the carbon–climate feedbacks in the low to medium emission scenarios is important because recent CO2 emission reduction commitments are trying to transition emissions to such a scenario. Our study highlights the need to better characterise the carbon–climate feedbacks and ensure we do not underestimate the projected ocean acidification.

Out of their depth? Isolated deep populations of the cosmopolitan coral Desmophyllum dianthus may be highly vulnerable to environmental change.

Directory of Open Access Journals (Sweden)

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.

Out of their depth? Isolated deep populations of the cosmopolitan coral Desmophyllum dianthus may be highly vulnerable to environmental change.

Science.gov (United States)

Miller, Karen J; Rowden, Ashley A; Williams, Alan; Häussermann, Vreni

2011-01-01

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.

Determination of the Anthropogenic Carbon Signal to the Total Change in Dissolved Carbon in the Coastal Upwelling Region Along the Washington-Oregon-California Continental Margin

Science.gov (United States)

Feely, R. A.

2016-02-01

The continental shelf region off the Washington-Oregon-California coast is seasonally exposed to water with a low aragonite saturation state by coastal upwelling of CO2-rich waters. To date, the spatial and temporal distribution of anthropogenic CO2 (Canthro) contribution to the CO2-rich waters is largely unknown. Here we use an adaptation of the linear regression approach described in Feely et al (2008) along with the GO-SHIP Repeat Hydrography data sets from the northeast Pacific to establish an annually updated relationship between Canthro and potential density. This relationship was then used with the NOAA Ocean Acidification Program west coast cruise data sets from 2007, 2011, 2012 and 2013 to determine the spatial variations of Canthro in the upwelled water. Our results show large spatial differences in Canthro in surface waters along the coast with the lowest surface values (40-45 µmol kg-1) in strong upwelling regions of off northern California and southern Oregon and higher values (50-70 µmol kg-1) to the north and south. Canthro contributes an average of about 70% of the increased amount of dissolved inorganic carbon in the upwelled waters at the surface. In contrast, at 50 m the Canthro contribution is approximately 31% and at 100 m it averages about 16%. The remaining contributions are primarily due to respiration processes in the water that was upwelled and transported to coastal regions or underwent respiration processes that occurred locally during the course of the upwelling season. The uptake of Canthro has caused the aragonite saturation horizon to shoal by approximately 30-50 m since preindustrial period so that the undersaturated waters are well within the regions that affect the biological communities on the continental shelf.

Pteropod Ecology and Physiology in Relation to Natural Variability in Carbonate Chemistry

Science.gov (United States)

Lawson, G. L.; Maas, A. E.; Wang, A. Z.; Bergan, A. J.; Wiebe, P. H.; Blanco-Bercial, L.; Lavery, A.; Copley, N. J.

2016-02-01

The thecosomatous pteropods are a group of aragonite-shelled zooplankton thought to be particularly vulnerable to ocean acidification. We seek to gain insight into both basic questions of pteropod biology and potential responses to ocean acidification by combining field sampling with shipboard experimental manipulations, capitalizing on natural spatial variability in modern-day carbonate chemistry between and within the Atlantic and Pacific Oceans. Two cruises were conducted, in 2011 and 2012, along open-ocean transects running between 35 and 50°N in the NW Atlantic and NE Pacific; strong differences in environmental conditions exist between these regions, as well as along the Pacific transect, notably in aragonite compensation and oxygen minimum depths. The transects overlapped with portions of WOCE/CLIVAR lines A20 and P17N and measurements of carbonate chemistry provided insight into rates of chemical change as well as information on the pteropods' chemical environment. The abundance and diversity of pteropods varied substantially within and between the study regions. Depth-stratified net sampling during day and night indicated that multiple pteropod species undertook the typical diel vertical migration employed by many zooplankton species as an anti-predation strategy; the amplitude of this migration differed among species as well as within sub-populations of certain cosmopolitan species found in both oceans. Shipboard experiments of short-duration (<18 hrs, intended to mimic the duration of diel vertical migrations to depth) exposing eight species of pteropod to high CO2 and low O2 found no effect of CO2 alone on metabolic rate and an effect of low O2 or interactive effect of CO2 and O2 only in two Atlantic species not known to naturally encounter low oxygen in their biogeographic range. The implications of these various findings to our understanding of the response of pteropods to environmental change will be discussed.

Spectrophotometric measurement of calcium carbonate saturation states in seawater.

Science.gov (United States)

Easley, Regina A; Patsavas, Mark C; Byrne, Robert H; Liu, Xuewu; Feely, Richard A; Mathis, Jeremy T

2013-02-05

Measurements of ocean pH and carbonate ion concentrations in the North Pacific and Arctic Oceans were used to determine calcium carbonate saturation states (Ω(CaCO(3))) from spectrophotometric methods alone. Total carbonate ion concentrations, [CO(3)(2-)](T), were for the first time at sea directly measured using Pb(II) UV absorbance spectra. The basis of the method is given by the following: [formula see text] where (CO(3))β(1) is the PbCO(3)(0) formation constant, e(i) are molar absorptivity ratios, and R = (250)A/(234)A (ratio of absorbances measured at 250 and 234 nm). On the basis of shipboard and laboratory Pb(II) data and complementary carbon-system measurements, the experimental parameters were determined to be (25 °C) the following: [formula see text]. The resulting mean difference between the shipboard spectrophotometric and conventional determinations of [CO(3)(2-)](T) was ±2.03 μmol kg(-1). The shipboard analytical precision of the Pb(II) method was ∼1.71 μmol kg(-1) (2.28%). Spectrophotometric [CO(3)(2-)](T) and pH(T) were then combined to calculate Ω(CaCO(3)). For the case of aragonite, 95% of the spectrophotometric aragonite saturation states (Ω(Aspec)) were within ±0.06 of the conventionally calculated values (Ω(Acalc)) when 0.5 ≤ Ω(A) ≤ 2.0. When Ω(A) > 2.0, 95% of the Ω(Aspec) values were within ±0.18 of Ω(Acalc). Our shipboard experience indicates that spectrophotometric determinations of [CO(3)(2-)](T) and Ω(CaCO(3)) are straightforward, fast, and precise. The method yields high-quality measurements of two important, rapidly changing aspects of ocean chemistry and offers capabilities suitable for long-term automated in situ monitoring.

The Tonian Beck Spring Dolomite: Marine dolomitization in a shallow, anoxic sea

Science.gov (United States)

Shuster, Alice Mary; Wallace, Malcolm William; van Smeerdijk Hood, Ashleigh; Jiang, Ganqing

2018-06-01

The reason for the abundance of dolomite lithologies in Earth's early geological record compared to modern environments remains contentious. This study provides new insight into this Precambrian "dolomite problem" by revisiting one of the most controversial dolomite localities, the Beck Spring Dolomite, of Death Valley, USA. Consistent with some previous studies, petrographic evidence indicates that although the Beck Spring Dolomite now consists almost entirely of dolomite, it was originally precipitated largely as aragonite and high-Mg calcite. Depositional constituents (microbialites and ooids) were likely originally aragonitic, and early marine length-fast cements (now dolomite) are suggested to have precipitated as high-Mg calcite then replaced syntaxially by dolomite. Based on petrographic and geochemical evidence, we suggest that marine dolomitization was the dominant synsedimentary diagenetic process in the unit, and for the most part, involved syntaxial and mimetic replacement. Further, a length-slow fibrous dolomite generation was precipitated during the later stages of marine diagenesis as a primary marine dolomite cement. This is indicated by the length-slow crystallographic structure of the cement and from its preserved geochemical and cathodoluminescence growth zonation. This new evidence for Tonian marine dolomite precipitation reinforces the idea of Precambrian marine environmental conditions, including the chemical composition of seawater, promoting dolomite formation at this time. The trace metal geochemical composition of well-preserved marine components, especially dolomite marine cements, reveals information about redox conditions in this Tonian shallow seawater. In terms of rare earth element geochemistry, the Beck Spring Dolomite has no significant Ce anomaly, and a ubiquitous positive Eu anomaly, consistent with widespread oceanic anoxia during deposition. Furthermore, the relatively low levels of iron and chalcophile elements Co, Cu, Pb and

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)

Howes, Ella L; Eagle, Robert A; 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

Slope and basinal deposits adjacent to isolated carbonate platforms in the Indian Ocean: Sedimentology, geomorphology, and a new 1.2 Ma record of highstand shedding

Science.gov (United States)

Counts, J. W.; Jorry, S.; Jouet, G.

2017-12-01

Newly analyzed bathymetric, seismic, and core data from carbonate-topped seamounts in the Mozambique Channel reveals a variety of depositional processes and products operating on platform slopes and adjacent basins. Mass transport complexes (including turbidites and debrites), leveed channel systems with basin-floor fans, and contourites are imaged in high resolution in both seafloor maps and cross-section, and show both differences and similarities compared with platform slopes in the Bahamas and elsewhere. In some, though not all, platforms, increased sedimentation can be observed on the leeward margins, and slope rugosity may be asymmetric with respect to prevailing wind direction. Deposition is also controlled by glacial-interglacial cycles; cores taken from the lower slopes (3000+ m water depth) of carbonate platforms reveal a causative relationship between sea level and aragonite export to the deep ocean. δ18O isotopes from planktonic and benthic foraminifera of two 27-meter cores, reveal a high-resolution, continuous depositional record of carbonate sediment dating back to 1.2 Ma. Sea level rise, as determined by correlation with the LR04 benthic stack, is coincident with increased aragonite flux from platform tops. Gravity flow deposits are also affected by platform flooding—the frequency of turbidite/debrite deposits on pinnacle slopes increases during highstand, although such deposits are also present during glacial episodes. The results reported here are the first record of highstand shedding in the southern Indian Ocean, and provide the longest Quaternary sediment record to date in the region, including the Mid-Brunhes transition (MIS 11) that serves as an analog for the current climate conditions. In addition, this is the first study to describe sedimentation on the slopes of these platforms, providing an important point of comparison that has the potential to influence source-to-sink carbonate facies models.

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.

Carbon-climate feedbacks accelerate ocean acidification

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Matear, Richard J.; Lenton, Andrew

2018-03-01

Carbon-climate feedbacks have the potential to significantly impact the future climate by altering atmospheric CO2 concentrations (Zaehle et al. 2010). By modifying the future atmospheric CO2 concentrations, the carbon-climate feedbacks will also influence the future ocean acidification trajectory. Here, we use the CO2 emissions scenarios from four representative concentration pathways (RCPs) with an Earth system model to project the future trajectories of ocean acidification with the inclusion of carbon-climate feedbacks. We show that simulated carbon-climate feedbacks can significantly impact the onset of undersaturated aragonite conditions in the Southern and Arctic oceans, the suitable habitat for tropical coral and the deepwater saturation states. Under the high-emissions scenarios (RCP8.5 and RCP6), the carbon-climate feedbacks advance the onset of surface water under saturation and the decline in suitable coral reef habitat by a decade or more. The impacts of the carbon-climate feedbacks are most significant for the medium- (RCP4.5) and low-emissions (RCP2.6) scenarios. For the RCP4.5 scenario, by 2100 the carbon-climate feedbacks nearly double the area of surface water undersaturated with respect to aragonite and reduce by 50 % the surface water suitable for coral reefs. For the RCP2.6 scenario, by 2100 the carbon-climate feedbacks reduce the area suitable for coral reefs by 40 % and increase the area of undersaturated surface water by 20 %. The sensitivity of ocean acidification to the carbon-climate feedbacks in the low to medium emission scenarios is important because recent CO2 emission reduction commitments are trying to transition emissions to such a scenario. Our study highlights the need to better characterise the carbon-climate feedbacks and ensure we do not underestimate the projected ocean acidification.

Biological forcing controls the chemistry of the coral exoskeleton

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Meibom, A.; Mostefaoui, S.; Cuif, J.; Yurimoto, H.; Dauphin, Y.; Houlbreque, F.; Dunbar, R.; Constantz, B.

2006-12-01

A multitude of marine organisms produce calcium carbonate skeletons that are used extensively to reconstruct water temperature variability of the tropical and subtropical oceans - a key parameter in global climate-change models. Such paleo-climate reconstructions are based on the notion that skeletal oxygen isotopic composition and certain trace-element abundances (e.g., Sr/Ca and Mg/Ca ratios) vary in response to changes in the water temperature. However, it is a fundamental problem that poorly understood biological processes introduce large compositional deviations from thermodynamic equilibrium and hinder precise calibrations of many paleo-climate proxies. Indeed, the role of water temperature in controlling the composition of the skeleton is far from understood. We have studied trace-element abundances as well as oxygen and carbon isotopic compositions of individual skeletal components in the zooxanthellate and non-zooxanthellate corals at ultra-structural, i.e. micrometer to sub-micrometer length scales. From this body of work we draw the following, generalized conclusions: 1) Centers of calcification (COC) are not in equilibrium with seawater. Notably, the Sr/Ca ratio is higher than expected for aragonite equilibrium with seawater at the temperature at which the skeleton was formed. Furthermore, the COC are further away from equilibrium with seawater than fibrous skeleton in terms of stable isotope composition. 2) COC are dramatically different from the fibrous aragonite skeleton in terms of trace element composition. 3) Neither trace element nor stable isotope variations in the fibrous (bulk) part of the skeleton are directly related to changes in SST. In fact, changes in SST can have very little to do with the observed compositional variations. 4) Trace element variations in the fibrous (bulk) part of the skeleton are not related to the activity of zooxanthellae. These observations are directly relevant to the issue of biological versus non

New High Pressure Phase of CaCO3: Implication for the Deep Diamond Formation

Science.gov (United States)

Mao, Z.; Li, X.; Zhang, Z.; Lin, J. F.; Ni, H.; Prakapenka, V.

2017-12-01

Surface carbon can be transported to the Earth's deep interior through sinking subduction slabs. Carbonates, including CaCO3, MgCO3 and MgCa(CO3)2, are important carbon carriers for the deep carbon cycle. Experimental studies on the phase stability of carbonates with coexisting mantle minerals at relevant pressure and temperature conditions are thus important for understanding the deep carbon cycle. In particular, recent petrological studies have revealed the evidence for the transportation of CaCO3 to the depth at least of the top lower mantle by analyzing the diamond inclusions. Yet the phase stability of CaCO3 at relevant pressure and temperature conditions of the top lower mantle is still unclear. Previous single-crystal study has shown that CaCO3 transforms from the CaCO3-III structure to CaCO3-VI at 15 GPa and 300 K. The CaCO3-VI is stable at least up to 40 GPa at 300 K. At high temperatures, CaCO3 in the aragonite structure will directly transform into the post-aragonite structure at 40 GPa. However, a recent theoretical study predicted a new phase of CaCO3 with a space group of P21/c between 32 and 48 GPa which is different from previous experimental results. In this study, we have investigated the phase stability of CaCO3 at high pressure-temperature conditions using synchrotron X-ray diffraction in laser-heated diamond anvil cells. We report the discovery of a new phase of CaCO3 at relevant pressure-temperature conditions of the top lower mantle which is consistent with previous theoretical predictions. This new phase is an important carrier for the transportation of carbon to the Earth's lower mantle and crucial for growing deep diamonds in the region.

Viral lysis of photosynthesizing microbes as a mechanism for calcium carbonate nucleation in seawater

Science.gov (United States)

Lisle, John T.; Robbins, Lisa L.

2016-01-01

Removal of carbon through the precipitation and burial of calcium carbonate in marine sediments constitutes over 70% of the total carbon on Earth and is partitioned between coastal and pelagic zones. The precipitation of authigenic calcium carbonate in seawater, however, has been hotly debated because despite being in a supersaturated state, there is an absence of persistent precipitation. One of the explanations for this paradox is the geochemical conditions in seawater cannot overcome the activation energy barrier for the first step in any precipitation reaction; nucleation. Here we show that virally induced rupturing of photosynthetic cyanobacterial cells releases cytoplasmic-associated bicarbonate at concentrations ~23-fold greater than in the surrounding seawater, thereby shifting the carbonate chemistry toward the homogenous nucleation of one or more of the calcium carbonate polymorphs. Using geochemical reaction energetics, we show the saturation states (Ω) in typical seawater for calcite (Ω = 4.3), aragonite (Ω = 3.1), and vaterite (Ω = 1.2) are significantly elevated following the release and diffusion of the cytoplasmic bicarbonate (Ωcalcite = 95.7; Ωaragonite = 68.5; Ωvaterite = 25.9). These increases in Ω significantly reduce the activation energy for nuclei formation thresholds for all three polymorphs, but only vaterite nucleation is energetically favored. In the post-lysis seawater, vaterite's nuclei formation activation energy is significantly reduced from 1.85 × 10−17 J to 3.85 × 10−20 J, which increases the nuclei formation rate from highly improbable (seawater describes a mechanism through which the initial step in the production of carbonate sediments may proceed. It also presents an additional role of photosynthesizing microbes and their viruses in marine carbon cycles and reveals these microorganisms are a collective repository for concentrated and reactive dissolved inorganic carbon (DIC) that is currently not accounted for

Response of C3 and C4 plants to middle-Holocene climatic variation near the prairie-forest ecotone of Minnesota, U.S.A.

Energy Technology Data Exchange (ETDEWEB)

Tian, J; Brown, T A; Hu, F S; Stefanova, I; Nelson, D M

2003-12-24

Paleorecords of the middle Holocene (MH) from the North American midcontinent can offer insights into ecological responses to pervasive drought that may accompany future climatic warming. We analyzed MH sediments from West Olaf Lake (WOL) and Steel Lake (SL) in Minnesota to examine the effects of warm/dry climatic conditions on prairie-woodland ecosystems. Mineral composition and carbonate {delta}{sup 18}O were used to determine climatic variations, whereas pollen assemblages, charcoal {delta}{sup 13}C, and charcoal accumulation rates were used to reconstruct vegetation composition, C{sub 3} and C{sub 4} plant abundance, and fire. The ratio of aragonite:calcite at WOL and {delta}{sup 18}O at SL suggest that pronounced droughts occurred during the MH but that drought severity decreased with time. From charcoal {delta}{sup 13}C data we estimated that the MH abundance of C{sub 4} plants averaged 50% at WOL and 43% at SL. At WOL C{sub 4} abundance was negatively correlated with aragonite:calcite, suggesting that severe moisture deficits suppressed C{sub 4} plants in favor of weedy C{sub 3} plants (e.g., Ambrosia). As climate ameliorated C{sub 4} abundance increased (from {approx}33 to 66%) at the expense of weedy species, enhancing fuel availability and fire occurrence. In contrast, farther east at SL climate was cooler and wetter than at WOL, and C{sub 4} abundance showed no correlation with {delta}{sup 18}O-inferred aridity. Woody C{sub 3} plants (e.g., Quercus) were more abundant, biomass flammability lower, and fires less important at SL than at WOL. Our results suggest that C{sub 4} plants are adapted to warm/dry climatic conditions, but not to extreme droughts, and that the fire regime is controlled by biomass-climate interactions.

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

Analytical techniques for extracting Quaternary climate data from speleothems

International Nuclear Information System (INIS)

Whittaker, T.

2007-01-01

Speleothems are deposits formed in caves as a result of chemical precipitation from groundwater flowing over or dripping onto a surface. In most limestone caves the precipitated mineral is calcite, although aragonite forms are also common. Over time, and with continued chemical precipitation, each form 'grows' layer by layer. Therefore, similar to tree rings (although speleothem layers may not be annually resolved), speleothems provide an archive of information about past climate. In addition they may provide further information on vegetation changes, hydrology, sea level, water-rock interaction, landscape evolution, tectonics and human action. For palaeoclimate studies the three most useful speleothem forms are stalagmites, stalactites (including Straws) and flowstones. (author). 23 refs

Changes in the marine carbonate system of the western Arctic: patterns in a rescued data set

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Lisa A. Miller

2014-11-01

Full Text Available A recently recovered and compiled set of inorganic carbon data collected in the Canadian Arctic since the 1970s has revealed substantial change, as well as variability, in the carbonate system of the Beaufort Sea and Canada Basin. Whereas the role of this area as a net atmospheric carbon sink has been confirmed, high pCO2 values in the upper halocline underscore the potential for CO2 outgassing as sea ice retreats and upwelling increases. In addition, increasing total inorganic carbon and decreasing alkalinity are increasing pCO2 and decreasing CaCO3 saturation states, such that undersaturation with respect to aragonite now occurs regularly in both deep waters and the upper halocline.

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

The role of crystal structure and fabrics in early diagenesis: examples from continental and marine settings

Science.gov (United States)

Frisia, Silvia; Borsato, Andrea; Bajo, Petra; Hellstrom, John

2015-04-01

Palaeoclimate research based on geological archives relies on the assumption that the system has remained closed to phase transformation and re-mobilization of chemical species, the extent of which depends on the crystallization pathways. Early diagenesis, in fact, encompasses processes that occur soon after deposition, from a few hours to centuries. In the last decade, speleothems-based palaeoclimate research has gained momentum. Speleothems (cave secondary mineral deposits) have provided geochemical records of climate, pollution, volcanism, land use and vegetation changes at seasonal to millennial scale for the past million year. Critically, the accuracy of their records relies on the absence of diagenetic modifications. Yet, contrary to late diagenetic dissolution and re-precipitation, early diagenesis is difficult to detect in stalagmites and flowstones. A striking example is a Holocene stalagmite from Corchia cave, whose fabrics appear compact and of primary origin. Nevertheless, U-Th dating by mass spectrometry of 5 out of 47 samples shows offset from neighboring samples of up to 40%. Careful petrographic observations reveal that elongated columnar fabric contains microstructural defects, expressed by irregular crystal boundaries, which allow for the percolation of diagenetic fluids and U loss. Speleothem allow for the precise dating of diagenetic processes. Aggradation of micrite into microsparite may occur in less than a hundred year. Similar aggrading neomorphism of micrite has been documented for subglacial carbonates, where aggradation occurred at secular scale. Aggradation can be fingerprinted by the stable isotope ratio values, commonly more positive than in the columnar fabrics. In speleothems, aragonite may be transformed into calcite in less than 100 years. The phase transformation may partially preserve the original fabric, and appears to commence from calcite nucleated on organic compounds at twin boundaries, taking advantage of crystal defects as

The major-ion composition of Carboniferous seawater

Science.gov (United States)

Holt, Nora M.; García-Veigas, Javier; Lowenstein, Tim K.; Giles, Peter S.; Williams-Stroud, Sherilyn

2014-06-01

a long interval, from the Early Cambrian to the Middle Devonian, when seawater had low Mg2+/Ca2+ ratios (<2) that coincide with calcite seas. The Mg2+/Ca2+ ratio of seawater rose from 0.9 in the Middle Devonian, to 2.5 in the Middle/Late Mississippian, 2.3 in the Middle Pennsylvanian, and 3.5 in the Early Permian. The transition from calcite seas to aragonite seas, established from the mineralogy of oölites and early marine cements, occurred in the Late Mississippian. Fluid inclusions show that seawater Mg2+/Ca2+ ratios rose above 2 by the Middle to Late Mississippian coinciding exactly with the shift to aragonite seas. Aragonite seas existed for ∼100 Myr, from the Late Mississippian until the Late Triassic/Early Jurassic.

Physical and nanomechanical properties of the synthetic anhydrous crystalline CaCO3 polymorphs: vaterite, aragonite and calcite

Czech Academy of Sciences Publication Activity Database

Ševčík, Radek; Šašek, Petr; Viani, Alberto

2018-01-01

Roč. 53, č. 6 (2018), s. 4022-4033 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LO1219; GA ČR(CZ) GA17-05030S Keywords : X-ray-diffraction * thermal expansion * mechanical characterization * relative-humidity * carbonates * mortars Subject RIV: CA - Inorganic Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 2.599, year: 2016 https://www.springerprofessional.de/en/physical-and-nanomechanical-properties-of-the-synthetic-anhydrou/15290962

Electron microscopy study of red mud after seawater neutralisation

International Nuclear Information System (INIS)

Toledo, S.P.; Kiyohara, P.K.; Antunes, M.L.P.; Frost, Ray

2012-01-01

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)

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

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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.

Radiocarbon age and diagenesis of oolitic sediments from the Persian Gulf

International Nuclear Information System (INIS)

Silar, J.

1980-01-01

Radiocarbon measurements of different parts of ooids of Pleistocene and Holocene oolitic sediments from the Persian Gulf on the coast of Kuwait indicated that atmospheric carbon dioxide had been involved in the recrystallization of aragonite and in the diagenesis of the oolitic sediments. The radiocarbon activity of different layers of sediments generally corresponds to their stratigraphic sequence. The radiocarbon ages of several earlier layers, however, seem to be reduced due to recrystallization and diagenesis. The radiocarbon ages of well-preserved shells of mollusks of the fossiliferous horizon are lower than their alleged Pleistocene geological age. The rate of emergence of the shore between one and several mm.yr -1 was established which corresponds to that recorded in the mouth of the Persian Gulf and in Qatar. (author)

CO{sub 2} mineral trapping: an experimental study on the carbonation of basalts from the eastern Deccan Volcanic Province, India

Energy Technology Data Exchange (ETDEWEB)

Rani, Nishi; Pathak, Vamdev; Shrivastava, J.P. [Department of Geology, University of Delhi, Delhi 110007 (India)

2013-07-01

Rock specimens from Deccan flood basalts have been reacted in the laboratory under high pCO{sub 2} (5 and 10 bars), total pressure (vessel pressure between 10 and 20 bars), and temperature (100 and 200 deg. C) conditions for 50, 60, 70, and 80 hours. XRD and SEM-EDS analyses show that calcite, aragonite, siderite and magnesite, and clays are derived from the alteration of Deccan basalts under water-saturated, hydrothermal-like conditions. Alteration reactions were accompanied by significant variation in the pH of the reacting aqueous solution, dependent upon time, pCO{sub 2}, and temperature variables of the experiment. Neo-formed secondary products also include significant amounts of smectite, chlorite, and smectite/chlorite mixed layer clays. (authors)

Complex life histories of fishes revealed through natural information storage devices: case studies of diadromous events as recorded by otoliths

International Nuclear Information System (INIS)

Elfman, M.; Limburg, K.E.; Kristiansson, P.; Svedaeng, H.; Westin, L.; Wickstroem, H.; Malmqvist, K.; Pallon, J.

2000-01-01

Diadromous fishes - species that move across salinity gradients as part of their life repertoire - form a major part of coastal and inland fisheries. Conventional mark-recapture techniques have long been used to track their movements, but give incomplete information at best. On the other hand, otoliths (ear-stones) of fishes can provide a complete record of major life history events, as reflected both in their microstructure and elemental composition. Strontium, which substitutes for calcium in the aragonite matrix of otoliths, is a powerful tracer of salinity histories in many migratory fishes. We measured Sr and Ca with a nuclear microprobe (PIXE) and show examples (eel, Anguilla anguilla; brown trout, Salmo trutta; American shad, Alosa sapidissima) of how the technique has solved several mysteries within fisheries biology

Cave breakdown by vadose weathering.

Directory of Open Access Journals (Sweden)

Osborne R. Armstrong L.

2002-01-01

Full Text Available Vadose weathering is a significant mechanism for initiating breakdown in caves. Vadose weathering of ore bodies, mineral veins, palaeokarst deposits, non-carbonate keystones and impure, altered or fractured bedrock, which is intersected by caves, will frequently result in breakdown. Breakdown is an active, ongoing process. Breakdown occurs throughout the vadose zone, and is not restricted to large diameter passages, or to cave ceilings. The surfaces of disarticulated blocks are commonly coated, rather than having fresh broken faces, and blocks continue to disintegrate after separating from the bedrock. Not only gypsum, but also hydromagnesite and aragonite are responsible for crystal wedging. It is impossible to study or identify potential breakdown foci by surface surveys alone, in-cave observation and mapping are essential.

Polarization-dependent imaging contrast in abalone shells

Science.gov (United States)

Metzler, Rebecca A.; Zhou, Dong; Abrecht, Mike; Chiou, Jau-Wern; Guo, Jinghua; Ariosa, Daniel; Coppersmith, Susan N.; Gilbert, P. U. P. A.

2008-02-01

Many biominerals contain micro- or nanocrystalline mineral components, organized accurately into architectures that confer the material with improved mechanical performance at the macroscopic scale. We present here an effect which enables us to observe the relative orientation of individual crystals at the submicron scale. We call it polarization-dependent imaging contrast (PIC), as it is an imaging development of the well-known x-ray linear dichroism. Most importantly, PIC is obtained in situ, in biominerals. We present here PIC in the prismatic and nacreous layers of Haliotis rufescens (red abalone), confirm it in geologic calcite and aragonite, and corroborate the experimental data with theoretical simulated spectra. PIC reveals different and unexpected aspects of nacre architecture that have inspired theoretical models for nacre formation.

Polygenetic Karsted Hardground Omission Surfaces in Lower Silurian Neritic Limestones: a Signature of Early Paleozoic Calcite Seas

Science.gov (United States)

James, Noel P.; Desrochers, André; Kyser, Kurt T.

2015-04-01

Exquisitely preserved and well-exposed rocky paleoshoreline omission surfaces in Lower Silurian Chicotte Formation limestones on Anticosti Island, Quebec, are interpreted to be the product of combined marine and meteoric diagenesis. The different omission features include; 1) planar erosional bedding tops, 2) scalloped erosional surfaces, 3) knobs, ridges, and swales at bedding contacts, and 4) paleoscarps. An interpretation is proposed that relates specific omission surface styles to different diagenetic-depositional processes that took place in separate terrestrial-peritidal-shallow neritic zones. Such processes were linked to fluctuations in relative sea level with specific zones of diagenesis such as; 1) karst corrosion, 2) peritidal erosion, 3) subtidal seawater flushing and cementation, and 4) shallow subtidal deposition. Most surfaces are interpreted to have been the result of initial extensive shallow-water synsedimentary lithification that were, as sea level fell, altered by exposure and subaerial corrosion, only to be buried by sediments as sea level rose again. This succession was repeated several times resulting in a suite of recurring polyphase omission surfaces through many meters of stratigraphic section. Synsedimentary cloudy marine cements are well preserved and are thus interpreted to have been calcitic originally. Aragonite components are rare and thought to have to have been dissolved just below the Silurian seafloor. Large molluscs that survived such seafloor removal were nonetheless leached and the resultant megamoulds were filled with synsedimentary calcite cement. These Silurian inner neritic-strandline omission surfaces are temporally unique. They are part of a suite of marine omission surfaces that are mostly found in early Paleozoic neritic carbonate sedimentary rocks. These karsted hardgrounds formed during a calcite-sea time of elevated marine carbonate saturation and extensive marine cement precipitation. The contemporaneous greenhouse

Seawater Carbonate Chemistry of Deep-sea Coral Beds off the Northwestern Hawaiian Islands

Science.gov (United States)

Brooks, J.; Shamberger, K.; Roark, E. B.; Miller, K.; Baco-Taylor, A.

2016-02-01

Many species of deep-sea octocorals produce calcium carbonate (CaCO3) skeletons and form coral beds that support diverse ecosystems crucial to fisheries. The geochemistry of deep-sea coral skeletons can provide valuable paleoceanographic information on ocean circulation and nutrient cycling. Deep-sea corals in the older bottom waters of the Pacific are naturally exposed to higher carbon dioxide (CO2) concentrations and lower pH than in the Atlantic where much of the previous deep-sea coral work has occurred. Therefore, some Pacific deep-sea corals may live and calcify in waters that are corrosive to their skeletons, but there have been few current seawater carbonate chemistry measurements of the waters surrounding deep-sea coral beds to assess this. The input of anthropogenic atmospheric CO2 known as ocean acidification (OA) lowers ocean pH and causes an expansion of these corrosive waters. Seawater carbonate chemistry must be characterized before accurate predictions can be made for the effects of OA on these important ecosystems. Total Alkalinity (TA) and Dissolved Inorganic Carbon (DIC) samples were collected in the fall of 2014 and 2015 from the surface to 1450 m depth off the Northwestern Hawaiian Island chain where deep-sea octocorals are found. The partial pressure of CO2 increased and pH, calcite saturation state (Ωca) and aragonite saturation state (Ωar) decreased with increasing latitude and depth. Notably, waters were undersaturated with respect to calcite and aragonite (Ωca and Ωar less than 1) below 800 m and 500 m, respectively. Therefore, deep-sea corals below these depths must calcify in waters that are thermodynamically favorable for CaCO3 dissolution. How deep-sea octocorals cope with such adverse seawater chemistry is critical to understanding future effects of OA. It is not known whether OA is currently negatively impacting deep-sea octocorals, but their naturally acidified environments could make them particularly susceptible to OA.

Chemical and biological impacts of ocean acidification along the west coast of North America

Science.gov (United States)

Feely, Richard A.; Alin, Simone R.; Carter, Brendan; Bednaršek, Nina; Hales, Burke; Chan, Francis; Hill, Tessa M.; Gaylord, Brian; Sanford, Eric; Byrne, Robert H.; Sabine, Christopher L.; Greeley, Dana; Juranek, Lauren

2016-12-01

The continental shelf region off the west coast of North America is seasonally exposed to water with a low aragonite saturation state by coastal upwelling of CO2-rich waters. To date, the spatial and temporal distribution of anthropogenic CO2 (Canth) within the CO2-rich waters is largely unknown. Here we adapt the multiple linear regression approach to utilize the GO-SHIP Repeat Hydrography data from the northeast Pacific to establish an annually updated relationship between Canth and potential density. This relationship was then used with the NOAA Ocean Acidification Program West Coast Ocean Acidification (WCOA) cruise data sets from 2007, 2011, 2012, and 2013 to determine the spatial variations of Canth in the upwelled water. Our results show large spatial differences in Canth in surface waters along the coast, with the lowest values (37-55 μmol kg-1) in strong upwelling regions off southern Oregon and northern California and higher values (51-63 μmol kg-1) to the north and south of this region. Coastal dissolved inorganic carbon concentrations are also elevated due to a natural remineralized component (Cbio), which represents carbon accumulated through net respiration in the seawater that has not yet degassed to the atmosphere. Average surface Canth is almost twice the surface remineralized component. In contrast, Canth is only about one third and one fifth of the remineralized component at 50 m and 100 m depth, respectively. Uptake of Canth has caused the aragonite saturation horizon to shoal by approximately 30-50 m since the preindustrial period so that undersaturated waters are well within the regions of the continental shelf that affect the shell dissolution of living pteropods. Our data show that the most severe biological impacts occur in the nearshore waters, where corrosive waters are closest to the surface. Since the pre-industrial times, pteropod shell dissolution has, on average, increased approximately 19-26% in both nearshore and offshore waters.

The effect of evaporation and nutrient enrichment on the erodability of mudflats in a mesotidal estuary

Science.gov (United States)

Fagherazzi, S.; Viggato, T.; Vieillard, A. M.; Fulweiler, R. W.

2014-12-01

The continental shelf region off the Washington-Oregon-California coast is seasonally exposed to water with a low aragonite saturation state by coastal upwelling of CO2-rich waters. To date, the spatial and temporal distribution of anthropogenic CO2 (Canth) contribution to the CO2-rich waters is largely unknown. Here we use an adaptation of the linear regression approach described in Feely et al. (2008) to utilize the GO-SHIP Repeat Hydrography data set from the northeast Pacific to establish an annually updated relationship between Canth and potential density. This relationship was then used with the NOAA Ocean Acidification Program West Coast cruise data sets from 2007, 2011, 2012 and 2013 to determine the spatial variations of Canth in the upwelled water. Our results show large spatial differences in Canth in surface waters along the coast with the lowest values (40-45 μmol kg-1) in strong upwelling regions of off northern California and southern Oregon and higher values (50-70 μmol kg-1) to the north and south of this region. Canth contributes an average of about 70 % of the increased amount of dissolved inorganic carbon in the upwelled waters at the surface relative to what would be expected from physical circulation and exchange with a preindustrial atmosphere alone. In contrast, Canth contributes an average of about 31%, and 16% of the increased amount of dissolved inorganic carbon at 50 m depth, and at 100 m depth respectively. The remaining contributions are either due to respiration processes in the water that was upwelled and transported to coastal regions or respiration processes that occurs locally during the course of the upwelling season. The uptake of Canth has caused the aragonite saturation horizon to shoal by approximately 30-50 m since preindustrial period so that the undersaturated waters are well within the regions of the continental shelf that affect the biological communities.

Authigenic carbonates from newly discovered active cold seeps on the northwestern slope of the South China Sea: Constraints on fluid sources, formation environments, and seepage dynamics

Science.gov (United States)

Liang, Qianyong; Hu, Yu; Feng, Dong; Peckmann, Jörn; Chen, Linying; Yang, Shengxiong; Liang, Jinqiang; Tao, Jun; Chen, Duofu

2017-06-01

Authigenic carbonates recovered from two newly discovered active cold seeps on the northwestern slope of the South China Sea have been studied using petrography, mineralogy, stable carbon and oxygen isotopic, as well as trace element compositions, together with AMS 14C ages of shells of seep-dwelling bivalves to unravel fluid sources, formation conditions, and seepage dynamics. The two seeps (ROV1 and ROV2), referred to as 'Haima seeps' herein, are approximately 7 kilometers apart, and are typified by abundant carbonate rocks represented bycrusts and nodules. Aragonite and high-Mg calcite are the main carbonate minerals. Based on low δ13Ccarbonate values ranging from -43.0‰ to -27.5‰ (V-PDB) methane is apparently the predominant carbon source of seep carbonates. The corresponding δ18O values, varying from 2.5‰ to 5.8‰ (V-PDB), mostly are higher than calculated values representing precipitation in equilibrium with seawater (2.5‰ to 3.8‰), which probably reflects past destabilization of locally abundant gas hydrates. In addition, we found that carbonates with bivalve shells are generally aragonite-dominated, and bear no barium enrichment but uranium enrichments, reflecting shallow formation depths close to the seafloor. In contrast, carbonate crusts without bivalve shells and nodules contain more calcite, and are characterized by major molybdenum enrichment and different degrees of barium enrichment, agreeing with precipitation at greater depth under strictly anoxic conditions. AMS 14C ages suggest that a major episode of carbonate precipitation occurred between 6.1 ka and 5.1 ka BP at the Haima seeps, followed by a possibly subordinate episode from approximately 3.9 ka to 2.9 ka BP. The common occurrence of dead bivalves at both sites indicates that chemosynthesis-based communities flourished to a greater extent in the past, probably reflecting a decline of seepage activity in recent times. Overall, these results confirm that authigenic carbonates from

Viral lysis of photosynthesizing microbes as a mechanism for calcium carbonate nucleation in seawater

Science.gov (United States)

Lisle, John T.; Robbins, Lisa L.

2016-01-01

Removal of carbon through the precipitation and burial of calcium carbonate in marine sediments constitutes over 70% of the total carbon on Earth and is partitioned between coastal and pelagic zones. The precipitation of authigenic calcium carbonate in seawater, however, has been hotly debated because despite being in a supersaturated state, there is an absence of persistent precipitation. One of the explanations for this paradox is the geochemical conditions in seawater cannot overcome the activation energy barrier for the first step in any precipitation reaction; nucleation. Here we show that virally induced rupturing of photosynthetic cyanobacterial cells releases cytoplasmic-associated bicarbonate at concentrations ~23-fold greater than in the surrounding seawater, thereby shifting the carbonate chemistry toward the homogenous nucleation of one or more of the calcium carbonate polymorphs. Using geochemical reaction energetics, we show the saturation states (Ω) in typical seawater for calcite (Ω = 4.3), aragonite (Ω = 3.1), and vaterite (Ω = 1.2) are significantly elevated following the release and diffusion of the cytoplasmic bicarbonate (Ωcalcite = 95.7; Ωaragonite = 68.5; Ωvaterite = 25.9). These increases in Ω significantly reduce the activation energy for nuclei formation thresholds for all three polymorphs, but only vaterite nucleation is energetically favored. In the post-lysis seawater, vaterite's nuclei formation activation energy is significantly reduced from 1.85 × 10−17 J to 3.85 × 10−20 J, which increases the nuclei formation rate from highly improbable (nucleation of calcium carbonate in seawater describes a mechanism through which the initial step in the production of carbonate sediments may proceed. It also presents an additional role of photosynthesizing microbes and their viruses in marine carbon cycles and reveals these microorganisms are a collective repository for concentrated and reactive dissolved inorganic carbon (DIC

New Proxies for Climate change parameters: Foram Culturing and Pteropod Potentials

Science.gov (United States)

Keul, N.; Schneider, R. R.; Langer, G.; Bijma, J.; Peijnenburg, K. T.

2017-12-01

Global climate change is one of the most pressing challenges our society is currently facing and strong efforts are made to simulate future climate conditions. To better validate models that aim at predicting global temperature rise as a consequence of anthropogenic CO2 emissions, accurate atmospheric paleo-CO2 estimates in combination with temperature reconstructions are necessary. Consequently there is a strong need for reliable proxies, allowing reconstruction of climate change. With respect to foraminifera a combination of laboratory experiments and modeling is presented, to show the isolated impact of the different parameters of the carbonate system on trace element composition of their shells. We focus on U/Ca and Sr/Ca ratios, which have recently been established as new proxies reflecting changes in the carbonate system of seawater. While U/Ca correlates with carbonate ion concentration, Sr/Ca is primarily influenced by DIC. The latter is particularly promising since the impact of additional parameters is relatively well constrained and hence, Sr/Ca ratios may allow higher accuracy in carbonate system parameter reconstructions. Furthermore, our results will be discussed on how to advance our knowledge about foraminiferal biomineralization. Pteropods, among the first responders to ocean acidification and warming, are explored as carriers of marine paleoenvironmental signals. In order to characterize the stable isotopic composition of aragonitic pteropod shells and their variation in response to climate change parameters, pteropod shells were collected along a latitudinal transect in the Atlantic Ocean. By comparing shell oxygen isotopic composition to depth changes of the calculated aragonite equilibrium oxygen isotope values, we infer shallow calcification depths for Heliconoides inflatus (75 m), rendering this species a good potential proxy carrier for past variations in surface ocean properties. Furthermore, we demonstrate that indeed, pteropod shells are

Shellfish face uncertain future in high CO2 world: influence of acidification on oyster larvae calcification and growth in estuaries.

Directory of Open Access Journals (Sweden)

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

Biogeochemical processes controlling authigenic carbonate formation within the sediment column from the Okinawa Trough

Science.gov (United States)

Li, Jiwei; Peng, Xiaotong; Bai, Shijie; Chen, Zhiyan; Van Nostrand, Joy D.

2018-02-01

Authigenic carbonates are one type of conspicuous manifestation in seep environments that can provide long-term archives of past seepage activity and methane cycling in the oceans. Comprehensive investigations of the microbial community functional structure and their roles in the process of carbonate formation are, however, lacking. In this study, the mineralogical, geochemical, and microbial functional composition were examined in seep carbonate deposits collected from the west slope of the northern section of the Okinawa Trough (OT). The aim of this work was to explore the correspondence between the mineralogical phases and microbial metabolism during carbonate deposit formation. The mineralogical analyses indicated that authigenic carbonate minerals (aragonite, magnesium-rich calcite, dolomite, ankerite and siderite) and iron-bearing minerals (limonite, chlorite, and biotite) were present in these carbonate samples. The carbon and oxygen isotopic values of the carbonate samples varied between -51.1‰ to -4.7‰ and -4.8‰ to 3.7‰, respectively. A negative linear correlation between carbon and oxygen isotopic compositions was found, indicating a mixture of methane-derived diagenetic (low δ13C/high 18O) carbonates and detrital origin (high δ13C/low 18O) carbonates at the OT. GeoChip analyses suggested that various metabolic activities of microorganisms, including methanogenesis, methane oxidation, sulfite oxidation, sulfate reduction, and metal biotransformations, all occurred during the formation process. On the basis of these findings, the following model for the methane cycle and seep carbonate deposit formation in the sediment column at the OT is proposed: (1) in the upper oxidizing zone, aerobic methane oxidation was the main way of methane consumption; (2) in the sulfate methane transition zone, sulfate-dependent AOM (anaerobic oxidation of methane) consumes methane, and authigenic minerals such as aragonite, magnesium-calcite, and sulfide minerals

Physicochemical and pharmacological assessment of a traditional biomedicine: Mukta shouktic bhasma

Directory of Open Access Journals (Sweden)

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.

The Biological Nature of Geochemical Proxies: algal symbionts affect coral skeletal chemistry

Science.gov (United States)

Owens, K.; Cohen, A. L.; Shimizu, N.

2001-12-01

The strontium-calcium ratio (Sr/Ca) of reef coral skeleton is an important ocean temperature proxy that has been used to address some particularly controversial climate change issues. However, the paleothermometer has sometimes proven unreliable and there are indications that the temperature-dependence of Sr/Ca in coral aragonite is linked to the photosynthetic activity of algal symbionts (zooxanthellae) in coral tissue. We examined the effect of algal symbiosis on skeletal chemistry using Astrangia danae, a small colonial temperate scleractinian that occurs naturally with and without zooxanthellae. Live symbiotic (deep brown) and asymbiotic (white) colonies of similar size were collected in Woods Hole where water temperatures fluctuate seasonally between -2oC and 23oC. We used a microbeam technique (Secondary Ion Mass Spectrometry) and a 30 micron diameter sampling beam to construct high-resolution Sr/Ca profiles, 2500 microns long, down the growth axes of the outer calical (thecal) walls. Profiles generated from co-occuring symbiotic and asymbiotic colonies are remarkably different despite their exposure to identical water temperatures. Symbiotic coral Sr/Ca displays four large-amplitude annual cycles with high values in the winter, low values in the summer and a temperature dependence similar to that of tropical reef corals. By comparison, Sr/Ca profiles constructed from asymbiotic coral skeleton display little variability over the same time period. Asymbiont Sr/Ca is relatively insensitive to the enormous temperature changes experienced over the year; the temperature dependence is similar to that of nighttime skeletal deposits in tropical reef corals and non-biological aragonite precipitates. We propose that the large variations in skeletal Sr/Ca observed in all symbiont-hosting coral species are not related to SST variability per se but are driven primarily by large seasonal variations in skeletal calcification rate associated with symbiont photosynthesis. Our

Radiogenic Isotopes As Paleoceanographic Tracers in Deep-Sea Corals: Advances in TIMS Measurements of Pb Isotopes and Application to Southern Ocean Corals

Science.gov (United States)

Wilson, D. J.; van de Flierdt, T.; Bridgestock, L. J.; Paul, M.; Rehkamper, M.; Robinson, L. F.; Adkins, J. F.

2014-12-01

Deep-sea corals have emerged as a valuable archive of deep ocean paleoceanographic change, with uranium-series dating providing absolute ages and the potential for centennial resolution. In combination with measurements of radiocarbon, neodymium isotopes and clumped isotopes, this archive has recently been exploited to reconstruct changes in ventilation, water mass sourcing and temperature in relation to millennial climate change. Lead (Pb) isotopes in both corals and seawater have also been used to track anthropogenic inputs through space and time and to trace transport pathways within the oceans. Better understanding of the oceanic Pb cycle is emerging from the GEOTRACES programme. However, while Pb isotopes have been widely used in environmental studies, their full potential as a (pre-anthropogenic) paleoceanographic tracer remains to be exploited. In deep-sea corals, challenges exist from low Pb concentrations in aragonite in comparison to secondary coatings, the potential for contamination, and the efficient elemental separation required for measurement by thermal ionisation mass spectrometry (TIMS). Here we discuss progress in measuring Pb isotopes in coral aragonite using a 207Pb-204Pb double spike on a ThermoFinnigan Triton TIMS. For a 2 ng NIST-981 Pb standard, the long term reproducibility (using 1011 Ω resistors) is ~1000 ppm (2 s.d.) on 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios. We now show that using a new 1012 Ω resistor to measure the small 204Pb beam improves the internal precision on these ratios from ~500 ppm (2 s.e.) to ~250 ppm (2 s.e.) and we envisage a potential improvement in the long term reproducibility as a consequence. We further assess the internal precision and external reproducibility of our method using a BCR-2 rock standard and an in-house coral standard. Preliminary evidence on the application of this method to natural samples is derived from cleaning experiments and replication tests on deep-sea corals from the Southern

The Cocos Ridge hydrothermal system revealed by microthermometry of fluid and melt inclusions

Science.gov (United States)

Brandstätter, J.; Kurz, W.; Krenn, K.

2017-12-01

Microthermometric analyses of fluid and melt inclusions in hydrothermal veins and in the Cocos Ridge (CCR) basalt were used to reveal the CCR thermal history at IODP Site 344-U1414 and to constrain fluid source and flow. Hydrothermal veins are hosted by lithified sediments and CCR basalt . Site 344-U1414, located 1 km seaward of the Middle American Trench offshore Costa Rica, serves to evaluate fluid/rock interaction, the hydrologic system and geochemical processes linked with the tectonic evolution of the incoming Cocos Plate from the Early Miocene up to recent times. The veins in the sedimentary rocks are mainly filled by blocky calcite, containing numerous fluid inclusions, and sometimes crosscut fibrous quartz/chalcedony veins. The veins in the basalt can be differentiated into three types: antitaxial fibrous calcite veins, composite veins with fibrous calcite and clay minerals at the vein margins and spherulitic quartz in the center, and syntaxial blocky aragonite veins surrounded by a clay selvage in the uppermost CCR basalt sections. Secondary minerals, clay minerals, fibrous calcite, quartz/chalcedony and pyrite also filled vesicles in the basalt. Fluid inclusions were mainly found in the aragonite veins and rarely in quartz in the composite veins and vesicles. Blocky veins with embedded wall rock fragments appear in the sediments and in the basalt indicate hydraulic fracturing. The occurrence of decrepitated fluid inclusions show high homogenization temperatures up to 400 °C. Decrepitated fluid inclusions are formed by increased internal overpressure, related to isobaric heating. Elongated fluid inclusion planes, arc-like fluid inclusions and low homogenization temperatures indicate subsequent isobaric cooling. The results obtained so far from Raman spectroscopy and microthermometry indicate CO2 inclusions and petrographic observations suggest the presence of silicate melt inclusions in phenocrysts in the basalt (mainly in clinopyroxene and plagioclase

Uncertainties in low γ-dose determinations by means of ESR using the biomaterial modern coral reef

International Nuclear Information System (INIS)

Hassan, Gamal M.; Sharaf, M.A.

2006-01-01

The ESR spectrum of unirradiated modern aragonite coral (CaCO 3 ) material from the Red Sea (Hurgada area) is characterized by four signals with spectroscopic splitting factors of g=2.0056, 2.0030, 2.0006 and 1.997. The most intensive and stable line in this spectrum is attributed to CO 2 - radicals at g=2.0006+/-0.0005. The dose response from 50mGy to 20Gy, energy dependence and effective atomic number are calculated so as to investigate coral as a dosimeter material in the clinical dose range. The lower experimental γ-dose limit was found to be 50mGy with signal-to-noise (S/N) ratio of 15. The combined and expanded uncertainties accompanying these measurements are 1.72% and 3.44%, respectively

Ocean Acidification Causes Increased Calcium Carbonate Turnover during Larval Shell Formation

Science.gov (United States)

Frieder, C.; Pan, F.; Applebaum, S.; Manahan, D. T.

2016-02-01

Mollusca is a major taxon for studies of the evolution and mechanisms of calcification. Under current and future ocean change scenarios, decreases in shell size have been observed in many molluscan species during early development. The mechanistic basis for these decreases are of significant interest. In this study, Pacific oyster larvae (Crassostrea gigas) reared at aragonite undersaturation (Ω > 1). Coupling radioisotope tracer assays with mineral mass measurements allowed calculation of calcification budgets for first shell formation in veliger stage larvae. Three primary mechanisms (in order of increasing effect) contributed to the change in shell mass at undersaturation: delayed onset of calcification, increased dissolution rates, and decreased net calcification rates. The observation of dissolution indicates turnover of the newly formed shell, and physicochemical constraints of undersaturation provide a mechanistic basis for decreased calcification.

Reconstruction of deglacial sea surface temperature in the tropical Pacific from selective analysis of a fossil coral

Energy Technology Data Exchange (ETDEWEB)

Allison, N.; Finch, A.A.; Tudhope, A.W.; Newville, M.; Sutton, S.R.; Ellam, R.M. (St Andrews); (Edinburgh); (Scottish); (UC); (St Andrews)

2010-07-13

The Sr/Ca of coral skeletons demonstrates potential as an indicator of sea surface temperatures (SSTs). However, the glacial-interglacial SST ranges predicted from Sr/Ca of fossil corals are usually higher than from other marine proxies. We observed infilling of secondary aragonite, characterized by high Sr/Ca ratios, along intraskeletal pores of a fossil coral from Papua New Guinea that grew during the penultimate deglaciation (130 {+-} 2 ka). Selective microanalysis of unaltered areas of the fossil coral indicates that SSTs at {approx}130 ka were {le} 1 C cooler than at present in contrast with bulk measurements (combining infilled and unaltered areas) which indicate a difference of 6-7 C. The analysis of unaltered areas of fossil skeletons by microprobe techniques may offer a route to more accurate reconstruction of past SSTs.

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.

Uncertainties in low {gamma}-dose determinations by means of ESR using the biomaterial modern coral reef

Energy Technology Data Exchange (ETDEWEB)

Hassan, Gamal M. [Department of Ionizing Radiation Metrology, National Institute for Standards (NIS), Tersa Street El-Haram El-Giza, P.O. Box 136 Giza, El-Giza (Egypt)]. E-mail: gamalhassan65@hotmail.com; Sharaf, M.A. [Department of Ionizing Radiation Metrology, National Institute for Standards (NIS), Tersa Street El-Haram El-Giza, P.O. Box 136 Giza, El-Giza (Egypt)

2006-01-15

The ESR spectrum of unirradiated modern aragonite coral (CaCO{sub 3}) material from the Red Sea (Hurgada area) is characterized by four signals with spectroscopic splitting factors of g=2.0056, 2.0030, 2.0006 and 1.997. The most intensive and stable line in this spectrum is attributed to CO{sub 2}{sup -} radicals at g=2.0006+/-0.0005. The dose response from 50mGy to 20Gy, energy dependence and effective atomic number are calculated so as to investigate coral as a dosimeter material in the clinical dose range. The lower experimental {gamma}-dose limit was found to be 50mGy with signal-to-noise (S/N) ratio of 15. The combined and expanded uncertainties accompanying these measurements are 1.72% and 3.44%, respectively.

Coral reefs will transition to net dissolving before end of century

Science.gov (United States)

Eyre, Bradley D.; Cyronak, Tyler; Drupp, Patrick; De Carlo, Eric Heinen; Sachs, Julian P.; Andersson, Andreas J.

2018-02-01

Ocean acidification refers to the lowering of the ocean’s pH due to the uptake of anthropogenic CO2 from the atmosphere. Coral reef calcification is expected to decrease as the oceans become more acidic. Dissolving calcium carbonate (CaCO3) sands could greatly exacerbate reef loss associated with reduced calcification but is presently poorly constrained. Here we show that CaCO3 dissolution in reef sediments across five globally distributed sites is negatively correlated with the aragonite saturation state (Ωar) of overlying seawater and that CaCO3 sediment dissolution is 10-fold more sensitive to ocean acidification than coral calcification. Consequently, reef sediments globally will transition from net precipitation to net dissolution when seawater Ωar reaches 2.92 ± 0.16 (expected circa 2050 CE). Notably, some reefs are already experiencing net sediment dissolution.

Discovery of the mineral brucite (magnesium hydroxide) in the tropical calcifying alga Polystrata dura (Peyssonneliales, Rhodophyta).

Science.gov (United States)

Nash, Merinda C; Russell, Bayden D; Dixon, Kyatt R; Liu, Minglu; Xu, Huifang

2015-06-01

Red algae of the family Peyssonneliaceae typically form thin crusts impregnated with aragonite. Here, we report the first discovery of brucite in a thick red algal crust (~1 cm) formed by the peyssonnelioid species Polystrata dura from Papua New Guinea. Cells of P. dura were found to be infilled by the magnesium-rich mineral brucite [Mg(OH)2 ]; minor amounts of magnesite and calcite were also detected. We propose that cell infill may be associated with the development of thick (> ~5 mm) calcified red algal crusts, integral components of tropical biotic reefs. If brucite infill within the P. dura crust enhances resistance to dissolution similarly to crustose coralline algae that infill with dolomite, then these crusts would be more resilient to future ocean acidification than crusts without infill. © 2015 Phycological Society of America.

Evaluation of the alkalinity in sea water by means of gran calculation. A procedure for titration in order to quantify the acidification of the seas by CO{sub 2} absorption; Bestimmung der Alkalinitaet in Meerwasser durch Granberechnung. Ein Titrationsverfahren zur Quantifizierung der Versauerung der Meere durch CO{sub 2}-Aufnahme

Energy Technology Data Exchange (ETDEWEB)

Peters, Juergen [SI Analytics GmbH, Mainz (Germany)

2012-04-15

In the last 200 years, the content of carbon dioxide in the air has risen from about 280 ppm to more than 380 ppm. Here, the increase of the concentration of CO{sub 2} is discussed as a reason for 'global warming'. While in the atmosphere about 800 billion tons of carbon dioxide (calculated as carbon) are located, 38,000 billion tons of carbon dioxide are dissolved in seawater, ie 50 times of the amount of CO{sub 2} in the atmosphere. The increase in the amount of CO{sub 2} in the atmosphere also results in an almost 50-fold increase in the total dissolved carbon dioxide in the sea. This results in a lowering of the pH value, and in an influencing of the equilibrium of aragonite and calcite. Many sea creatures are hampered in their growth.

Calcium carbonate scaling kinetics determined from radiotracer experiments with calcium-47

International Nuclear Information System (INIS)

Turner, C.W.; Smith, D.W.

1998-01-01

The deposition rate of calcium carbonate on a heat-transfer surface has been measured using a calcium-47 radiotracer and compared to the measured rate of thermal fouling. The crystalline phase of calcium carbonate that precipitates depends on the degree of supersaturation at the heat-transfer surface, with aragonite precipitating at higher supersaturations and calcite precipitating at lower supersaturations. Whereas the mass deposition rates were constant with time, the thermal fouling rates decreased throughout the course of each experiment as a result of densification of the deposit. It is proposed that the densification was driven by the temperature gradient across the deposit together with the retrograde solubility of calcium carbonate. The temperature dependence of the deposition rate yielded an activation energy of 79 ± 4 kJ/mol for the precipitation of calcium carbonate on a heat-transfer surface. (author)

First chelonian eggs and carapace fragments from the Pliocene of Rhodes, Greece

DEFF Research Database (Denmark)

Mueller-Töwe, Inken J.; Kjeldahl-Vallon, Tina A.; Milàn, Jesper

2011-01-01

Well-preserved fossil eggs and eggshell fragments from the Pliocene Apolakkia Formation of Rhodes (Greece) are described. The eggs were found in-situ in a clutch. They are sub-spherical with lengths of 53-60 mm and widths of about 40 mm. All eggs are diagenetically compressed and their original...... diameters are estimated at 45-50 mm. The eggshells are 0.3-0.5 mm thick, partly recrystallized, but widely still aragonitic. They consist of needle-like crystals that form individual shell units. A few pores are preserved between these shell units. This shell-structure allows assignment to chelonian eggs...... in the oofamily Testudoolithidae and the oogenus Testudolithus. The external morphology, microstructure and mineralogical composition of the eggshells show close resemblance to eggs of the extant tortoise Geochelone elephantopus. Together with a small association of turtle carapace fragments from the same...

Soda Creek springs - metamorphic waters in the eastern Alaska Range

Science.gov (United States)

Richter, D.H.; Donaldson, D.E.; Lamarre, R.A.

1973-01-01

The Soda Creek springs are a group of small, cold mineral springs on the southern flank of the eastern Alaska Range. The spring waters contain anomalous concentrations of carbon dioxide, sodium, chlorine, sulfate, boron, and ammonia and are actively precipitating deposits of calcite and aragonite. Sparingly present in these deposits are mixed-layer illite-montmorillonite clays and zeolite minerals. Low-temperaturemetamorphic reactions in subjacent marine sedimentary rocks of Jurassic and Cretaceous age may have produced the fluids and silicate minerals. With only a few exceptions, cool bicarbonate-rich springs in Alaska are concentrated south of the Denali fault system in south-central Alaska, southeastern Alaska, and along the Kaltag-Tintina fault system. These areas are characterized by active or recently activetectonism, major faults and folds, and an abundance of marine sedimentary rocks.

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

Science.gov (United States)

Vanderdeelen, Jan

2012-06-01

The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO3 types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO3. H2O), the hexahydrate ikaite (CaCO3.6H2O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

On morphology of methane-derived authigenic carbonates

Science.gov (United States)

Logvina, E.; Matveeva, T.

2009-04-01

Studies of methane-derived carbonates revealed a great variety their morphological types. Although the processes of these carbonates formation is not clearly understood, it has been suggested that in general bacterially mediated processes of hydrocarbon oxidation, coupled with sulphate reduction, produce unusually high levels of alkalinity and dissolved inorganic carbon in the pore fluids that is partitioned between the precipitating carbonate and CO2 rich plumes which emanate into the water column (Aharon, 1994). These carbonates consist by three main CaCO3 polymorphs - calcite, aragonite and dolomite. Carbonates with different petrography cemented from these polymorphs can be classified according to their specific locality mode of formation and biogenic or non-biogenic origin (Greinert et al., 2002). There are classifications for the authigenic carbonates which are based on petrography, morphology, or based on age and origin. In this work we will consider the petrographical and morphological differences of authigenic carbonates. The large structures vary from 10 to 200 m size, named as chemoherm carbonates. Usually they cemented by pure aragonite with minor Mg-calcite admixture. These chemoherms rise up to 50 m above the seafloor. The structures are irregular in shape and have numerous pores and open pathways resulting from plumbing system of fluid expulsion. This type of authigenic carbonates was observed in the NE Black Sea (Michaelis et al., 2002), at the Hydrate Ridge area (Greinert et al., 2001), at Aleutian accretionary margin (Greinert et al., 2002). Diagenetic carbonates - carbonate cemented sediments both growing at the seafloor or within the sediment framework and showing a large variety of shapes (chimneys, crusts, concretions est.), with grey to dark-grey color. Petrographically the carbonate cement represents by Mg-calcite, protodolomite and dolomite. The diagenetic carbonates occur widely in the fluid venting areas. In particular, diagenetic

Grainstones and cementstone mounds: The Trogkofel summit section (Lower Permian, Carnic Alps, Austria).

Science.gov (United States)

Schaffhauser, M.; Sanders, D.; Krainer, K.

2009-04-01

In the Carnic Alps, Austria, an Artinskian succession 400 m thick of shallow-water bioclastic limestones and of mounds composed of ?Archaeolithophyllum, Archaeolithoporella and abundant fibrous cementstone (after former aragonite) records deposition along a "grainstone-dominated" platform margin. The section was taken along the route through the east-facing cliff of Trogkofel. The Trogkofel Limestone (Artinskian pro parte) is excellently exposed and preserved the most complete along this route, but no section has hitherto been logged. The total thickness of the Trogkofel Limestone probably is about 550 meters; the summit section comprises its upper 400 meters. The section consists mainly of shallow-water bioclastic limestones (grainstones, packstones, rudstones) intercalated with cementstone mounds. Both the bioclastic limestones and the mounds typically are thick-bedded to, more commonly, unbedded. Throughout the section, intervals a few tens of meters in thickness dominated by bioclastic limestones change vertically with intervals dominated by cementstone mounds. Up-section, no clear-cut trend with respect to prevalent facies, mean depositional water depth, and energy index is obvious. Furthermore, no lime-muddy, meter-scale peritidal cycles, and no teepee structures and no pisolite levels were identified; thin intervals of fenestral lime mudstones and/or of cryptmicrobially-laminated limestones are very rare. The bioclastic limestones commonly weather out unstratified, or show subhorizontal stratification or, more rarely, low-angle cross-stratification. In the upper 100 meters of section, grainstones to fine-grained rudstones rich in keystone vugs are prevalent. The cementstone mounds comprise intervals up to a few meters in thickness; the biogenic component is characterized by foliose crusts pertaining to ?Archaeolithophyllum hidensis and Archaeolithoporella, overgrown by Tubiphytes and fenestrate bryozoans. The ?Archaeolithophyllum-Archaeolithoporella crusts

Use of a Land-Based, Dual-Parameter Analyzer for Tracking Ocean Acidification in Nearshore Coastal Habitats

Science.gov (United States)

Shea, M.; Alin, S. R.; Evans, W.; Sutton, A.; Hales, B. R.; Newton, J.; Feely, R. A.

2016-12-01

In 2007 to 2008, U.S. Pacific Northwest shellfish hatcheries experienced unprecedented larval mortality, attributed to upwelling along the Washington-Oregon coast that brought seawater enriched in anthropogenic CO2 and undersaturated with respect to aragonite to the surface. In response, several hatcheries have been outfitted with land-based analyzers to measure CO2 partial pressure (pCO2) and total dissolved CO2 (TCO2) through U.S. IOOS and NOAA OAP funding. This analyzer, developed at Oregon State University and known as the `Burke-O-Lator,' allows users to track CO2 system parameters in real-time. The data are available in near real-time on the IOOS Pacific Region Ocean Acidification (IPACOA) data portal, which feeds to the Global Ocean Acidification Observing Network (GOA-ON). Here, we explore the broader use of this system as an environmental monitoring tool. Most of the high-quality OA time-series locations in GOA-ON are in the open and coastal ocean, yet many areas of biological interest—such as shellfish hatcheries, shellfish farms, and coastal laboratories—are in the nearshore area of the coastal zone. A truly globally integrated assessment of OA must include nearshore conditions, which have been shown to be quite different in terms of variability, drivers, and range. We evaluated two pCO2 time-series from the coastal nearshore: the Taylor Shellfish Hatchery Burke-O-Lator system on the shore of Dabob Bay in Puget Sound, WA, and the nearby but offshore Dabob ORCA buoy MAPCO2 system within the bay. Preliminary comparison of three years of data reveals similar patterns despite differences in location and seawater intake depth, highlighting the opportunity for the addition of coupled nearshore biology and biogeochemistry measurements in GOA-ON. In addition, the well-calibrated, dual-parameter nature of the system is important for constraining nearshore chemistry, as biology, groundwater, and river inputs can lead to strong variability in carbonate

Coral Reef Habitat Suitability in Future Climate Scenarios from NCAR CESM1 considering a Suite of Biogeochemical Variables

Science.gov (United States)

Freeman, L. A.; Kleypas, J. A.; Miller, A. J.

2013-12-01

A maximum entropy species distribution model (Maxent) is used to describe coral reef habitat in current climate conditions and to predict changes to that habitat during the 21st century. Two climate change scenarios (RCP4.5 and RCP8.5) from the National Center for Atmospheric Research's Community Earth System Model version 1 (CESM1) were used with Maxent to determine environmental suitability for the family of corals Scleractina in 1° by 1° cells. Input environmental variables most suitable for representing coral habitat limitation are isolated using a principal component analysis and include cumulative thermal stress, salinity, light availability, current speed, phosphate levels and aragonite saturation state. Considering a suite of environmental variables allows for a more synergistic view of future habitat suitability, although individual variables are found to be limiting in certain areas- for example, aragonite saturation state is limiting at higher latitudes. Climate-driven coral reef habitat changes depend strongly on the oceanic region of interest and the region of corals used to train the niche model. Increased global coral habitat loss occurred in both RCP4.5 and RCP8.5 climate projections as time progressed through the 21th century. Maximum suitable habitat loss was 82% by 2100 for RCP8.5. When only Caribbean/Atlantic coral reef environmental data is applied globally, 88% of global habitat was lost by 2100 for RCP8.5. The global runs utilizing only Pacific Ocean reefs' ability to survive showed the most significant worldwide loss, 90% by 2100 for RCP8.5. When Maxent was trained with Indian Ocean reefs, an increase in suitable habitat worldwide was estimated. Habitat suitability was found to increase by 38% in RCP4.5 by 2100 and 28% in RCP8.5 by 2050. This suggests that shallow tropical sites in the Indian Ocean basin experience conditions today that are most similar to future worldwide climate projections. Indian Ocean reefs may be ideal candidate

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.

Effect of Hydrochemistry on Mineral Precipitation and Textural Diversity in Serpentinization-driven Alkaline Environments; Insights from Thermal Springs in the Oman Ophiolite.

Science.gov (United States)

Bach, W.; Giampouras, M.; Garcia-Ruiz, J. M.; Garrido, C. J.; Los, C.; Fussmann, D.; Monien, P.

2017-12-01

Interactions between meteoric water and ultramafic rocks within Oman ophiolite give rise to the formation of thermal spring waters of variable composition and temperature. Discharge of two different types of water forms complex hydrological networks of streams and ponds, in which the waters mix, undergo evaporation, and take up atmospheric CO2. We conducted a pond-by-pond sampling of waters and precipitates in two spring sites within the Wadi Tayin massif, Nasif and Khafifah, and examined how hydrochemistry and associated mineral saturation states affect the variations in mineral phases and textures. Three distinctive types of waters were identified in the system: a) Mg-type (7.9 11.6); Ca-OH-rich waters, and c) Mix-type (9.6 < pH < 11.5); waters arising upon mixing of Mg-type and Ca-type. PHREEQC was used to evaluate the role of mixing in aqueous speciation and the evolution of the saturation index value of different mineral phases. Mineral and textural characterization by X-ray diffraction, Raman spectroscopy and scanning electron microscopy were combined with these hydrogeochemical constraints to determine the factors controlling mineralogical and textural diversity in the system. In Ca-type waters, uptake of CO2 during the exposure of the fluids to the atmosphere is the predominant precipitation mechanism of CaCO3. High Mg:Ca ratios and high supersaturation rate of CaCO3 favor the growth of aragonite over calcite in mixed fluids. Changes in morphology and texture of aragonite crystals and crystal aggregates indicate the variations in the values of supersaturation and supersaturation rate of CaCO3 in the different water types. Brucite precipitation is common and driven by fluid mixing, while interaction with air-derived CO2 causes its alteration to hydromagnesite. The proximity of gabbroic lithologies appears to affect the presence of Al-bearing layered double hydroxides (LDHs). Furthermore, transformation of nesquehonite to dypingite in Mg-type waters record a

Freshwater Mussel Shell δ13C Values as a Proxy for δ13CDIC in a Polluted, Temperate River

Science.gov (United States)

Graniero, L. E.; Gillikin, D. P.; Surge, D. M.

2017-12-01

Freshwater mussel shell δ13C values have been examined as an indicator of ambient δ13C composition of dissolved inorganic carbon (DIC) in temperate rivers. However, shell δ13C values may be obscured by the assimilation of respired, metabolic carbon (CM) derived from the organism's diet. Water δ18O and δ13CDIC values were collected fortnightly from August 2015 through July 2017 from three sites (one agricultural, one downstream of a wastewater treatment plant, one urban) in the Neuse River, NC to test the reliability of Elliptio complanata shell δ13C values as a proxy for δ13CDIC values. Muscle, mantle, gill, and stomach δ13C values were analyzed to approximate the %CM incorporated into the shell. All tissue δ13C values were within 2‰ of each other, which equates to a ±1% difference in calculated %CM. As such, muscle tissue δ13C values will be used for calculating the %CM, because they have the slowest turnover rate of the tissues sampled. Water temperature and δ18O values were used to calculate predicted aragonite shell δ18O­ values (δ18O­ar) based on the aragonite-water fractionation relationship. To assign dates to each shell microsample, predicted δ18O­ar values were compared to high-resolution serially sampled shell values. Consistent with previous studies, E. complanata cease growth in winter when temperatures are below about 12ºC. Preliminary results indicate that during the growing season, shell δ13C values are lower than expected equilibrium values, reflecting the assimilation of 15% CM, on average. Shell δ13C values are not significantly different than δ13CDIC values, but do not capture the full range of δ13CDIC values during each growing season. Thus, δ13C values of E. complanata shells can be used to reliably reconstruct past δ13CDIC values within 2‰ of coeval values. Further research will investigate how differing land-use affects the relationship between shell δ13C, CM, and δ13CDIC values.

Sr evolution in the Upper Permian and Lower Triassic carbonates, northeast Sichuan basin, China: Constraints from chemistry, isotope and fluid inclusions

International Nuclear Information System (INIS)

Li, Kaikai; Cai, Chunfang; Jiang, Lei; Cai, Liulu; Jia, Lianqi; Zhang, Bing; Xiang, Lei; Yuan, Yuyang

2012-01-01

Petrographic features, C, O and Sr isotopes, rare earth and trace elements were determined, and fluid inclusions were analyzed on various stages of interparticle cements and vug-fillings from the Upper Permian and Lower Triassic sour reservoirs in northeastern Sichuan basin. The aim was to assess the origin and evolution of palaeo-waters in the carbonates. The original water was contemporary seawater, from which marine cements precipitated with slightly high Sr contents (mean 1911 ppm), 87 Sr/ 86 Sr ratios from 0.7067 to 0.7082 and nonluminescent CL. The palaeo-seawater was diluted by meteoric water, as indicated by bright cathodoluminescence (CL) and Sr-depletion (0–516 ppm) in low-temperature calcite. When buried to temperatures of about 60–90 °C during Middle to Late Triassic, the palaeo-water was enriched in Sr released from the transformation of precursor aragonite and calcite to dolomite, resulting in precipitation of substantial pre-bitumen Sr-rich minerals (SrSO 4 and SrCO 3 ). For un-dolomitized limestone sections, aragonite neomorphism may have contributed Sr to the precipitation of small amounts of Sr-bearing minerals and calcite crystals with elevated homogenization temperatures (HTs, mainly from 90 to 130 °C) and wide Sr contents (from 34 to 3825 ppm), as recorded in stage III calcite. Since the Middle Jurassic, almost all of the early stage celestite and significant amounts of solid CaSO 4 have been consumed by reactions with hydrocarbons (i.e., TSR), resulting in water enriched in isotopically light CO 2 and HCO 3 - ,Sr 2+ ,Ba 2+ and Eu 2+ , as recorded in calcite with low δ 13 C values (down to −18.9‰), 87 Sr/ 86 Sr ratios from 0.7072 to 0.7076, high HTs (mainly 110–198 °C), positive Eu anomalies and high Sr and Ba contents. Subsequently, the water was uplifted and cooled down to about 115 °C, celestite and strontianite were precipitated with the occurrence of natural elemental S immiscible inclusions. TSR may have produced

Mineralogy, early marine diagenesis, and the chemistry of shallow-water carbonate sediments

Science.gov (United States)

Higgins, J. A.; Blättler, C. L.; Lundstrom, E. A.; Santiago-Ramos, D. P.; Akhtar, A. A.; Crüger Ahm, A.-S.; Bialik, O.; Holmden, C.; Bradbury, H.; Murray, S. T.; Swart, P. K.

2018-01-01

Shallow-water carbonate sediments constitute the bulk of sedimentary carbonates in the geologic record and are widely used archives of Earth's chemical and climatic history. One of the main limitations in interpreting the geochemistry of ancient carbonate sediments is the potential for post-depositional diagenetic alteration. In this study, we use paired measurements of calcium (44Ca/40Ca or δ44Ca) and magnesium (26Mg/24Mg or δ26Mg) isotope ratios in sedimentary carbonates and associated pore-fluids as a tool to understand the mineralogical and diagenetic history of Neogene shallow-water carbonate sediments from the Bahamas and southwest Australia. We find that the Ca and Mg isotopic composition of bulk carbonate sediments at these sites exhibits systematic stratigraphic variability that is related to both mineralogy and early marine diagenesis. The observed variability in bulk sediment Ca isotopes is best explained by changes in the extent and style of early marine diagenesis from one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the fluid (fluid-buffered) to one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the precursor sediment (sediment-buffered). Our results indicate that this process, together with variations in carbonate mineralogy (aragonite, calcite, and dolomite), plays a fundamental and underappreciated role in determining the regional and global stratigraphic expressions of geochemical tracers (δ13C, δ18O, major, minor, and trace elements) in shallow-water carbonate sediments in the geologic record. Our results also provide evidence that a large shallow-water carbonate sink that is enriched in 44Ca can explain the mismatch between the δ44/40Ca value of rivers and deep-sea carbonate sediments and call into question the hypothesis that the δ44/40Ca value of seawater depends on the mineralogy of primary carbonate precipitations (e.g. 'aragonite seas' and

Mineral phases identification inside an abandoned Zn/Pb mine

International Nuclear Information System (INIS)

Goienaga, N.; Carrero, J.A.; Olivares, M.; Castro, K.; Fernandez, L.A.; Madariaga, J.M.

2009-01-01

Complete text of publication follows. The aim of the work is the identification of the sulphurated phase's outbreak on an aragonite, dolomite and calcite-based original rock inside an abandoned mine. The studied Blende/Galena (ZnS/PbS) Mine, located in Lanestosa (Bizkaia, North of Spain) was operative until 1950. After decades, the area has only supported wild life and thus nowadays it could be considered as a polluted site which has become naturalized. The main alteration factors inside the mine are percolated water, gases come from the outside (CO 2 , O 2 ) and biological activities. Mining activities generates loads of ore minerals and unwanted materials that with the time impact the surrounding environment. The waste includes granular, broken rock and soils ranging in size from the fine sand to large boulders, with the content of fine material largely dependent on the nature of the formation and extraction methods employed during mining. Waste materials geochemistry varies widely from mine to mine and may vary significantly at individual mines over time as different lithologic strata are exposed and geochemical processes alter characteristics of the waste. In order to determine the finest mineral composition in the galleries, several samples were collected. Once dried in a fume hood and sieved, the portions below 250 μm were subjected to non-destructive Raman spectroscopic analysis. The measurements reflected the ore precursors (primary phases: Blende, and Galena), several primary carbonates (dolomite, calcite and aragonite) with secondary minerals in trace levels (Brookite, Libethenite, Fluorapatita, Anatasa, Quartz, Apatite, Augite, Diopside, Anthracite, Hematite, Cosalite, Epidote, Rutile) and transformation products, probably of recent formation (Smithsonite, Massicot, Plattnerite, Gypsum, Siderite, Mendiphite, Escorodite, Gauberite, Goethite or Mascagnite). The origin of the secondary mineral may be related to percolated rain and snow water. This

Detection of food irradiation with luminescence methods

International Nuclear Information System (INIS)

Anderle, H.

1997-06-01

Food irradiation is applied as method for the preservation of foods, the prevention of food spoilage and the inhibition of food-borne pathogens. Doses exceeding 10 kGy (10 kJ/kg) are not recommended by the WHO. The different legislation requires methods for the detection and the closimetry of irradiated foods. Among the physical methods based on the radiation-induced changes in inorganic, nonhygroscopic crystalline solids are thermoluminescence (TL), photostimulated luminescence (PSL) and lyoluminescence (LL) measurement. The luminescence methods were tested on natural minerals. Pure quartz, feldspars, calcite, aragonite and dolomite of known origin were irradiated, read out and analyzed to determine the influence of luminescence-activators and deactivators. Carbonate minerals show an orange-red TL easily detectable by blue-sensitive photomultiplier tubes. TIL-inactive carbonate samples may be identified by a lyoluminescence method using the reaction of trapped irradiation-generated charge carriers with the solvent during crystal-lattice breakup. The fine-ground mineral is dissolved in an alkaline complexing agent/chemiluminescence sensitizer/chemiluminescence catalyst (EDTA/luminol/hemin) reagent mixture. The TL and PSL of quartz is too weak to contribute a significant part for the corresponding signals in polymineral dust. Alkali and soda feldspar show intense TL and PSL. The temperature maxima in the TL glow curves allow a clear distinction. PSL does not give this additional information, it suffers from bleaching by ambient light and requires light-protection. Grain disinfestated with low irradiation doses (500 Gy) may not identified by both TL and PSL measurement. The natural TL of feldspar particles may be overlap with the irradiation-induced TL of other minerals. As a routine method, irradiated spices are identified with TL measurement. The dust particles have to be enriched by heavy-liquid flotation and centrifugation. The PSL method allows a clear

Evaluation of I/Ca ratios in benthic foraminifera from the Peruvian oxygen minimum zone as proxy for redox conditions in the ambient water masses

Science.gov (United States)

Glock, N.; Liebetrau, V.; Eisenhauer, A.

2014-12-01

Tropical oxygen minimum zones (OMZs) are most important areas of oxygen depletion in today´s oceans and nutrient cycling in these regions has a large socio-economic impact because they account for about 17% of the global commercial fish catches(1). Possibly increasing magnitude and area of oxygen depletion in these regions, might endanger rich pelagic fish habitats in the future threatening the global marine food supply. By the use of a quantitative redox proxy in OMZs, reconstruction of the temporal variation in OMZ extension eventually providing information about past and future changes in oxygenation and the anthropogenic role in the recent trend of expanding OMZs(2). Recent work has shown that iodine/calcium (I/Ca) ratios in marine carbonates are a promising proxy for ambient oxygen concentration(3). Our study explores the correlation of I/Ca ratios in four benthic foraminiferal species (three calcitic, one aragonitic) from the Peruvian OMZ to bottom water oxygen concentrations ([O2]BW) and evaluates foraminiferal I/Ca ratios as a possible redox proxy for the ambient water masses. Our results show that all species have a positive trend in the I/Ca ratios as a function of [O2]BW. Only for the aragonitic species Hoeglundina elegans this trend is not significant. The highest significance has been found for Uvigerina striata (I/Ca = 0.032(±0.004).[O2]BW + 0.29(±0.03), R² = 0.61, F = 75, P solutions, (ii) a species dependency of the I/Ca-[O2]BW relationship which is either related to a strong vital effect or toa species dependency on the calcification depth within sediment, and (iii) the inter-test variability of I/Ca between different specimens from the same species and habitat. (1): FAO FishStat: Fisheries and aquaculture software. In: FAO Fisheries and Aquaculture Department[online]. Rome. Updated 28 Nov. 2013. (2): Stramma et al.: Expanding Oxygen-Minimum Zones in the Tropical Oceans, Science, 320, 655-658, 2008. (3): Lu et al.: Iodine to calcium ratios in

Chemistry of a serpentinization-controlled hydrothermal system at the Lost City hydrothermal vent field

Science.gov (United States)

Ludwig, K. A.; Kelley, D. S.; Butterfield, D. A.; Nelson, B. K.; Karson, J. A.

2003-12-01

The Lost City Hydrothermal Field (LCHF), at 30° N near the Mid-Atlantic Ridge, is an off-axis, low temperature, high-pH, ultramafic-hosted vent system. Within the field, carbonate chimneys tower up to 60 m above the seafloor, making them the tallest vent structures known. The chemistry of the vent structures and fluids at the LCHF is controlled by reactions between seawater and ultramafic rocks beneath the Atlantis massif. Mixing of warm alkaline vent fluids with seawater causes precipitation of calcium carbonate and growth of the edifaces, which range from tall, graceful pinnacles to fragile flanges and colloform deposits. Geochemical and petrological analyses of the carbonate rocks reveal distinct differences between the active and extinct structures. Actively venting chimneys and flanges are extremely porous, friable formations composed predominantly of aragonite and brucite. These structures provide important niches for well-developed microbial communities that thrive on and within the chimney walls. Some of the active chimneys may also contain the mineral ikaite, an unstable, hydrated form of calcium carbonate. TIMS and ICP-MS analyses of the carbonate chimneys show that the most active chimneys have low Sr isotope values and that they are low in trace metals (e.g., Mn, Ti, Pb). Active structures emit high-pH, low-Mg fluids at 40-90° C. The fluids also have low Sr values, indicating circulation of hydrothermal solutions through the serpentinite bedrock beneath the field. In contrast to the active structures, extinct chimneys are less porous, are well lithified, and they are composed predominantly of calcite that yields Sr isotopes near seawater values. Prolonged lower temperature seawater-hydrothermal fluid interaction within the chimneys results in the conversion of aragonite to calcite and in the enrichment of some trace metals (e.g., Mn, Ti, Co, Zn). It also promotes the incorporation of foraminifera within the outer, cemented walls of the carbonate

Nanoscale elasticity mappings of micro-constituents of abalone shell by band excitation-contact resonance force microscopy

Science.gov (United States)

Li, Tao; Zeng, Kaiyang

2014-01-01

The macroscopic mechanical properties of the abalone shell have been studied extensively in the literature, but the in situ nanoscale elasticity of various micro-constituents in the shell have not been characterized and reported yet. In this study, the nanoscale elasticity mappings including different micro-constituents in abalone shell were observed by using the Contact Resonance Force Microscopy (CR-FM) technique. CR-FM is one of the advanced scanning probe microscopy techniques that is able to quantify the local elastic moduli of various materials in a non-destructive manner. Instead of an average value, an elasticity mapping that reveals the nanoscale variations of elastic moduli with location can be extracted and correlated with the topography of the structure. Therefore in this study, by adopting the CR-FM technique that is incorporated with the band excitation technique, the elasticity variations of the abalone shell caused by different micro-constituents and crystal orientations are reported, and the elasticity values of the aragonite and calcite nanograins are quantified.The macroscopic mechanical properties of the abalone shell have been studied extensively in the literature, but the in situ nanoscale elasticity of various micro-constituents in the shell have not been characterized and reported yet. In this study, the nanoscale elasticity mappings including different micro-constituents in abalone shell were observed by using the Contact Resonance Force Microscopy (CR-FM) technique. CR-FM is one of the advanced scanning probe microscopy techniques that is able to quantify the local elastic moduli of various materials in a non-destructive manner. Instead of an average value, an elasticity mapping that reveals the nanoscale variations of elastic moduli with location can be extracted and correlated with the topography of the structure. Therefore in this study, by adopting the CR-FM technique that is incorporated with the band excitation technique, the

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.

Radon, carbon dioxide and fault displacements in central Europe related to the Tohoku earthquake

International Nuclear Information System (INIS)

Briestensky, M.; Stemberk, J.; Rowberry, M.D.; Thinova, L.; Knejflova, Z.; Praksova, R.

2014-01-01

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 Mladec Caves and by carbon dioxide monitoring in the Zbrasov 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 M W = 9.0 Tohoku Earthquake, which hit eastern Japan on 11 March 2011. It is tentatively suggested that the Tohoku Earthquake in the Pacific Ocean and the unusual geodynamic activity recorded in the Bohemian Massif and Western Carpathians both reflect contemporaneous global tectonic changes. (authors)

Decadal Anthropogenic Carbon Storage Along P16 and P02

Science.gov (United States)

Carter, B. R.; Feely, R. A.; Talley, L. D.; Cross, J. N.; Macdonald, A. M.; Mecking, S.; Siedlecki, S. A.

2016-02-01

The Pacific Ocean has the largest ocean basin anthropogenic carbon (Canth) inventory due to the large size of the basin. We estimate anthropogenic carbon (Canth) concentrations and decadal storages along the meridional P16 and zonal P02 lines since the mid 90s using a modified version of the extended multiple linear regression (EMLR) technique with data from the WOCE, CLIVAR, and GO-SHIP occupations of these lines. We present our estimates and map the aragonite saturation state (ΩA) decreases and saturation horizon shoaling resulting from continued Canth storage. The average storage rate was larger along both sections during the most recent decade (2000's to 2010's) than during the previous decade (1990's to 2000's), especially along P02. Significant decadal concentration increases were found in the mixed layers, shallow thermoclines, mode waters, and portions of the intermediate water masses.

Comparative genomics explains the evolutionary success of reef-forming corals

KAUST Repository

Bhattacharya, Debashish; Agrawal, Shobhit; Aranda, Manuel; Baumgarten, Sebastian; Belcaid, Mahdi; Drake, Jeana L; Erwin, Douglas; Foret, Sylvian; Gates, Ruth D; Gruber, David F; Kamel, Bishoy; Lesser, Michael P; Levy, Oren; Liew, Yi Jin; MacManes, Matthew; Mass, Tali; Medina, Monica; Mehr, Shaadi; Meyer, Eli; Price, Dana C; Putnam, Hollie M; Qiu, Huan; Shinzato, Chuya; Shoguchi, Eiichi; Stokes, Alexander J; Tambutté , Sylvie; Tchernov, Dan; Voolstra, Christian R.; Wagner, Nicole; Walker, Charles W; Weber, Andreas PM; Weis, Virginia; Zelzion, Ehud; Zoccola, Didier; Falkowski, Paul G

2016-01-01

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.

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.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

Science.gov (United States)

Guzmán, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2009-02-01

Variations in the chemical composition of fossil biogenic carbonates, and in particular of mollusc shells, have been used in a range of palaeoenvironmental reconstructions. It is of primary importance, therefore, to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Holocene and Pleistocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusc shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to verify the conservation state of shell samples is insufficient.

On flaw tolerance of nacre: a theoretical study

Science.gov (United States)

Shao, Yue; Zhao, Hong-Ping; Feng, Xi-Qiao

2014-01-01

As a natural composite, nacre has an elegant staggered ‘brick-and-mortar’ microstructure consisting of mineral platelets glued by organic macromolecules, which endows the material with superior mechanical properties to achieve its biological functions. In this paper, a microstructure-based crack-bridging model is employed to investigate how the strength of nacre is affected by pre-existing structural defects. Our analysis demonstrates that owing to its special microstructure and the toughening effect of platelets, nacre has a superior flaw-tolerance feature. The maximal crack size that does not evidently reduce the tensile strength of nacre is up to tens of micrometres, about three orders higher than that of pure aragonite. Through dimensional analysis, a non-dimensional parameter is proposed to quantify the flaw-tolerance ability of nacreous materials in a wide range of structural parameters. This study provides us some inspirations for optimal design of advanced biomimetic composites. PMID:24402917

Comparative study of carp otolith hardness: lapillus and asteriscus.

Science.gov (United States)

Ren, Dongni; Meyers, Marc André; Zhou, Bo; Feng, Qingling

2013-05-01

Otoliths are calcium carbonate biominerals in the inner ear of vertebrates; they play a role in balance, movement, and sound perception. Two types of otoliths in freshwater carp are investigated using nano- and micro-indentation: asteriscus and lapillus. The hardness, modulus, and creep of asteriscus (vaterite crystals) and lapillus (aragonite crystals) are compared. The hardness and modulus of lapillus are higher than those of asteriscus both in nano- and micro-testing, which is attributed to the different crystal polymorphs. Both materials exhibit a certain degree of creep, which indicates some time dependence of the mechanical behavior and is attributed to the organic components. The nano-indentation hardnesses are higher than micro-hardnesses for both otoliths, a direct result of the scale dependence of strength; fewer flaws are encountered by the nano than by the microindenter. Copyright © 2012 Elsevier B.V. All rights reserved.

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 (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.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae in the hyper-arid conditions of Northern Chile – implications for palaeoenvironmental reconstructions

Directory of Open Access Journals (Sweden)

L. Ortlieb

2009-02-01

Full Text Available Variations in the chemical composition of fossil biogenic carbonates, and in particular of mollusc shells, have been used in a range of palaeoenvironmental reconstructions. It is of primary importance, therefore, to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Holocene and Pleistocene shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusc shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to verify the conservation state of shell samples is insufficient.

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

International Nuclear Information System (INIS)

De Visscher, Alex; Vanderdeelen, Jan

2012-01-01

The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO 3 types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO 3 · H 2 O), the hexahydrate ikaite (CaCO 3 ·6H 2 O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

Preparation, physical-chemical characterisation and cytocompatibility of calcium carbonate cements.

Science.gov (United States)

Combes, C; Miao, Baoji; Bareille, Reine; Rey, Christian

2006-03-01

The feasibility of calcium carbonate cements involving the recrystallisation of metastable calcium carbonate varieties has been demonstrated. Calcium carbonate cement compositions presented in this paper can be prepared straightforwardly by simply mixing water (liquid phase) with two calcium carbonate phases (solid phase) which can be easily obtained by precipitation. An original cement composition was obtained by mixing amorphous calcium carbonate and vaterite with an aqueous medium. The cement set and hardened within 2h at 37 degrees C in an atmosphere saturated with water and the final composition of the cement consisted mostly of aragonite. The hardened cement was microporous and showed poor mechanical properties. Cytotoxicity tests revealed excellent cytocompatibility of calcium carbonate cement compositions. Calcium carbonates with a higher solubility than the apatite formed for most of the marketed calcium phosphate cements might be of interest to increase biomedical cement resorption rates and to favour its replacement by bone tissue.

Hydrochemistry and groundwater system of the Zerka Ma'in-Zara thermal field, Jordan

Science.gov (United States)

Rimawi, Omar; Salameh, Elias

1988-03-01

A groundwater flow model through the different geological successions from the Upper Cretaceous through the Lower Cretaceous Sandstone and older units is presented in this paper. The model is supported by the hydrochemical evolution of water types from the recharge areas in the highlands to discharge sites of thermal water at the slopes overlooking the Dead Sea. The thermal water discharged in the Zerka Ma'in-Zara areas consists of three end members mixed in different ratios with a component of old (many thousands of years) thermal water undersaturated in carbonate minerals and containing hundreds of milligrams per liter of free CO 2. The release of CO 2 gas upon discharge renders the water oversaturated with respect to carbonate minerals which results in aragonite precipitation. The elevated temperature of the water in the reservoir (73-82°C) is attributed to the presence of a heat-storing layer topping the aquifer.

Quantifying Porosity through Automated Image Collection and Batch Image Processing: Case Study of Three Carbonates and an Aragonite Cemented Sandstone

Directory of Open Access Journals (Sweden)

Jim Buckman

2017-08-01

Full Text Available Modern scanning electron microscopes often include software that allows for the possibility of obtaining large format high-resolution image montages over areas of several square centimeters. Such montages are typically automatically acquired and stitched, comprising many thousand individual tiled images. Images, collected over a regular grid pattern, are a rich source of information on factors such as variability in porosity and distribution of mineral phases, but can be hard to visually interpret. Additional quantitative data can be accessed through the application of image analysis. We use backscattered electron (BSE images, collected from polished thin sections of two limestone samples from the Cretaceous of Brazil, a Carboniferous limestone from Scotland, and a carbonate cemented sandstone from Northern Ireland, with up to 25,000 tiles per image, collecting numerical quantitative data on the distribution of porosity. Images were automatically collected using the FEI software Maps, batch processed by image analysis (through ImageJ, with results plotted on 2D contour plots with MATLAB. These plots numerically and visually clearly express the collected porosity data in an easily accessible form, and have application for the display of other data such as pore size, shape, grain size/shape, orientation and mineral distribution, as well as being of relevance to sandstone, mudrock and other porous media.

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.

Study and characterization of ceramic materials from natural origin for application in jewellery design using laser texturing as innovation

International Nuclear Information System (INIS)

Elesbao, T.R.; Carus, L.A.; Tabarelli, A.C.; Vieira, R.P.; Takimi, A.S.

2012-01-01

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)

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)

Occurrence and genesis of Quaternary microbialitic tufa at Hammam Al Ali, Oman

Science.gov (United States)

Khalaf, Fikry I.

2017-05-01

Remnants of late Quaternary microbialitic tufa occurs within a shallow depression in the Hammam Al Ali hot spring area, which is located approximately 14.5 km to the southwest of Muscat, Oman. The tufa precipitated from hot spring water supersaturated with respect to calcium carbonate and is mostly of a porous phytogenic type, with occasional detrital and stromatolitic types. Microscopic and nanoscopic examination revealed that the tufa deposits developed through two successive processes of calcite precipitation, biotic and abiotic, preceded by limited precipitation of unstable aragonite. It is suggested that biologically mediated precipitation results in the construction of incomplete skeletal calcite crystals. The latter provide a base for classical physiochemical precipitation and, eventually, the development of complete sparry calcite crystals. The initiation of dendritic calcite crystals in the stromatolitic tufa as incomplete biogenic skeletal crystals and their characteristic growth pattern indicates that the tufa represents a clear example of hot spring calcitic microbialite.

Coral skeletal tin and copper concentrations at Pohnpei, Micronesia: possible index for marine pollution by toxic anti-biofouling paints

Energy Technology Data Exchange (ETDEWEB)

Inoue, Mayuri; Suzuki, Atsushi; Nohara, Masato; Kan, Hironobu; Edward, Ahser; Kawahata, Hodaka

2004-06-01

We present 40 year-long skeletal chronologies of tin (Sn) and copper (Cu) from an annually-banded coral (Porites sp.) collected from Pohnpei Island, Micronesia (western equatorial Pacific). Both the elements are present in antifouling marine paints and are released inadvertently into ambient seawater. Especially, Sn has often been used in the form of tributyltin (TBT). Based on a stepwise pretreatment examination, Sn and Cu both inside and outside the aragonite lattice of the coral skeleton show a potential for providing marine pollution indicators. High values of extra-skeletal Cu/Ca and Sn/Ca atomic ratios were found between late 1960s and late 1980s during a period of active use of TBT-based antifouling paints worldwide. However, a significant decrease in both the ratios in the beginning of 1990s can be attributed to regulation of the use of TBT on cargo ships by countries such as the USA, Japan and Australia. - A new index of coral marine pollution is proposed.

Coral skeletal tin and copper concentrations at Pohnpei, Micronesia: possible index for marine pollution by toxic anti-biofouling paints

International Nuclear Information System (INIS)

Inoue, Mayuri; Suzuki, Atsushi; Nohara, Masato; Kan, Hironobu; Edward, Ahser; Kawahata, Hodaka

2004-01-01

We present 40 year-long skeletal chronologies of tin (Sn) and copper (Cu) from an annually-banded coral (Porites sp.) collected from Pohnpei Island, Micronesia (western equatorial Pacific). Both the elements are present in antifouling marine paints and are released inadvertently into ambient seawater. Especially, Sn has often been used in the form of tributyltin (TBT). Based on a stepwise pretreatment examination, Sn and Cu both inside and outside the aragonite lattice of the coral skeleton show a potential for providing marine pollution indicators. High values of extra-skeletal Cu/Ca and Sn/Ca atomic ratios were found between late 1960s and late 1980s during a period of active use of TBT-based antifouling paints worldwide. However, a significant decrease in both the ratios in the beginning of 1990s can be attributed to regulation of the use of TBT on cargo ships by countries such as the USA, Japan and Australia. - A new index of coral marine pollution is proposed

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.

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.

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.

Diverse coral communities in naturally acidified waters of a Western Pacific reef

Science.gov (United States)

Shamberger, Kathryn E. F.; Cohen, Anne L.; Golbuu, Yimnang; McCorkle, Daniel C.; Lentz, Steven J.; Barkley, Hannah C.

2014-01-01

Anthropogenic carbon dioxide emissions are acidifying the oceans, reducing the concentration of carbonate ions ([CO32-]) that calcifying organisms need to build and cement coral reefs. To date, studies of a handful of naturally acidified reef systems reveal depauperate communities, sometimes with reduced coral cover and calcification rates, consistent with results of laboratory-based studies. Here we report the existence of highly diverse, coral-dominated reef communities under chronically low pH and aragonite saturation state (Ωar). Biological and hydrographic processes change the chemistry of the seawater moving across the barrier reefs and into Palau's Rock Island bays, where levels of acidification approach those projected for the western tropical Pacific open ocean by 2100. Nevertheless, coral diversity, cover, and calcification rates are maintained across this natural acidification gradient. Identifying the combination of biological and environmental factors that enable these communities to persist could provide important insights into the future of coral reefs under anthropogenic acidification.

Vulnerability of a semienclosed estuarine sea to ocean acidification in contrast with hypoxia

Science.gov (United States)

Ianson, Debby; Allen, Susan E.; Moore-Maley, Benjamin L.; Johannessen, Sophia C.; Macdonald, Robie W.

2016-06-01

The Strait of Georgia (SoG) is a large semienclosed estuary that spatially dominates the Salish Sea on the North American Pacific coast. The region is well populated, harbors significant aquaculture, and is vulnerable to climate change. We present the first inorganic carbon data collected in the SoG covering all seasons (2003 and 2010-2012) and put them into the context of local circulation and oxygen cycles. Results show that the SoG has a higher carbon content and lower pH than surrounding waters. Aragonite saturation horizons in the SoG do not become deeper than 20-30 m and shoal to the surface for extended periods. Furthermore, incoming upwelled "acidified" water from the outer coast actually increases local pH. Finally, intense mixing in the physically restricted channels connecting the SoG to the outer coast allows significant oxygen uptake but minimal CO2 out gassing, protecting the SoG from hypoxia but not from ocean acidification.

Coral skeletal tin and copper concentrations at Pohnpei, Micronesia: possible index for marine pollution by toxic anti-biofouling paints.

Science.gov (United States)

Inoue, Mayuri; Suzuki, Atsushi; Nohara, Masato; Kan, Hironobu; Edward, Ahser; Kawahata, Hodaka

2004-06-01

We present 40 year-long skeletal chronologies of tin (Sn) and copper (Cu) from an annually-banded coral (Porites sp.) collected from Pohnpei Island, Micronesia (western equatorial Pacific). Both the elements are present in antifouling marine paints and are released inadvertently into ambient seawater. Especially, Sn has often been used in the form of tributyltin (TBT). Based on a stepwise pretreatment examination, Sn and Cu both inside and outside the aragonite lattice of the coral skeleton show a potential for providing marine pollution indicators. High values of extra-skeletal Cu/Ca and Sn/Ca atomic ratios were found between late 1960s and late 1980s during a period of active use of TBT-based antifouling paints worldwide. However, a significant decrease in both the ratios in the beginning of 1990s can be attributed to regulation of the use of TBT on cargo ships by countries such as the USA, Japan and Australia.

Ocean Acidification of the Pacific Northwest Coastal Waters: A Modeling Study

Science.gov (United States)

Siedlecki, S. A.; MacCready, P.; McCabe, R. M.; Feely, R. A.; Alin, S. R.; Newton, J.; Barth, J. A.; Durski, S. M.

2016-02-01

Total inorganic carbon and alkalinity is incorporated into a regional bio-physical model to examine inorganic carbon variability along the Washington and Oregon continental margin. Results are compared to output from an existing oxygen model (Siedlecki et al., 2015) combined with observationally-based empirical relationships between carbon system parameters, oxygen, and temperature (Alin et al., in prep). Model hindcasts for 2007 and 2013 are also validated against local observations of dissolved oxygen, pH, and the saturation state of aragonite. Challenges and benefits of each approach are discussed. The model suggests that the volume of hypoxic and undersaturated water present over the continental shelf increases over the upwelling season, occupying more of the water column later in the upwelling season. This would result in increasingly stressful conditions for biota over most of the water column as the upwelling season progresses. Spatial variability in the volume of undersaturated water in the region will also be discussed.

Ocean Acidification of the coastal waters of the Pacific Northwest: A modeling study

Science.gov (United States)

Siedlecki, S. A.; Hermann, A. J.; Bond, N. A.; Alin, S. R.; Feely, R. A.; Hales, B. R.; Newton, J.; Migliaccio, L.

2013-12-01

A regional oxygen model of the Washington and Oregon shelves (Siedlecki, S.A., Banas, N., Davis, K.A., Giddings, S., P. MacCready, Connolly, T., & B. Hickey. Seasonal Oxygen variability on the continental shelves of Washington and Oregon, in prep) is combined with the empirical relationships between the carbonate system, oxygen and temperature (Alin et al, in prep) to simulate the carbonate chemistry in this region. A model hindcast for 2009 is compared to local observations of oxygen, and aragonite saturation. The model is able to reproduce the seasonal change in oxygen observed on the Oregon shelf. Challenges of this approach are discussed. The volume of hypoxic and undersaturated water increases over the upwelling season, occupying more of the water column later in the upwelling season. This results in increasingly stressful conditions over most of the water column for biota on the shelf as the upwelling season progresses. How the rate of ascension and presence of this undersaturated water varies regionally will be discussed.

High ordered biomineralization induced by carbon nanoparticles in the sea urchin Paracentrotus lividus

International Nuclear Information System (INIS)

Manno, Daniela; Buccolieri, Alessandro; Filippo, Emanuela; Serra, Antonio; Carata, Elisabetta; Tenuzzo, Bernadetta A; Panzarini, Elisa; Dini, Luciana; Rossi, Marco

2012-01-01

A surprising and unexpected biomineralization process was observed during toxicological assessment of carbon nanoparticles on Paracentrotus lividus (sea urchin) pluteus larvae. The larvae activate a process of defense against external material, by incorporating the nanoparticles into microstructures of aragonite similarly to pearl oysters. Aiming at a better understanding of this phenomenon, the larvae were exposed to increasing concentrations of carbon nanoparticles and the biomineralization products were analyzed by electron microscopy, x-ray diffraction and Raman spectroscopy. In order to evaluate the possible influence of Sp-CyP-1 expression on this biomineralization process by larvae, analyses of gene expression (Sp-CyP-1) and calcein labeling were performed. Overall, we report experimental evidence about the capability of carbon nanoparticles to induce an increment of Sp-CyP-1 expression with the consequent activation of a biomineralization process leading to the production of a new pearl-like biomaterial never previously observed in sea urchins. (paper)

Gasification catalysts prepared by the reaction of CaCO3 and coal. Tansan karushiumu to sekitan no ion kokan hanno ni yori choseishita kokassei gas ka shokubai

Energy Technology Data Exchange (ETDEWEB)

Otsuka, Y.; Asami, K. (Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science)

1991-11-07

Properties of the active gasification catalysts prepared by ion exchange reaction of CaCO3 and coal were studied. Several kinds of Ca-loaded coal specimens were prepared to compare their properties among them by physically mixing coal particles with CaCO3 ones in air, by kneading both materials in pure water while crashing and by impregnating CaCO3 into coal while agitating them in pure water. Although Ca-loading onto the impregnated specimen was nearly one-half that of the kneaded one, its catalysis was equal to the kneaded one. CaCO3 greatly accelerated steam gasification only by mixing it with low rank coal in water, and such a high catalytic activity was caused by ion-exchanged Ca produced by the reaction between CaCO3 and COOH radical in coal. Aragonite of seashells yielded more Ca-loading than calcite of limestone, suggesting one of the useful treatment of seashell waste. 3 refs., 4 figs., 2 tabs.

Studying the formation of CaCO3 polymorphs during the carbonation of nano-lime suspension in ethanol

International Nuclear Information System (INIS)

Sevcik, R.; Perez-Estebanez, M.; Macova, P.

2015-01-01

The paper is devoted to studying nano-lime and the formation of CaCO 3 polymorphs during this process. Nano-lime means a suspension of Ca(OH) 2 in alcohol, in this case ethanol (CaLoSil(R) E25). Carbonation reaction of nano-lime suspension having a concentration of 25 g l -1 and 5 ml was studied in a climatic chamber at a constant temperature and humidity conditions (T = 20 (1) DEG C., 65 (5), RH). At regular intervals (7, 14, 21 and 28 days), the samples were analyzed by infrared spectroscopy (FTIR), X-ray powder diffraction (XRPD) and observed under a scanning electron microscope (SEM). Quantitative determination was performed by Rietvelde's smoothing from XPRD data. It was found that the samples contained three crystalline forms of CaCO 3 - calcite, aragonite and vaterite, the percentage of their time was variable. These results will be used in further research on the application of nano-lime on calcareous materials. (Authors)

Calcification response of Pleurochrysis carterae to iron concentrations in batch incubations: implication for the marine biogeochemical cycle

Science.gov (United States)

Zou, Xiang; Sun, Shiyong; Lin, Sen; Shen, Kexuan; Dong, Faqin; Tan, Daoyong; Nie, Xiaoqin; Liu, Mingxue; Wei, Jie

2017-12-01

Calcified coccolithophores, a diverse and widely distributed group of marine microalgae, produce biogenic calcite in the form of coccoliths located on the cell surface. Using batch incubations of the coccolithophorid Pleurochrysis carterae, we investigated the responses of this calcification process to iron concentrations by changing the iron supply in the initial culture media from a normal concentration to 1 ppm (parts per million), 5 ppm, and 10 ppm. Time-dependent measurements of cell population, production of inorganic carbon (coccoliths), and organic carbon (organic cellular components) showed that elevated iron supply in the growth medium of P. carterae stimulates carbon sequestration by increasing growth along enhanced photosynthetic activity and calcification. In addition, the acquired time-dependent UV-Vis and FT-IR spectra revealed that iron fertilization-enhanced coccolith calcification is accompanied by a crystalline phase transition from calcite to aragonite or amorphous phase. Our results suggest that iron concentration has a significant influence on the marine carbon cycle of coccolithophores.

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 marine carbonate factories function both today and in the past.

Strontium and zinc concentrations in otoliths of common fish species in the northern Baltic Sea

Energy Technology Data Exchange (ETDEWEB)

Lill, J.-O., E-mail: jlill@abo.fi [Accelerator Laboratory, Turku PET Centre, Åbo Akademi University, Porthansgatan 3, FI-20500 Turku (Finland); Himberg, M. [Laboratory of Aquatic Pathobiology, Husö Biological Station, Environmental and Marine Biology, Department of Biosciences, Åbo Akademi University, Artillerigatan 6, FI-20520 Turku (Finland); Harju, L.; Ek, P. [Analytical Chemistry, Department of Chemical Engineering, Åbo Akademi University, Biskopsgatan 8, FI-20500 Turku (Finland); Lindroos, A. [Geology and Mineralogy, Department of Natural Sciences, Åbo Akademi University, Domkyrkotorget, FI-20500 Turku (Finland); Wiklund, T. [Laboratory of Aquatic Pathobiology, Husö Biological Station, Environmental and Marine Biology, Department of Biosciences, Åbo Akademi University, Artillerigatan 6, FI-20520 Turku (Finland); Gunnelius, K.; Smått, J.-H. [Physical Chemistry, Department of Natural Sciences, Åbo Akademi University, Porthansgatan 3, FI-20500 Turku (Finland); Heselius, S.-J. [Accelerator Laboratory, Turku PET Centre, Åbo Akademi University, Porthansgatan 3, FI-20500 Turku (Finland); Hägerstrand, H. [Laboratory of Aquatic Pathobiology, Husö Biological Station, Environmental and Marine Biology, Department of Biosciences, Åbo Akademi University, Artillerigatan 6, FI-20520 Turku (Finland)

2014-01-01

Otoliths of perch (Perca fluviatilis), pike (Esox lucius) and European whitefish (Coregonus lavaretus) caught at different locations in the northern Baltic Sea along the Finnish west coast and at some rivers and lakes were subjected to elemental analyses with particle induced X-ray emission and laser ablation inductively coupled plasma mass spectrometry. The strontium concentration in otoliths from whitefish (∼3300 μg/g) was 2–3 times higher than that of perch and pike (∼1400 μg/g), while within species the strontium concentration of otoliths from fish caught at different locations was in the same range. The strontium concentrations were lowest in fish from the lakes (∼450 μg/g). Whitefish otoliths contained more zinc (∼60 μg/g) than those of pike (∼30 μg/g), while the zinc concentration in perch otoliths were below the detection limit. No spatial intraspecies variations in zinc concentrations were observed. X-ray diffraction showed that the otoliths consisted of aragonite solely.

Sr/Ca-Sea surface temperature calibration in the branching Caribbean coral Acropora palmata

Science.gov (United States)

Gallup, Christina D.; Olson, Donna M.; Edwards, R. Lawrence; Gruhn, Leah M.; Winter, Amos; Taylor, Frederick W.

2006-02-01

We measured Sr/Ca ratios by thermal ionization mass spectrometry in radial and axial growth of modern Caribbean Acropora palmata corals. Comparison of our results with sea surface temperature (SST) allows radial and axial Sr/Ca-SST calibrations of Sr/Ca (mmol/mol) = 11.30 - 0.07072 × SST (°C) and Sr/Ca (mmol/mol) = 11.32 - 0.06281 x SST (°C), respectively. Application of the calibrations to fossil Acropora palmata from the last glacial maximum in Barbados (Guilderson et al., 1994) imply ~7°C cooler conditions than the present, much larger than the 1-1.5° cooling suggested by modern analog technique foraminifera-based estimates (Trend-Staid and Prell, 2002). If the foraminifera-based estimates are correct, then the excess cooling suggested by the Barbados corals could be explained by a 5% shift in the marine Sr/Ca ratio or an addition of ~20% abiotic secondary aragonite.

Radiocarbon and stable isotopes in Palmyra corals during the past century

Science.gov (United States)

Druffel-Rodriguez, Kevin C.; Vetter, Desiree; Griffin, Sheila; Druffel, Ellen R. M.; Dunbar, Robert B.; Mucciarone, David A.; Ziolkowski, Lori A.; Sanchez-Cabeza, Joan-Albert

2012-04-01

Annual samples from two Palmyra Atoll corals (Porites lutea) that lived during the past 110 years were analyzed for radiocarbon (Δ14C) and δ18O. The Δ14C values decreased 7.6‰ from 1896 to 1953, similar to other coral records from the tropical and subtropical Pacific. Δ14C values rose from ˜-60‰ to ˜+110‰ by 1980 due to the input of bomb radiocarbon from the atmosphere. Elevated Δ14C values were observed for the mid- to late-1950s, suggesting early input of bomb radiocarbon, possibly from the largest Marshall Islands bomb tests in 1954. Secondary aragonite precipitation was identified in a portion of one core using scanning electron microscopy and X-radiography, and was responsible for high δ18O and δ13C values and a correlation between them. The Δ14C results were more resistant to alteration, except when contamination was from the bomb era (>1956).

Multifunctional, supramolecular, continuous artificial nacre fibres

Science.gov (United States)

Hu, Xiaozhen; Xu, Zhen; Gao, Chao

2012-10-01

Nature has created amazing materials during the process of evolution, inspiring scientists to studiously mimic them. Nacre is of particular interest, and it has been studied for more than half-century for its strong, stiff, and tough attributes resulting from the recognized ``brick-and-mortar'' (B&M) layered structure comprised of inorganic aragonite platelets and biomacromolecules. The past two decades have witnessed great advances in nacre-mimetic composites, but they are solely limited in films with finite size (centimetre-scale). To realize the adream target of continuous nacre-mimics with perfect structures is still a great challenge unresolved. Here, we present a simple and scalable strategy to produce bio-mimic continuous fibres with B&M structures of alternating graphene sheets and hyperbranched polyglycerol (HPG) binders via wet-spinning assembly technology. The resulting macroscopic supramolecular fibres exhibit excellent mechanical properties comparable or even superior to nacre and bone, and possess fine electrical conductivity and outstanding corrosion-resistance.

Bioinspired, Graphene/Al2O3 Doubly Reinforced Aluminum Composites with High Strength and Toughness.

Science.gov (United States)

Zhang, Yunya; Li, Xiaodong

2017-11-08

Nacre, commonly referred to as nature's armor, has served as a blueprint for engineering stronger and tougher bioinspired materials. Nature organizes a brick-and-mortar-like architecture in nacre, with hard bricks of aragonite sandwiched with soft biopolymer layers. However, cloning nacre's entire reinforcing mechanisms in engineered materials remains a challenge. In this study, we employed hybrid graphene/Al 2 O 3 platelets with surface nanointerlocks as hard bricks for primary load bearer and mechanical interlocking, along with aluminum laminates as soft mortar for load distribution and energy dissipation, to replicate nacre's architecture and reinforcing effects in aluminum composites. Compared with aluminum, the bioinspired, graphene/Al 2 O 3 doubly reinforced aluminum composite demonstrated an exceptional, joint improvement in hardness (210%), strength (223%), stiffness (78%), and toughness (30%), which are even superior over nacre. This design strategy and model material system should guide the synthesis of bioinspired materials to achieve exceptionally high strength and toughness.

Microstructural characterization of archaeological materials from the Chapatongo-Los Cerritos, Tula, Hidalgo site through Sem and XRD

International Nuclear Information System (INIS)

Rodriguez L, V.; Espinosa P, M.; Fournier, P.

2004-01-01

In one of the main epiclase s establishments of the region of Tula, they have been carried out extensive excavations recently in several sectors. Among the funeral offerings, as well as among the waste materials and recovered in architectural fillers of the place of Chapatongo-Los Cerritos. Diverse stony materials are included stone-beads fundamentally; and they were characterized through Scanning Electron Microscopy (MEB), Energy Dispersive X-ray Spectroscopy (EDS) and X-ray Diffraction (DRX). Morphologies with habits were identified as grooved with great ruggedness that present particles like inclusions of metallic oxides, surfaces with great porosity, lamellar structures, agglomerates, fibers of great extension. Likewise the constituent crystalline phases of the samples were identified: calcite, aragonite, calcium and potassium aluminosilicates, microcline and quartz. In the case of the crystalline phases like omphacite, nacrite and dickite are characteristic of the green stone-beads, these belong to the family of the jadeite phase, considered as precious materials in the pre hispanic world. (Author) 20 refs., 20 tabs., 23 figs

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'. © 2016 The Author(s).

Structure and expression of an unusually acidic matrix protein of pearl oyster shells

International Nuclear Information System (INIS)

Tsukamoto, Daiki; Sarashina, Isao; Endo, Kazuyoshi

2004-01-01

We report identification and characterization of the unusually acidic molluscan shell matrix protein Aspein, which may have important roles in calcium carbonate biomineralization. The Aspein gene (aspein) encodes a sequence of 413 amino acids, including a high proportion of Asp (60.4%), Gly (16.0%), and Ser (13.2%), and the predicted isoelectric point is 1.45; this is the most acidic of all the molluscan shell matrix proteins sequenced so far, or probably even of all known proteins on earth. The main body of Aspein is occupied by (Asp) 2-10 sequences punctuated with Ser-Gly dipeptides. RT-PCR demonstrated that the transcript of aspein is expressed at the outer edge of the mantle, corresponding to the calcitic prismatic layer, but not at the inner part of the mantle, corresponding to the aragonitic nacreous layer. Our findings and previous in vitro experiments taken together suggest that Aspein is responsible for directed formation of calcite in the shell of the pearl oyster Pinctada fucata

Unravelling the role of zooxanthellae in the uptake and depuration of an essential metal in Exaiptasia pallida; an experiment using a model cnidarian.

Science.gov (United States)

Hardefeldt, Jannah M; Reichelt-Brushett, Amanda J

2015-07-15

Coral skeletons record historical trace metal levels in the environment, however, the use of coral skeletal records for biomonitoring studies mostly fail to consider the influence of metal regulation by the living components of coral and subsequent incorporation into the skeleton. This study presents Exaiptasia pallida as a representative of the living components of coral and shows metal partitioning between the tissue and zooxanthellae after chronic exposure to Zn. A strong tendency for preferential accumulation in the zooxanthellae occurred after 32 days exposure and Zn concentrations in tissue and zooxanthellae were 123.3±0.7 mg kg(-1) and 294.9±8.5 respectively. This study shows zooxanthellae density plays an important role in controlling Zn loading in whole anemones and must be considered when investigating metal uptake and loading in zooxanthellate organisms. Further studies that investigate links between aragonite deposition rates and zooxanthellae density and incorporation pathways of metals into skeleton are warranted. Copyright © 2015 Elsevier Ltd. All rights reserved.

Strontium and zinc concentrations in otoliths of common fish species in the northern Baltic Sea

International Nuclear Information System (INIS)

Lill, J.-O.; Himberg, M.; Harju, L.; Ek, P.; Lindroos, A.; Wiklund, T.; Gunnelius, K.; Smått, J.-H.; Heselius, S.-J.; Hägerstrand, H.

2014-01-01

Otoliths of perch (Perca fluviatilis), pike (Esox lucius) and European whitefish (Coregonus lavaretus) caught at different locations in the northern Baltic Sea along the Finnish west coast and at some rivers and lakes were subjected to elemental analyses with particle induced X-ray emission and laser ablation inductively coupled plasma mass spectrometry. The strontium concentration in otoliths from whitefish (∼3300 μg/g) was 2–3 times higher than that of perch and pike (∼1400 μg/g), while within species the strontium concentration of otoliths from fish caught at different locations was in the same range. The strontium concentrations were lowest in fish from the lakes (∼450 μg/g). Whitefish otoliths contained more zinc (∼60 μg/g) than those of pike (∼30 μg/g), while the zinc concentration in perch otoliths were below the detection limit. No spatial intraspecies variations in zinc concentrations were observed. X-ray diffraction showed that the otoliths consisted of aragonite solely

IUPAC-NIST Solubility Data Series. 95. Alkaline Earth Carbonates in Aqueous Systems. Part 2. Ca

Energy Technology Data Exchange (ETDEWEB)

De Visscher, Alex; Vanderdeelen, Jan [Department of Chemical and Petroleum Engineering, and Centre for Environmental Engineering Research and Education (CEERE), Schulich School of Engineering, University of Calgary, Calgary, Alberta, T2N 1N4 (Canada); Department of Applied Analytical and Physical Chemistry, Faculty of Bioscience Engineering, Ghent University, B-9000 Ghent (Belgium)

2012-06-15

The alkaline earth carbonates are an important class of minerals. This article is part of a volume in the IUPAC-NIST Solubility Data Series that compiles and critically evaluates solubility data of the alkaline earth carbonates in water and in simple aqueous electrolyte solutions. Part 1 outlined the procedure adopted in this volume, and presented the beryllium and magnesium carbonates. Part 2, the current paper, compiles and critically evaluates the solubility data of calcium carbonate. The chemical forms included are the anhydrous CaCO{sub 3} types calcite, aragonite, and vaterite, the monohydrate monohydrocalcite (CaCO{sub 3}{center_dot} H{sub 2}O), the hexahydrate ikaite (CaCO{sub 3}{center_dot}6H{sub 2}O), and an amorphous form. The data were analyzed with two model variants, and thermodynamic data of each form consistent with each of the models and with the CODATA key values for thermodynamics are presented.

The identification of growth lines in abalone shell using a nuclear microprobe

International Nuclear Information System (INIS)

Bettiol, A.A.; Yang, C.; Hawkes, G.P.; Jamieson, D.N.; Malmqvist, K.G.; Day, R.W.

1999-01-01

Ionoluminescence (IL) combined with particle induced X-ray emission (PIXE) imaging has been employed to identify intrinsic growth bands in the spire region, and extrinsic bands at the growth edge of Australian Black-lip abalone shell (Haliotis rubra). Previous studies using optical flood cathodoluminescence, scanning electron microscope cathodoluminescence (SEM-CL) and Raman spectroscopy on samples from the same population suggest that the visible luminescence is due to Mn 2+ activated calcium carbonate. In this study we confirm Mn 2+ as the activator in both the spire and growth edge regions of the shell. The sensitivity of ionoluminescence to the co-ordination environment of the Mn 2+ activators in the shell allows for the spatial identification of the calcium carbonate polymorph responsible for the growth lines observed optically. Furthermore the detection and mapping of trace elements such as Mn and Sr with the PIXE technique enables comparisons to be made between calcite and aragonite biomineralized in the wild and under laboratory conditions

The identification of growth lines in abalone shell using a nuclear microprobe

Energy Technology Data Exchange (ETDEWEB)

Bettiol, A.A.; Yang, C.; Hawkes, G.P.; Jamieson, D.N. E-mail: dnj@physics.unimelb.edu.au; Malmqvist, K.G.; Day, R.W

1999-09-02

Ionoluminescence (IL) combined with particle induced X-ray emission (PIXE) imaging has been employed to identify intrinsic growth bands in the spire region, and extrinsic bands at the growth edge of Australian Black-lip abalone shell (Haliotis rubra). Previous studies using optical flood cathodoluminescence, scanning electron microscope cathodoluminescence (SEM-CL) and Raman spectroscopy on samples from the same population suggest that the visible luminescence is due to Mn{sup 2+} activated calcium carbonate. In this study we confirm Mn{sup 2+} as the activator in both the spire and growth edge regions of the shell. The sensitivity of ionoluminescence to the co-ordination environment of the Mn{sup 2+} activators in the shell allows for the spatial identification of the calcium carbonate polymorph responsible for the growth lines observed optically. Furthermore the detection and mapping of trace elements such as Mn and Sr with the PIXE technique enables comparisons to be made between calcite and aragonite biomineralized in the wild and under laboratory conditions.

Microelectrode characterization of coral daytime interior pH and carbonate chemistry.

Science.gov (United States)

Cai, Wei-Jun; Ma, Yuening; Hopkinson, Brian M; Grottoli, Andréa G; Warner, Mark E; Ding, Qian; Hu, Xinping; Yuan, Xiangchen; Schoepf, Verena; Xu, Hui; Han, Chenhua; Melman, Todd F; Hoadley, Kenneth D; Pettay, D Tye; Matsui, Yohei; Baumann, Justin H; Levas, Stephen; Ying, Ye; Wang, Yongchen

2016-04-04

Reliably predicting how coral calcification may respond to ocean acidification and warming depends on our understanding of coral calcification mechanisms. However, the concentration and speciation of dissolved inorganic carbon (DIC) inside corals remain unclear, as only pH has been measured while a necessary second parameter to constrain carbonate chemistry has been missing. Here we report the first carbonate ion concentration ([CO3(2-)]) measurements together with pH inside corals during the light period. We observe sharp increases in [CO3(2-)] and pH from the gastric cavity to the calcifying fluid, confirming the existence of a proton (H(+)) pumping mechanism. We also show that corals can achieve a high aragonite saturation state (Ωarag) in the calcifying fluid by elevating pH while at the same time keeping [DIC] low. Such a mechanism may require less H(+)-pumping and energy for upregulating pH compared with the high [DIC] scenario and thus may allow corals to be more resistant to climate change related stressors.

Accumulation of fossil CO/sub 2/ in the atmosphere and the sea

Energy Technology Data Exchange (ETDEWEB)

Fairhall, A W

1973-09-07

A model is presented which accounts quantitatively for the buildup of fossil CO/sub 2/ in the atmosphere. The model also predicts something not previously recognized: a significant uptake of fossil CO/sub 2/ by the sea. The sea is presently supersaturated with respect to aragonite and calcite, which calcareous organisms form in building their shells. Should the sea become unsaturated in CaCO/sub 3/ the shells of these organisms would tend to dissolve, as would the ocean's coral reefs. One test of the model would be afforded by careful monitoring of total CO/sub 2/ levels in the mixed layer over the next few years. The model predicts an increase in the mixed layer of about 1.4 per cent in the next decade. Because this is about double the accuracy of the present methods for measuring total CO/sub 2/ in seawater, this trend, if present, should be detectable within 3 to 5 years. (MFB)

Pteropods in Southern Ocean ecosystems

Science.gov (United States)

Hunt, B. P. V.; Pakhomov, E. A.; Hosie, G. W.; Siegel, V.; Ward, P.; Bernard, K.

2008-09-01

To date, little research has been carried out on pelagic gastropod molluscs (pteropods) in Southern Ocean ecosystems. However, recent predictions are that, due to acidification resulting from a business as usual approach to CO 2 emissions (IS92a), Southern Ocean surface waters may begin to become uninhabitable for aragonite shelled thecosome pteropods by 2050. To gain insight into the potential impact that this would have on Southern Ocean ecosystems, we have here synthesized available data on pteropod distributions and densities, assessed current knowledge of pteropod ecology, and highlighted knowledge gaps and directions for future research on this zooplankton group. Six species of pteropod are typical of the Southern Ocean south of the Sub-Tropical Convergence, including the four Thecosomes Limacina helicina antarctica, Limacina retroversa australis, Clio pyramidata, and Clio piatkowskii, and two Gymnosomes Clione limacina antarctica and Spongiobranchaea australis. Limacina retroversa australis dominated pteropod densities north of the Polar Front (PF), averaging 60 ind m -3 (max = 800 ind m -3) and 11% of total zooplankton at the Prince Edward Islands. South of the PF L. helicina antarctica predominated, averaging 165 ind m -3 (max = 2681 ind m -3) and up to >35% of total zooplankton at South Georgia, and up to 1397 ind m -3 and 63% of total zooplankton in the Ross Sea. Combined pteropods contributed 40% of community grazing impact. Further research is required to quantify diet selectivity, the effect of phytoplankton composition on growth and reproductive success, and the role of carnivory in thecosomes. Life histories are a significant knowledge gap for Southern Ocean pteropods, a single study having been completed for L. retroversa australis, making population studies a priority for this group. Pteropods appear to be important in biogeochemical cycling, thecosome shells contributing >50% to carbonate flux in the deep ocean south of the PF. Pteropods may also

Pliocene Te Aute limestones, New Zealand : expanding concepts for cool-water shelf carbonates

International Nuclear Information System (INIS)

Nelson, C.S.; Winefield, P.R.; Hood, S.D.; Caron, V.; Pallentin, A.; Kamp, P.J.J.

2003-01-01

Acceptance of a spectrum of warm- through cold-water shallow-marine carbonate facies has become of fundamental importance for correctly interpreting the origin and significance of all ancient platform limestones. Among other attributes, properties that have become a hallmark for characterising many Cenozoic non-tropical occurrences include: (1) the presence of common bryozoan and epifaunal bivalve skeletons; (2) a calcite-dominated mineralogy; (3) relatively thin deposits exhibiting low rates of sediment accumulation; (4) an overall destructive early diagenetic regime; and (5) that major porosity destruction and lithification occur mainly in response to chemical compaction of calcitic skeletons during moderate to deep burial. The Pliocene Te Aute limestones are non-tropical skeletal carbonates formed at paleolatitudes near 40-42 degrees S under the influence of commonly strong tidal flows along the margins of an actively deforming and differentially uplifting forearc basin seaway, immediately inboard of the convergent Pacific-Australian plate boundary off eastern North Island, New Zealand. This dynamic depositional and tectonic setting strongly influenced both the style and subsequent diagenetic evolution of the limestones. Some of the Te Aute limestones exhibit the above kinds of 'normal' non-tropical characteristics, but others do not. For example, many are barnacle and/or bivalve dominated, and several include attributes that at least superficially resemble properties of certain tropical carbonates. In this regard, a number of the limestones are infaunal bivalve rich and dominated by an aragonite over a calcite primary mineralogy, with consequently relatively high diagenetic potential. Individual limestone units are also often rather thick (e.g., up to 50-300 m), with accumulation rates from 0.2 to 0.5 m/ka, and locally as high as 1 m/ka. Moreover, there can be a remarkable array of diagenetic features in the limestones, involving grain alteration and

Experimental examination of the Mg-silicate-carbonate system at ambient temperature: Implications for alkaline chemical sedimentation and lacustrine carbonate formation

Science.gov (United States)

Tutolo, Benjamin M.; Tosca, Nicholas J.

2018-03-01

Despite their clear economic significance, Cretaceous presalt carbonates of the South Atlantic continental margins are not well-described by published facies models. This knowledge gap arises, in part, because the chemical processes that generate distinctive sedimentary products in alkaline, non-marine environments are poorly understood. Here, we use constraints inferred from reported mineralogical and geochemical features of presalt carbonate rocks to design and perform a suite of laboratory experiments to quantify the processes of alkaline chemical sedimentation. Using real-time observations of in-situ fluid chemistry, post-experiment analysis of precipitated solids, and geochemical modeling tools, we illustrate that spherulitic carbonates and Mg-silicate clays observed in presalt carbonates were likely precipitated from elevated pH (∼10-10.5) waters with high concentrations of silica and alkali cations typical of intermediate to felsic rocks, such as Na+ and K+. Charge balance constraints require that these cations were not counterbalanced to any significant degree by anions typical of seawater, such as Cl- and SO4-, which implies minimal seawater involvement in presalt deposition. Experimental data suggest that, at this alkaline pH, only modest concentrations (i.e., ∼0.5-1 mmol/kg) of Ca++ would have been required to precipitate spheroidal CaCO3. Given the rapid rates of CaCO3 nucleation and growth under such conditions, it is unlikely that Ca++ concentrations in lake waters ever exceeded these values, and sustained chemical fluxes are therefore required for extensive sediment accumulation. Moreover, our experiments indicate that the original mineralogy of presalt CaCO3 could have been calcite or aragonite, but the differing time scales of precipitation between CaCO3 and Mg-silicates would have tended to skew the Mg/Ca ratio in solution towards elevated values which favor aragonite. Mg-silicate nucleation and growth rates measured during our experiments

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

Late Quaternary Halimeda bioherms and aragonitic faecal pellet-dominated sediments on the carbonate platform of the western continental shelf of India

Digital Repository Service at National Institute of Oceanography (India)

Rao, V.P; Veerayya, M.; Nair, R.R.; Dupeuble, P; Lamboy, M.

brought by river runoff and shelf edge currents favoured the growth of algal bioherms dominated by Halimeda between 13,700 (?) and 8300 yr B.P. The absence of Late Holocene and modern carbonates on the platform may be due to the combined influence...

Complexity of nearshore strontium-to-calcium ratio variability in a core sample of the massive coral Siderastrea siderea obtained in Coral Bay, St. John, U.S. Virgin Islands

Science.gov (United States)

Reich, Christopher D.; Kuffner, Ilsa B.; Hickey, T. Don; Morrison, Jennifer M.; Flannery, Jennifer A.

2013-01-01

Strontium-to-calcium ratios (Sr/Ca) were measured on the skeletal matrix of a core sample from a colony of the massive coral Siderastrea siderea collected in Coral Bay, St. John, U.S. Virgin Islands. Strontium and calcium are incorporated into the coral skeleton during the precipitation of aragonite by the coral polyps and their ratio is highly temperature dependent. The robustness of this temperature dependence makes Sr/Ca a reliable proxy for sea surface temperature (SST). Details presented from the St. John S. siderea core indicate that terrestrial inputs of sediment and freshwater can disrupt the chemical balance and subsequently complicate the utility of Sr/Ca in reconstructing historical SST. An approximately 44-year-long record of Sr/Ca shows that an annual SST signal is recorded but with an increasing Sr/Ca trend from 1980 to present, which is likely the result of runoff from the mountainous terrain of St. John. The overwhelming influence of the terrestrial fingerprint on local seawater chemistry makes utilizing Sr/Ca as a SST proxy in nearshore environments very difficult.

Probing for heavy element impurities in the shell of the Pacific oyster, Crassostrea gigas, with nuclear microscopy

International Nuclear Information System (INIS)

Markwitz, A.; Barry, B.; Gauldie, R.W.; Roberts, R.D.

2003-01-01

Nuclear microscopy was performed on shells of the Pacific oyster, Crassostrea gigas, to probe for heavy element impurities. For the studies 14 shells from the Auckland and the Marlborough Sounds region were chosen. In sections, the shells appear as opaque with white and grey zones, which are related to alternating layers of calcite and aragonite. Raster scans with 2.5 MeV protons over the sections (scan area 5 x 5 mm) were used in the experiment to measure trace elements in the ppm region using proton induced X-ray spectroscopy. Two dimensional maps and line scans revealed the presence of bromine in all shells investigated. Bromine was found to be related with the pattern of calcium. Hot spots of iron proved to be a common feature in the shells as well. In some shells, copper and zinc were also measured in hot spots of a few micrometers in diameter. Spatially resolved results on the micrometer level indicate the usefulness of nuclear microscopy for the detection of heavy elements in shells of the Pacific oyster

Decadal changes in the CaCO3 saturation state along 179°E in the Pacific Ocean

Science.gov (United States)

Murata, Akihiko; Saito, Shu

2012-06-01

To assess degrees of ocean acidification, we mainly investigated decadal changes in the saturation state of seawater with respect to aragonite (Ωarg), which is a more vulnerable mineral form of CaCO3, along the 179°E meridian (WOCE P14N) in the Pacific Ocean. We found a maximum decrease of Ωarg of -0.48 (-0.034 a-1) at 200-300 dbar (isopycnal surfaces of 24.0-25.8 kg m-3) at 20°N. Between 1993 and 2007, the saturation horizon rose by 17 dbar (1.2 dbar a-1) at latitudes 10°N-50°N. Although ΔΩarg mostly reflected changes in normalized dissolved inorganic carbon (ΔnCT), it was larger than could be explained by anthropogenic CO2 storage alone. Decomposition of ΔnCT revealed that ΔΩarg was enhanced by approximately 50% by a non-anthropogenic CO2 contribution represented by changes in apparent oxygen utilization. Our results suggest that ocean acidification can be temporarily accelerated by temporal changes in oceanic conditions.

Characteristics of pulsed photo-stimulated luminescence and thermoluminescence for the identification of gamma irradiated poultry eggs

International Nuclear Information System (INIS)

Bhatti, I.A.; Kwon, J.-H.

2006-01-01

Pulsed photo-stimulated luminescence (PPSL) is a simple screening method that can be employed qualitatively at the spot for the detection of eggs treated with ionizing radiation. In spite of the variations in the results during storage, the eggs of ostrich, duck, hen and quail irradiated to doses of 0, 1, 2 and 3 kGy, most of the samples were correctly identified up to six months during storage after irradiation. Thermoluminescence (TL) technique was also tried by using eggshells in order to confirm the PPSL results. TL glow curves were recorded between the temperatures 50 to 400 degree C at the rate of 5 degree per second for all the control and irradiated samples. On the basis of integrated areas of first glow curves (TL1), the glow curve ratios (TL1/TL2) and the shapes of maxima of TL1, the irradiation treatment of all the eggs was confirmed. Furthermore, the presence of calcite and aragonite minerals that cause the TL signal in the eggshells were studied using X-ray diffraction spectrometry. (authors)

Characteristics of pulsed photo-stimulated luminescence and thermoluminescence for the identification of gamma irradiated poultry eggs

International Nuclear Information System (INIS)

Bhatti, I.A.; Kwon, J.-H.; Ur-rehman, S.

2007-01-01

Pulsed photo-stimulated luminescence (PPSL) is a simple screening method that can be employed qualitatively at the spot for the detection of eggs treated with ionizing radiation. Due to the variations in the results during storage, the eggs of ostrich, duck, hen, and quail were irradiated to doses of 0, 1, 2, and 3 kGy. Most of the samples were incorrectly identified during storage after four months of irradiation. Thermoluminescence (TL) technique was also tried by using egg shells in order to confirm the irradiation treatment in eggs. TL glow curves were recorded between the temperatures 50 degree C to 400 degree C at the rate of 5 degree/s for all the control and irradiated samples. On the basis of integrated areas of first glow curves (TL1), the glow curve ratios (TL1/TL2) and the shapes of maxima of TL1, the irradiation treatment of all the eggs was confirmed. Furthermore, the presence of calcite and aragonite minerals that cause the TL signal in the egg shells were studied using X-ray diffraction spectrometry. (authors)

Ion-exchanged calcium from calcium carbonate and low-rank coals: high catalytic activity in steam gasification

Energy Technology Data Exchange (ETDEWEB)

Ohtsuka, Y.; Asami, K. [Tokoku University, Sendai (Japan). Inst. for Chemical Reaction Science

1996-03-01

Interactions between CaCO{sub 3} and low-rank coals were examined, and the steam gasification of the resulting Ca-loaded coals was carried out at 973 K with a thermobalance. Chemical analysis and FT-IR spectra show that CaCO{sub 3} can react readily with COOH groups to form ion-exchanged Ca and CO{sub 2} when mixed with brown coal in water at room temperature. The extent of the exchange is dependent on the crystalline form of CaCO{sub 3}, and higher for aragonite naturally present in seashells and coral reef than for calcite from limestone. The FT-IR spectra reveal that ion-exchange reactions also proceed during kneading CaCO{sub 3} with low-rank coals. The exchanged Ca promotes gasification and achieves 40-60 fold rate enhancement for brown coal with a lower content of inherent minerals. Catalyst effectiveness of kneaded CaCO{sub 3} depends on the coal type, in other words, the extent of ion exchange. 11 refs., 7 figs., 3 tabs.

Barium variation in Acropora palmata and Montastrea annularis

Science.gov (United States)

Pingitore, Nicholas E.; Rangel, Yolanda; Kwarteng, Andrew

1989-06-01

The barium contents of Acropora palmata and Montastrea annularis are distinct both in their averages (6 and 9 ppm, respectively) and, more impressively, in their variability (5 to 7 ppm and 6 to 15 ppm). A. palmata contained about 50% more Ba2+ than M. annularis and exhibited more than three times as much variation, as measured by their respective coefficients of variation. In contrast, the means and coefficients of variation of Sr2+ in these groups differed by only 6% and 15%. No obvious environmental or post-depositional causes for the inter-and intra-specific variation of Ba2+ could be found. Previous experiments indicate that the partitioning of Ba2+ into aragonite depends directly on the rate of precipitation. This suggests that Ba2+ does not substitute for Ca2+ but instead is incorporated by occlusion. Since growth rates in A. palmata often exceed those of M. annularis, this appears to be the mechanism which generates higher and more variable concentrations of Ba2+ in A. palmata.

Blood Cockle Shells Waste as Renewable Source for the Production of Biogenic CaCO3 and Its Characterisation

Science.gov (United States)

Asmi, D.; Zulfia, A.

2017-11-01

The prowess to reuse and recycle of blood cockle shells for raw material in bio-ceramics applications is an attractive component of integrated waste management program. In this paper an attempt is made to introduce a simple process to manufacture biogenic CaCO3 powder from blood cockle shells waste. The biogenic CaCO3 powder was produced from rinsing of blood cockle shells waste using deionised water and oxalic acid for cleaning the dirt and stain on the shells, then drying and grinding followed by heat treatment at 500 and 800 °C for 5 h. The powder obtained was characterised by XRF, DTA/TG, SEM, FTIR, and XRD analysis. The amount of 97.1 % CaO was obtained from XRF result. The thermal decomposition of CaCO3 become CaO due to mass loss was observed in the TG curve. The SEM result shows the needle-like aragonite morphology of blood cockle shells powder transformed to cubic-like calcite after heat treated at 500 °C. These results were consistent with FTIR and XRD results.

USGS Field Activities 12BHM01, 12BHM02, 12BHM03, 12BHM04, and 12BHM05 on the West Florida Shelf, in February, April, May, June, and August 2012

Science.gov (United States)

Robbins, Lisa L.; Knorr, Paul O.; Daly, Kendra L.; Barrera, Kira E.

2014-01-01

Atmospheric carbon dioxide (CO2) is absorbed by the ocean’s surface where it combines with seawater to form a weak, naturally occurring acid called carbonic acid (H2CO3).   Increasing carbon dioxide in the atmosphere results in the absorption of more CO2 by the ocean and, therefore, increases in the acidity of seawater.  This process, known as ocean acidification, has the potential to elicit change in ecosystems and organisms by disrupting biological processes.   For example, ocean acidification is a problem for marine organisms such as corals, foraminifera, and algae that precipitate calcium carbonate to form their skeletons and shells (Kleypas and others, 2006). The effects are related to corresponding changes in the carbonate saturation state (Ω), where Ω is the ratio of the ion concentration product (Ca2+ x CO32-) to the stoichiometric aragonite solubility product (K*sp) (Langdon and Atkinson, 2005). Because pH and CO32- are strongly interdependent through the inorganic carbon system, the decrease in pH will cause a proportionally greater decrease in CO32-.   

Electron spin resonance (ESR), electron nuclear double resonance (ENDOR) and general triple resonance of irradiated biocarbonates

International Nuclear Information System (INIS)

Schramm, D.U.; Rossi, A.M.

1996-01-01

Several irradiated bicarbonates were studied by magnetic resonance techniques. Seven paramagnetic species, attributed to CO 2 - , SO 2 - and SO 3 - were identified. Comparison between radiation induced defects in bioaragonites and aragonite single-crystals show that isotropic and orthorhombic CO 2 - centers with broad line spectra are not produced in the latter samples. Vibrational and rotational properties of isotropic CO 2 - centers were studied from low temperature Q-band spectras. Vibrational frequency is determined from the 13 CO 2 - hyperfine spectrum and yielded ν 1.54 x 10 13 s -1 . The correlation time for isotropic CO 2 - , τc) = 1.2 x 10 -11 s (T = 300 K0, is typical of radicals rotating in liquids. ENDOR and General Triple spectroscopy show that orthorhombic CO 2 - centres are surrounded by water molecules located in the second nearest CO 2 2- sites at 5.14, 5.35 and 6.02 A. Water molecules replacing carbonates or as liquid inclusion of growth solution in local crystal imperfections may be responsible for the variety of orthorhombic and isotropic CO 2 - species, respectively. (author)

NOAA's efforts to map extent, health and condition of deep sea corals and sponges and their habitat on the banks and island slopes of Southern California

Science.gov (United States)

Etnoyer, P. J.; Salgado, E.; Stierhoff, K.; Wickes, L.; Nehasil, S.; Kracker, L.; Lauermann, A.; Rosen, D.; Caldow, C.

2015-12-01

Southern California's deep-sea corals are diverse and abundant, but subject to multiple stressors, including corallivory, ocean acidification, and commercial bottom fishing. NOAA has surveyed these habitats using a remotely operated vehicle (ROV) since 2003. The ROV was equipped with high-resolution cameras to document deep-water groundfish and their habitat in a series of research expeditions from 2003 - 2011. Recent surveys 2011-2015 focused on in-situ measures of aragonite saturation and habitat mapping in notable habitats identified in previous years. Surveys mapped abundance and diversity of fishes and corals, as well as commercial fisheries landings and frequency of fishing gear. A novel priority setting algorithm was developed to identify hotspots of diversity and fishing intensity, and to determine where future conservation efforts may be warranted. High density coral aggregations identified in these analyses were also used to guide recent multibeam mapping efforts. The maps suggest a large extent of unexplored and unprotected hard-bottom habitat in the mesophotic zone and deep-sea reaches of Channel Islands National Marine Sanctuary.

Effects of ocean acidification on the shells of four Mediterranean gastropod species near a CO2 seep.

Science.gov (United States)

Duquette, Ashley; McClintock, James B; Amsler, Charles D; Pérez-Huerta, Alberto; Milazzo, Marco; Hall-Spencer, Jason M

2017-11-30

Marine CO 2 seeps allow the study of the long-term effects of elevated pCO 2 (ocean acidification) on marine invertebrate biomineralization. We investigated the effects of ocean acidification on shell composition and structure in four ecologically important species of Mediterranean gastropods (two limpets, a top-shell snail, and a whelk). Individuals were sampled from three sites near a volcanic CO 2 seep off Vulcano Island, Italy. The three sites represented ambient (8.15pH), moderate (8.03pH) and low (7.73pH) seawater mean pH. Shell mineralogy, microstructure, and mechanical strength were examined in all four species. We found that the calcite/aragonite ratio could vary and increased significantly with reduced pH in shells of one of the two limpet species. Moreover, each of the four gastropods displayed reductions in either inner shell toughness or elasticity at the Low pH site. These results suggest that near-future ocean acidification could alter shell biomineralization and structure in these common gastropods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Coccolithophores and calcite saturation state in the Baltic and Black Seas

Directory of Open Access Journals (Sweden)

T. Tyrrell

2008-04-01

Full Text Available The Baltic and Black Seas are both brackish, that is to say both have salinities intermediate between freshwater and seawater. The coccolithophore Emiliania huxleyi is abundant in one, the Black Sea, but absent from the other, the Baltic Sea. Here we present summertime coccolithophore measurements confirming this difference, as well as data on the calcium carbonate saturation state of the Baltic Sea. We find that the Baltic Sea becomes undersaturated (or nearly so in winter, with respect to both the aragonite and calcite mineral forms of CaCO₃. Data for the Black Sea are more limited, but it appears to remain strongly supersaturated year-round. The absence of E. huxleyi from the Baltic Sea could therefore potentially be explained by dissolution of their coccoliths in winter, suggesting that minimum annual (wintertime saturation states could be most important in determining future ocean acidification impacts. In addition to this potential importance of winter saturation state, alternative explanations are also possible, either related to differences in salinity or else to differences in silicate concentrations.

Formation of Mg-aluminosilicates During Early Diagenesis of Carbonate Sediments in the Volcanic Crater Lake of Dziani Dzaha (Mayotte - Indian Ocean)

Science.gov (United States)

Milesi, V. P.; Jezequel, D.; Debure, M.; Marty, N.; Guyot, F. J.; Claret, F.; Virgone, A.; Gaucher, E.; Ader, M.

2017-12-01

Authigenic clays are increasingly reported in ancient carbonate rocks, but their origin remains poorly understood, strongly limiting paleoenvironmental interpretations. To tackle this issue, the carbonate sediments of the volcanic crater lake Dziani Dzaha are studied and reactive transport modeling is performed to assess the processes originating carbonate sediments associated with Mg-rich silicates during early diagenesis. The Dziani Dzaha is characterized by CO2-rich gases bubbling in three different locations, a high primary productivity leading to organic carbon contents of up to 30wt.% in the sediment, an alkalinity of 0.26 molal in the water column and pH values of 9 to 9.5. Characterization of bulk samples and clay fraction (fueled by inputs of CO2-rich volcanic gases, which generates high pH, promoting the formation of saponite, aragonite and hydromagnesite, which precipitates at first before being destabilized at depth due to organic matter mineralization. The observed carbon cycle, influenced by volcanic gases, may thus play a key role in the development of carbonate rocks associated with Mg-silicates.

Quality and petrographic characteristics of the lacustrine Ermenek coal (early Miocene), Turkey

Energy Technology Data Exchange (ETDEWEB)

Demirel, I.H.; Karayigit, A.I. [Hacettepe Univ., Beytepe-Ankara (Turkey). Dept. of Geological Engineering

1999-05-01

The early Miocene Yenimahalle Formation including alluvial-lacustrine sediments and a mineable coal steam with an average of 5 m in thickness rests unconformably upon the basement and is also unconformably overlain by marine limestones of the middle-late Miocene Mut Formation in the Ermenek coal basin. The coal basin in the present study has been subdivided into two areas, Canakci and Pamuklu-Tepebasi, which are separated by the basement and a fault, in order to determine coal properties in detail. The investigated subbituminous coals with an average of 0.40%Ro huminite reflectance often contain gastropod shells (Planorbidae) which commonly maintain the original aragonite and calcite composition. The coals have similar chemical properties and petrographic composition in the two areas, but their sulphur contents are clearly different. In the Canakci area the coals on an air-dried basis contain distinctly less total sulphur (avg. 1.3%) and organic sulphur contents (0.13--0.15%) than in the Pamuklu-Tepebasi area (avg. 4.5% and 4.25%, respectively). This difference is interpreted to be controlled by mire chemistry and sedimentation during peat formation.

A novel biphasic calcium phosphate derived from fish otoliths

Science.gov (United States)

Montañez-Supelano, N. D.; Sandoval-Amador, A.; Estupiñan-Durán, H. A.; Y Peña-Ballesteros, D.

2017-12-01

Calcium phosphates are bioceramics that have been widely used as bone substitutes because they encourage the formation of bone on their surface and can improve the healing of the bone. Hydroxyapatite HA (calcium/phosphorus ratio of 1.67) and tricalcium phosphate TCP (calcium/phosphorus ratio of 1.50) are the most common calcium phosphates. Natural materials have begun to be tested to make HA or TCP such as shells of cardiidae (family of mollusks) and eggshells. The calcium phosphate obtained has a high ability to precipitate apatite. In this work, the mixed phase ceramic of beta-Tri-calcium phosphate / hydroxyapatite (β-TCP/HA) was synthesized by aqueous precipitation from fish otoliths, which are monomineralic species composed of aragonite. Otoliths of the specie Plagioscion squamosissimus, commonly called the river croaker, were used. Techniques such as DRX, Raman spectroscopy and SEM-EDS were used to characterize the raw material and the obtained material. X-ray diffraction analysis revealed the presence of two crystalline phases of calcium phosphates with 86.2% crystallinity. SEM micrographs showed agglomeration of particles with porous structure and submicron particle sizes.