WorldWideScience

Sample records for surfaces geochemical complexities

  1. Microstructural and geochemical evolution of sliding surfaces in landslides

    Science.gov (United States)

    Schaebitz, M.; Janssen, C.; Wirth, R.; Dresen, G. H.

    2014-12-01

    The formation of basal sliding surfaces in mass movements is known to be associated with chemical and physical alteration of rock and regolith. To evaluate its microstructural and geochemical evolution we collected samples from the host rock to the sliding surface and adjacent deposits within landslides in Kirgizstan and central China. The sample locations represent different morphological and geological conditions to evaluate if the weakness of the sliding surface derives from general factors such as (micro)structural or mineralogical changes within the landslide body. Based on qualitative and quantitative geochemical analysis we could not find neither indication for notable weathering of the parent bedrock nor accumulation of clay minerals along the sliding surface to explain its reduced shear strength in the investigated near-surface landslides. The cataclasites are mainly composed of quartz, illite, calcite, kaolinite and feldspar with grain sizes between 5 μm down to contents towards the sliding surface, pointing to alteration processes. Transmission electron microscopy and focused ion beam technique for TEM sample preparation were used to compare the microstructures. It clearly revealed a severe reduction of grain size, and increase of pore space due to grain comminution by creeping and moving processes, indicating that elevated pore pressures are the main reason for the weakness of the sliding surfaces in shallow landslides. The comminution process within sliding surface formation seems to be comparable to fault gauge formation.

  2. Surface complexation of antimony on kaolinite.

    Science.gov (United States)

    Rakshit, Sudipta; Sarkar, Dibyendu; Datta, Rupali

    2015-01-01

    Geochemical fate of antimony (Sb) - a similar oxyanion as arsenic (As) - in a variety of environment is largely unexplored. Kaolinite is an important, naturally occurring clay mineral in soils and aquifers and is known to control the fate of several contaminants via a multitude of geochemical processes, primarily adsorption. Here we report adsorption of antimony on kaolinite as a function of solution chemistry: initial antimony concentration, pH, ionic strength, and a competing anion. A surface complexation modeling (SCM) approach was undertaken to understand the potential mechanistic implications of sorption envelope data. In the SCM, a multicomponent additive approach, in which kaolinite is assumed to be a (1:1) mixture of quartz (≡SiOH) and gibbsite (≡AlOH), was tested. Results indicated that ionic strength has a minimal effect on antimony adsorption. For the lower initial antimony concentration (4.11 μM), the additive model with binuclear surface complexes on quartz and gibbsite showed a better fit at pH3.5. However, the additive model with binuclear surface complex on quartz and mononuclear surface complex on gibbsite showed an excellent fit of the data. Phosphate greatly influenced antimony adsorption on kaolinite at both low and high antimony loadings, indicating competition for available surface sites. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Predictive Surface Complexation Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Sverjensky, Dimitri A. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Earth and Planetary Sciences

    2016-11-29

    Surface complexation plays an important role in the equilibria and kinetics of processes controlling the compositions of soilwaters and groundwaters, the fate of contaminants in groundwaters, and the subsurface storage of CO2 and nuclear waste. Over the last several decades, many dozens of individual experimental studies have addressed aspects of surface complexation that have contributed to an increased understanding of its role in natural systems. However, there has been no previous attempt to develop a model of surface complexation that can be used to link all the experimental studies in order to place them on a predictive basis. Overall, my research has successfully integrated the results of the work of many experimentalists published over several decades. For the first time in studies of the geochemistry of the mineral-water interface, a practical predictive capability for modeling has become available. The predictive correlations developed in my research now enable extrapolations of experimental studies to provide estimates of surface chemistry for systems not yet studied experimentally and for natural and anthropogenically perturbed systems.

  4. Geochemical characterization of surface water and spring water in ...

    Indian Academy of Sciences (India)

    The time series data on solute chemistry suggest that the hydrochemical processes controlling the chemistry of spring waters is more complex than the surface water. This is attributed to more time available for infiltrating water to interact with the diverse host lithology. Total dissolved solids (TDS), in general, increases with ...

  5. On the bioavailability of trace metals in surface sediments: a combined geochemical and biological approach.

    Science.gov (United States)

    Roosa, Stéphanie; Prygiel, Emilie; Lesven, Ludovic; Wattiez, Ruddy; Gillan, David; Ferrari, Benoît J D; Criquet, Justine; Billon, Gabriel

    2016-06-01

    The bioavailability of metals was estimated in three river sediments (Sensée, Scarpe, and Deûle Rivers) impacted by different levels of Cu, Cd, Pb, and Zn (Northern France). For that, a combination of geochemistry and biological responses (bacteria and chironomids) was used. The results obtained illustrate the complexity of the notion of "bioavailability." Indeed, geochemical indexes suggested a low toxicity, even in surface sediments with high concentrations of total metals and a predicted severe effect levels for the organisms. This was also suggested by the abundance of total bacteria as determined by DAPI counts, with high bacterial cell numbers even in contaminated areas. However, a fraction of metals may be bioavailable as it was shown for chironomid larvae which were able to accumulate an important quantity of metals in surface sediments within just a few days.We concluded that (1) the best approach to estimate bioavailability in the selected sediments is a combination of geochemical and biological approaches and that (2) the sediments in the Deûle and Scarpe Rivers are highly contaminated and may impact bacterial populations but also benthic invertebrates.

  6. Environmental and geochemical assessment of surface sediments on irshansk ilmenite deposit area

    Directory of Open Access Journals (Sweden)

    Наталия Олеговна Крюченко

    2015-03-01

    Full Text Available It is revealed the problem of pollution of surface sediments of Irshansk ilmenite deposit area of various chemical elements hazard class (Mn, V, Ba, Ni, Co, Cr, Mo, Cu, Pb, Zn. It is determined its average content in surface sediments of various functional areas (forest and agricultural land, flood deposits, reclaimed land, calculated geochemical criteria, so given ecological and geochemical assessment of area

  7. Surface-complexation modelling for describing adsorption of ...

    African Journals Online (AJOL)

    2013-06-08

    Jun 8, 2013 ... Adsorption of dissolved phosphate onto synthetic hydrous ferric oxide (HFO) was measured in the laboratory as a function of pH, ionic strength, and phosphate relative concentration. Experimental data were used to constrain optimal values of surface complexation reactions using a geochemical modeling ...

  8. Surface and Subsurface Geochemical Monitoring of an EOR-CO2 Field: Buracica, Brazil.

    OpenAIRE

    Magnier, Caroline,; Rouchon, Virgile; Bandeira, Carlos; Goncalves, R.; Miller, D.; Dino, R.

    2012-01-01

    This paper presents a surface and subsurface geochemical survey of the Buracica EOR-CO2 field onshore Brazil. We adopted a methodology coupling the stable isotopes of carbon with noble gases to investigate the adequacy of geochemical monitoring to track deep fluid leakage at the surface. Three campaigns of CO2 flux and concentration in soils were performed to understand the CO2 variability across the field. The distribution of the CO2 soil contents between 0.8 and 14% is in great part c...

  9. Soil Iodine Determination in Deccan Syneclise, India: Implications for Near Surface Geochemical Hydrocarbon Prospecting

    International Nuclear Information System (INIS)

    Mani, Devleena; Kumar, T. Satish; Rasheed, M. A.; Patil, D. J.; Dayal, A. M.; Rao, T. Gnaneshwar; Balaram, V.

    2011-01-01

    The association of iodine with organic matter in sedimentary basins is well documented. High iodine concentration in soils overlying oil and gas fields and areas with hydrocarbon microseepage has been observed and used as a geochemical exploratory tool for hydrocarbons in a few studies. In this study, we measure iodine concentration in soil samples collected from parts of Deccan Syneclise in the west central India to investigate its potential application as a geochemical indicator for hydrocarbons. The Deccan Syneclise consists of rifted depositional sites with Gondwana–Mesozoic sediments up to 3.5 km concealed under the Deccan Traps and is considered prospective for hydrocarbons. The concentration of iodine in soil samples is determined using ICP-MS and the values range between 1.1 and 19.3 ppm. High iodine values are characteristic of the northern part of the sampled region. The total organic carbon (TOC) content of the soil samples range between 0.1 and 1.3%. The TOC correlates poorly with the soil iodine (r 2 < 1), indicating a lack of association of iodine with the surficial organic matter and the possibility of interaction between the seeping hydrocarbons and soil iodine. Further, the distribution pattern of iodine compares well with two surface geochemical indicators: the adsorbed light gaseous hydrocarbons (methane through butane) and the propane-oxidizing bacterial populations in the soil. The integration of geochemical observations show the occurrence of elevated values in the northern part of the study area, which is also coincident with the presence of exposed dyke swarms that probably serve as conduits for hydrocarbon microseepage. The corroboration of iodine with existing geological, geophysical, and geochemical data suggests its efficacy as one of the potential tool in surface geochemical exploration of hydrocarbons. Our study supports Deccan Syneclise to be promising in terms of its hydrocarbon prospects.

  10. Machining of Complex Sculptured Surfaces

    CERN Document Server

    2012-01-01

    The machining of complex sculptured surfaces is a global technological topic in modern manufacturing with relevance in both industrialized and emerging in countries particularly within the moulds and dies sector whose applications include highly technological industries such as the automotive and aircraft industry. Machining of Complex Sculptured Surfaces considers new approaches to the manufacture of moulds and dies within these industries. The traditional technology employed in the manufacture of moulds and dies combined conventional milling and electro-discharge machining (EDM) but this has been replaced with  high-speed milling (HSM) which has been applied in roughing, semi-finishing and finishing of moulds and dies with great success. Machining of Complex Sculptured Surfaces provides recent information on machining of complex sculptured surfaces including modern CAM systems and process planning for three and five axis machining as well as explanations of the advantages of HSM over traditional methods ra...

  11. Geochemical characterization of surface water and spring water in ...

    Indian Academy of Sciences (India)

    The results show that some karst springs are recharged by surface water; Achabalnag by the. Bringi stream and ... and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as ...... India 30. 1–70. Gunn J 2007 Contributory zone definition for groundwa-.

  12. Smart Kd-values, their uncertainties and sensitivities - Applying a new approach for realistic distribution coefficients in geochemical modeling of complex systems.

    Science.gov (United States)

    Stockmann, M; Schikora, J; Becker, D-A; Flügge, J; Noseck, U; Brendler, V

    2017-11-01

    One natural retardation process to be considered in risk assessment for contaminants in the environment is sorption on mineral surfaces. A realistic geochemical modeling is of high relevance in many application areas such as groundwater protection, environmental remediation, or disposal of hazardous waste. Most often concepts with constant distribution coefficients (K d -values) are applied in geochemical modeling with the advantage to be simple and computationally fast, but not reflecting changes in geochemical conditions. In this paper, we describe an innovative and efficient method, where the smart K d -concept, a mechanistic approach mainly based on surface complexation modeling, is used (and modified for complex geochemical models) to calculate and apply realistic distribution coefficients. Using the geochemical speciation code PHREEQC, multidimensional smart K d -matrices are computed as a function of varying (or uncertain) environmental conditions. On the one hand, sensitivity and uncertainty statements for the distribution coefficients can be derived. On the other hand, smart K d -matrices can be used in reactive transport (or migration) codes (not shown here). This strategy has various benefits: (1) rapid computation of K d -values for large numbers of environmental parameter combinations; (2) variable geochemistry is taken into account more realistically; (3) efficiency in computing time is ensured, and (4) uncertainty and sensitivity analysis are accessible. Results are presented exemplarily for the sorption of uranium(VI) onto a natural sandy aquifer material and are compared to results based on the conventional K d -concept. In general, the sorption behavior of U(VI) in dependence of changing geochemical conditions is described quite well. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Toward a better understanding of the complex geochemical processes governing subsurface contaminant transport

    International Nuclear Information System (INIS)

    Puls, R.W.

    1990-01-01

    Identification and understanding of the geochemical processes, including ion exchange, precipitation, organic partitioning, chemisorption, aqueous complexation, and colloidal stability and transport, controlling subsurface contamination is essential for making accurate predictions of the fate and transport of these constituents. Current approaches to quantify the effect of these processes primarily involve laboratory techniques, including the use of closed static systems (batch experiments) where small amounts of aquifer solids or minerals are contacted with an aqueous phase containing the components of interest for relatively short durations; and dynamic systems (column experiments) where a larger segment of the aquifer is investigated by analyzing the breakthrough profiles of reactive and non-reactive species. Both approaches are constrained by differences in scale, alteration of media during sample collection and use, and spatial variability. More field reactivity studies are needed to complement established laboratory approaches for the determination of retardation factors and scaling factors, corroboration of batch and column results, and validation of sampling techniques. These studies also serve to accentuate areas of geochemical process research where data deficiencies exist, such as the kinetics of adsorption-desorption, metal-organic-mineral interactions, and colloidal mobility. The advantages and disadvantages of the above approaches are discussed in the context of achieving a more completely integrated approach to geochemical transport experiments, with supportive data presented from selected studies. (Author) (16 refs., 4 figs., 2 tabs.)

  14. Establishing geochemical background variation and threshold values for 59 elements in Australian surface soil.

    Science.gov (United States)

    Reimann, Clemens; de Caritat, Patrice

    2017-02-01

    During the National Geochemical Survey of Australia over 1300 top (0-10cm depth) and bottom (~60-80cm depth) sediment samples (including ~10% field duplicates) were collected from the outlet of 1186 catchments covering 81% of the continent at an average sample density of 1 site/5200km 2 . The Australian surface soil. Different methods of obtaining geochemical threshold values, which differentiate between background and those samples with unusually high element concentrations and requiring attention, are presented and compared to Western Australia's 'ecological investigation levels' (EILs) established for 14 PTEs. For Mn and V these EILs are so low that an unrealistically large proportion (~24%) of the sampled sites would need investigation in Australia. For the 12 remaining elements (As, Ba, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sn and Zn) few sample sites require investigation and as most of these are located far from human activity centres, they potentially suggest either minor local contamination or mineral exploration potential rather than pollution. No major diffuse source of contamination by PTEs affects Australian soil at the continental scale. Of the statistical methods used to establish geochemical threshold values, the most pertinent results come from identifying breaks in cumulative probability distributions, the Tukey inner fence and the 98th percentile. Geochemical threshold values for 59 elements, including emerging 'high-tech' critical elements such as lanthanides, Be, Ga or Ge, for which no EILs currently exist, are presented. Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.

  15. Microstructural and geochemical evolution of sliding surfaces in landslides and comparisons with crustal fault zones

    Science.gov (United States)

    Schäbitz, Maike; Janssen, Christoph; Wirth, Richard; Dresen, Georg

    2015-04-01

    The formation of basal sliding surfaces in mass movements is known to be associated with chemical and physical alteration of rock and regolith. To evaluate their microstructural and geochemical evolution we collected samples from bedrock, the sliding surface (gouge) and adjacent deposits within two different landslides in Central China. The sample locations reflect different geological conditions. Comparing qualitative and quantitative geochemical analysis we found indications for weathering of the sliding surface area and the accumulation and genesis of clay minerals, explaining its reduced shear strength. The cataclasites (gouge) are mainly composed of quartz, illite, calcite, pyrophyllite, kaolinite and feldspar with grain sizes in the range 0.5 - 5μm. XRF data show an increase in Al2O3, Fe2O3, K2O and decrease in SiO2 and CaO contents towards the sliding surface, pointing to alteration processes. The existence and increase of pyrophyllite content in sliding surface samples may indicate its initial formation to be caused by a high energy event, because pyrophyllite forms by hydrothermal alteration at approximately 450 ° C. The accumulation of pyrophyllite at the sliding surface is expected to result in reduced shear strength. Comparison of the microstructures, using transmission electron microscopy and focused ion beam technique for sample preparation shows a significant reduction of grain size and increase of pore space due to grain comminution by creeping and moving processes. High- angle annular dark field images show the occurrence of amorphous carbon which may indicate the occurrence of graphite. Graphitization (crystallization) of amorphous carbon was recognized in the slip zone of several fault zones, which underwent frictional heating due to rapid sliding. Graphite is well known as a solid lubricant in fault zones with a friction coefficient as low as that of smectite (μ = 0.1). The process of sliding surface formation in some landslides seems to be

  16. Geochemical constraints on the link between volcanism and plutonism at the Yunshan caldera complex, SE China

    Science.gov (United States)

    Yan, Lili; He, Zhenyu; Beier, Christoph; Klemd, Reiner

    2018-01-01

    The Yunshan caldera complex is part of a larger scale, ca. 2000-km-long volcanic-plutonic complex belt in the coastal region of SE China. The volcanic rocks in the caldera complex are characterized by high-silica peraluminous and peralkaline rhyolites associated with an intracaldera porphyritic quartz monzonite pluton. In this study, we present zircon U-Pb, Hf and stable O isotopes along with geochemical data of both volcanic and plutonic rocks to evaluate the potential petrogenetic link between volcanism and plutonism in the Yunshan caldera complex. SHRIMP zircon U-Pb geochronology of both volcanic and plutonic rocks yields almost identical ages ranging from 95.6 to 93.1 Ma. The peraluminous and peralkaline rhyolites show negative anomalies of Sr, P, Ti and Ba and to a lesser extent negative Nb and Ta anomalies, along with positive Rb anomalies and `seagull-like' rare earth element (REE) patterns with negative Eu anomalies and low (La/Yb)N ratios. The intracaldera porphyritic quartz monzonite displays minor negative Rb, Nb, Ta, Sr, P and Ti anomalies and a positive Ba anomaly with REE patterns characterized by relatively high (La/Yb)N ratios and lack significant Eu anomalies. The peraluminous and peralkaline rhyolites and the porphyritic quartz monzonite exhibit consistent ɛ Nd( t) of - 3.7 to - 2.2 and display zircon ɛ Hf( t) values of - 2.1 to 3.7. They further have similar, mantle-like, zircon oxygen isotopic compositions (δ18OVSMOW mainly = 4.63 to 5.76‰). We interpret these observations to be in agreement with a crystal mush model in which the parental magma of the volcanic and plutonic rocks of the Yunshan caldera complex was likely produced by interaction of asthenosphere melts with subduction-influenced enriched mantle wedge. The peralkaline rhyolites are interpreted to represent the most differentiated magma that has subsequently experienced significant fluid-melt interactions, whereas the porphyritic quartz monzonite may be representative of the

  17. Calc-alkaline lavas from the volcanic complex of Santorini, Aegean Sea, Greece : a petrological, geochemical and stratigraphic study

    NARCIS (Netherlands)

    Huijsmans, J.P.P.

    1985-01-01

    This thesis presents the results of a petrological-geochemical- and stratigraphic study of the calc-alkaline lavas from Santorini, Aegean Sea, Greece. The volcanic complex of Santorini consists of seven eruption centres, of which some have been active contemporaneous. The eruption centres in the

  18. Subduction between the Jiamusi and Songliao blocks: Geological, geochronological and geochemical constraints from the Heilongjiang Complex

    Science.gov (United States)

    Zhu, Chloe Yanlin; Zhao, Guochun; Ji, Jianqing; Sun, Min; Han, Yigui; Liu, Qian; Eizenhöfer, Paul R.; Zhang, Xiaoran; Hou, Wenzhu

    2017-06-01

    In Northeast China, oceanic subduction between the Jiamusi and Songliao blocks remains topic of hot debate. The Heilongjiang Complex has been regarded as an accretionary belt resulting from the subduction of an intervening ocean between the two blocks. In this study, we carry out extensive geological, geochemical and geochronological investigations on the sedimentary rocks, amphibolites and blueschists from the Heilongjiang Complex. The detrital zircons from meta-sedimentary rocks yield U-Pb age spams ranging from 268 to 780 Ma. Whereas the interlayered amphibolites show negative Nb-Ta-Ti and positive Pb anomalies and have a protolithic age of 188.2 ± 1.0 Ma, suggesting a subduction zone or magmatic arc origin in the Jurassic. The elevated initial Sr isotopic ratios (0.708-0.711) and negative εNd(t) values (- 4.3 to - 1.3) provide further evidence of the modification by upper continental crust during the magma ascending. LREE/HREE and MREE/HREE ratios suggest that the magma was likely derived from the mixing of lithospheric and asthenospheric melts. The presence of low Th/Ce (0.04-0.12) and Hf/Sm (0.35-0.55), but high Zr/Hf (35.4-43.4) and Pb/Ce (0.25-0.49) ratios strongly implies a contribution from subducted sediments. The identification of active continental margin type magmas of Early Jurassic age suggests that the subduction of the oceanic plate between the Jiamusi and Songliao blocks may have started around Early Jurassic time. In addition, the blueschists have a protolithic age of 186 ± 1.1 Ma and display geochemical affinities of oceanic island basalts, suggesting that the ocean between the Jiamusi and Songliao blocks closed sometime after 186 Ma. Mineral 40Ar/39Ar dating results from the Heilongjiang Complex further indicate that blueschist- to greenschist-facies metamorphism occurred in the Middle to Late Jurassic (158-175 Ma), marking the onset of termination of the oceanic subduction.

  19. Surface complexation modeling of americium sorption onto volcanic tuff.

    Science.gov (United States)

    Ding, M; Kelkar, S; Meijer, A

    2014-10-01

    Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways. Published by Elsevier Ltd.

  20. Arsenic transport between surface and groundwater in a moderately reducing zone: Geochemical approach

    Science.gov (United States)

    Khaska, Mahmoud; Le Gal La Salle, Corinne; Verdoux, Patrick

    2015-04-01

    Arsenic contamination represents a major risk to human health as one of the most prominent environmental causes of cancer mortality. Mining activities, particularly those involving arsenic rich ores have an impact on the environment and on human health that may persist for many decades after mine closure. The relationships between As released from alluvial aquifer in the vicinity of the sulfide-rich mine dumps was demonstrated with geochemical and isotopic tracers (major and traces elements, 87Sr/86Sr, 18O, 2H). Strontium isotopes were used to trace the transport of As downstream from a As rich tailing dam. Increasing As and Fe concentrations in surface water are explained by As release associated with alluvial groundwater discharge to the stream. This process occurs in a moderately reduced section of the stream downgradient from the sulfide-rich tailing dam. High As, total Fe and low Eh in groundwater confirm the discharge of alluvial groundwater and explain its impact on surface water. Transport of As between surface and groundwater can be described as follows: 1- Subsurface moderately reducing conditions prevail in groundwater downgradient from the tailing dams. This suggests a flux of reduced water from sulfide-rich tailing dams which is characterized by its high As and Fe content resulting from the reduction of Fe-sulfides. 2- Upon mixing with surface water, oxidizing conditions prevails and precipitate as Fe hydroxide on the stream bed. As and Sr subsequently adsorbed on the Fe -oxyhydroxide surface. This process contributes to the immobilization of As in surface water. Remaining dissolved As in surface water can be re-introduced in alluvial groundwater downstream of the reducing zone.

  1. Geochemical and mineralogical interpretation of the Viking inorganic chemical results. [for Martian surface materials

    Science.gov (United States)

    Toulmin, P., III; Rose, H. J., Jr.; Christian, R. P.; Baird, A. K.; Evans, P. H.; Clark, B. C.; Keil, K.; Kelliher, W. C.

    1977-01-01

    The current status of geochemical, mineralogical, petrological interpretation of refined Viking Lander data is reviewed, and inferences that can be drawn from data on the composition of Martian surface materials are presented. The materials are dominantly fine silicate particles admixed with, or including, iron oxide particles. Both major element and trace element abundances in all samples are indicative of mafic source rocks (rather than more highly differentiated salic materials). The surface fines are nearly identical in composition at the two widely separated Lander sites, except for some lithologic diversity at the 100-m scale. This implies that some agency (presumably aeolian processes) has thoroughly homogenized them on a planetary scale. The most plausible model for the mineralogical constitution of the fine-grained surface materials at the two Lander sites is a fine-grained mixture dominated by iron-rich smectites, or their degradation products, with ferric oxides, probably including maghemite and carbonates (such as calcite), but not such less stable phases as magnesite or siderite.

  2. Mineralogical and geochemical patterns of urban surface soils, the example of Pforzheim, Germany

    International Nuclear Information System (INIS)

    Norra, Stefan; Lanka-Panditha, Mahesh; Kramar, Utz; Stueben, Doris

    2006-01-01

    This study presents a combined geochemical and mineralogical survey of urban surface soils. Many studies on urban soils are restricted to purely chemical surveys in order to investigate soil pollution caused by anthropogenic activities such as traffic, heating, industrial processing, waste disposal and many more. In environmental studies, chemical elements are often distinguished as lithogenic and anthropogenic elements. As a novel contribution to those studies, the authors combined the analysis of a broad set of chemical elements with the analysis of the main mineralogical phases. The semi-quantification of mineralogical phases supported the assignment of groups of chemical elements to lithogenic or anthropogenic origin. Minerals are important sinks for toxic elements. Thus, knowledge about their distribution in soils is crucial for the assessment of the environmental hazards due to pollution of urban soils. In Pforzheim, surface soils (0-5 cm depth) from various land use types (forest, agriculture, urban green space, settlement areas of various site densities) overlying different geological units (clastic and chemical sediments) were investigated. Urban surface soils of Pforzheim reflect to a considerable degree the mineral and chemical composition of parent rocks. Irrespective of the parent rocks, elevated concentrations of heavy metals (Zn, Cu, Pb, Sn, Ag) were found in soils throughout the whole inner urban settlement area of Pforzheim indicating pollution. These pollutants will tend to accumulate in inner urban surface soils according to the available adsorption capacity, which is normally higher in soils overlying limestone than in soils overlying sandstone. However, inner urban surface soils overlying sandstone show elevated concentrations of carbonates, phyllo-silicates and Fe and elevated pH values compared with forest soils overlying sandstone. Thus, in comparison to forest soils overlying sandstones, inner urban soils overlying sandstone affected by

  3. Complex multiplication of abelian surfaces

    NARCIS (Netherlands)

    Streng, Theodorus Cornelis

    2010-01-01

    The theory of complex multiplication makes it possible to construct certain class fields and abelian varieties. The main theme of this thesis is making these constructions explicit for the case where the abelian varieties have dimension 2. Chapter I is an introduction to complex

  4. Computational Complexity of Combinatorial Surfaces

    NARCIS (Netherlands)

    Vegter, Gert; Yap, Chee K.

    1990-01-01

    We investigate the computational problems associated with combinatorial surfaces. Specifically, we present an algorithm (based on the Brahana-Dehn-Heegaard approach) for transforming the polygonal schema of a closed triangulated surface into its canonical form in O(n log n) time, where n is the

  5. Geochemical characteristics and origin of the Lebowa Granite Suite, Bushveld Complex

    Science.gov (United States)

    Hill, M.; Barker, F.; Hunter, D.; Knight, R.

    1996-01-01

    The ??? 2052-Ma Lebowa Granite Suite (LGS) represents the culminating phase of an Early Proterozoic magmatic cycle in the Central Transvaal area of the Kaapvaal Province. Following extrusion of at least 200,000 km3 of intermediate to acid volcanics (Rooiberg Felsite), mafic and ultramafic magmas intruded at 2065 Ma to form the Rustenburg Layered Suite (RLS). The LGS includes the Nebo, Makhutso, Bobbejaankop, Lease, and Klipkloof granites. The Nebo Granite intruded the Rooiberg Felsite as sheets up to 4 km thick above the RLS. Smaller stocks of the other granites crosscut the Nebo. We determined major- and trace-element compositions and oxygen, Rb-Sr, and Sm-Nd isotope ratios for samples of: Nebo Granite; Rooiberg Felsite; granophyre and granophyric granite; Makhutso, Bobbejaankop, and Lease granites; and feldspar porphyry from areas throughout the exposed area of the LGS (Dennilton, Verena Balmoral, Enkeldoorn, Sekhukhune Plateau, Zaaiplaats-Potgeitersrus, and Western Transvaal). Coherent floor-to-roof geochemical trends exist in some areas, although it is not possible to model them convincingly. Regional variations in geochemistry exist and likely are related to source variations in the estimated 200,000 km3 of the Nebo Granite sheets. ??18O for the LGS range from +5.9??? to +9.5???; if these are approximate primary magmatic values, pelitic sediments cannot have been an important source for the LGS. The Rb-Sr isotope system has been altered, a finding consistent with previous studies. A mineral isochron for Nebo Granite near Dennilton yields a York regression age of 1995 ?? 99 Ma, with initial 143Nd/144Nd = 0.50978??8 and ???CHUR=-5.12. Samples from the Sekhukhune Plateau have higher 143Nd/144Nd ratios than do Dennilton-area samples, suggesting that the former originated from older or less LREE-enriched sources. We suggest that intrusion of mafic to ultramafic magmas at depth in the continental crust triggered melting of Archean quartzofeldspathic crystalline

  6. Geochemical evidence for a complex origin for the Kelso dunes, Mojave National Preserve, California USA

    Science.gov (United States)

    Muhs, Daniel; Lancaster, Nicholas; Skipp, Gary L.

    2017-01-01

    The Kelso Dune field in southern California is intriguing because although it is of limited areal extent (~ 100 km2), it has a wide variety of dune forms and contains many active dunes (~ 40 km2), which is unusual in the Mojave Desert. Studies over the past eight decades have concluded that the dunes are derived primarily from a single source, Mojave River alluvium, under a dominant, westerly-to-northwesterly wind regime. The majority of these studies did not, however, present data to support the Mojave River as the only source. We conducted mineralogical and geochemical studies of most of the 14 geomorphically defined dune groups of the Kelso Dune field as well as potential sand sources, alluvial sediments from the surrounding mountain ranges. Results indicate that sands in the nine western dune groups have K/Rb and K/Ba (primarily from K-feldspar) compositions that are indistinguishable from Mojave River alluvium (westerly/northwesterly winds) and Budweiser Wash alluvium (southwesterly winds), permitting an interpretation of two sources. In contrast, sands from the five eastern dune groups have K/Rb and K/Ba values that indicate significant inputs from alluvial fan deposits of the Providence Mountains. This requires either rare winds from the east or southeast or, more likely, aeolian reworking of distal Providence Mountain fan sediments by winds from the west, at a rate greater than input from the Mojave River or other western sources. The results indicate that even a small dune field can have a complex origin, either from seasonally varying winds or complex alluvial-fan-dune interaction. Application of K/Rb and K/Ba in K-feldspar as a provenance indicator could be used in many of the world's ergs or sand seas, where dune origins are still not well understood or are controversial. Four examples are given from Africa and the Middle East where such an approach could yield useful new information about dune sand provenance.

  7. The growth and contamination mechanism of the Cana Brava layered mafic-ultramafic complex: new field and geochemical evidences

    Science.gov (United States)

    Giovanardi, Tommaso; Girardi, Vicente A. V.; Correia, Ciro T.; Sinigoi, Silvano; Tassinari, Colombo C. G.; Mazzucchelli, Maurizio

    2017-04-01

    The Cana Brava complex is the northernmost of three layered complexes outcropping in the Goiás state (central Brasil). New field and geochemical evidences suggest that Cana Brava underwent hyper- to subsolidus deformation during its growth, acquiring a high-temperature foliation that is generally interpreted as the result of a granulite-facies metamorphic event. The increase along the stratigraphy of the incompatible elements abundances (LREE, Rb, Ba) and of the Sr isotopic composition, coupled with a decrease in ɛNd(790), indicate that the complex was contaminated by the embedded xenoliths from the Palmeirópolis Sequence. The geochemical data suggest that the contamination occurred along the entire magma column during the crystallization of the Upper Mafic Zone, with in situ variations determined by the abundance and composition of the xenoliths. These features of the Cana Brava complex point to an extremely similarity with the Lower Sequence of the most known Niquelândia intrusion (the central of the three complexes). This, together with the evidences that the two complexes have the same age (c.a. 790 Ma) and their thickness and units decrease northwards suggests that Cana Brava and Niquelândia are part of a single giant Brasilia body grown through several melt impulses.

  8. Large Early Permian eruptive complexes in northern Saxony, Germany: Volcanic facies analysis and geochemical characterization

    Science.gov (United States)

    Hübner, Marcel; Breitkreuz, Christoph; Repstock, Alexander; Heuer, Franziska

    2017-04-01

    In the course of formation of extensional basins during the Early Permian a widespread volcanic activity led to the deposition of volcanic and volcanosedimentary units in Saxony (Walter 2006, Hoffmann et al. 2013). Situated east of Leipzig, the North Saxonian Volcanic Complex (NSVC) hosts two large caldera complexes, the Rochlitz and Wurzen Volcanic Systems, with diameters of 90 and 52 km, respectively. Volume estimates (> 1000 km3) qualify these as supereruptions according to Mason et al. (2004). In addition to the large caldera systems, the NSVC hosts several small pyroclastic flow deposits ranging from crystal-poor (e.g. Cannewitz and vitrophyric Ebersbach ignimbrites) to crystal-rich units (Wermsdorf and Dornreichenbach ignimbrites). Additionally rhyolitic lava and subvolcanic units are present. The Chemnitz basin (Schneider et al. 2012), located to the south of the NSVC, harbours caldera-outflow facies deposits of the Rochlitz eruption (Fischer 1991), i.e. the partially vitrophyric Planitz ignimbrite. The Rochlitz and Wurzen caldera-fill ignimbrites exhibit relatively high crystal contents with maxima up to 52 and 58 vol.-%, for corresponding 66 and 68 wt.-% SiO2. This is comparable with the 'monotonous intermediates' (Hildreth 1981) in the Cenozoic western USA investigated by Huber et al. (2012). In contrast, the Planitz ignimbrite in the Chemnitz basin reveals predominantly crystal-poor pyroclastics ( 70 analyses), and mineral geochemistry to reconstruct the eruption history and magma genesis of this large Late Paleozoic magmatic complex in Central Europe. Volcanic textures and geochemical trends indicate magma mingling and mixing to have been important during the formation of the Wurzen caldera system. Geothermometric and -barometric calculations based on composition of pyroxene and feldspar suggest deeply seated crustal magma chambers for the NSVC and the Planitz ignimbrite. Fischer, F. (1991): Das Rotliegende des ostthüringisch-westsächsischen Raumes

  9. Surface geochemical data evaluation and integration with geophysical observations for hydrocarbon prospecting, Tapti graben, Deccan Syneclise, India

    OpenAIRE

    Satish Kumar, T.; Dayal, A.M.; Sudarshan, V.

    2014-01-01

    The Deccan Syneclise is considered to have significant hydrocarbon potential. However, significant hydrocarbon discoveries, particularly for Mesozoic sequences, have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks. In this study, near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area. Soil samples were collected from favorable...

  10. The granitic complex of Brame/Saint-Sylvestre/Saint-Goussaud (French Massif Central), geochemical mapping applied to uranium prospecting

    International Nuclear Information System (INIS)

    Valois, J.P.

    1991-01-01

    Obtained geochemic data from the granitic complex of Brame/Saint-Sylvestre/Saint-Goussaud (French Massif Central), which is known as uranium ore bearing. Friedrich's data were reinterpreted using a different statistical method (principal component analysis with oblic rotation of the factors). The resulting trace element associations are interpreted according to the several mineral paragenesis previously described in this complex. These associations can be related to the successive stages of granitic cristallisation, and their mapping is in agreement with previous mapping obtained from quite different data (structural petrology for example). New results concern an U, Zn, Y, R.E association which is attributed to the uraninite paragenesis, previously described on this granitic complex. Mapping this last association contributes to emphasize the central part of the complex as a favourable zone for prospecting [fr

  11. Geochemical signature of land-based activities in Caribbean coral surface samples

    Science.gov (United States)

    Prouty, N.G.; Hughen, K.A.; Carilli, J.

    2008-01-01

    Anthropogenic threats, such as increased sedimentation, agrochemical run-off, coastal development, tourism, and overfishing, are of great concern to the Mesoamerican Caribbean Reef System (MACR). Trace metals in corals can be used to quantify and monitor the impact of these land-based activities. Surface coral samples from the MACR were investigated for trace metal signatures resulting from relative differences in water quality. Samples were analyzed at three spatial scales (colony, reef, and regional) as part of a hierarchical multi-scale survey. A primary goal of the paper is to elucidate the extrapolation of information between fine-scale variation at the colony or reef scale and broad-scale patterns at the regional scale. Of the 18 metals measured, five yielded statistical differences at the colony and/or reef scale, suggesting fine-scale spatial heterogeneity not conducive to regional interpretation. Five metals yielded a statistical difference at the regional scale with an absence of a statistical difference at either the colony or reef scale. These metals are barium (Ba), manganese (Mn), chromium (Cr), copper (Cu), and antimony (Sb). The most robust geochemical indicators of land-based activities are coral Ba and Mn concentrations, which are elevated in samples from the southern region of the Gulf of Honduras relative to those from the Turneffe Islands. These findings are consistent with the occurrence of the most significant watersheds in the MACR from southern Belize to Honduras, which contribute sediment-laden freshwater to the coastal zone primarily as a result of human alteration to the landscape (e.g., deforestation and agricultural practices). Elevated levels of Cu and Sb were found in samples from Honduras and may be linked to industrial shipping activities where copper-antimony additives are commonly used in antifouling paints. Results from this study strongly demonstrate the impact of terrestrial runoff and anthropogenic activities on coastal water

  12. Final Report: Molecular Basis for Microbial Adhesion and Geochemical Surface Reactions: A Study Across Scales

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-06-27

    Computational chemistry was used to help provide a molecular level description of the interactions of Gram-negative microbial membranes with subsurface materials. The goal is to develop a better understanding of the molecular processes involved in microbial metal binding, microbial attachment to mineral surfaces, and, eventually, oxidation/reduction reactions (electron transfer) that can occur at these surfaces and are mediated by the bacterial exterior surface. The project focused on the interaction of the outer microbial membrane, which is dominated by an exterior lipopolysaccharide (LPS) portion, of Pseudomonas aeruginosa with the mineral goethite and with solvated ions in the environment. This was originally a collaborative project with T.P. Straatsma and B. Lowery of the Pacific Northwest National Laboratory. The University of Alabama effort used electronic structure calculations to predict the molecular behavior of ions in solution and the behavior of the sugars which form a critical part of the LPS. The interactions of the sugars with metal ions are expected to dominate much of the microscopic structure and transport phenomena in the LPS. This work, in combination with the molecular dynamics simulations of Straatsma and the experimental electrochemistry and microscopy measurements of Lowry, both at PNNL, is providing new insights into the detailed molecular behavior of these membranes in geochemical environments. The effort at The University of Alabama has three components: solvation energies and structures of ions in solution, prediction of the acidity of the critical groups in the sugars in the LPS, and binding of metal ions to the sugar anions. An important aspect of the structure of the LPS membrane as well as ion transport in the LPS is the ability of the sugar side groups such as the carboxylic acids and the phosphates to bind positively charged ions. We are studying the acidity of the acidic side groups in order to better understand the ability of

  13. Geochemical evolution of acidic ground water at a reclaimed surface coal mine in western Pennsylvania

    Science.gov (United States)

    Cravotta,, Charles A.

    1991-01-01

    Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous

  14. Surface Complexation Modelling in Metal-Mineral-Bacteria Systems

    Science.gov (United States)

    Johnson, K. J.; Fein, J. B.

    2002-12-01

    The reactive surfaces of bacteria and minerals can determine the fate, transport, and bioavailability of aqueous heavy metal cations. Geochemical models are instrumental in accurately accounting for the partitioning of the metals between mineral surfaces and bacteria cell walls. Previous research has shown that surface complexation modelling (SCM) is accurate in two-component systems (metal:mineral and metal:bacteria); however, the ability of SCMs to account for metal distribution in mixed metal-mineral-bacteria systems has not been tested. In this study, we measure aqueous Cd distributions in water-bacteria-mineral systems, and compare these observations with predicted distributions based on a surface complexation modelling approach. We measured Cd adsorption in 2- and 3-component batch adsorption experiments. In the 2-component experiments, we measured the extent of adsorption of 10 ppm aqueous Cd onto either a bacterial or hydrous ferric oxide sorbent. The metal:bacteria experiments contained 1 g/L (wet wt.) of B. subtilis, and were conducted as a function of pH; the metal:mineral experiments were conducted as a function of both pH and HFO content. Two types of 3-component Cd adsorption experiments were also conducted in which both mineral powder and bacteria were present as sorbents: 1) one in which the HFO was physically but not chemically isolated from the system using sealed dialysis tubing, and 2) others where the HFO, Cd and B. subtilis were all in physical contact. The dialysis tubing approach enabled the direct determination of the concentration of Cd on each sorbing surface, after separation and acidification of each sorbent. The experiments indicate that both bacteria and mineral surfaces can dominate adsorption in the system, depending on pH and bacteria:mineral ratio. The stability constants, determined using the data from the 2-component systems, along with those for other surface and aqueous species in the systems, were used with FITEQL to

  15. Geochemical modeling research related to the surface disposal of processed oil shale solid waste. [Elements and compounds in oil shale wastes

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, K. J.; Drever, J. I.

    1987-10-01

    Several geochemical codes are available in the literature to model chemical processes such as oxidation-reduction, precipitation-dissolution, formation of solution complex, adsorption, and ion exchange. However, these models differ in the environments to which they apply. The objective of this research was to evaluate the applicability of existing geochemical codes to predict water quality from an oil shale solid waste environment. We selected EQ3/EQ6, GEOCHEM, MINTEQ, PHREEQE, SOLMNEQ, and WATEQFC geochemical models for further evaluation. We concluded that all these models lack thermodynamic data for minerals and solution complexes which are important for oil shale solid waste studies. Selection of any one of the models would require development of a more reliable thermodynamic database, and this report describes the initiation of that work. So far, critical evaluation of thermodynamic data has been completed for Sr, F, Mo, and Se. 64 refs., 15 tabs.

  16. Holographic subregion complexity for singular surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bakhshaei, Elaheh [Isfahan University of Technology, Department of Physics, Isfahan (Iran, Islamic Republic of); Mollabashi, Ali [Institute for Research in Fundamental Sciences (IPM), School of Physics, Tehran (Iran, Islamic Republic of); Shirzad, Ahmad [Isfahan University of Technology, Department of Physics, Isfahan (Iran, Islamic Republic of); Institute for Research in Fundamental Sciences (IPM), School of Particles and Accelerators, Tehran (Iran, Islamic Republic of)

    2017-10-15

    Recently holographic prescriptions were proposed to compute the quantum complexity of a given state in the boundary theory. A specific proposal known as 'holographic subregion complexity' is supposed to calculate the complexity of a reduced density matrix corresponding to a static subregion. We study different families of singular subregions in the dual field theory and find the divergence structure and universal terms of holographic subregion complexity for these singular surfaces. We find that there are new universal terms, logarithmic in the UV cut-off, due to the singularities of a family of surfaces including a kink in (2 + 1) dimensions and cones in even dimensional field theories. We also find examples of new divergent terms such as squared logarithm and negative powers times the logarithm of the UV cut-off parameter. (orig.)

  17. Complex burrows of the mud shrimp Callianassa truncata and their geochemical impact in the sea bed

    DEFF Research Database (Denmark)

    Ziebis, W.; Forster, S.; Huettel, M.

    1996-01-01

    the overlying water and rapid consumption within the sea bed, Macrofauna organisms living within the sea bed affect the physical structure of the sea floor, its chemical zonations and the exchange processes across the sediment-water interface(3,4). Thalassinidean mud-shrimps are often abundant in tropical...... and temperate coastal regions(5-7) and build burrows with a species-specific architecture, The deepest reported burrows reach down to 2.5 m sediment depth(8). It is difficult to study the activities of these secretive animals and their effect on sediment biogeochemistry without disturbing the sediment system(9......). Here we report the use of a diver observatory within the seabed, along with in situ measurements, to assess the geochemical impact of the mud-shrimp Callianassa truncata Giard and Bonnier (Decapoda, Thalassinidea), a species that commonly inhabits sandy sediments in the Mediterranean sea....

  18. Analysis of the geochemical gradient created by surface-groundwater interactions within riverbanks of the East River in Crested Butte, Colorado

    Science.gov (United States)

    Lunzer, J.; Williams, K. H.; Malenda, H. F.; Nararne-Sitchler, A.

    2016-12-01

    An improved understanding of the geochemical gradient created by the mixing of surface and groundwater of a river system will have considerable impact on our understanding of microorganisms, organic cycling and biogeochemical processes within these zones. In this study, the geochemical gradient in the hyporheic zone is described using a variety of geochemical properties. A system of shallow groundwater wells were installed in a series of transects along a stream bank. Each transect consists of several wells that progress away from the river bank in a perpendicular fashion. From these wells, temperature, conductivity and pH of water samples were obtained via hand pumping or bailing. These data show a clear geochemical gradient that displays a distinct zone in the subsurface where the geochemical conditions change from surface water dominated to groundwater dominated. For this study, the East River near Crested Butte, Colorado has been selected as the river of interest due the river being a relatively undisturbed floodplain. Additionally, the specific section chosen on the East River displays relatively high sinuosity meaning that these meandering sections will produce hyporheic zones that are more laterally expansive than what would be expected on a river of lower sinuosity. This increase in lateral extension of the hyporheic zone will make depicting the subtle changes in the geochemical gradient much easier than that of a river system in which the hyporheic zone is not as laterally extensive. Data has been and will be continued to be collected at different river discharges to evaluate the geochemical gradient at differing rates. Overall, this characterization of the geochemical gradient along stream banks will produce results that will aid in the further use of geochemical methods to classify and understand hyporheic exchange zones and the potential expansion of these techniques to river systems of differing geologic and geographic conditions.

  19. Surface-complexation models for sorption onto heterogeneous surfaces

    International Nuclear Information System (INIS)

    Harvey, K.B.

    1997-10-01

    This report provides a description of the discrete-logK spectrum model, together with a description of its derivation, and of its place in the larger context of surface-complexation modelling. The tools necessary to apply the discrete-logK spectrum model are discussed, and background information appropriate to this discussion is supplied as appendices. (author)

  20. GEOQUIMICO : an interactive tool for comparing sorption conceptual models (surface complexation modeling versus K[D])

    International Nuclear Information System (INIS)

    Hammond, Glenn E.; Cygan, Randall Timothy

    2007-01-01

    Within reactive geochemical transport, several conceptual models exist for simulating sorption processes in the subsurface. Historically, the K D approach has been the method of choice due to ease of implementation within a reactive transport model and straightforward comparison with experimental data. However, for modeling complex sorption phenomenon (e.g. sorption of radionuclides onto mineral surfaces), this approach does not systematically account for variations in location, time, or chemical conditions, and more sophisticated methods such as a surface complexation model (SCM) must be utilized. It is critical to determine which conceptual model to use; that is, when the material variation becomes important to regulatory decisions. The geochemical transport tool GEOQUIMICO has been developed to assist in this decision-making process. GEOQUIMICO provides a user-friendly framework for comparing the accuracy and performance of sorption conceptual models. The model currently supports the K D and SCM conceptual models. The code is written in the object-oriented Java programming language to facilitate model development and improve code portability. The basic theory underlying geochemical transport and the sorption conceptual models noted above is presented in this report. Explanations are provided of how these physicochemical processes are instrumented in GEOQUIMICO and a brief verification study comparing GEOQUIMICO results to data found in the literature is given

  1. COMPLEX SURFACE HARDENING OF STEEL ARTICLES

    Directory of Open Access Journals (Sweden)

    A. V. Kovalchuk

    2014-01-01

    Full Text Available The method of complex surface hardening of steel detailswas designed. The method is a compound of two processes of hardening: chemical heat treatment and physical vapor deposition (PVD of the coating. The result, achieved in this study is much higher, than in other work on this topic and is cumulative. The method designed can be used in mechanical engineering, medicine, energetics and is perspective for military and space technologies.

  2. Geochemical fractionation and pollution assessment of Zn, Cu, and Fe in surface sediments from Shadegan Wildlife Refuge, southwest of Iran.

    Science.gov (United States)

    Chaharlang, Behnam Heidari; Bakhtiari, Alireza Riyahi; Mohammadi, Jahangard; Farshchi, Parvin

    2017-09-01

    This research focuses on the fractionation and distribution patterns of heavy metals (Zn, Cu, and Fe) in surficial sediments collected from Shadegan Wildlife Refuge, the biggest wetland in southern part of Iran, to provide an overall classification for the sources of metals in the study area using a sequential extraction method. For this purpose, a four-step sequential extraction technique was applied to define the partitioning of the metals into different geochemical phases of the sediment. The results illustrated that the average total level of Zn, Cu, and Fe in surface sediments were 55.20 ± 16.04, 22.86 ± 5.68, and 25,979.01 ± 6917.91 μg/g dw, respectively. On the average, the chemical partitioning of all metals in most stations was in the order of residual >oxidizable-organic > acid-reducible > exchangeable. In the same way, the results of calculated geochemical indices revealed that Cu, Zn, and Fe concentrations are mainly influenced by lithogenic origins. Compared with consensus-based SQGs, Cu was likely to result in occasionally harmful biological effects on the biota.

  3. Interaction of natural complexing agents with soil bound heavy metals -geochemical and environmental technical aspects

    International Nuclear Information System (INIS)

    Fischer, K.

    1994-01-01

    The sanitation of heavy metal polluted soils requires the application of an adequate technology, which should be consistent in its ecological aims and methodology. Therefore a research programme has been developed at the 'Institute of Ecological Chemistry' of the 'GSF-Research Center', Neuherberg, which has its starting point in the study of influences of natural organic complexing agents on the chemical activity and dynamic of heavy metals in soils. The groundlaying idea is to elevate the concentration of complexing agents in the soil solution by additional application and possible stimulation of their microbial production to such an extent, that heavy metals will be enhanced solubilized, mobilized and removed together with the seepage water. Batch experiments in order to extract heavy metals from typical soil components (bentonite, peat) by amino acids demonstrate, that removal rates up to 95% can be obtained. (orig.) [de

  4. Surface geochemical data evaluation and integration with geophysical observations for hydrocarbon prospecting, Tapti graben, Deccan Syneclise, India

    Directory of Open Access Journals (Sweden)

    T. Satish Kumar

    2014-05-01

    Full Text Available The Deccan Syneclise is considered to have significant hydrocarbon potential. However, significant hydrocarbon discoveries, particularly for Mesozoic sequences, have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks. In this study, near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area. Soil samples were collected from favorable areas identified by integrated geophysical studies. The compositional and isotopic signatures of adsorbed gaseous hydrocarbons (methane through butane were used as surface indicators of petroleum micro-seepages. An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons (C1–C4 and their carbon isotopes from the western part of Tapti graben, Deccan Syneclise, India. The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases. High concentrations of adsorbed thermogenic methane (C1 = 518 ppb and ethane plus higher hydrocarbons (ΣC2+ = 977 ppb were observed. Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents. This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks, beneath Deccan Traps. The carbon isotopic composition of methane, ethane and propane ranges are from −22.5‰ to −30.2‰ PDB, −18.0‰ to 27.1‰ PDB and 16.9‰–32.1‰ PDB respectively, which are in thermogenic source. Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks. Prominent hydrocarbon concentrations were associated with dykes, lineaments and presented on thinner basaltic cover in the study area

  5. Geochemical studies, magmatic evolution, microstructures and replacement mechanisms in Jebale-Barez granitoid Complex (East and Southeast Jiroft

    Directory of Open Access Journals (Sweden)

    Jamal Rasouli

    2017-08-01

    samples and full matrix correction, the sum of all major oxides was equal to about 100 wt.%. The concentration of trace elements in the selected samples has been performed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS. The uncertainty is <10% for trace element contents higher than 2 ppm (except for Pb, <15% and <15% for all the other trace elements. Results The microstructures observed in thin sections in this study were grouped into three types: (i magmatic microstructures; (ii submagmatic microstructures and (iii mylonitic microstructures. Magmatic and submagmatic microstructures occurred simultaneously with the emplacement of granitoid complex and mylonitic microstructures that occurred after emplacement of granitoid complex. The magma nature of these rocks is sub-alkaline-(calc-alkaline, which fall into calc-alkaline series with high potassium in SiO2-K2O plots. The geochemical variation diagrams of major oxides, the continuous spectrum of rock compositions has been carried out which indicates the crystallization of magmatic differentiation and extensive appendices. Field observations, petrographic and geochemical studies suggest that the rocks in this area have type I and CAG subsections. Studying the geochemical diagrams of the rocks in the studied area indicates that these rocks have been formed in active continental margin tectononic settings. It seems that the Jebale-Barez granitoid Complex is located within a shear zone. Magma has been percolated through Mijan caldera and emplacement Forms of Sill along the shear zone during various periods and the structural setting of granitoid complex in the Jebale-Barez is extensional-shear fractures which are the product of transpression tectonic regime. Discussion The JBPC is calc-alkaline, high-K, subalkaline, and mostly metaluminous except granite and alkali-granite units which are slightly peraluminous and I type in character. These geochemical properties of the studied granitoids suggest subduction

  6. Heavy metal transport processes in surface water and groundwater. Geochemical and isotopic aspects

    International Nuclear Information System (INIS)

    Tricca, A.

    1997-01-01

    This work deals with the transport mechanisms of trace elements in natural aquatic systems. The experimental field is situated in the Upper Rhine Rift Valley because of the density and variety of its hydrological net. This study focused on three aspects: the isotopic tracing with Sr, Nd and O allowed to characterize the hydro-system. The 87 Sr/ 86 Sr and 143 Nd/ 144 Nd ratios show that the system is controlled by two natural end members a carbonate and a silicate one and a third end member of anthropogenic origin. The isotopic data allowed also to investigate the exchange processes between the dissolved and the particulate phases of the water samples. Because of their use in the industry and their very low concentrations in natural media, the Rare Earth Elements (REE) are very good tracers of anthropogenic contamination. Furthermore, due to their similar chemical properties with the actinides,they constitute excellent analogues to investigate the behaviour of fission products in the nature. In this study we determined the distribution of the REE within a river between the dissolved, the colloidal and the particulate phases. Among the REE of the suspended load, we distinguished between the exchangeable and the residual REE by means OF IN HCl leading experiments. The third topic is the investigation of uranium series disequilibrium using α-Spectrometry. The determination of ratios 234 U/ 238 U as well as of the activities short-lived radionuclides like 222 Rn, 224 Ra, 226 Ra, 228 Ra, 210 Po and 210 Pb have been performed. Their activities are controlled by chemical and physical parameters and depend also on the lithology of the source area. The combination of the three aspects provided relevant informations about the exchanges between the different water masses, about the transport mechanisms of the REE. Furthermore, the uranium series disequilibrium provided informations about the geochemical processes at a micro-scale. (author)

  7. Mineralogical, geochemical, and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

    Science.gov (United States)

    Gamboa, Adriana; Montero-Serrano, Jean-Carlos; St-Onge, Guillaume; Rochon, André; Desiage, Pierre-Arnaud

    2017-02-01

    Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

  8. Geochemical assessment of light gaseous hydrocarbons in near-surface soils of Kutch-Saurashtra: Implication for hydrocarbon prospects

    Science.gov (United States)

    Rao, P. Lakshmi Srinivasa; Madhavi, T.; Srinu, D.; Kalpana, M. S.; Patil, D. J.; Dayal, A. M.

    2013-02-01

    Light hydrocarbons in soil have been used as direct indicators in geochemical hydrocarbon exploration, which remains an unconventional path in the petroleum industry. The occurrence of adsorbed soil gases, methane and heavier homologues were recorded in the near-surface soil samples collected from Kutch-Saurashtra, India. Soil gas alkanes were interpreted to be derived from deep-seated hydrocarbon sources and have migrated to the surface through structural discontinuities. The source of hydrocarbons is assessed to be thermogenic and could have been primarily derived from humic organic matter with partial contribution from sapropelic matter. Gas chromatographic analyses of hydrocarbons desorbed from soil samples through acid extraction technique showed the presence of methane through n-butane and the observed concentrations (in ppb) vary from: methane (C1) from 4-291, ethane (C2) from 0-84, propane (C3) from 0-37, i-butane (iC4) from 0-5 and n-butane (nC4) from 0-4. Carbon isotopes measured for methane and ethane by GC-C-IRMS, range between -42.9‰ to -13.3‰ (Pee Dee Belemnite - PDB) and -21.2‰ to -12.4‰ (PDB), respectively. The increased occurrence of hydrocarbons in the areas near Anjar of Kutch and the area south to Rajkot of Saurashtra signifies the area potential for oil and gas.

  9. MOSAIC: An organic geochemical and sedimentological database for marine surface sediments

    Science.gov (United States)

    Tavagna, Maria Luisa; Usman, Muhammed; De Avelar, Silvania; Eglinton, Timothy

    2015-04-01

    Modern ocean sediments serve as the interface between the biosphere and the geosphere, play a key role in biogeochemical cycles and provide a window on how contemporary processes are written into the sedimentary record. Research over past decades has resulted in a wealth of information on the content and composition of organic matter in marine sediments, with ever-more sophisticated techniques continuing to yield information of greater detail and as an accelerating pace. However, there has been no attempt to synthesize this wealth of information. We are establishing a new database that incorporates information relevant to local, regional and global-scale assessment of the content, source and fate of organic materials accumulating in contemporary marine sediments. In the MOSAIC (Modern Ocean Sediment Archive and Inventory of Carbon) database, particular emphasis is placed on molecular and isotopic information, coupled with relevant contextual information (e.g., sedimentological properties) relevant to elucidating factors that influence the efficiency and nature of organic matter burial. The main features of MOSAIC include: (i) Emphasis on continental margin sediments as major loci of carbon burial, and as the interface between terrestrial and oceanic realms; (ii) Bulk to molecular-level organic geochemical properties and parameters, including concentration and isotopic compositions; (iii) Inclusion of extensive contextual data regarding the depositional setting, in particular with respect to sedimentological and redox characteristics. The ultimate goal is to create an open-access instrument, available on the web, to be utilized for research and education by the international community who can both contribute to, and interrogate the database. The submission will be accomplished by means of a pre-configured table available on the MOSAIC webpage. The information on the filled tables will be checked and eventually imported, via the Structural Query Language (SQL), into

  10. Post-Eocene volcanics of the Abazar district, Qazvin, Iran: Mineralogical and geochemical evidence for a complex magmatic evolution

    Science.gov (United States)

    Asiabanha, A.; Bardintzeff, J. M.; Kananian, A.; Rahimi, G.

    2012-02-01

    The style of volcanism of post-Eocene volcanism in the Alborz zone of northern Iran is different to that of Eocene volcanism (Karaj Formation). Indeed, the volcanic succession of the Abazar district, located in a narrow volcanic strip within the Alborz magmatic assemblage, is characterized by distinct mineralogical and chemical compositions linked to a complex magmatic evolution. The succession was produced by explosive eruptions followed by effusive eruptions. Two main volcanic events are recognized: (1) a thin rhyolitic ignimbritic sheet underlain by a thicker lithic breccia, and (2) lava flows including shoshonite, latite, and andesite that overlie the first event across a reddish soil horizon. Plagioclase in shoshonite (An 48-92) shows normal zoning, whereas plagioclase in latite and andesite (An 48-75) has a similar composition but shows reverse and oscillatory zoning. QUILF temperature calculations for shoshonites and andesites yield temperatures of 1035 °C and 1029 °C, respectively. The geothermometers proposed by Ridolfi et al. (2010) and Holland and Blundy (1994) yield temperatures of 960 °C and 944 °C for latitic lava, respectively. The samples of volcanic rock show a typical geochemical signature of the continental arc regime, but the andesites clearly differ from the shoshonites, the latites and the rhyolites. The mineralogical and chemical characteristics of these rocks are explained by the following petrogenesis: (1) intrusion of a hot, mantle-depth mafic (shoshonitic) magma, which differentiated in the magma chamber to produce a latitic and then a rhyolitic liquid; (2) rhyolitic ignimbritic eruptions from the top of the magma chamber, following by shoshonitic and then latitic extrusions; (3) magma mingling between the latitic and andesitic magmas, as indicated by the occurrence of andesite clasts within the latite; and (4) andesitic effusions. The youngest volcanic events in the Alborz zone show a close chemical relationship with continental arc

  11. Tectonic origin of serpentinites on Syros, Greece: Geochemical signatures of abyssal origin preserved in a HP/LT subduction complex

    Science.gov (United States)

    Cooperdock, Emily H. G.; Raia, Natalie H.; Barnes, Jaime D.; Stockli, Daniel F.; Schwarzenbach, Esther M.

    2018-01-01

    This study combines whole rock trace and major element geochemistry, and stable isotope (δD and δ18O) analyses with petrographic observations to deduce the origin and tectonic setting of serpentinization of ultramafic blocks from the exhumed HP/LT Aegean subduction complex on Syros, Greece. Samples are completely serpentinized and are characterized by mineral assemblages that consist of variable amounts of serpentine, talc, chlorite, and magnetite. δD and δ18O values of bulk rock serpentinite powders and chips (δD = - 64 to - 33‰ and δ18O = + 5.2 to + 9.0‰) reflect hydration by seawater at temperatures < 250 °C in an oceanic setting pre-subduction, or by fluids derived from dehydrating altered oceanic crust during subduction. Fluid-mobile elements corroborate the possibility of initial serpentinization by seawater, followed by secondary fluid-rock interactions with a sedimentary source pre- or syn-subduction. Whole rock major element, trace element, and REE analyses record limited melt extraction, exhibit flat REE patterns, and do not show pronounced Eu anomalies. The geochemical signatures preserved in these serpentinites argue against a mantle wedge source, as has been previously speculated for ultramafic rocks on Syros. Rather, the data are consistent with derivation from abyssal peridotites in a hyper-extended margin setting or mid-ocean ridge and fracture zone environment. In either case, the data suggest an extensional and/or oceanic origin associated with the Cretaceous opening of the Pindos Ocean and not a subduction-related derivation from the mantle wedge.

  12. Behaviour of uranium series radionuclides in surface water (Crouzille, Limousin). Geochemical implications

    International Nuclear Information System (INIS)

    Moulin, J.

    2008-06-01

    Understanding natural radionuclides behaviour in surface water is a required step to achieve uranium mine rehabilitation and preserve water quality. The first objective of this thesis is to determine which are the radionuclides sources in a drinking water reservoir. The second objective is to improve the knowledge about the behaviour of uranium series radionuclides, especially actinium. The investigated site is a brook (Sagnes, Limousin, France) which floods a peat bog contaminated by a former uranium mine and which empties into the Crouzille lake. It allows studying radionuclides transport in surface water and radionuclides retention through organic substance or water reservoir. Radionuclides distribution in particulate, colloidal and dissolved phases is determined thanks to ultra-filtrations. Gamma spectrometry allows measuring almost all natural radionuclides with only two counting stages. However, low activities of 235 U series radionuclides impose the use of very low background well-type Ge detectors, such as those of the Underground Laboratory of Modane (France). Firstly, this study shows that no or few radionuclides are released by the Sagnes peat bog, although its radioactivity is important. Secondly, it provides details on the behaviour of uranium series radionuclides in surface water. More specifically, it provides the first indications of actinium solubility in surface water. Actinium's behaviour is very close to uranium's even if it is a little less soluble. (author)

  13. Calibration of a PHREEQC-based geochemical model to predict surface water discharge from an operating uranium mill in the Athabasca Basin

    International Nuclear Information System (INIS)

    Mahoney, J.; Ryan, F.

    2014-01-01

    A PHREEQC based geochemical model has been developed to predict impacts from the McClean Lake Mill discharges through three lakes in the Athabasca Basin, Saskatchewan, Canada. The model is primarily a mixing calculation that uses site specific water balances and water compositions from five sources: 1) two water treatment plants, 2) waters from pit dewatering wells, 3) run-off into the lakes from surface waters, 4) ambient lake compositions, and 5) precipitation (rain and snow) onto the pit lake surface. The model allows for the discharge of these waters into the first lake, which then flows into another nearby lake and finally into a third larger lake. Water losses through evaporation and the impact of subsequent evapoconcentration processes are included in the model. PHREEQC has numerous mass transfer options including mixing, user specified reactions, equilibration with gas and solid phases, and surface complexation. Thus this program is ideally suited to this application. Preparation of such a complicated model is facilitated by an EXCEL Spreadsheet, which converts the water balance into appropriately formatted mixing proportions and to prepare portions of the PHREEQC input file in a format directly useable by PHREEQC. This allows for a high level of flexibility, while reducing transcription errors. For each scenario, the model path involves mixing of the waters in the first lake, followed by evapoconcentration, equilibration of the resulting solution with gas phases, including carbon dioxide and oxygen and with minerals and surfaces. The resultant composition is mixed in the second lake with more surface water, lake water and precipitation, and then re-equilibrated. This water represents the flow into the final lake; further mixing/dilution is accommodated; chemical equilibration may also occur. Because of the numerous steps and processes that define the pathway, each annual step requires approximately 200 lines of input in PHREEQC. Models used in the initial

  14. Early Marine Diagenesis In Corals and Geochemical Consequences For Sea Surface Temperature Reconstructions

    Science.gov (United States)

    Mueller, A.; Gagan, M. K.

    Sea surface temperatures (SSTs) are an important quantity for understanding past cli- mate dynamics, and estimates of SSTs are an essential boundary condition used in general circulation models of past and future climate. Large negative SST anomalies of 4 to 6.5rC have been reconstructed for the last deglaciation and the last glacial max- imum (LGM) using two supposedly independent paleothermometers based on d18O and Sr/Ca measurements in scleractinian corals. The tropical sea surface tempera- tures recorded from fossil coral for the LGM, however, are much lower than those recorded from other marine proxies. These proxies, which include foraminifera spe- ciation, foraminiferal oxygen isotopes and alkenone results, suggest a cooling of no more than 3rC. At present it is not clear if this difference reflects regional differences in the extent of cooling, or if one of the proxies is misleading. Another surprising finding is the large warming and/or freshening trends for the ocean surface over the last 200 years indicated by many recent coral d18O records. These long-term trends generally exceed those of the 20th century instrumental records and suggest that tracers in corals may overestimate cooling of the ocean in the past. Here we show that early marine di- agenesis, i.e. secondary precipitation of marine inorganic aragonite, can cause errors in past climate reconstructions from coral. We compare coral skeletal d18O and Sr/Ca data for two long coral cores spanning 1839-1994 AD at Ningaloo Reef, Western Aus- tralia, one of which includes significant secondary precipitation of marine inorganic aragonite. Long-term trends in reconstructed sea surface temperatures (SSTs) for the well preserved coral correlate strongly with instrumental SST records spanning the 20th century. In contrast, the d18O and Sr/Ca for the diagenetically altered coral give identical cool SST anomalies of 4-5rC, as a consequence of the addition of secondary aragonite enriched in 18O and Sr. Our

  15. Remote sensing and geochemical investigations of selected surface processes in Egypt and Missouri

    Science.gov (United States)

    Crombie, Mary Katherine

    This thesis consists of three studies of surface processes on Earth: 1. Age and isotopic constraints of pluvial episodes in the Western Desert of Egypt. North Africa has undergone drastic climatic change over the past several hundred thousand years. Timing of humid intervals called pluvials was investigated by uranium- series disequilibrium dating of travertines from the Kurkur Oasis, Western Desert, Egypt. Stable oxygen isotopes of the travertines were used in equilibrium oxygen isotope fractionation calculations indicating the Kurkur travertines have δ18O values similar to ancient Western Desert groundwaters (~[- ]11/perthous). The ages of the of the travertines correspond to times of monsoonal maxima, eustatic sea level high stands and interglacial maxima. Increased precipitation, recharge of Western Desert groundwaters, and resultant travertine deposition are interpreted to be consequences of Milankovitch cycle forcing, through enhanced Atlantic and Indian Ocean monsoons during periods of enhanced northern summer insolation. 2. Identification of soil moisture as an environmental risk factor for filariasis in Egypt. Bancroftian filariasis is a deforming illness transmitted by mosquitoes (Culex. pipiens) and caused by the parasite Wuchereria bancrofti (WHO technical report 821; Neva and Brown, 1994). Environmental variables, such as humidity, play an important role in the transmission cycle of filariasis. Landsat Thematic Mapper data were used to model the surface soil moisture conditions of the southern Nile Delta region of Egypt as a proxy for environmental humidity. Filariasis infection rates were found to be negligible for areas with low surface soil moisture availability (>20%). Variable infection rates were observed for regions with higher surface soil moisture content, possibly due to anthropogenic influences such as insect control and the use of anti- filarial drugs. 3. Monitoring of Pb aerosol fallout in the vicinity of the Glover smelter, Southeastern

  16. Geochemical speciation, bioavailability and source identification of selected metals in surface sediments of the Southern Caspian Sea.

    Science.gov (United States)

    Bastami, Kazem Darvish; Neyestani, Mahmoud Reza; Esmaeilzadeh, Marjan; Haghparast, Sarah; Alavi, Camelia; Fathi, Sanaz; Nourbakhsh, Shahram; Shirzadi, Emam Ali; Parhizgar, Reyhane

    2017-01-30

    Geochemical speciation of As, Cd, Co, Cr, Cu, Ni, Pb, V and Zn were determined in the surface sediments of the southern Caspian Sea. A five-step sequential extraction technique was used to determine the chemical forms of metals. Mean concentrations (ppm) of heavy metals were (mean±S.D.) As: 9.94±1.71, Cd: 0.87±0.23, Co: 14.85±2.80, Cr: 72.29±19.48, Cu: 18.91±4.48, Ni: 32.87±5.25, Pb: 12.48±3.22, V: 86.07±20.71 and Zn: 66.85±10.11. Among the metals, Cu, As, Pb and Zn exhibited relatively higher mobility, while Cd, Co, Cr, Ni and V were found mainly in the residual fractions. Cu and As showed the highest percentages in the exchangeable phase while Co and Cr had the lowest percentages in the phase. The Risk Assessment Code (RAC) values indicated that As, Cu and V had medium risk at some sampling sites. According to pollution load index (PLI), sediments from some sampling sites were polluted. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Geochemical characteristics of rare earth elements in the surface sediments from the Spratly Islands of China.

    Science.gov (United States)

    Li, Jingxi; Sun, Chengjun; Zheng, Li; Yin, Xiaofei; Chen, Junhui; Jiang, Fenghua

    2017-01-30

    The geochemistry of rare earth elements (REE) in surface sediment from Cuarteron reef (N1), Johnson reef (N2), Hugh reef (N3), Gaven reef (N4), Fiery cross reef (N5), and Subi reef (N6) were firstly studied. The total REE abundance (∑REE) varied from 2.244μg·g -1 to 21.661μg·g -1 , with an average of 4.667μg·g -1 . The LREE/HREE was from 2.747 to 9.869, with an average of 3.687, which indicated that the light REE was evidently enriched. Fractionation was observed between LREE and HREE. Gd with a negative anomaly was also detected in all of the stations. The negative anomalies of δEu from 0.11 to 0.25, with an average of 0.22, and the positive anomalies of δCe from 1.38 to 3.86, with an average of 1.63. The REE individual correlation values with Ca, Mn, Mg, Sr were r Ca =-0.05, r Mn =0.26, r Mg =-0.14, and r Sr =0.08. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

    Directory of Open Access Journals (Sweden)

    Krishnamoorthy Arumugam

    2014-04-01

    Full Text Available Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the

  19. Integrated manufacturing of complex freeform surfaces

    Science.gov (United States)

    Niehaus, Frank; Huttenhuis, Stephan; Pisarski, Alex

    2013-09-01

    Innovative freeform optical systems such as head-up displays or LED headlights often require high quality and high volume optics. Injection molded polymer optics offer a cost effective solution. However, mold manufacturing for this process is extremely challenging as the machining of freeform surfaces is currently characterized by several independent production steps which can limit surface accuracy. By integrating diamond turning, milling, and metrology onto a single platform, the UPC 400 improves surface accuracy. Advanced software for machining and measurement data further reduces surface inaccuracies. This combination makes the UPC 400 efficient for prototyping free-form optics and manufacturing high precision molds.

  20. Marked fatgraph complexes and surface automorphisms

    DEFF Research Database (Denmark)

    Kuno, Yusuke; Penner, Robert; Turaev, Vladimir

    2013-01-01

    Combinatorial aspects of the Torelli-Johnson-Morita theory of surface automorphisms are extended to certain subgroups of the mapping class groups. These subgroups are defined relative to a specified homomorphism from the fundamental group of the surface onto an arbitrary group $K$. For $K$ abelia...

  1. DESIGNING OF DEVELOPED SURFACES OF COMPLEX PARTS

    Directory of Open Access Journals (Sweden)

    S. S. Tyshchenko

    2017-04-01

    Full Text Available Purpose. The paper focuses on ensuring the rational choice of parameters of the mating surfaces of parts when designing process equipment based on the methods of artificial intelligence. Methodology. The paper considers the geometric model of a ruled developed surface, the conditions of existence of such a surface and provides a generalized algorithm for surface plotting regardless of the type of the working element or the machine-building product. One of the most common technical surfaces are the ruled ones, among which a special position is occupied by developed surfaces (thanks to their differential-parametric properties: surface tangent plane is n contact along the rectilinear generator and does not change its position in space when changing the point of contact; surfaces can be produced by bending sheet metal. These provisions enable a product manufacturer to save significant material and energy means, therefore, the development of geometric models of such surfaces is an important task. Findings. We analyzed the geometrical model of the developed surface which is incident to two guides. Experimental studies have shown the applicationprospectivity of semi-digger moldboards on moldboard plows, particularly on the double-deck ones. Taking into account the operating speed of the plow 2.8 m/s, the plant residues plowing percentage for plow with semi-digger moldboards is 98.9%, and with the digger ones – 96.1%. Originality. According to results: 1 the approaches to solving the problem of recognition of wear conditions of the tested interface, depicted by its conceptual model, were elaborated; 2 the corresponding algorithms of the computational procedures were built; 3 the mathematical model that determines the effect of the parameters of the contacting surfaces on their performance properties – linear wear rate during the normal wear and tear was developed; 4 for this model the theoretical prerequisite of use for the random mating study were

  2. Observations of mechanical-hydraulic-geochemical interactions due to drainage of a surface water reservoir in Switzerland

    Science.gov (United States)

    Lunn, R. J.; Kinali, M.; Pytharouli, S.; Shipton, Z.; Stillings, M.; Lord, R.

    2016-12-01

    The drainage and refilling of a surface water reservoir beside the Grimsel Test Site (GTS) underground rock laboratory in Switzerland, has provided a unique opportunity to study in-situ rock mechanical, hydraulic and chemical interactions under large-scale stress changes. The reservoir was drained in October/November 2014 to enable dam maintenance and extension of the regional hydropower tunnel system. Reservoir drainage will have caused rapid unloading of the surrounding rock mass. The GTS sits 37m below the top of the reservoir and 200-600m away laterally within the mountainside on the eastern bank of the reservoir. Gradual refilling of the reservoir, via natural snowmelt and runoff, commenced in February 2015. As part of the European LASMO Project, researchers at Strathclyde, funded by Radioactive Waste Management Ltd., have been investigating mechanical-chemical-hydraulic coupling within the rock mass as an analogue for glacial unloading and loading of a future Geological Disposal Facility. We have deployed three 3-component and 6 single-component micro-seismometers within the GTS and surrounding hydropower tunnel network. In parallel, we have implemented a groundwater sampling programme, using boreholes within the GTS, for temporal determination of geochemistry and flow rate. Preliminary data analyses show geochemical anomalies during unloading, as well as detection of microseismic events. The signal-to-noise ratio of the micro-seismic data is extremely poor. Noise amplitude, and frequency content, variy throughout each day, between days, and from month-to-month on a highly unpredictable basis. This is probably due to the multitude of hydropower turbines and pump-storage systems within the surrounding mountains. To discriminate micro-seismic events, we have developed a new methodology for characterizing background noise within the seismic signal and combined this with cross-correlations techniques generally applied in microseismic analysis of hydraulic

  3. Surface nucleation in complex rheological systems

    Science.gov (United States)

    Herfurth, J.; Ulrich, J.

    2017-07-01

    Forced nucleation induced by suitable foreign seeds is an important tool to control the production of defined crystalline products. The quality of a surface provided by seed materials represents an important variable in the production of crystallizing layers that means for the nucleation process. Parameters like shape and surface structure, size and size distribution of the seed particles as well as the ability to hold up the moisture (the solvent), can have an influence on the nucleation process of different viscous supersaturated solutions. Here the properties of different starch powders as seeds obtained from corn, potato, rice, tapioca and wheat were tested. It could be found, that the best nucleation behavior of a sugar solution could be reached with the use of corn starch as seed material. Here the surface of the crystallized sugar layer is smooth, crystallization time is short (<3 h) and the shape of the product is easily reproducible. Beneficial properties of seed materials are therefore an edged, uneven surface, small particle sizes as well as low moisture content at ambient conditions within the seed materials.

  4. New Route to Synthesize Surface Organometallic Complexes (SOMC): An Approach by Alkylating Halogenated Surface Organometallic Fragments

    KAUST Repository

    Hamieh, Ali Imad

    2017-02-01

    The aim of this thesis is to explore new simpler and efficient routes for the preparation of surface organometallic complexes (SOMC) for the transformation of small organic molecules to valuable products. The key element in this new route relies on surface alkylation of various halogenated surface coordination complexes or organometallic fragments (SOMF).

  5. Use of environmental isotope techniques in studying surface and groundwaters in the Damascus basin (Al-Ghotta): A case study of geochemical modeling of elements and pollutants transport

    International Nuclear Information System (INIS)

    Kattan, Z.

    2004-09-01

    This work discuses in details the hydrochemical and isotopic characteristics of surface and groundwaters in the Damascus Ghotta basin. In addition, it deals with the chemical and isotopic compositions of rainfall of some surrounding stations (Damascus, Bloudan, Arneh, Al-Kounietra, Izraa, Al-Souweida, Homs and Tartous). The objective of this research was to make new assessment of the available water resources in this basin, together with conducting essays to model geochemically the elements and pollutants transport in the groundwater, by the use of PHREEQM code.(author)

  6. Formation of oxygen complexes in controlled atmosphere at surface ...

    Indian Academy of Sciences (India)

    The effects of boron and phosphorus incorporation in phenolic resin precursor to the oxidation resistance of glassy carbon have been studied. In order to reveal the nature and composition of the oxygen complexes formed at the surface of doped glassy carbon, under controlled atmosphere, the surface of the samples was ...

  7. Formation of oxygen complexes in controlled atmosphere at surface ...

    Indian Academy of Sciences (India)

    Abstract. The effects of boron and phosphorus incorporation in phenolic resin precursor to the oxidation resistance of glassy carbon have been studied. In order to reveal the nature and composition of the oxygen complexes formed at the surface of doped glassy carbon, under controlled atmosphere, the surface of the ...

  8. Removal of arsenate by ferrihydrite via surface complexation and surface precipitation

    International Nuclear Information System (INIS)

    Jiang, Xiuli; Peng, Changjun; Fu, Dun; Chen, Zheng; Shen, Liang; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

    2015-01-01

    Graphical abstract: - Highlights: • Surface complexation and surface precipitation of As on ferrihydrite happen at pH 3–6. • The formation of surface precipitation enhanced As(V) adsorption. • The dissolved Fe 3+ had a good linear relationship with the amount of arsenate re-adsorption. - Abstract: In this study, macroscopic and spectroscopic experimental methods accurately modeled the sorption process of arsenate on ferrihydrite. EXAFS, X-ray diffraction and infrared (IR) spectroscopy indicated that the behavior of As(V) adsorption onto ferrihydrite took place mainly via surface complexation and surface precipitation at acidic pH (3.0–6.0), while the surface precipitation was dominated at longer time intervals and higher Fe 3+ concentration. The macroscopic competitive adsorption experiment between arsenate with phosphate indicated two types of adsorption sites existing on the surface of ferrihydrite, i.e., non-exchangeable sites, which are responsible for a rapid surface complex formation; and exchangeable sites for a slow build-up of surface precipitates. In the slow build-up precipitates, the As(V) surface coverage (mmol/g) exhibited a good linear relationship (R 2 = 0.952) with the amount of dissolved Fe 3+ . Three steps are involved during the process of surface precipitation, i.e., (1) an initial uptake of As(V) via surface complexation; (2) re-adsorption of Fe 3+ leaching from ferrihydrite on the surface complex; and (3) As(V) adsorption via surface complexation again and finally forming the surface precipitate.

  9. Surface complexation modeling of Cd(II) sorption to montmorillonite, bacteria, and their composite

    Science.gov (United States)

    Wang, Ning; Du, Huihui; Huang, Qiaoyun; Cai, Peng; Rong, Xingmin; Feng, Xionghan; Chen, Wenli

    2016-10-01

    Surface complexation modeling (SCM) has emerged as a powerful tool for simulating heavy metal adsorption processes on the surface of soil solid components under different geochemical conditions. The component additivity (CA) approach is one of the strategies that have been widely used in multicomponent systems. In this study, potentiometric titration, isothermal adsorption, zeta potential measurement, and extended X-ray absorption fine-structure (EXAFS) spectra analysis were conducted to investigate Cd adsorption on 2 : 1 clay mineral montmorillonite, on Gram-positive bacteria Bacillus subtilis, and their mineral-organic composite. We developed constant capacitance models of Cd adsorption on montmorillonite, bacterial cells, and mineral-organic composite. The adsorption behavior of Cd on the surface of the composite was well explained by CA-SCM. Some deviations were observed from the model simulations at pH SCM closely coincided with the estimated value of EXAFS at pH 6. The model could be useful for the prediction of heavy metal distribution at the interface of multicomponents and their risk evaluation in soils and associated environments.

  10. Compact complex surfaces with geometric structures related to split quaternions

    International Nuclear Information System (INIS)

    Davidov, Johann; Grantcharov, Gueo; Mushkarov, Oleg; Yotov, Miroslav

    2012-01-01

    We study the problem of existence of geometric structures on compact complex surfaces that are related to split quaternions. These structures, called para-hypercomplex, para-hyperhermitian and para-hyperkähler, are analogs of the hypercomplex, hyperhermitian and hyperkähler structures in the definite case. We show that a compact 4-manifold carries a para-hyperkähler structure iff it has a metric of split signature together with two parallel, null, orthogonal, pointwise linearly independent vector fields. Every compact complex surface admitting a para-hyperhermitian structure has vanishing first Chern class and we show that, unlike the definite case, many of these surfaces carry infinite-dimensional families of such structures. We provide also compact examples of complex surfaces with para-hyperhermitian structures which are not locally conformally para-hyperkähler. Finally, we discuss the problem of non-existence of para-hyperhermitian structures on Inoue surfaces of type S 0 and provide a list of compact complex surfaces which could carry para-hypercomplex structures.

  11. Compact complex surfaces with geometric structures related to split quaternions

    Energy Technology Data Exchange (ETDEWEB)

    Davidov, Johann, E-mail: jtd@math.bas.bg [Institute of Mathematics and Informatics, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); ' L. Karavelov' Civil Engineering Higher School, 175 Suhodolska Str., 1373 Sofia (Bulgaria); Grantcharov, Gueo, E-mail: grantchg@fiu.edu [Department of Mathematics and Statistics, Florida International University, Miami, FL 33199 (United States); Mushkarov, Oleg, E-mail: muskarov@math.bas.bg [Institute of Mathematics and Informatics, Bulgarian Academy of Sciences, 1113 Sofia (Bulgaria); Yotov, Miroslav, E-mail: yotovm@fiu.edu [Department of Mathematics and Statistics, Florida International University, Miami, FL 33199 (United States)

    2012-12-11

    We study the problem of existence of geometric structures on compact complex surfaces that are related to split quaternions. These structures, called para-hypercomplex, para-hyperhermitian and para-hyperkaehler, are analogs of the hypercomplex, hyperhermitian and hyperkaehler structures in the definite case. We show that a compact 4-manifold carries a para-hyperkaehler structure iff it has a metric of split signature together with two parallel, null, orthogonal, pointwise linearly independent vector fields. Every compact complex surface admitting a para-hyperhermitian structure has vanishing first Chern class and we show that, unlike the definite case, many of these surfaces carry infinite-dimensional families of such structures. We provide also compact examples of complex surfaces with para-hyperhermitian structures which are not locally conformally para-hyperkaehler. Finally, we discuss the problem of non-existence of para-hyperhermitian structures on Inoue surfaces of type S{sup 0} and provide a list of compact complex surfaces which could carry para-hypercomplex structures.

  12. Surface Complexation of Calcium Minerals in Aqueous Solution.

    Science.gov (United States)

    Wu; Forsling; Holmgren

    2000-04-15

    The complexation of Alizarin Red S (ARS) at the surface of hydrous fluorite particles has been investigated by means of potentiometric titrations, adsorption experiments, and zeta-potential measurements in 0.1 mol dm(-3) KCl ionic medium at 25.0 degrees C, as well as by UV/visible specular reflectance, FT-IR, and FT-Raman spectroscopy. Chemical reaction models describing the equilibria of ARS (HA(2-)) at the aqueous fluorite surfaces ( identical withX) have been established as follows: Experimental data were evaluated using the computer program FITEQL on the basis of a constant capacitance model for the electric double layer. Surface complexation mechanisms involving the R-SO(3)(-), R-beta-OH, and R-alpha-OH active groups of the ARS molecule are proposed to describe coordination to the fluorite surface. Copyright 2000 Academic Press.

  13. Geochemical and Sr-Nd-Pb-O isotope composition of granitoids of the Early Cretaceous Copiapó plutonic complex (27°30'S), Chile

    Science.gov (United States)

    Marschik, Robert; Fontignie, Denis; Chiaradia, Massimo; Voldet, Pia

    2003-10-01

    Early Cretaceous plutonic rocks exposed south of Copiapó form part of the Coastal Batholith of northern Chile. These rocks intrude arc-derived volcanic and volcaniclastic rocks and marine limestones that were deposited in the Early Cretaceous Atacama backarc basin. The Copiapó plutonic complex consists mainly of calc-alkaline, medium- to coarse-grained diorite, granodiorite, tonalite, monzodiorite, and quartz monzonite. The plutonic rocks are subalkaline to alkaline, metaluminous, magnetite-series, volcanic arc, I-type granitoids. Batholithic magmas are a heat, potential fluid, metal, and sulphur source for the hydrothermal iron oxide-rich Cu-Au mineralization in the Candelaria-Punta del Cobre district. Ore-related hydrothermal alteration affected large portions of the Copiapó complex. The least altered batholithic rocks have initial 87Sr/ 86Sr of 0.703070-0.703231; initial 143Nd/ 144Nd of 0.512733-0.512781; and 206Pb/ 204Pb, 207Pb/ 204Pb, and 208Pb/ 204Pb of 18.428-18.772, 15.550-15.603, and 38.127-38.401, respectively. The δ18O values for these rocks range from +6.9 to +8.6‰. Isotope signatures and trace element distributions suggest that the magmas are mantle derived. A subduction fluid-modified mantle source may explain the geochemical characteristics of the Copiapó complex. The ascent of magmas occurred along deep-rooted structures without significant crustal contamination, though minor contamination by relatively young (e.g. Jurassic) igneous rocks during ascent is possible. Intrusive rocks with high-K to shoshonitic characteristics probably represent residual liquids of less evolved magmas. The regional geologic context suggests that the plutons of the Copiapó complex were emplaced at a relatively shallow crustal level of 2-3 km.

  14. Complex confining layers : a physical and geochemical characterization of heterogeneous unconsolidated fluvial deposits using a facies-based approach

    NARCIS (Netherlands)

    Helvoort, Pieter-Jan van

    2003-01-01

    A proper characterization of physical and chemical heterogeneities in the subsoil is an important condition for successful modeling of groundwater flow and solute transport. This study focuses on the physical and chemical characterization of a complex confining layer in the Rhine–Meuse deltaic plain

  15. Tectonic significance of the Xilin Gol Complex, Inner Mongolia, China: Petrological, geochemical and U–Pb zircon age constraints

    NARCIS (Netherlands)

    Li, Y.; Zhou, H; Brouwer, F.M.; Wijbrans, J.R.; Zhong, Z.; Liu, H.

    2011-01-01

    The Xilin Gol Complex, consisting of strongly deformed and metamorphosed rocks, is exposed as a large tectonic unit within the Central-Asian Orogenic Belt (CAOB). It is located on the Xilinhot-Sonidzuoqi north-dipping thrust belt and near the Solonker suture zone that is widely regarded to record

  16. Mars Geochemical Instrument (MarGI): An instrument for the analysis of the Martian surface and the search for evidence of life

    Science.gov (United States)

    Kojiro, Daniel R.; Mancinelli, Rocco; Martin, Joe; Holland, Paul M.; Stimac, Robert M.; Kaye, William J.

    2005-01-01

    The Mars Geochemical Instrument, MarGI, was developed to provide a comprehensive analysis of the rocks and surface material on Mars. The instrument combines Differential Thermal Analysis (DTA) with miniature Gas Chromatography-Ion Mobility Spectrometry (GC-IMS) to identify minerals, the presence and state of water, and organic compounds. Miniature pyrolysis ovens are used to both, conduct DTA analysis of soil or crushed rocks samples, and pyrolyze the samples at temperatures up to 1000 degrees C for GC-IMS analysis of the released gases. This combination of analytical processes and techniques, which can characterize the mineralogy of the rocks and soil, and identify and quantify volatiles released during pyrolysis, has applications across a wide range of target sites including comets, planets, asteroids, and moons such as Titan and Europa. The MarGI analytical approach evolved from the Cometary Ice and Dust Experiment (CIDEX) selected to fly on the Comet Rendezvous Asteroid Flyby Mission (CRAF).

  17. Hirshfeld surface analysis of new organotin(IV)-phosphoramide complexes

    Czech Academy of Sciences Publication Activity Database

    Pourayoubi, M.; Bayraq, S.S.; Tarahhomi, A.; Nečas, M.; Fejfarová, Karla; Dušek, Michal

    2014-01-01

    Roč. 751, SI (2014), s. 508-518 ISSN 0022-328X R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : organotin(IV)-phosphoramide complexes * Hirshfeld surfaces * two-dimensional fingerprint plots * crystal packing Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.173, year: 2014

  18. Photoelectrochemical etching of gallium nitride surface by complexation dissolution mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao-Rong [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China); University of Chinese Academy of Sciences, 100049 Beijing (China); Hou, Fei; Wang, Zu-Gang; Zhang, Shao-Hui [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China); Changchun University of Science and Technology, 130022 Changchun (China); Pan, Ge-Bo, E-mail: gbpan2008@sinano.ac.cn [Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 215123 Suzhou (China)

    2017-07-15

    Graphical abstract: GaN surface was etched by 0.3 M EDTA-2Na. The proposed complexation dissolution mechanism can be applicable to almost all neutral etchants under the prerequisite of strong light and electric field. - Highlights: • GaN surface was etched by EDTA-2Na. • GaN may be dissolved into EDTA-2Na by forming Ga–EDTA complex. • We propose the complexation dissolution mechanism for the first time. - Abstract: Gallium nitride (GaN) surface was etched by 0.3 M ethylenediamine tetraacetic acid disodium (EDTA-2Na) via photoelectrochemical etching technique. SEM images reveal the etched GaN surface becomes rough and irregular. The pore density is up to 1.9 × 10{sup 9} per square centimeter after simple acid post-treatment. The difference of XPS spectra of Ga 3d, N 1s and O 1s between the non-etched and freshly etched GaN surfaces can be attributed to the formation of Ga–EDTA complex at the etching interface between GaN and EDTA-2Na. The proposed complexation dissolution mechanism can be broadly applicable to almost all neutral etchants under the prerequisite of strong light and electric field. From the point of view of environment, safety and energy, EDTA-2Na has obvious advantages over conventionally corrosive etchants. Moreover, as the further and deeper study of such nearly neutral etchants, GaN etching technology has better application prospect in photoelectric micro-device fabrication.

  19. Photoelectrochemical etching of gallium nitride surface by complexation dissolution mechanism

    International Nuclear Information System (INIS)

    Zhang, Miao-Rong; Hou, Fei; Wang, Zu-Gang; Zhang, Shao-Hui; Pan, Ge-Bo

    2017-01-01

    Graphical abstract: GaN surface was etched by 0.3 M EDTA-2Na. The proposed complexation dissolution mechanism can be applicable to almost all neutral etchants under the prerequisite of strong light and electric field. - Highlights: • GaN surface was etched by EDTA-2Na. • GaN may be dissolved into EDTA-2Na by forming Ga–EDTA complex. • We propose the complexation dissolution mechanism for the first time. - Abstract: Gallium nitride (GaN) surface was etched by 0.3 M ethylenediamine tetraacetic acid disodium (EDTA-2Na) via photoelectrochemical etching technique. SEM images reveal the etched GaN surface becomes rough and irregular. The pore density is up to 1.9 × 10 9 per square centimeter after simple acid post-treatment. The difference of XPS spectra of Ga 3d, N 1s and O 1s between the non-etched and freshly etched GaN surfaces can be attributed to the formation of Ga–EDTA complex at the etching interface between GaN and EDTA-2Na. The proposed complexation dissolution mechanism can be broadly applicable to almost all neutral etchants under the prerequisite of strong light and electric field. From the point of view of environment, safety and energy, EDTA-2Na has obvious advantages over conventionally corrosive etchants. Moreover, as the further and deeper study of such nearly neutral etchants, GaN etching technology has better application prospect in photoelectric micro-device fabrication.

  20. Geochemical studies in watersheds expanded

    Science.gov (United States)

    Church, M. Robbins

    In the past, geochemical research in forested watersheds has focused on understanding the basic processes that occur in soils and rocks. Watershed geochemical processes, however, are greatly influenced by, and in turn, greatly influence, both organisms and biological process in soils, and hydrologic responses of catchments. To date, geochemical research has dealt principally with basic chemical processes in soils and rocks, and much less with questions concerning hydrologic routing through catchments and the effects such routing has on temporal variation in chemical composition of surface waters.Research on flow generation in catchments has focused on intensive field studies on plots, hillslope sections, and small catchments, with extension to larger scales necessarily involving the application of conceptual models that might (or might not) be valid. The acquisition of direct experimental evidence (for example, verifying flow generation mechanisms) on larger-scale watersheds has always been problematic. Although geochemists understand that the explanation of some geochemical observations requires that flow pathways be explicitly identified, and hydrologists understand that flow generation can be better elucidated if the geochemical history of waters is known, critical integrated communication between the disciplines is often lacking. In turn, biologists require physical and geochemical information to interpret biological effects in watersheds, and hydrologists and geochemists need to be aware of the effects of biological processes on hydrochemical response of catchments.

  1. Surface active complexes formed between keratin polypeptides and ionic surfactants.

    Science.gov (United States)

    Pan, Fang; Lu, Zhiming; Tucker, Ian; Hosking, Sarah; Petkov, Jordan; Lu, Jian R

    2016-12-15

    Keratins are a group of important proteins in skin and hair and as biomaterials they can provide desirable properties such as strength, biocompatibility, and moisture regaining and retaining. The aim of this work is to develop water-soluble keratin polypeptides from sheep wool and then explore how their surface adsorption behaves with and without surfactants. Successful preparation of keratin samples was demonstrated by identification of the key components from gel electrophoresis and the reproducible production of gram scale samples with and without SDS (sodium dodecylsulphate) during wool fibre dissolution. SDS micelles could reduce the formation of disulphide bonds between keratins during extraction, reducing inter-molecular crosslinking and improving keratin polypeptide solubility. However, Zeta potential measurements of the two polypeptide batches demonstrated almost identical pH dependent surface charge distributions with isoelectric points around pH 3.5, showing complete removal of SDS during purification by dialysis. In spite of different solubility from the two batches of keratin samples prepared, very similar adsorption and aggregation behavior was revealed from surface tension measurements and dynamic light scattering. Mixing of keratin polypeptides with SDS and C 12 TAB (dodecyltrimethylammonium bromide) led to the formation of keratin-surfactant complexes that were substantially more effective at reducing surface tension than the polypeptides alone, showing great promise in the delivery of keratin polypeptides via the surface active complexes. Neutron reflection measurements revealed the coexistence of surfactant and keratin polypeptides at the interface, thus providing the structural support to the observed surface tension changes associated with the formation of the surface active complexes. Copyright © 2016. Published by Elsevier Inc.

  2. Synthesizing Earth's geochemical data for hydrogeochemical analysis

    Science.gov (United States)

    Brantley, S. L.; Kubicki, J.; Miller, D.; Richter, D.; Giles, L.; Mitra, P.

    2007-12-01

    For over 200 years, geochemical, microbiological, and chemical data have been collected to describe the evolution of the surface earth. Many of these measurements are data showing variations in time or in space. To forward predict hydrologic response to changing tectonic, climatic, or anthropogenic forcings requires synthesis of these data and utilization in hydrogeochemical models. Increasingly, scientists are attempting to synthesize such data in order to make predictions for new regions or for future time periods. However, to make such complex geochemical data accessible requires development of sophisticated cyberinfrastructures that both invite uploading as well as usage of data. Two such cyberinfrastructure (CI) initiatives are currently developing, one to invite and promote the use of environmental kinetics data (laboratory time course data) through ChemxSeer, and the other to invite and promote the use of spatially indexed geochemical data for the Earth's Critical Zone through CZEN.org. The vision of these CI initiatives is to provide cyber-enhanced portals that encourage domain scientists to upload their data before publication (in private cyberspace), and to make these data eventually publicly accessible (after an embargo period). If the CI can be made to provide services to the domain specialist - e.g. to provide data analysis services or data comparison services - we envision that scientists will upload data. In addition, the CI can promote the use and comparison of datasets across disciplines. For example, the CI can facilitate the use of spatially indexed geochemical data by scientists more accustomed to dealing with time-course data for hydrologic flow, and can provide user-friendly interfaces with CI established to facilitate the use of hydrologic data. Examples of the usage of synthesized data to predict soil development over the last 13ky and its effects on active hydrological flow boundaries in surficial systems will be discussed for i) a N

  3. Arc-continent collision and the formation of continental crust: A new geochemical and isotopic record from the Ordovician Tyrone Igneous Complex, Ireland

    Science.gov (United States)

    Draut, Amy E.; Clift, Peter D.; Amato, Jeffrey M.; Blusztajn, Jerzy; Schouten, Hans

    2009-01-01

    Collisions between oceanic island-arc terranes and passive continental margins are thought to have been important in the formation of continental crust throughout much of Earth's history. Magmatic evolution during this stage of the plate-tectonic cycle is evident in several areas of the Ordovician Grampian-Taconic orogen, as we demonstrate in the first detailed geochemical study of the Tyrone Igneous Complex, Ireland. New U-Pb zircon dating yields ages of 493 2 Ma from a primitive mafic intrusion, indicating intra-oceanic subduction in Tremadoc time, and 475 10 Ma from a light rare earth element (LREE)-enriched tonalite intrusion that incorporated Laurentian continental material by early Arenig time (Early Ordovician, Stage 2) during arc-continent collision. Notably, LREE enrichment in volcanism and silicic intrusions of the Tyrone Igneous Complex exceeds that of average Dalradian (Laurentian) continental material that would have been thrust under the colliding forearc and potentially recycled into arc magmatism. This implies that crystal fractionation, in addition to magmatic mixing and assimilation, was important to the formation of new crust in the Grampian-Taconic orogeny. Because similar super-enrichment of orogenic melts occurred elsewhere in the Caledonides in the British Isles and Newfoundland, the addition of new, highly enriched melt to this accreted arc terrane was apparently widespread spatially and temporally. Such super-enrichment of magmatism, especially if accompanied by loss of corresponding lower crustal residues, supports the theory that arc-continent collision plays an important role in altering bulk crustal composition toward typical values for ancient continental crust. ?? 2009 Geological Society of London.

  4. A complex origin for the Kelso Dunes, Mojave National Preserve, California, USA: A case study using a simple geochemical method with global applications

    Science.gov (United States)

    Muhs, Daniel R.; Lancaster, Nicholas; Skipp, Gary L.

    2017-01-01

    The Kelso Dune field in southern California is intriguing because although it is of limited areal extent ( 100 km2), it has a wide variety of dune forms and contains many active dunes ( 40 km2), which is unusual in the Mojave Desert. Studies over the past eight decades have concluded that the dunes are derived primarily from a single source, Mojave River alluvium, under a dominant, westerly-to-northwesterly wind regime. The majority of these studies did not, however, present data to support the Mojave River as the only source. We conducted mineralogical and geochemical studies of most of the 14 geomorphically defined dune groups of the Kelso Dune field as well as potential sand sources, alluvial sediments from the surrounding mountain ranges. Results indicate that sands in the nine western dune groups have K/Rb and K/Ba (primarily from K-feldspar) compositions that are indistinguishable from Mojave River alluvium (westerly/northwesterly winds) and Budweiser Wash alluvium (southwesterly winds), permitting an interpretation of two sources. In contrast, sands from the five eastern dune groups have K/Rb and K/Ba values that indicate significant inputs from alluvial fan deposits of the Providence Mountains. This requires either rare winds from the east or southeast or, more likely, aeolian reworking of distal Providence Mountain fan sediments by winds from the west, at a rate greater than input from the Mojave River or other western sources. The results indicate that even a small dune field can have a complex origin, either from seasonally varying winds or complex alluvial-fan-dune interaction. Application of K/Rb and K/Ba in K-feldspar as a provenance indicator could be used in many of the world's ergs or sand seas, where dune origins are still not well understood or are controversial. Four examples are given from Africa and the Middle East where such an approach could yield useful new information about dune sand provenance.

  5. Retrieving complex surface impedances from statistical absorption coefficients

    DEFF Research Database (Denmark)

    Mondet, Boris Jean-Francois; Brunskog, Jonas; Jeong, Cheol-Ho

    2017-01-01

    coefficients, prior information about the absorber of interest can be used as constraints, which is shown to help determine the correct impedance from absorption coefficient. Further stability and sensitivity investigations indicate that the method presented constitutes an efficient solution to convert sound......In room acoustic simulations the surface materials are commonly represented with energy parameters, such as the absorption and scattering coefficients, which do not carry phase information. This paper presents a method to transform statistical absorption coefficients into complex surface impedances...... that the impedance found has a physical meaning and respects causality in the time domain. Known material models, such as Miki’s and Maa’s models, are taken as references to assess the validity of the suggested model. Due to the non-uniqueness of retrieving complex-valued impedances from real-valued absorption...

  6. Geochemically structural characteristics of municipal solid waste incineration fly ash particles and mineralogical surface conversions by chelate treatment.

    Science.gov (United States)

    Kitamura, Hiroki; Sawada, Takaya; Shimaoka, Takayuki; Takahashi, Fumitake

    2016-01-01

    Leaching behaviors of heavy metals contained in municipal solid waste incineration (MSWI) fly ash have been studied well. However, micro-characteristics of MSWI fly ash particles are still uncertain and might be non-negligible to describe their leaching behaviors. Therefore, this study investigated micro-characteristics of MSWI fly ash particles, especially their structural properties and impacts of chelate treatment on surface characteristics. According to SEM observations, raw fly ash particles could be categorized into four types based on their shapes. Because chelate treatment changed the surface of fly ash particles dramatically owing to secondary mineral formations like ettringite, two more types could be categorized for chelate-treated fly ash particles. Acid extraction experiments suggest that fly ash particles, tested in this study, consist of Si-base insoluble core structure, Al/Ca/Si-base semi-soluble matrices inside the body, and KCl/NaCl-base soluble aggregates on the surface. Scanning electron microscope (SEM) observations of the same fly ash particles during twice moistening treatments showed that KCl/NaCl moved under wet condition and concentrated at different places on the particle surface. However, element mobility depended on secondary mineral formations. When insoluble mineral like gypsum was generated and covered the particle surface, it inhibited element transfer under wet condition. Surface characteristics including secondary mineral formation of MSWI fly ash particles are likely non-negligible to describe trace element leaching behaviors.

  7. Self-Organization during Friction in Complex Surface Engineered Tribosystems

    Directory of Open Access Journals (Sweden)

    Ben D. Beake

    2010-02-01

    Full Text Available Self-organization during friction in complex surface engineered tribosystems is investigated. The probability of self-organization in these complex tribosystems is studied on the basis of the theoretical concepts of irreversible thermodynamics. It is shown that a higher number of interrelated processes within the system result in an increased probability of self-organization. The results of this thermodynamic model are confirmed by the investigation of the wear performance of a novel Ti0.2Al0.55Cr0.2Si0.03Y0.02N/Ti0.25Al0.65Cr0.1N (PVD coating with complex nano-multilayered structure under extreme tribological conditions of dry high-speed end milling of hardened H13 tool steel.

  8. Exploring complex networks via topological embedding on surfaces.

    Science.gov (United States)

    Aste, Tomaso; Gramatica, Ruggero; Di Matteo, T

    2012-09-01

    We demonstrate that graphs embedded on surfaces are a powerful and practical tool to generate, to characterize, and to simulate networks with a broad range of properties. Any network can be embedded on a surface with sufficiently high genus and therefore the study of topologically embedded graphs is non-restrictive. We show that the local properties of the network are affected by the surface genus which determines the average degree, which influences the degree distribution, and which controls the clustering coefficient. The global properties of the graph are also strongly affected by the surface genus which is constraining the degree of interwovenness, changing the scaling properties of the network from large-world kind (small genus) to small- and ultrasmall-world kind (large genus). Two elementary moves allow the exploration of all networks embeddable on a given surface and naturally introduce a tool to develop a statistical mechanics description for these networks. Within such a framework, we study the properties of topologically embedded graphs which dynamically tend to lower their energy towards a ground state with a given reference degree distribution. We show that the cooling dynamics between high and low "temperatures" is strongly affected by the surface genus with the manifestation of a glass-like transition occurring when the distance from the reference distribution is low. We prove, with examples, that topologically embedded graphs can be built in a way to contain arbitrary complex networks as subgraphs. This method opens a new avenue to build geometrically embedded networks on hyperbolic manifolds.

  9. A 2-D model for friction of complex anisotropic surfaces

    Science.gov (United States)

    Costagliola, Gianluca; Bosia, Federico; Pugno, Nicola M.

    2018-03-01

    The friction force observed at macroscale is the result of interactions at various lower length scales that are difficult to model in a combined manner. For this reason, simplified approaches are required, depending on the specific aspect to be investigated. In particular, the dimensionality of the system is often reduced, especially in models designed to provide a qualitative description of frictional properties of elastic materials, e.g. the spring-block model. In this paper, we implement for the first time a two dimensional extension of the spring-block model, applying it to structured surfaces and investigating by means of numerical simulations the frictional behaviour of a surface in the presence of features like cavities, pillars or complex anisotropic structures. We show how friction can be effectively tuned by appropriate design of such surface features.

  10. Energetic Surface Smoothing of Complex Metal-Oxide Thin Films

    International Nuclear Information System (INIS)

    Willmott, P.R.; Herger, R.; Schlepuetz, C.M.; Martoccia, D.; Patterson, B.D.

    2006-01-01

    A novel energetic smoothing mechanism in the growth of complex metal-oxide thin films is reported from in situ kinetic studies of pulsed laser deposition of La 1-x Sr x MnO 3 on SrTiO 3 , using x-ray reflectivity. Below 50% monolayer coverage, prompt insertion of energetic impinging species into small-diameter islands causes them to break up to form daughter islands. This smoothing mechanism therefore inhibits the formation of large-diameter 2D islands and the seeding of 3D growth. Above 50% coverage, islands begin to coalesce and their breakup is thereby suppressed. The energy of the incident flux is instead rechanneled into enhanced surface diffusion, which leads to an increase in the effective surface temperature of ΔT≅500 K. These results have important implications on optimal conditions for nanoscale device fabrication using these materials

  11. Zinc surface complexes on birnessite: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Kideok D.; Refson, Keith; Sposito, Garrison

    2009-01-05

    Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.

  12. Geochemical Analyses of Surface and Shallow Gas Flux and Composition Over a Proposed Carbon Sequestration Site in Eastern Kentucky

    Energy Technology Data Exchange (ETDEWEB)

    Thomas Parris; Michael Solis; Kathryn Takacs

    2009-12-31

    Using soil gas chemistry to detect leakage from underground reservoirs (i.e. microseepage) requires that the natural range of soil gas flux and chemistry be fully characterized. To meet this need, soil gas flux (CO{sub 2}, CH{sub 4}) and the bulk (CO{sub 2}, CH{sub 4}) and isotopic chemistry ({delta}{sup 13}C-CO2) of shallow soil gases (<1 m, 3.3 ft) were measured at 25 locations distributed among two active oil and gas fields, an active strip mine, and a relatively undisturbed research forest in eastern Kentucky. The measurements apportion the biologic, atmospheric, and geologic influences on soil gas composition under varying degrees of human surface disturbance. The measurements also highlight potential challenges in using soil gas chemistry as a monitoring tool where the surface cover consists of reclaimed mine land or is underlain by shallow coals. For example, enrichment of ({delta}{sup 13}C-CO2) and high CH{sub 4} concentrations in soils have been historically used as indicators of microseepage, but in the reclaimed mine lands similar soil chemistry characteristics likely result from dissolution of carbonate cement in siliciclastic clasts having {delta}{sup 13}C values close to 0{per_thousand} and degassing of coal fragments. The gases accumulate in the reclaimed mine land soils because intense compaction reduces soil permeability, thereby impeding equilibration with the atmosphere. Consequently, the reclaimed mine lands provide a false microseepage anomaly. Further potential challenges arise from low permeability zones associated with compacted soils in reclaimed mine lands and shallow coals in undisturbed areas that might impede upward gas migration. To investigate the effect of these materials on gas migration and composition, four 10 m (33 ft) deep monitoring wells were drilled in reclaimed mine material and in undisturbed soils with and without coals. The wells, configured with sampling zones at discrete intervals, show the persistence of some of the

  13. Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS)

    Science.gov (United States)

    Getty, Stephanie A.; Cook, Jamie E.; Balvin, Manuel; Brinckerhoff, William B.; Li, Xiang; Grubisic, Andrej; Cornish, Timothy; Ferrance, Jerome; Southard, Adrian

    2017-01-01

    The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.

  14. Spatial variation, source identification, and quality assessment of surface water geochemical composition in the Indus River Basin, Pakistan.

    Science.gov (United States)

    Rehman Qaisar, Faizan Ur; Zhang, Fan; Pant, Ramesh Raj; Wang, Guanxing; Khan, Sardar; Zeng, Chen

    2018-02-22

    The Indus River Basin (IRB) with an area of 139,202 km 2 is the lifeline river basin of Pakistan. An intensive study was conducted in six subcatchments of the IRB with five in the Upper Indus Basin (UIB) and one of the Lower Indus Basin (LIB; between Tarbela Dam and Panjand), i.e., the Gilgit River Basin (UIB-I), Hunza River Basin (UIB-II), UIB-III, UIB-IV and UIB-V, and LIB. A total of 84 surface water samples were collected from main stream and tributaries from June to August, 2016. The pH, electric conductivity (EC), and total dissolved solids (TDS) were measured in situ, whereas major ions (Ca 2+ , Mg 2+ , K + , Na + , Cl - , SO 4 2- , and NO 3 - ) and Si were analyzed in the laboratory. The results exhibited alkaline pH (8.55 ± 0.20) with diverse TDS (114.69 ± 77.65 mg L -1 ) and ion concentrations that were characterized primarily by the Ca-Mg-HCO 3 type in the whole basin. The average TDS in the UIB and LIB were 93.99 ± 39.73 and 181.67 ± 167.82 mg L -1 , respectively, under the influence of the arid to semi-arid climatic conditions and relatively higher anthropogenic interference in LIB compared to the UIB. The order of dominant major cations was different in the UIB and LIB, reflecting the diverse nature of geological formation. Gibbs plot, mixing diagrams, and ionic ratios were used to identify the controlling mechanism of river geochemistry in the IRB as carbonate weathering in general with different degrees of silicate weathering and minor contribution by evaporite dissolution. In addition, principal component/factor analysis also indicated that the major sources of dissolved loads in the basin are carbonates followed by silicates. Significant influences of silicate minerals were observed in the LIB, and there was a large contribution of evaporites in the UIB-II, UIB-III, and LIB. The suitability assessment showed that the river water fits the WHO permissible limits for drinking purposes from the perspective of major ions

  15. Reliability of surface EMG measurements from the suprahyoid muscle complex

    DEFF Research Database (Denmark)

    Kothari, Mohit; Stubbs, Peter William; Pedersen, Asger Roer

    2017-01-01

    of using the suprahyoid muscle complex (SMC) using surface electromyography (sEMG) to assess changes to neural pathways by determining the reliability of measurements in healthy participants over days. Methods: Seventeen healthy participants were recruited. Measurements were performed twice with one week...... between sessions. Single pulse (at 120% and 140% of the resting motor threshold (rMT)) and paired pulse (2 ms and 15 ms paired pulse) transcranial magnetic stimulation (TMS) were used to elicit MEPs in the SMC which were recorded using sEMG. Results: ≈50% of participants (range: 42%-58%; depending...... on stimulus type/intensity) had significantly different MEP values between day 1 and day 2 for single pulse and paired pulse TMS. A large stimulus artefact resulted in MEP responses that could not be assessed in four participants. Conclusions: The assessment of the SMC using sEMG following TMS was poorly...

  16. The effects of physical and geochemical heterogeneities on hydro-geochemical transport and effective reaction rates

    Science.gov (United States)

    Atchley, Adam L.; Navarre-Sitchler, Alexis K.; Maxwell, Reed M.

    2014-09-01

    The role of coupled physical and geochemical heterogeneities in hydro-geochemical transport is investigated by simulating three-dimensional transport in a heterogeneous system with kinetic mineral reactions. Ensembles of 100 physically heterogeneous realizations were simulated for three geochemical conditions: 1) spatially homogeneous reactive mineral surface area, 2) reactive surface area positively correlated to hydraulic heterogeneity, and 3) reactive surface area negatively correlated to hydraulic heterogeneity. Groundwater chemistry and the corresponding effective reaction rates were calculated at three transverse planes to quantify differences in plume evolution due to heterogeneity in mineral reaction rates and solute residence time (τ). The model is based on a hypothetical CO2 intrusion into groundwater from a carbon capture utilization and storage (CCUS) operation where CO2 dissolution and formation of carbonic acid created geochemical dis-equilibrium between fluids and the mineral galena that resulted in increased aqueous lead (Pb2 +) concentrations. Calcite dissolution buffered the pH change and created conditions of galena oversaturation, which then reduced lead concentrations along the flow path. Near the leak kinetic geochemical reactions control the release of solutes into the fluid, but further along the flow path mineral solubility controls solute concentrations. Simulation results demonstrate the impact of heterogeneous distribution of geochemical reactive surface area in coordination with physical heterogeneity on the effective reaction rate (Krxn,eff) and Pb2 + concentrations within the plume. Dissimilarities between ensemble Pb2 + concentration and Krxn,eff are attributed to how geochemical heterogeneity affects the time (τeq) and therefore advection distance (Leq) required for the system to re-establish geochemical equilibrium. Only after geochemical equilibrium is re-established, Krxn,eff and Pb2 + concentrations are the same for all three

  17. The effects of physical and geochemical heterogeneities on hydro-geochemical transport and effective reaction rates.

    Science.gov (United States)

    Atchley, Adam L; Navarre-Sitchler, Alexis K; Maxwell, Reed M

    2014-09-01

    The role of coupled physical and geochemical heterogeneities in hydro-geochemical transport is investigated by simulating three-dimensional transport in a heterogeneous system with kinetic mineral reactions. Ensembles of 100 physically heterogeneous realizations were simulated for three geochemical conditions: 1) spatially homogeneous reactive mineral surface area, 2) reactive surface area positively correlated to hydraulic heterogeneity, and 3) reactive surface area negatively correlated to hydraulic heterogeneity. Groundwater chemistry and the corresponding effective reaction rates were calculated at three transverse planes to quantify differences in plume evolution due to heterogeneity in mineral reaction rates and solute residence time (τ). The model is based on a hypothetical CO2 intrusion into groundwater from a carbon capture utilization and storage (CCUS) operation where CO2 dissolution and formation of carbonic acid created geochemical dis-equilibrium between fluids and the mineral galena that resulted in increased aqueous lead (Pb(2+)) concentrations. Calcite dissolution buffered the pH change and created conditions of galena oversaturation, which then reduced lead concentrations along the flow path. Near the leak kinetic geochemical reactions control the release of solutes into the fluid, but further along the flow path mineral solubility controls solute concentrations. Simulation results demonstrate the impact of heterogeneous distribution of geochemical reactive surface area in coordination with physical heterogeneity on the effective reaction rate (Krxn,eff) and Pb(2+) concentrations within the plume. Dissimilarities between ensemble Pb(2+) concentration and Krxn,eff are attributed to how geochemical heterogeneity affects the time (τeq) and therefore advection distance (Leq) required for the system to re-establish geochemical equilibrium. Only after geochemical equilibrium is re-established, Krxn,eff and Pb(2+) concentrations are the same for all

  18. Surface complexation model of uranyl sorption on Georgia kaolinite

    Science.gov (United States)

    Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

    2004-01-01

    The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

  19. Ternary Complexation on Bacterial Surfaces: Implications for Subsurface Anion Transport

    Science.gov (United States)

    Maclean, L. C.; Higginbottom, C. M.; Fowle, D. A.

    2002-12-01

    The physical, chemical, and biological controls on contaminant mobilities in aquatic ecosystems must be determined to establish the threat that contamination poses to the environment. Quantitative models of contaminant mobilities are required as a prerequisite to guide remediation efforts and to prioritize the potential hazard to the ecosystem of each contaminated site. It is well established that mineral surface adsorption is an important control on contaminant mobilities, and many studies have utilized thermodynamics to quantify metal/organic adsorption in order to yield predictive models of contaminant transport. However, these models of contaminant transport may not be representative of the reactions which control contaminant mobilities as most mineral surfaces are coated with organic acids, bacteria, and extracellular polymers. Numerous laboratory studies have demonstrated that bacterial cell walls have a high affinity for binding metal cations, and field studies indicate that a significant proportion of bacteria cells and associated extracellular matrices are coated with small scale hydrous metal oxides. The small size of bacteria, and in many cases the nanoscale of their associated mineral phases, suggests these bacteria-mineral composites may represent a large proportion of surface area exposed to fluid flow. Therefore, due to the affinity of bacterial cell walls for cations and biominerals, bacteria may also have a significant impact on anionic contaminant mobility in many natural systems. The extent of metal-bacteria adsorption reactions varies drastically as a function of pH and solution chemistry. Current adsorption models have focused on the interactions of positively charged metal cations with bacterial surfaces, however in many oxidizing environments metals such as Cr exist as anions or anionic complexes. We have studied the ability of non-metabolizing cells of the bacterial species Bacillus subtilis and Shewanella putrifaciens to adsorb aqueous Cr

  20. Corrected Debye-Hückel analysis of surface complexation. II. A theory of surface charging.

    Science.gov (United States)

    Gunnarsson, Magnus; Abbas, Zareen; Ahlberg, Elisabet; Gobom, Sylvia; Nordholm, Sture

    2002-05-01

    A theory of surface charging of colloidal particles suspended in an electrolyte solution is presented. The charging at the particle surface is assumed to originate from the adsorption and desorption of protons and is therefore strongly dependent on the acidity of the solution. The surface binding of protons occurs locally at sites of occupancy zero or one that are described by a binding energy u(0) and a three-dimensional vibration of frequency nu. The diffuse screening of ions at the surface is described by the corrected Debye-Hückel analysis assuming linear response. The model contains a capacitor layer close to the charged surface and the finite size of the electrolyte ions is taken into account. The theory has been applied to titrated surface charge data on goethite (alpha-FeOOH) at NaClO(4) background concentrations ranging from 0.01 to 1.0 M. The protonation mechanism used in the modeling of these data corresponds to the 1-pK approach. A very good description of the experimental data was obtained at the highest ionic strength. Close to the pH(pzc) the theory also gave a good description at lower ionic strengths. However, at low salt concentrations and pH values far away from the pH(pzc) the electrostatic potential outside the capacitor layer becomes so high that nonlinear electrostatic effects become important and the theory therefore underestimates the surface charge. These results were compared with model calculations obtained using existing surface complexation models.

  1. Uncertainty analysis of point-by-point sampling complex surfaces using touch probe CMMs DOE for complex surfaces verification with CMM

    DEFF Research Database (Denmark)

    Barini, Emanuele Modesto; Tosello, Guido; De Chiffre, Leonardo

    2010-01-01

    The paper describes a study concerning point-by-point sampling of complex surfaces using tactile CMMs. A four factor, two level completely randomized factorial experiment was carried out, involving measurements on a complex surface configuration item comprising a sphere, a cylinder and a cone, co...

  2. Adaptive Surface Modeling of Soil Properties in Complex Landforms

    Directory of Open Access Journals (Sweden)

    Wei Liu

    2017-06-01

    Full Text Available Abstract: Spatial discontinuity often causes poor accuracy when a single model is used for the surface modeling of soil properties in complex geomorphic areas. Here we present a method for adaptive surface modeling of combined secondary variables to improve prediction accuracy during the interpolation of soil properties (ASM-SP. Using various secondary variables and multiple base interpolation models, ASM-SP was used to interpolate soil K+ in a typical complex geomorphic area (Qinghai Lake Basin, China. Five methods, including inverse distance weighting (IDW, ordinary kriging (OK, and OK combined with different secondary variables (e.g., OK-Landuse, OK-Geology, and OK-Soil, were used to validate the proposed method. The mean error (ME, mean absolute error (MAE, root mean square error (RMSE, mean relative error (MRE, and accuracy (AC were used as evaluation indicators. Results showed that: (1 The OK interpolation result is spatially smooth and has a weak bull's-eye effect, and the IDW has a stronger ‘bull’s-eye’ effect, relatively. They both have obvious deficiencies in depicting spatial variability of soil K+. (2 The methods incorporating combinations of different secondary variables (e.g., ASM-SP, OK-Landuse, OK-Geology, and OK-Soil were associated with lower estimation bias. Compared with IDW, OK, OK-Landuse, OK-Geology, and OK-Soil, the accuracy of ASM-SP increased by 13.63%, 10.85%, 9.98%, 8.32%, and 7.66%, respectively. Furthermore, ASM-SP was more stable, with lower MEs, MAEs, RMSEs, and MREs. (3 ASM-SP presents more details than others in the abrupt boundary, which can render the result consistent with the true secondary variables. In conclusion, ASM-SP can not only consider the nonlinear relationship between secondary variables and soil properties, but can also adaptively combine the advantages of multiple models, which contributes to making the spatial interpolation of soil K+ more reasonable.

  3. An initial research on solute migration model coupled with adsorption of surface complexation in groundwater

    International Nuclear Information System (INIS)

    Qian Tianwei; Chen Fanrong

    2003-01-01

    The influence of solution chemical action in groundwater on solute migration has attracted increasing public attention, especially adsorption action occurring on surface of solid phase and liquid phase, which has play a great role in solute migration. There are various interpretations on adsorption mechanism, in which surface complexion is one of successful hypothesis. This paper first establishes a geochemical model based on surface complexion and then coupled it with traditional advection-dispersion model to constitute a solute migration model, which can deal with surface complexion action. The simulated results fit very well with those obtained by the precursors, as compared with a published famous example, which indicates that the model set up by this paper is successful. (authors)

  4. Complexity in Surfaces of Densest Packings for Families of Polyhedra

    Directory of Open Access Journals (Sweden)

    Elizabeth R. Chen

    2014-02-01

    Full Text Available Packings of hard polyhedra have been studied for centuries due to their mathematical aesthetic and more recently for their applications in fields such as nanoscience, granular and colloidal matter, and biology. In all these fields, particle shape is important for structure and properties, especially upon crowding. Here, we explore packing as a function of shape. By combining simulations and analytic calculations, we study three two-parameter families of hard polyhedra and report an extensive and systematic analysis of the densest known packings of more than 55 000 convex shapes. The three families have the symmetries of triangle groups (icosahedral, octahedral, tetrahedral and interpolate between various symmetric solids (Platonic, Archimedean, Catalan. We find optimal (maximum packing-density surfaces that reveal unexpected richness and complexity, containing as many as 132 different structures within a single family. Our results demonstrate the importance of thinking about shape not as a static property of an object, in the context of packings, but rather as but one point in a higher-dimensional shape space whose neighbors in that space may have identical or markedly different packings. Finally, we present and interpret our packing results in a consistent and generally applicable way by proposing a method to distinguish regions of packings and classify types of transitions between them.

  5. LOCALIZATION OF PATHOLOGY ON COMPLEX ARCHITECTURE BUILDING SURFACES

    Directory of Open Access Journals (Sweden)

    A. A. Sidiropoulos

    2017-02-01

    Full Text Available The technology of 3D laser scanning is considered as one of the most common methods for heritage documentation. The point clouds that are being produced provide information of high detail, both geometric and thematic. There are various studies that examine techniques of the best exploitation of this information. In this study, an algorithm of pathology localization, such as cracks and fissures, on complex building surfaces is being tested. The algorithm makes use of the points’ position in the point cloud and tries to distinguish them in two groups-patterns; pathology and non-pathology. The extraction of the geometric information that is being used for recognizing the pattern of the points is being accomplished via Principal Component Analysis (PCA in user-specified neighborhoods in the whole point cloud. The implementation of PCA leads to the definition of the normal vector at each point of the cloud. Two tests that operate separately examine both local and global geometric criteria among the points and conclude which of them should be categorized as pathology. The proposed algorithm was tested on parts of the Gazi Evrenos Baths masonry, which are located at the city of Giannitsa at Northern Greece.

  6. Surface complexation models for uranium adsorption in the sub-surface environment

    International Nuclear Information System (INIS)

    Payne, T.E.

    2007-01-01

    Adsorption experiments with soil component minerals under a range of conditions are being used to develop models of uranium(VI) uptake in the sub-surface environment. The results show that adsorption of U on iron oxides and clay minerals is influenced by chemical factors including the pH, partial pressure of CO 2 , and the presence of ligands such as phosphate. Surface complexation models (SCMs) can be used to simulate U adsorption on these minerals. The SCMs are based on plausible mechanistic assumptions and describe the experimental data more adequately than Kd values or sorption isotherms. It is conceptually possible to simulate U sorption data on complex natural samples by combining SCMs for individual component minerals. This approach was used to develop a SCM for U adsorption to mineral assemblages from Koongarra (Australia), and produced a reasonable description of U uptake. In order to assess the applicability of experimental data to the field situation, in-situ measurements of U distributions between solid and liquid phases were undertaken at the Koongarra U deposit. This field partitioning data showed a satisfactory agreement with laboratory sorption data obtained under comparable conditions. (author)

  7. Geochemical exploration for uranium

    International Nuclear Information System (INIS)

    1988-01-01

    This Technical Report is designed mainly to introduce the methods and techniques of uranium geochemical exploration to exploration geologists who may not have had experience with geochemical exploration methods in their uranium programmes. The methods presented have been widely used in the uranium exploration industry for more than two decades. The intention has not been to produce an exhaustive, detailed manual, although detailed instructions are given for a field and laboratory data recording scheme and a satisfactory analytical method for the geochemical determination of uranium. Rather, the intention has been to introduce the concepts and methods of uranium exploration geochemistry in sufficient detail to guide the user in their effective use. Readers are advised to consult general references on geochemical exploration to increase their understanding of geochemical techniques for uranium

  8. The geochemical chararateristics of the marble deposits east of ...

    African Journals Online (AJOL)

    ), marbles were investigated with the view to establishing marble occurrences and their geochemical characteristics. Crystalline rocks of the Nigerian Basement Complex (migmatite – gneiss complex) underlie the area. Ten marble bodies were ...

  9. Surface complexation at calcium mineral-water interfaces

    OpenAIRE

    Wu, Liuming

    1994-01-01

    Surface reactions occurring at solid-water interfaces in calcium mineral-ligands systems have been studied. Both hydrous apatite and fluorite surfaces show clear amphoteric properties. An ion exchange process between lattice ions of F- on fluorite and OH- ions in bulk solution is discovered. The surface adsorption of Alizarin Red S and sodium oleate are determined. Surface chemical reaction models are established based on acidbase potentiometric titrations, solubility, adsorption and zeta-pot...

  10. Assessment of WRF Surface Layer Formulations Over a Complex Terrain

    Science.gov (United States)

    Srivastava, P.; Sharan, M.

    2017-12-01

    The accurate and efficient estimation of surface turbulent fluxes is crucial to predict an adequate atmospheric evolution by atmospheric models. The Monin-Obukhov similarity theory, which is used to compute these fluxes in numerical models, utilizes the empirical stability correction functions. In the present study, impact of various functional forms of similarity functions on the computation of the surface fluxes under both unstable and stable stratification is analyzed. In addition, this study compares two surface layer parametrization schemes in the Weather Research and Forecasting model over Ranchi (India). The model is run with three nested domains at a high resolution (1 Km) for `five' 4-day periods covering 15 days of Premonsoon season. The two surface layer schemes chosen for the analysis includes MM5 surface layer scheme having Businger-Dyer similarity functions, and revised MM5 scheme utilizing the functions those are valid for full ranges of atmospheric stabilities. The five planetary boundary layer (PBL) schemes are selected to assess the influence of the surface layer schemes on the structure of the boundary layer. The schemes are- Asymmetric Convective Model Version 2 (ACM2), Bougeault-Lacarrere (Boulac), Medium Range Forecast (MRF), Mellor-Yamada-Nakanishi-Niino (MYNN), and Yonsei University (YSU) PBL schemes. The impact of surface layer parametrizations on the near surface diagnostic variables is analyzed and results are compared with the observations.The bias in the 2 m temperature (T2) and 10 m wind speed (U) across the PBL schemes is very small and each PBL scheme is able to reproduce the diurnal variation of T2 irrespective of the surface layer scheme used for the simulations. A relatively higher value nocturnal T2 is predicted with the revised MM5 surface layer scheme as compared to that obtained with the old MM5 scheme, while both the surface layer schemes reproduce almost similar T2 during convective conditions. However, compare to the

  11. Geochemical exploration for uranium

    International Nuclear Information System (INIS)

    Rose, A.W.

    1977-01-01

    The processes and types of dispersion that produce anomalies in stream water, stream sediment, and ground water, and the factors that must be considered in planning and interpreting geochemical surveys are reviewed. Examples of surveys near known deposits show the types of results to be expected. Background values depend mainly on the content of U in rocks of the drainage area. In igneous rocks, U tends to increase with potassium from ultramafic rocks (0.01 ppM) to granitic rocks (1 to 5 ppM). Some alkalic rocks have unusually high contents of U (15 to 100 ppM). Uranium-rich provinces marked by igneous rocks unusually rich in U are recognized in several areas and appear to have a deep crustal or mantle origin. In western U.S., many tertiary tuffaceous rocks have a high U content. Sandstones, limestones, and many shales approximate the crustal abundance at 0.5 to 4 ppM, but black shales, phosphates, and some organic materials are notably enriched in U. Uranium is very soluble in most oxidizing waters at the earth's surface, but is precipitated by reducing agents (organic matter, H 2 S) and adsorbed by organic material and some Fe oxides. In most surface and ground waters, U correlates approximately with the total dissolved solids, conductivity, and bicarbonate concentration of the water, and with the U content of rocks it comes into contact with. Most surveys of stream water near known districts show distinct anomalies extending a few km to tens of km downstream. A complication with water is the large variability with time, up to x 50, as a result of changes in the ratio of ground water to direct runoff, and changes in rate of oxidation and leaching. Collection and analysis of water samples also pose some difficulties

  12. Immuno-targeting of Staphylococcus aureus via surface remodeling complexes.

    Science.gov (United States)

    Sabulski, Mary J; Pidgeon, Sean E; Pires, Marcos M

    2017-10-01

    Agents with novel mechanisms of action are needed to complement traditional antibiotics. Towards these goals, we have exploited the surface-homing properties of vancomycin to tag the surface of Gram-positive pathogens with immune cell attractants in two unique modes. First, vancomycin was conjugated to the small molecule hapten 2,4-dinitrophenol (DNP) to promote bacterial opsonization. Second, we built on these results by improving the tagging specificity and mechanism of incorporation by coupling it to a sortase A substrate peptide. We demonstrated, for the first time, that the surface of Staphylococcus aureus ( S. aureus ) can be metabolically labeled in live Caenorhabditis elegans hosts. These constructs represent a class of promising narrow-spectrum agents that target S. aureus for opsonization and establish a new surface labeling modality in live host organisms, which should be a powerful tool in dissecting features of host-pathogen interactions.

  13. Uncertainty analysis of point by point sampling complex surfaces using touch probe CMMs

    DEFF Research Database (Denmark)

    Barini, Emanuele; Tosello, Guido; De Chiffre, Leonardo

    2007-01-01

    The paper describes a study concerning point by point scanning of complex surfaces using tactile CMMs. A four factors-two level full factorial experiment was carried out, involving measurements on a complex surface configuration item comprising a sphere, a cylinder and a cone, combined in a singl...

  14. Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model

    International Nuclear Information System (INIS)

    Um, Wooyong; Serne, R. Jeffrey; Brown, Christopher F.; Rod, Kenton A.

    2008-01-01

    Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent-sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO U O 2 HCO 3 and SO U O 2 OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions

  15. Symplectic geometry on moduli spaces of holomorphic bundles over complex surfaces

    OpenAIRE

    Khesin, Boris; Rosly, Alexei

    2000-01-01

    We give a comparative description of the Poisson structures on the moduli spaces of flat connections on real surfaces and holomorphic Poisson structures on the moduli spaces of holomorphic bundles on complex surfaces. The symplectic leaves of the latter are classified by restrictions of the bundles to certain divisors. This can be regarded as fixing a "complex analogue of the holonomy" of a connection along a "complex analogue of the boundary" in analogy with the real case.

  16. Methods for geochemical analysis

    Science.gov (United States)

    Baedecker, Philip A.

    1987-01-01

    The laboratories for analytical chemistry within the Geologic Division of the U.S. Geological Survey are administered by the Office of Mineral Resources. The laboratory analysts provide analytical support to those programs of the Geologic Division that require chemical information and conduct basic research in analytical and geochemical areas vital to the furtherance of Division program goals. Laboratories for research and geochemical analysis are maintained at the three major centers in Reston, Virginia, Denver, Colorado, and Menlo Park, California. The Division has an expertise in a broad spectrum of analytical techniques, and the analytical research is designed to advance the state of the art of existing techniques and to develop new methods of analysis in response to special problems in geochemical analysis. The geochemical research and analytical results are applied to the solution of fundamental geochemical problems relating to the origin of mineral deposits and fossil fuels, as well as to studies relating to the distribution of elements in varied geologic systems, the mechanisms by which they are transported, and their impact on the environment.

  17. Graph Complexes and the Moduli Space of Riemann Surfaces

    DEFF Research Database (Denmark)

    Egas Santander, Daniela

    In this thesis we compare several combinatorial models for the moduli space of open-closed cobordisms and their compactifications. More precisely, we study Godin's category of admissible fat graphs, Costello's chain complex of black and white graphs, and Bödigheimer's space of radial slit......, that the complex of black and white graphs is a homological model of this mapping class group. Beyond giving new proofs of these results, the methods used give a new interpretation of Costello's model in terms of admissible fat graphs, which is a more classical model of moduli space. This connection could...... potentially allow to transfer constructions in fat graphs to the black and white model. Moreover, we compare Bödigheimer's radial slit configurations and the space of metric admissible fat graphs, producing an explicit homotopy equivalence using a "critical graph" map. This critical graph map descends...

  18. Adsorption of polymer/solvent complexes on silica surfaces

    Czech Academy of Sciences Publication Activity Database

    Grohens, Y.; Carriere, P.; Hamon, L.; Castelein, O.; Holl, Y.; Spěváček, Jiří

    2001-01-01

    Roč. 166, - (2001), s. 59-70 ISSN 1022-1360. [International Conference on Polymer-solvent Complexes and Intercalates /3./. Besancon, 28.08.2000-30.08.2000] R&D Projects: GA AV ČR KSK4050111 Institutional research plan: CEZ:AV0Z4050913 Keywords : polymer/solvent interactions * stereocomplexes Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.634, year: 2001

  19. A Novel Field Apparatus for Conducting Linked Geochemical-Microbiological Experiments in Shallow Sediments

    Science.gov (United States)

    Smith, E. W.; Voytek, M. A.; McGuire, J. T.; Cozzarelli, I. M.; Kneeshaw, T. A.; Baez-Cazull, S. E.

    2008-12-01

    Collecting in-situ experimental data for microbially mediated geochemical reactions is complex because it is difficult to assess the impact of the heterogeneity of natural systems. Specifically it is often difficult to constrain the degree of interaction between the pore water collected for geochemical analysis and a sampled microbial population. The newly developed apparatus, called a Native Organism Geochemical Experimentation Enclosure (NOGEE), provides the means to measure changes in well defined geochemical solutions that have been in direct contact with a known in-situ microbial population. The sampling apparatus is similar to a drive-point well. A short screened chamber (~60 ml) at the tip houses a polycarbonate sponge, which serves as a substrate for colonization by native microorganisms when it is open to the surrounding sediment. Following a colonization period dependent on season and temperature, the sponge chamber is closed to the surrounding environment by lowering an inner pipe and amended test solutions are introduced from the surface via tubing. An advantage to this method over laboratory microcosms is that the in-situ setting provides a natural, intrinsic control over environmental variables and minimizes disturbance to the system. To date, NOGEE's have been used to evaluate kinetic controls on sulfate reduction. Experimental results showed changing rates of sulfate reduction coincident with changes in microbial population and demonstrate the utility of using NOGEEs to quantify linkages between geochemistry and microbiology in complex natural environments.

  20. Visualization of pool boiling from complex surfaces with internal tunnels

    Directory of Open Access Journals (Sweden)

    Pastuszko Robert

    2012-04-01

    Full Text Available The paper presents experimental investigations of boiling heat transfer for a system of connected narrow horizontal and vertical tunnels. These extended surfaces, named narrow tunnel structure (NTS, can be applied to electronic element cooling. The experiments were carried out with ethanol at atmospheric pressure. The tunnel external covers were manufactured out of 0.1 mm thick perforated copper foil (hole diameters 0.5 mm, sintered with the mini-fins, formed on the vertical side of the 10 mm high rectangular fins and horizontal inter-fin surface. Visualization studies were conducted with a transparent structured model of joined narrow tunnels limited with the perforated foil. The visualization investigations aimed to formulate assumptions for the boiling model through distinguishing boiling types and defining all phases of bubble growth.

  1. Organic matter geochemical signatures (TOC, TN, C/N ratio, δ13C and δ15N) of surface sediment from lakes distributed along a climatological gradient on the western side of the southern Andes.

    Science.gov (United States)

    Contreras, Sergio; Werne, Josef P; Araneda, A; Urrutia, R; Conejero, C A

    2018-07-15

    Paleolimnological studies in western South America, where meteorological stations are scarce, are critical to obtain more realistic and reliable regional reconstructions of past climate and environmental changes, including vegetation and water budget variability. However, climate and environmental geochemical indicators must be tested before they can be applied with confidence. Here we present a survey of lacustrine surface sediment (core top, 0 to ~1cm) biogeochemical proxies (total organic carbon [TOC], total nitrogen [TN], carbon/nitrogen ratio [C/N ratio] and bulk organic δ 13 C and total δ 15 N) from a suite of 72 lakes spanning the transition from a Mediterranean climate with a patchwork of cultivated vegetation, pastureland, and conifers in central Chile to a rainy temperate climate dominated by broadleaf deciduous and evergreen forest further south. Sedimentary data are compared to the latitudinal and orographic climatic trends of the region based on the climatology (precipitation and temperature) produced with Climate Forecast System Reanalysis (CFSR) data and the modern Southern Hemisphere Westerly Winds (SWW) location. The geochemical data show inflection points at ~42°S latitude and ~1500m elevation that are likely related to the northern limit of influence of the SWW and elevation of the snow line, respectively. Overall the organic proxies were able to mimic climatic trends (Mean Annual Precipitation [MAP] and temperature [MAT]), indicating that they are a useful tool to be included in paleoclimatological reconstruction of the region. Copyright © 2018 Elsevier B.V. All rights reserved.

  2. Copper complexation capacity in surface waters of the Venice Lagoon.

    Science.gov (United States)

    Delgadillo-Hinojosa, Francisco; Zirino, Alberto; Nasci, Cristina

    2008-10-01

    Total copper (Cu(T)), copper ion activity (pCu) and the copper complexation capacity (CuCC) were determined in samples of seawater collected in July 2003 from the Venice Lagoon. Cu(T) and CuCC showed considerable spatial variability: Cu(T) ranged from 1.8 to 70.0nM, whereas the CuCC varied from 195 to 573nM. pCu values varied from 11.6 to 12.6 and are consistent with those previously reported in estuarine and coastal areas (10.9-14.1). The range of Cu(T) values compares well with those reported in the past in the lagoon and in the adjacent Adriatic Sea. The highest concentrations of Cu(T) were found in samples collected near the industrial area of Porto Marghera, whereas the lowest were measured near the Chioggia and Malamocco inlets, where an intense tidally-driven renewal of seawater takes place. Although CuCC showed a high degree of spatial variability, the values recorded in the Venice Lagoon are comparable to those reported in other estuarine systems. In addition, CuCC was positively correlated with dissolved organic carbon (DOC), suggesting that organic ligands responsible for Cu complexation are part of the bulk organic matter pool in the lagoon. The CuCC:Cu(T) molar ratio was, on average 55:1, indicating that a large excess of complexation capacity exists in the Venice Lagoon. The high levels of CuCC and the narrow range of pCu indicates the importance of the role played by organic ligands in controlling the free ion Cu concentrations in the lagoon, and as a consequence, regulating its availability and/or toxicity.

  3. Complex Surface Concentration Gradients by Stenciled "Electro Click Chemistry"

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Lind, Johan Ulrik; Daugaard, Anders Egede

    2010-01-01

    Complex one- or two-dimensional concentration gradients of alkynated molecules are produced on azidized conducting polymer substrates by stenciled "electro click chemistry". The latter describes the local electrochemical generation of catalytically active Cu(I) required to complete a "click...... reaction" between alkynes and azides at room temperature. A stencil on the counter electrode defines the shape and multiplicity of the gradient(s) on the conducting polymer substrate, while the specific reaction conditions control gradient steepness and the maximum concentration deposited. Biologically...

  4. Graph Complexes and the Moduli Space of Riemann Surfaces

    DEFF Research Database (Denmark)

    Egas Santander, Daniela

    potentially allow to transfer constructions in fat graphs to the black and white model. Moreover, we compare Bödigheimer's radial slit configurations and the space of metric admissible fat graphs, producing an explicit homotopy equivalence using a "critical graph" map. This critical graph map descends...... to a homeomorphism between the Unimodular Harmonic compactification and the space of Sullivan diagrams, which are natural compactifications of the space of radial slit configurations and the space of metric admissible fat graphs, respectively. Finally, we use experimental methods to compute the homology of the chain......In this thesis we compare several combinatorial models for the moduli space of open-closed cobordisms and their compactifications. More precisely, we study Godin's category of admissible fat graphs, Costello's chain complex of black and white graphs, and Bödigheimer's space of radial slit...

  5. Geochemical Data for Stream-Sediment, Surface-Water, Rock, and Vegetation Samples from Red Mountain (Dry Creek), an Unmined Volcanogenic Massive Sulfide Deposit in the Bonnifield District, Alaska Range, East-Central Alaska

    Science.gov (United States)

    Giles, Stuart A.; Eppinger, Robert G.; Granitto, Matthew; Zelenak, Philip P.; Adams, Monique G.; Anthony, Michael W.; Briggs, Paul H.; Gough, Larry P.; Hageman, Philip L.; Hammarstrom, Jane M.; Horton, John D.; Sutley, Stephan J.; Theodorakos, Peter M.; Wolf, Ruth E.

    2007-01-01

    North-central and northeast Nevada contains numerous large plutons and smaller stocks but also contains many small, shallowly emplaced intrusive bodies, including dikes, sills, and intrusive lava dome complexes. Decades of geologic investigations in the study area demonstrate that many ore deposits, representing diverse ore deposit types, are spatially, and probably temporally and genetically, associated with these igneous intrusions. However, despite the number and importance of igneous instrusions in the study area, no synthesis of geochemical data available for these rocks has been completed. This report presents a synthesis of composition and age data for these rocks. The product represents the first phases of an effort to evaluate the time-space-compositional evolution of Mesozoic and Cenozoic magmatism in the study area and identify genetic associations between magmatism and mineralizing processes in this region.

  6. Geochemical prospecting in Guiana

    International Nuclear Information System (INIS)

    Coulomb, R.

    1957-01-01

    During the last few years geochemical prospecting techniques have become common usage in the field of mineral deposit prospecting. The real scope of these methods lies in their use in the prospecting of large areas. The most promising use of the geochemistry and hydro-geochemistry of uranium is in heavily forested tropical territories, with few outcrops, where radiometry is strongly handicapped. (author) [fr

  7. Reconnaissance Geochemical Study

    African Journals Online (AJOL)

    Geochemical exploration of Orle district within the Igarra schist belt in southwestern Nigeria was carried out using reconnaissance ... The occurrence of pathfinder elements such as As and W; and of rock units, such as amphibolites and pegmatites, within the schist belt that ...... house for national prosperity. Inaugural.

  8. Chromate Adsorption on Selected Soil Minerals: Surface Complexation Modeling Coupled with Spectroscopic Investigation.

    Czech Academy of Sciences Publication Activity Database

    Veselská, V.; Fajgar, Radek; Číhalová, S.; Bolanz, R.M.; Göttlicher, J.; Steininger, R.; Siddique, J.A.; Komárek, M.

    2016-01-01

    Roč. 318, NOV 15 (2016), s. 433-442 ISSN 0304-3894 Institutional support: RVO:67985858 Keywords : surface complexation modeling * chromate * soil minerals Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.065, year: 2016

  9. Technology of magnetic abrasive finishing in machining of difficult-to-machine alloy complex surface

    Directory of Open Access Journals (Sweden)

    Fujian MA

    2016-10-01

    Full Text Available The technology of magnetic abrasive finishing is one of the important finishing technologies. Combining with low-frequency vibration and ultrasonic vibration, it can attain higher precision, quality and efficiency. The characteristics and the related current research of magnetic abrasive finishing, vibration assisted magnetic abrasive finishing and ultrasonic assisted magnetic abrasive finishing are introduced. According to the characteristics of the difficult-to-machine alloy's complex surface, the important problems for further study are presented to realize the finishing of complex surface with the technology of magnetic abrasive finishing, such as increasing the machining efficiency by enhancing the magnetic flux density of machining gap and compounding of magnetic energy and others, establishing of the control function during machining and the process planning method for magnetic abrasive finishing of complex surface under the space geometry restraint of complex surface on magnetic pole, etc.

  10. Status report on geochemical modelling

    International Nuclear Information System (INIS)

    Read, D.

    1991-12-01

    This report describes the findings of a review undertaken on behalf of the project management group of the programme 'Endlagersicherheit in der Nachbetriebsphase' based at GSF-IfT (Forschungszentrum fuer Umwelt und Gesundheit - Institut fuer Tieflagerung) to establish the current status of research into the simulation of geochemical processes relevant to radiological assessment. The review is intended to contribute to Stage 1 of a strategy formulated to enhance the use of geochemical models in Germany. Emphasis has been placed on processes deemed to be of greatest relevance to performance assessment for a HLW-repository in a salt dome principally, speciation-solubility in high salinity solutions, complexation by natural organics and generation-transport of colloids. For each of these and other topics covered, a summary is given of fundamental concepts, theoretical representations and their limitations, highlighting, where appropriate, the advantages and disadvantages of alternative approaches. The availability of data to quantify any given representation is addressed, taking into account the need for information at elevated temperatures and pressures. Mass transfer is considered in terms of aqueous, particulate and gas-mediated transport, respectively. (orig.) [de

  11. Surface-Enhanced Raman Scattering of the Complexes of Silver with Adenine and dAMP

    OpenAIRE

    Otto, Cornelis; Hoeben, F.P.; Hoeben, F.P.; Greve, Jan

    1991-01-01

    The behaviour of adenine and 2'-deoxyadenosine-5'-monophosphate (dAMP) at positive surface potentials of a silver working electrode was investigated using surface-enhanced Raman scattering (SERS). The use of positive potentials in the presence of adenine or dAMP leads to a rapid accumulation of an intense spectrum. It is proposed that complexes of adenine (dAMP) with silver generate the observed spectra. Adenine and dAMP can be distinguished spectroscopically due to various different complexe...

  12. Surface and permeability properties of membranes from polyelectrolyte complexes and polyelectrolyte surfactant complexes

    Czech Academy of Sciences Publication Activity Database

    Schwarz, H. H.; Lukáš, Jaromír; Richau, K.

    2003-01-01

    Roč. 218, 1-2 (2003), s. 1-9 ISSN 0376-7388 R&D Projects: GA AV ČR KSK4050111 Keywords : polyelectrolyte complex membranes * pervaporation * dehydration of organics Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.081, year: 2003

  13. Identification of Uranyl Surface Complexes an Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

    NARCIS (Netherlands)

    Rossberg, A.; Ulrich, K.U.; Weiss, S.; Tsushima, S.; Hiemstra, T.; Scheinost, A.C.

    2009-01-01

    Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in

  14. Geochemical character and petrogenesis of Pan-African Amspoort suite of the Boundary Igneous Complex in the Kaoko Belt (NW Namibia)

    Czech Academy of Sciences Publication Activity Database

    Janoušek, V.; Konopásek, J.; Ulrich, Stanislav; Erban, V.; Tajčmanová, L.; Jeřábek, P.

    2010-01-01

    Roč. 18, č. 4 (2010), s. 688-707 ISSN 1342-937X Grant - others:GA ČR(CZ) GA205/07/1409 Institutional research plan: CEZ:AV0Z30120515 Keywords : whole-rock geochemistry * Pan-African * Damara Orogeny * Boundary Igneous Complex * Kaoko Belt * Namibia Subject RIV: DD - Geochemistry Impact factor: 5.503, year: 2010

  15. Surface complexation of carbonate on goethite: IR spectroscopy, structure & charge distribution

    NARCIS (Netherlands)

    Hiemstra, T.; Rahnemaie, R.; Riemsdijk, van W.H.

    2004-01-01

    The adsorption of carbonate on goethite has been evaluated, focussing on the relation between the structure of the surface complex and corresponding adsorption characteristics, like pH dependency and proton co-adsorption. The surface structure of adsorbed CO3-2 has been assessed with (1) a

  16. Direct observation of surface reconstruction and termination on a complex metal oxide catalyst by electron microscopy

    KAUST Repository

    Zhu, Yihan

    2012-03-19

    On the surface: The surface reconstruction of an MoVTeO complex metal oxide catalyst was observed directly by various electron microscopic techniques and the results explain the puzzling catalytic behavior. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy

    KAUST Repository

    Pump, Eva

    2016-08-15

    Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy (DNP SENS) is an emerging technique that allows access to high-sensitivity NMR spectra from surfaces. However, DNP SENS usually requires the use of radicals as an exogenous source of polarization, which has so far limited applications for organometallic surface species to those that do not react with the radicals. Here we show that reactive surface species can be studied if they are immobilized inside porous materials with suitably small windows, and if bulky nitroxide bi-radicals (here TEKPol) are used as the polarization source and which cannot enter the pores. The method is demonstrated by obtaining significant DNP enhancements from highly reactive complelxes [(equivalent to Si-O-)W(Me)(5)] supported on MCM-41, and effects of pore size (6.0, 3.0 and 2.5 nm) on the performance are discussed.

  18. Differential topology of complex surfaces elliptic surfaces with p g=1 smooth classification

    CERN Document Server

    Morgan, John W

    1993-01-01

    This book is about the smooth classification of a certain class of algebraicsurfaces, namely regular elliptic surfaces of geometric genus one, i.e. elliptic surfaces with b1 = 0 and b2+ = 3. The authors give a complete classification of these surfaces up to diffeomorphism. They achieve this result by partially computing one of Donalson's polynomial invariants. The computation is carried out using techniques from algebraic geometry. In these computations both thebasic facts about the Donaldson invariants and the relationship of the moduli space of ASD connections with the moduli space of stable bundles are assumed known. Some familiarity with the basic facts of the theory of moduliof sheaves and bundles on a surface is also assumed. This work gives a good and fairly comprehensive indication of how the methods of algebraic geometry can be used to compute Donaldson invariants.

  19. Cell surface expression and function of the macromolecular C1 complex on the surface of human monocytes

    Directory of Open Access Journals (Sweden)

    Kinga K Hosszu

    2012-03-01

    Full Text Available The synthesis of the subunits of the C1 complex (C1q, C1s, C1r, and its regulator C1 inhibitor (C1-Inh by human monocytes has been previously established. However, surface expression of these molecules by monocytes has not been shown. Using flow cytometry and antigen-capture ELISA, we show here for the first time that, in addition to C1q, PB monocytes and the monocyte-derived U937 cells express C1s and C1r, as well as Factor B and C1-Inh on their surface. C1s and C1r immunoprecipitated with C1q, suggesting that at least some of the C1q on these cells is part of the C1 complex. Furthermore, the C1 complex on U937 cells was able to trigger complement activation via the classical pathway. The presence of C1-Inh may ensure that an unwarranted autoactivation of the C1 complex does not take place. Since C1-Inh closely monitors the activation of the C1 complex in a sterile or infectious inflammatory environment, further elucidation of the role of C1 complex is crucial to dissect its function in monocyte, DC and T cell activities, and its implications in host defense and tolerance.

  20. Surface Complexation Model for Strontium Sorption to Amorphous Silica and Goethite

    Energy Technology Data Exchange (ETDEWEB)

    Carroll, S; Robers, S; Criscenti, L; O' Day, P

    2007-11-30

    Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr{sup 2+} and SrOH{sup +} complexes on the {beta}-plane and a monodentate Sr{sup 2+} complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH{sup +} complexes and a tetradentate binuclear Sr{sup 2+} species on the {beta}-plane. The binuclear complex is needed to account for enhanced sorption at high strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr{sup 2+} and SrOH{sup +} carbonate surface complexes on the {beta}-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate

  1. Surface complexation model for strontium sorption to amorphous silica and goethite

    Directory of Open Access Journals (Sweden)

    Criscenti Louise J

    2008-01-01

    Full Text Available Abstract Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr2+ and SrOH+ complexes on the β-plane and a monodentate Sr2+complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH+ complexes and a tetradentate binuclear Sr2+ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr2+ and SrOH+ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces. Strontium surface complexation equilibrium constants determined in this study combined with other alkaline earth surface complexation constants are used to recalibrate a predictive model based on Born solvation and crystal-chemistry theory. The model is accurate to about 0.7 log K units. More studies are needed to determine the dependence of alkaline earth sorption on ionic strength and dissolved carbonate and sulfate concentrations for the development of

  2. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    Science.gov (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  3. Oriented coupling of major histocompatibility complex (MHC) to sensor surfaces using light assisted immobilisation technology

    DEFF Research Database (Denmark)

    Snabe, Torben; Røder, Gustav Andreas; Neves-Petersen, Maria Teresa

    2005-01-01

    histocompatibility complex (MHC class I) to a sensor surface is presented. The coupling was performed using light assisted immobilisation--a novel immobilisation technology which allows specific opening of particular disulphide bridges in proteins which then is used for covalent bonding to thiol-derivatised surfaces...... via a new disulphide bond. Light assisted immobilisation specifically targets the disulphide bridge in the MHC-I molecule alpha(3)-domain which ensures oriented linking of the complex with the peptide binding site exposed away from the sensor surface. Structural analysis reveals that a similar...

  4. Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation

    International Nuclear Information System (INIS)

    Liu, Chongxuan; Shi, Zhenqing; Zachara, John M.

    2009-01-01

    Stirred-flow cell experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments

  5. Geochemical modeling: a review

    International Nuclear Information System (INIS)

    Jenne, E.A.

    1981-06-01

    Two general families of geochemical models presently exist. The ion speciation-solubility group of geochemical models contain submodels to first calculate a distribution of aqueous species and to secondly test the hypothesis that the water is near equilibrium with particular solid phases. These models may or may not calculate the adsorption of dissolved constituents and simulate the dissolution and precipitation (mass transfer) of solid phases. Another family of geochemical models, the reaction path models, simulates the stepwise precipitation of solid phases as a result of reacting specified amounts of water and rock. Reaction path models first perform an aqueous speciation of the dissolved constituents of the water, test solubility hypotheses, then perform the reaction path modeling. Certain improvements in the present versions of these models would enhance their value and usefulness to applications in nuclear-waste isolation, etc. Mass-transfer calculations of limited extent are certainly within the capabilities of state-of-the-art models. However, the reaction path models require an expansion of their thermodynamic data bases and systematic validation before they are generally accepted

  6. Natural and EDTA-complexed lanthanides used as a geochemical probe for aquifers: a case study of Orleans valley's alluvial and karstic aquifers

    International Nuclear Information System (INIS)

    Le Borgne, F.; Treuil, M.; Joron, J.L.; Lepiller, M.

    2005-01-01

    The transit of chemical elements within the different parts of Orleans valley's aquifer is studied by two complementary methods. Those methods rely on the fractionation of lanthanides (Ln) during their migration in natural waters. The first method consists in studying natural lanthanides patterns within the watershed, at its entries and exits. second one lies on multi-tracer experiments with Ln-EDTA complexes. This work is completed through an observation network consisting of 52 piezometers set on a sand and gravel quarry, and the natural entries and exits of the aquifer. Orleans valley's aquifer, which is made of an alluvial watershed lying on a karstic aquifer, is mainly fed by Loire river via a large karstic network. At the entries of the aquifer (Loire river at Jargeau), the Ln concentrations in the dissolved fraction ( heavy Ln. On the other hand, the filtration of alluvial groundwater with high colloids content induces no significant Ln fractionation when the solution contains no strong chelating agent. Hence, the transit of natural and artificial Ln in Orleans valley aquifer can be explained by two complementary processes. (I) Decanting/filtering or, on the opposite, stirring of colloids. Those processes induce no important Ln fractionation. (2) Exchanges of Ln between solute complexes, colloids and sediments due to the presence of strong chelating agents. Those exchanges fractionate the Ln in the order of their stability constants. Considering the natural Ln fractionation that occurs in the Loire river and in the studied aquifer, the carbonates, the stability constants of which follow the order light Ln < heavy Ln, are the best candidates as natural strong chelating agents. From the hydrodynamic point of view, both tracer experiments and natural Ln concentrations show that the transfer of elements within the alluvial watershed is pulsed by the Loire river movements. During an ascent phase, the elements migrate away from and perpendicularly to the karstic

  7. Geochronological, geochemical, and Nd-Hf isotopic studies of the Qinling Complex, central China: Implications for the evolutionary history of the North Qinling Orogenic Belt

    Directory of Open Access Journals (Sweden)

    Chunrong Diwu

    2014-07-01

    The available data indicate that the NQOB was an independent micro-continent at least prior to the Neoproterozoic, and included a portion of the Grenville orogenic belt during the period of 1.2–0.8 Ga. The NQOB has experienced a unique geological history, which is obviously different from that of the North China Craton (NCC and the Yangtze Craton during the Precambrian. The Neoproterozoic granitoids that intruded the Qinling Complex can be interpreted as the products of assembly of the supercontinent Rodinia. The NQOB was separated from Rodinia at ca. 830–740 Ma. Subsequently, the NQOB moved closer to the northern margin of the NCC, and the initial accretion or collision with the NCC occurred from the late Cambrian to the early Ordovician.

  8. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    International Nuclear Information System (INIS)

    Bertolino, María Candelaria; Granados, Alejandro Manuel

    2016-01-01

    Highlights: • Fischer carbene 1-W reacts via cycloaddition without Cu(I) with azide terminal surface. • This reaction on the surface is regioselective to internal triple bond of 1-W. • 1-W bound to glass surface produce AuNps in situ fixed to the surface. • This ability is independent of how 1-W is bonded to the surface. • This hybrid surface can be valuable as SERS substrate or in heterogeneous catalysis. - Abstract: In this work we present a detailed study of classic reactions such as “click reaction” and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV–vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  9. The significance of surface complexation reactions in hydrologic systems: a geochemist's perspective

    Science.gov (United States)

    Koretsky, C.

    2000-05-01

    Complexation reactions at the mineral-water interface affect the transport and transformation of metals and organic contaminants, nutrient availability in soils, formation of ore deposits, acidification of watersheds and the global cycling of elements. Such reactions can be understood by quantifying speciation reactions in homogeneous aqueous solutions, characterizing reactive sites at mineral surfaces and developing models of the interactions between aqueous species at solid surfaces. In this paper, the application of thermodynamic principles to quantify aqueous complexation reactions is described. This is followed by a brief overview of a few of the methods that have been used to characterize reactive sites on mineral surfaces. Next, the application of empirical and semi-empirical models of adsorption at the mineral-water interface, including distribution coefficients, simple ion exchange models, and Langmuir and Freundlich isotherms is discussed. Emphasis is placed on the limitations of such models in providing an adequate representation of adsorption in hydrological systems. These limitations arise because isotherms do not account for the structure of adsorbed species, nor do they account for the development of surface charge with adsorption. This is contrasted with more sophisticated models of adsorption, termed 'surface complexation models', which include the constant capacitance model, the diffuse layer model, the triple layer model and the MUSIC model. In these models, speciation reactions between surface functional groups and dissolved species control the variable surface charge build-up and the specific adsorption properties of minerals in aqueous solutions. Next, the influence of mineral surface speciation on the reactivity of adsorbed species and on far from equilibrium dissolution rates of minerals is discussed. Finally, the applicability of microscopic models of surface complexation to field-scale systems is explored and the need to integrate

  10. Petrographic, mineralogical and geochemical characterization of the Serrinha coal waste pile (Douro Coalfield, Portugal) and the potential environmental impacts on soil, sediments and surface waters

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, J. [Centro de Geologia, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto (Portugal); Ferreira da Silva, E. [GeoBioTec, Geobiosciences, Geotechnologies and Geoengineering Research Center, Universidade de Aveiro, Campus de Santiago, 3810-193 Aveiro (Portugal); Li, Z.; Ward, C. [School of Biological, Earth and Environmental Sciences, University of New South Wales. Sydney, NSW 2052 (Australia); Flores, D. [Departamento de Geociencias, Ambiente e Ordenamento do Territorio, Faculdade de Ciencias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto (Portugal)

    2010-09-01

    Serrinha is the largest coal waste pile resulting from mining activities in the Douro Coalfield, Portugal. The exploitation of anthracite in tens of small mines caused some environmental impacts, as is the case of the coal waste piles that exist in old mines and adjacent areas. The Serrinha waste pile is essentially made up of 2 million tonnes of shales and carbonaceous shales, deposited in a topographical depression over about 30 years. Despite the environmental restoration accomplished in the Serrinha waste pile, some environmental problems seem to persist. In this study a petrographic, mineralogical and geochemical characterization was done in order to recognize and understand these problems. The materials studied were coal waste, sediments and waters from the drainage system and decanting basins, soils from the surrounding areas, leachates from waste material and neoformed minerals formed at the bottom of the waste pile. The main lithologies (carbonaceous shale and lithic arenite) and coal from the Douro Coalfield were also analyzed. Petrographic analysis shows some evidence of weathering (on organic and inorganic matter) related to the time of exposure to the weathering agents and the easy access of air within the waste pile (due to both the poor compaction and the heterogeneity of the material). Mineralogically, the composition of coal waste material has contributions from both the coal and the associated lithologies. R-type cluster analysis of the waste pile material allows two distinct clusters to be identified. In the first cluster a sulfide fraction is represented by the association of As, Cd, Cu, Pb, Ni and Zn, while Fe clustered with Al, Co, and Ti indicates that some of the Fe and the other elements are likely associated with silicate minerals such as clays. The second cluster, represented by Cr, V, Zr, Rb, REE, Mn, Li and Ba, probably represent a silicate fraction, perhaps detrital accessory minerals. The waste pile material, leachates, soils

  11. Effects of electric field on a copper–dioxolene complex adsorbed on a gold surface

    Energy Technology Data Exchange (ETDEWEB)

    Kostyrko, T., E-mail: tkos@amu.edu.pl; Ślusarski, T.

    2016-06-15

    Highlights: • Cu–dioxolene complex at Au(1 1 1) surface in electric field was studied with a DFT+U method. • Two valence tautomers of the adsorbed Cu–dioxolene complex were described. • Coulomb correlations on Cu make driving force for valence tautomeric transitions. • Electric field of strength of 0.5 V/Å can almost fully ionize the adsorbed complex. - Abstract: A model of a copper–dioxolene complex linked to Au(1 1 1) surface with butanethiol linker is investigated using first-principles methods. It is shown that the complex adsorbed at the surface may appear in various locally stable structural forms differing in electron charge and spin density distribution, the symmetric high spin (HS) one and the twisted low spin (LS) structure. The electric field directed perpendicular to the surface controls the amount of the charge transfer between the complex and the substrate, starting from the zero-field value of Q = +0.18 |e| up to the value of Q = +0.94 |e| for the field strength of E = 0.5 V/Å. The field modifies also the mutual stability of the two structural forms, reducing the energy gap between the more energetically stable LS twisted form and the symmetrical HS one, from a value of Δ ∼ 0.29 eV in absence of the field to Δ ∼ 0.11 eV for the field strength of E = 0.35 V/Å.

  12. Shallow groundwater monitoring at the SACROC oilfield, Scurry County, TX: good news for geologic storage of CO2 despite a complex hydrogeologic and geochemical setting (Invited)

    Science.gov (United States)

    Smyth, R. C.; Romanak, K.; Yang, C.; Hovorka, S.

    2009-12-01

    The SACROC water study is the first comprehensive research project with application to geologic storage (GS) of CO2 that focuses on collection and interpretation of field measurements of groundwater (water level and water chemistry data). CO2 has been injected for enhanced oil recovery at the SACROC oilfield in Scurry County, TX since 1972. Hence, we have a perfect natural laboratory and an analog for monitoring future commercial CO2 sequestration sites. Kinder Morgan currently operates the SACROC oilfield where over 150 million metric tons (MMT) of CO2 has been injected for EOR at ~2 km depth; over 75 MMT of the CO2 has been produced and re-injected. CO2 is assumed to be trapped in the deep subsurface at SACROC. The goals of monitoring shallow groundwater over CO2 injection sites are to (1) confirm that CO2 has remained in the deep subsurface and (2) assess impacts to water quality if CO2 were to migrate upward along conduit flow paths (e.g. leaking well bores). We collected groundwater and stratigraphic data within an ~3,000 km2 area centered on SACROC to establish regional variability prior to assessing potential impacts to groundwater from CO2 injection. Groundwater data include results from five sampling trips between June 2006 and November 2008, and a compilation of historical data from the Texas Water Development Board database, dating back to 1936. Sources of complexity that contribute to data interpretation challenges include: (1) regional historic oilfield activity, (2) multiple freshwater-bearing strata in the regional Dockum aquifer, (3) sampled wells screened in shallowest (30 m), deepest (150 m), or across both water-bearing zones, (4) variable discharge rate of sampled wells (250 gpm), (5) groundwater flow divide that bisects SACROC, (6) variable aquifer recharge mechanisms, (7) temporal variability in groundwater levels and chemistry, (8) cation exchange, (9) presence of biogenically-produced CO2 in aquifer, and (10) incongruent dissolution of

  13. Applicability of surface complexation modelling in TVO's studies on sorption of radionuclides

    International Nuclear Information System (INIS)

    Carlsson, T.

    1994-03-01

    The report focuses on the possibility of applying surface complexation theories to the conditions at a potential repository site in Finland and of doing proper experimental work in order to determine necessary constants for the models. The report provides background information on: (1) what type experiments should be carried out in order to produce data for surface complexation modelling of sorption phenomena under potential Finnish repository conditions, and (2) how to design and perform properly such experiments, in order to gather data, develop models or both. The report does not describe in detail how proper surface complexation experiments or modelling should be carried out. The work contains several examples of information that may be valuable in both modelling and experimental work. (51 refs., 6 figs., 4 tabs.)

  14. A pre-Paleogene unconformity surface of the Sikeshu Sag, Junggar Basin: Lithological, geophysical and geochemical implications for the transportation of hydrocarbons

    Directory of Open Access Journals (Sweden)

    Xiaoyue Gao

    2013-11-01

    Full Text Available The unconformity surface at the bottom of the Paleogene is one of the most important migration pathways in the Sikeshu Sag of the Junggar Basin, which consists of three layers: upper coarse clastic rock, lower weathering crust and leached zone. The upper coarse clastic rock is characterized by higher density and lower SDT and gamma-ray logging parameters, while the lower weathering crust displays opposite features. The transport coefficient of the unconformity surface is controlled by its position in respect to the basal sandstone; it is higher in the ramp region but lower in the adjacent uplifted and sag areas. The content of saturated hydrocarbons increases with the decrease of the content of non-hydrocarbons and asphaltenes. The content of benzo[c] carbazole decreases as the content of benzo[a] carbazole and [alkyl carbazole]/[alkyl + benzo carbazole] increases. This suggests that the unconformity surface is an efficient medium for the transportation of hydrocarbons.

  15. Coupling geochemical, mineralogical and microbiological approaches to assess the health of contaminated soil around the Almalyk mining and smelter complex, Uzbekistan

    International Nuclear Information System (INIS)

    Shukurov, Nosir; Kodirov, Obidjon; Peitzsch, Mirko; Kersten, Michael; Pen-Mouratov, Stanislav; Steinberger, Yosef

    2014-01-01

    This study describes the impact of airborne pollution resulting from mining and smelting activities on the soils of the Almalyk mining and industrial area (NE Uzbekistan). Samples were collected along a transect downwind of the industrial area. Enriched contents of some metals were found in the upper soil layers near the metallurgical complex (Zn ≤ 3010 mg kg −1 , Pb ≤ 630 mg kg −1 , Cd ≤ 30 mg kg −1 ) which suggests that these metals were derived from local stack emissions. The morphology and internal microstructure of metal-bearing spherical particles found in the heavy mineral fraction suggest that these particles were probably a result of inefficient flue gas cleaning technique of the smelter. The highest metal concentrations were found also in soil solutions and exchangeable solid fractions from the first three locations, and decreased with increasing distance from the pollution source along transect. Thermodynamic equilibrium calculations suggest that the mobile metal pool in the contaminated soil is mainly controlled by dissolution of metal carbonates formed as weathering product of the metalliferous particles. The health of the microbiological soil ecosystem was assessed by measurements of basal respiration, nematode abundance, biomass-related C and N content, and microbial metabolic quotient qCO 2 . Significant correlations were found between the dissolved metal content and the microbiological health parameters, a negative one for C mic /C org ratio, and a positive one for qCO 2 . A negative correlation was found between the amount of nematodes and the metal contents suggesting that the contaminated soil has significant impact on the functioning of the microbiological community. A better understanding of the spatial variations in the whole ecosystem functioning due to airborne impact could be very useful for establishing suitable land use and best management practices for the polluted areas. - Highlights: • Soil samples were collected along a

  16. Coupling geochemical, mineralogical and microbiological approaches to assess the health of contaminated soil around the Almalyk mining and smelter complex, Uzbekistan

    Energy Technology Data Exchange (ETDEWEB)

    Shukurov, Nosir; Kodirov, Obidjon; Peitzsch, Mirko [Geosciences Institute, Johannes Gutenberg University, Mainz 55099 (Germany); Kersten, Michael, E-mail: kersten@uni-mainz.de [Geosciences Institute, Johannes Gutenberg University, Mainz 55099 (Germany); Pen-Mouratov, Stanislav; Steinberger, Yosef [The Mina and Everard Goodman Faculty of Life Sciences, Bar-Ilan University, Ramat Gan 52900 (Israel)

    2014-04-01

    This study describes the impact of airborne pollution resulting from mining and smelting activities on the soils of the Almalyk mining and industrial area (NE Uzbekistan). Samples were collected along a transect downwind of the industrial area. Enriched contents of some metals were found in the upper soil layers near the metallurgical complex (Zn ≤ 3010 mg kg{sup −1}, Pb ≤ 630 mg kg{sup −1}, Cd ≤ 30 mg kg{sup −1}) which suggests that these metals were derived from local stack emissions. The morphology and internal microstructure of metal-bearing spherical particles found in the heavy mineral fraction suggest that these particles were probably a result of inefficient flue gas cleaning technique of the smelter. The highest metal concentrations were found also in soil solutions and exchangeable solid fractions from the first three locations, and decreased with increasing distance from the pollution source along transect. Thermodynamic equilibrium calculations suggest that the mobile metal pool in the contaminated soil is mainly controlled by dissolution of metal carbonates formed as weathering product of the metalliferous particles. The health of the microbiological soil ecosystem was assessed by measurements of basal respiration, nematode abundance, biomass-related C and N content, and microbial metabolic quotient qCO{sub 2}. Significant correlations were found between the dissolved metal content and the microbiological health parameters, a negative one for C{sub mic}/C{sub org} ratio, and a positive one for qCO{sub 2}. A negative correlation was found between the amount of nematodes and the metal contents suggesting that the contaminated soil has significant impact on the functioning of the microbiological community. A better understanding of the spatial variations in the whole ecosystem functioning due to airborne impact could be very useful for establishing suitable land use and best management practices for the polluted areas. - Highlights: • Soil

  17. Actinides sorption onto hematite. Experimental data, surface complexation modeling and linear free energy relationship

    Energy Technology Data Exchange (ETDEWEB)

    Romanchuk, Anna Y.; Kalmykov, Stephan N. [Lomonosov Moscow State Univ., Moscow (Russian Federation). Dept. of Chemistry

    2014-07-01

    The sorption of actinides in different valence states - Am(III), Th(IV), Np(V) and U(VI) onto hematite have been revisited with the special emphasis on the equilibrium constants of formation of surface species. The experimental sorption data have been treated using surface complexation modeling from which the set of new values of equilibrium constants were obtained. Formation of inner sphere monodentate surface species adequately describes the pH-sorption edges for actinide ions indicative the ionic electrostatic nature of bonding with small or no covalency contribution. The linear free energy relationship representing the correlation between the hydrolysis constants and surface complexation constants has been developed for various cations including K(I), Li(I), Na(I), Ag(I), Tl(I), Sr(II), Cu(II), Co(II), La(III), Eu(III), Ga(III), Am(III), Th(IV), Np(V), U(VI). (orig.)

  18. The assembly of rotaxane-like dye/cyclodextrin/surface complexes on aluminium trihydroxide or goethite.

    Science.gov (United States)

    Cooper, Rachel J; Camp, Philip J; Gordon, Ross J; Henderson, David K; Henry, Dorothy C R; McNab, Hamish; De Silva, Sonali S; Tackley, Daniel; Tasker, Peter A; Wight, Paul

    2006-06-21

    Simple azo-dyes carrying phosphonic acid and arsonic acid substituents such as 4-(4-hydroxyphenyl azo)phenylphosphonic acid (5) and 4-(4-hydroxyphenylazo)phenylarsonic acid (6) bind more strongly to high surface area oxides such as aluminium trihydroxide and goethite than their carboxylic and sulfonic acid analogues and the phosphonate-functionalized dyes have been shown to have greater humidity fastness when printed onto commercial alumina-coated papers. Adsorption isotherm measurements provide evidence for the formation of ternary dye/cyclodextrin/surface complexes. Dyes which form such ternary complexes show higher light fastness when printed onto alumina coated papers in an ink formulation containing alpha-cyclodextrin.

  19. Muscle fatigue and contraction intensity modulates the complexity of surface electromyography.

    Science.gov (United States)

    Cashaback, Joshua G A; Cluff, Tyler; Potvin, Jim R

    2013-02-01

    Nonlinear dynamical techniques offer a powerful approach for the investigation of physiological time series. Multiscale entropy analyses have shown that pathological and aging systems are less complex than healthy systems and this finding has been attributed to degraded physiological control processes. A similar phenomenon may arise during fatiguing muscle contractions where surface electromyography signals undergo temporal and spectral changes that arise from the impaired regulation of muscle force production. Here we examine the affect of fatigue and contraction intensity on the short and long-term complexity of biceps brachii surface electromyography. To investigate, we used an isometric muscle fatigue protocol (parsed into three windows) and three contraction intensities (% of maximal elbow joint moment: 40%, 70% and 100%). We found that fatigue reduced the short-term complexity of biceps brachii activity during the last third of the fatiguing contraction. We also found that the complexity of surface electromyography is dependent on contraction intensity. Our results show that multiscale entropy is sensitive to muscle fatigue and contraction intensity and we argue it is imperative that both factors be considered when evaluating the complexity of surface electromyography signals. Our data contribute to a converging body of evidence showing that multiscale entropy can quantify subtle information content in physiological time series. Copyright © 2012 Elsevier Ltd. All rights reserved.

  20. Toroidal surface complexes of bacteriophage φ12 are responsible for host-cell attachment

    International Nuclear Information System (INIS)

    Leo-Macias, Alejandra; Katz, Garrett; Wei Hui; Alimova, Alexandra; Katz, A.; Rice, William J.; Diaz-Avalos, Ruben; Hu Guobin; Stokes, David L.; Gottlieb, Paul

    2011-01-01

    Cryo-electron tomography and subtomogram averaging are utilized to determine that the bacteriophage φ12, a member of the Cystoviridae family, contains surface complexes that are toroidal in shape, are composed of six globular domains with six-fold symmetry, and have a discrete density connecting them to the virus membrane-envelope surface. The lack of this kind of spike in a reassortant of φ12 demonstrates that the gene for the hexameric spike is located in φ12's medium length genome segment, likely to the P3 open reading frames which are the proteins involved in viral-host cell attachment. Based on this and on protein mass estimates derived from the obtained averaged structure, it is suggested that each of the globular domains is most likely composed of a total of four copies of P3a and/or P3c proteins. Our findings may have implications in the study of the evolution of the cystovirus species in regard to their host specificity. - Research Highlights: → Subtomogram averaging reveals enhanced detail of a φ12 cystovirus surface protein complex. → The surface protein complex has a toroidal shape and six-fold symmetry. → It is encoded by the medium-size genome segment. → The proteins of the surface complex most likely are one copy of P3a and three copies of P3c.

  1. Geochemical modelling: what phenomena are missing

    International Nuclear Information System (INIS)

    Jacquier, P.

    1989-12-01

    In the framework of safety assessment of radioactive waste disposal, retention phenomena are usually taken into account by the Kd concept. It is well recognized that this concept is not enough for safety assessment models, because of the several and strong assumptions which are involved in this kind of representation. One way to have a better representation of the retention phenomena, is to substitute for this Kd concept an explicit description of geochemical phenomena and then couple transport codes with geochemical codes in a fully or a two-step procedure. We use currently such codes, but the scope of this paper is to display the limits today of the geochemical modelling in connection with sites analysis for deep disposal. In this paper, we intend to give an overview of phenomena which are missing in the geochemical models, or which are not completely introduced in the models. We can distinguish, on one hand phenomena for which modelling concepts exist such as adsorption/desorption and, on the other hand, phenomena for which modelling concepts do not exist for the moment such as colloids, and complexation by polyelectrolyte solutions (organics). Moreover we have to take care of very low concentrations of radionuclides, which can be expected from the leaching processes in the repository. Under those conditions, some reactions may not occur. After a critical review of the involved phenomena, we intend to stress the main directions of the wishful evolution of the geochemical modelling. This evolution should improve substantially the quality of the above-mentioned site assessments

  2. Colour interceptions, thermal stability and surface morphology of polyester metal complexes

    International Nuclear Information System (INIS)

    Zohdy, M.H.

    2005-01-01

    Chelating copolymers via grafting of acrylic acid (AAc) and acrylamide (AAm/AAc) comonomer mixture onto polyester micro fiber fabrics (PETMF) using gamma-radiation technique were prepared. The prepared graft chains (PETMF-g-AAc) and (PETMF-g-PAAc/PAAm) acted as chelating sites for some selected transition metal ions. The prepared graft copolymers and their metal complexes were characterized using thermogravimetric analysis (TGA), colour parameters and surface morphology measurements. The colour interception and strength measurements showed that the metal complexation is homogeneously distributed. The results showed that the thermal stability of PETMF was improved after graft copolymerization and metal complexes. Moreover, the degree of grafting enhanced the thermal stability values of the grafted and complexed copolymers up to 25% of magnitude, on the other hand the activation energy of the grafted-copolymer with acrylic acid increased up to 80%. The SEM observation gives further supports to the homogenous distribution of grafting and metal complexation

  3. The Lavoisier mission : A system of descent probe and balloon flotilla for geochemical investigation of the deep atmosphere and surface of Venus

    Science.gov (United States)

    Chassefière, E.; Berthelier, J. J.; Bertaux, J.-L.; Quèmerais, E.; Pommereau, J.-P.; Rannou, P.; Raulin, F.; Coll, P.; Coscia, D.; Jambon, A.; Sarda, P.; Sabroux, J. C.; Vitter, G.; Le Pichon, A.; Landeau, B.; Lognonné, P.; Cohen, Y.; Vergniole, S.; Hulot, G.; Mandéa, M.; Pineau, J.-F.; Bézard, B.; Keller, H. U.; Titov, D.; Breuer, D.; Szego, K.; Ferencz, Cs.; Roos-Serote, M.; Korablev, O.; Linkin, V.; Rodrigo, R.; Taylor, F. W.; Harri, A.-M.

    Lavoisier mission is a joint effort of eight European countries and a technological challenge aimed at investigating the lower atmosphere and the surface of Venus. The mission consists of a descent probe and three balloons to be deployed below the cloud deck. Its main scientific objectives may be summarized as following : (i) composition of the deep atmosphere : noble gas (elemental/isotopic), molecular species (elemental/ isotopic), oxygen fugacity; vertical/horizontal/temporal variability; (ii) infrared spectroscopy and radiometry (molecular composition, radiative transfer); (iii) dynamics of the atmosphere : p, T, acceleration measurements, balloon localization through VLBI, meteorological events signed by acoustic waves, atmospheric mixing as imprinted on radioactive tracers; (iv) surface morphology and mineralogy through near infrared imaging on dayside, surface temperature through NIR imaging on nightside. Additional tentative objectives are search for (a) atmospheric electrical activity (optically, radioelectrically, acoustically), (b) crustal outgassing and/or volcanic activity : acoustic activity, horizontal/vertical distribution of radioactive tracers, (c) seismic activity : acoustic waves transmitted from crust to atmosphere, and (d) remanent and/or intrinsic magnetic field. Lavoisier was proposed to ESA in response to the F2/F3 mission Announcement of Opportunity at the beginning of 2000, but it was not selected for the assessment study. A wide international partnership was created for this occasion, including Finland (FMI), France (IPSL, MAGIE, Université Orsay, IPSN, INPG, CEA, IPGP, Obs. Paris-Meudon), Germany (MPAe, Univ. Muenster), Hungary (KFKI, Univ. Eotvos), Portugal (OAL), Russia (IKI), Spain (IAA), United Kingdom (Univ. Oxford).

  4. Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

    Science.gov (United States)

    Sharif, M.S.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Hays, P.D.; Kresse, T.M.; Fazio, J.A.

    2011-01-01

    The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6. m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6. m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory. ?? 2011 Elsevier Ltd.

  5. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

    International Nuclear Information System (INIS)

    Bonten, Luc T.C.; Groenenberg, Jan E.; Meesenburg, Henning; Vries, Wim de

    2011-01-01

    Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: → Surface complexation models can be well applied in field studies. → Soil chemistry under a forest site is adequately modelled using generic parameters. → The model is easily extended with extra elements within the existing framework. → Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

  6. Surface Wind Regionalization over Complex Terrain: Evaluation and Analysis of a High-Resolution WRF Simulation

    NARCIS (Netherlands)

    Jiménez, P.A.; González-Rouco, J.F.; García-Bustamante, E.; Navarro, J.; Montávez, J.P.; Vilà-Guerau de Arellano, J.; Dudhia, J.; Muñoz-Roldan, A.

    2010-01-01

    This study analyzes the daily-mean surface wind variability over an area characterized by complex topography through comparing observations and a 2-km-spatial-resolution simulation performed with the Weather Research and Forecasting (WRF) model for the period 1992–2005. The evaluation focuses on the

  7. Two new organotin(IV) phosphoryl complexes: crystal structure and Hirshfeld surface analysis.

    Czech Academy of Sciences Publication Activity Database

    Pourayoubi, M.; Saneei, A.; Dušek, Michal; Rostami, S.A.; Crochet, A.; Kučeráková, Monika

    2015-01-01

    Roč. 12, č. 12 (2015), s. 2093-2103 ISSN 1735-2428 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Hirshfeld surfaces * tin * organotin(IV)-phosphoryl complex * crystal structure Subject RIV: BM - Solid Matter Physics ; Magnetism

  8. Ab initio potential-energy surface and rovibrational states of the HCN-HCl complex

    NARCIS (Netherlands)

    Avoird, A. van der; Pedersen, T.B.; Dhont, G.S.F.; Fernandez, B.; Koch, H.

    2006-01-01

    A four-dimensional intermolecular potential-energy surface has been calculated for the HCN-HCl complex, with the use of the coupled cluster method with single and double excitations and noniterative inclusion of triples. Data for more than 13 000 geometries were represented by an angular expansion

  9. Hydrogeologic and geochemical characterization and evaluation of two arroyos for managed aquifer recharge by surface infiltration in the Pojoaque River Basin, Santa Fe County, New Mexico, 2014–15

    Science.gov (United States)

    Robertson, Andrew J.; Cordova, Jeffrey; Teeple, Andrew; Payne, Jason; Carruth, Rob

    2017-02-22

    In order to provide long-term storage of diverted surface water from the Rio Grande as part of the Aamodt water rights settlement, managed aquifer recharge by surface infiltration in Pojoaque River Basin arroyos was proposed as an option. The initial hydrogeologic and geochemical characterization of two arroyos located within the Pojoaque River Basin was performed in 2014 and 2015 in cooperation with the Bureau of Reclamation to evaluate the potential suitability of these two arroyos as sites for managed aquifer recharge through surface infiltration.The selected reaches were high-gradient (average 3.0–3.5 percent) braided channels filled with unconsolidated sand and gravel-sized deposits that were generally 30–50 feet thick. Saturation was not observed in the unconsolidated channel sands in four subsurface borings but was found at 7–60 feet below the contact between the unconsolidated channel sands and the bedrock. The poorly to well-cemented alluvial deposits that make up the bedrock underlying the unconsolidated channel material is the Tesuque Formation. The individual beds of the Tesuque Formation are reported to be highly heterogeneous and anisotropic, and the bedrock at the site was observed to have variable moisture and large changes in lithology. Surface electrical-resistivity geophysical survey methods showed a sharp contrast between the electrically resistive unconsolidated channel sands and the highly conductive bedrock; however, because of the high conductivity, the resistivity methods were not able to image the water table or preferential flow paths (if they existed) in the bedrock.Infiltration rates measured by double-ring and bulk infiltration tests on a variety of channel morphologies in the study reaches were extremely large (9.7–94.5 feet per day), indicating that the channels could potentially accommodate as much as 6.6 cubic feet per second of applied water without generating surface runoff out of the reach; however, the small volume

  10. Surface complexation of neptunium (V) onto whole cells and cell componets of Shewanella alga

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Donald Timothy [Los Alamos National Laboratory; Deo, Randhir P [ASU; Rittmann, Bruce E [ASU; Songkasiri, Warinthorn [UNAFFILIATED

    2008-01-01

    We systematically quantified surface complexation of neptunium(V) onto whole cells of Shewanella alga strain BrY and onto cell wall and extracellular polymeric substances (EPS) of S. alga. We first performed acid and base titrations and used the mathematical model FITEQL with constant-capacitance surface-complexation to determine the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl site associated with amino acids (pK{sub a} {approx} 2.4), a carboxyl group not associated with amino acids (pK{sub a} {approx} 5), a phosphoryl site (pK{sub a} {approx} 7.2), and an amine site (pK{sub a} > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components at different pHs. Results show that solution pH influenced the speciation of Np(V) and each of the surface functional groups. We used the speciation sub-model of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, NpO{sub 2}{sup +} was the dominant form of Np(V), and its log K values for the low-pK{sub a} carboxyl, other carboxyl, and phosphoryl groups were 1.75, 1.75, and 2.5 to 3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH3+, which complexed with NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-}. The log K for NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-} complexed onto the amine groups was 3.1 to 3.6. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results point towards the important role of surface complexation in defining key actinide-microbiological interactions in the subsurface.

  11. Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

    Science.gov (United States)

    Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.

    2018-01-01

    Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

  12. Geochemical and isotopic evidences from groundwater and surface water for understanding of natural contamination in chronic kidney disease of unknown etiology (CKDu) endemic zones in Sri Lanka.

    Science.gov (United States)

    Edirisinghe, E A N V; Manthrithilake, H; Pitawala, H M T G A; Dharmagunawardhane, H A; Wijayawardane, R L

    2017-09-26

    Chronic kidney disease of unknown etiology (CKDu) is the main health issue in the dry zone of Sri Lanka. Despite many studies carried out, causative factors have not been identified yet clearly. According to the multidisciplinary researches carried out so far, potable water is considered as the main causative factor for CKDu. Hence, the present study was carried out with combined isotopic and chemical methods to understand possible relationships between groundwater; the main drinking water source, and CKDu in four endemic areas in the dry zone. Different water sources were evaluated isotopically ( 2 H, 3 H and 18 O) and chemically from 2013 to 2015. Results revealed that prevalence of CKDu is significantly low with the groundwater replenished by surface water inputs. It is significantly high with the groundwater stagnated as well as groundwater recharged from regional flow paths. Thus, the origin, recharge mechanism and flow pattern of groundwater, as well as geological conditions which would be responsible for natural contamination of groundwater appear as the main causative factors for CKDu. Therefore, detailed investigations should be made in order to identify the element(s) in groundwater contributing to CKDu. The study recommends providing drinking water to the affected zones using water sources associated with surface waters.

  13. Infrared spectroscopy of the Ar-C2HD complex: Potential energy surfaces

    International Nuclear Information System (INIS)

    Bemish, R.J.; Miller, R.E.

    1996-01-01

    The argon-acetylene complex has been studied by a number of experimental and theoretical groups, with the aim in mind of determining an accurate potential energy surface for this system. Both microwave and infrared spectroscopy have provided detailed rotational and vibrational constants for this system. In addition, scattering experiments have been reported and ab initio calculation performed. Even with all of this, there are still some fundamental questions that remain unanswered with regards to the shape of the potential surface. The authors will review some of this work to outline the current situation. In the present study, the authors have obtained high resolution infrared spectra of the Ar-C 2 HD complex with the aim of providing additional molecular constants that could be used to help constrain the potential. Collocation calculations are reported, using a number of potential surfaces, for this and the normal isotopomer. This additional data helps to answer some of these open questions

  14. Quantitative evaluation and modeling of two-dimensional neovascular network complexity: the surface fractal dimension

    International Nuclear Information System (INIS)

    Grizzi, Fabio; Russo, Carlo; Colombo, Piergiuseppe; Franceschini, Barbara; Frezza, Eldo E; Cobos, Everardo; Chiriva-Internati, Maurizio

    2005-01-01

    Modeling the complex development and growth of tumor angiogenesis using mathematics and biological data is a burgeoning area of cancer research. Architectural complexity is the main feature of every anatomical system, including organs, tissues, cells and sub-cellular entities. The vascular system is a complex network whose geometrical characteristics cannot be properly defined using the principles of Euclidean geometry, which is only capable of interpreting regular and smooth objects that are almost impossible to find in Nature. However, fractal geometry is a more powerful means of quantifying the spatial complexity of real objects. This paper introduces the surface fractal dimension (D s ) as a numerical index of the two-dimensional (2-D) geometrical complexity of tumor vascular networks, and their behavior during computer-simulated changes in vessel density and distribution. We show that D s significantly depends on the number of vessels and their pattern of distribution. This demonstrates that the quantitative evaluation of the 2-D geometrical complexity of tumor vascular systems can be useful not only to measure its complex architecture, but also to model its development and growth. Studying the fractal properties of neovascularity induces reflections upon the real significance of the complex form of branched anatomical structures, in an attempt to define more appropriate methods of describing them quantitatively. This knowledge can be used to predict the aggressiveness of malignant tumors and design compounds that can halt the process of angiogenesis and influence tumor growth

  15. Surface-illuminant ambiguity and color constancy: effects of scene complexity and depth cues.

    Science.gov (United States)

    Kraft, James M; Maloney, Shannon I; Brainard, David H

    2002-01-01

    Two experiments were conducted to study how scene complexity and cues to depth affect human color constancy. Specifically, two levels of scene complexity were compared. The low-complexity scene contained two walls with the same surface reflectance and a test patch which provided no information about the illuminant. In addition to the surfaces visible in the low-complexity scene, the high-complexity scene contained two rectangular solid objects and 24 paper samples with diverse surface reflectances. Observers viewed illuminated objects in an experimental chamber and adjusted the test patch until it appeared achromatic. Achromatic settings made tinder two different illuminants were used to compute an index that quantified the degree of constancy. Two experiments were conducted: one in which observers viewed the stimuli directly, and one in which they viewed the scenes through an optical system that reduced cues to depth. In each experiment, constancy was assessed for two conditions. In the valid-cue condition, many cues provided valid information about the illuminant change. In the invalid-cue condition, some image cues provided invalid information. Four broad conclusions are drawn from the data: (a) constancy is generally better in the valid-cue condition than in the invalid-cue condition: (b) for the stimulus configuration used, increasing image complexity has little effect in the valid-cue condition but leads to increased constancy in the invalid-cue condition; (c) for the stimulus configuration used, reducing cues to depth has little effect for either constancy condition: and (d) there is moderate individual variation in the degree of constancy exhibited, particularly in the degree to which the complexity manipulation affects performance.

  16. A hybrid 3D SEM reconstruction method optimized for complex geologic material surfaces.

    Science.gov (United States)

    Yan, Shang; Adegbule, Aderonke; Kibbey, Tohren C G

    2017-08-01

    Reconstruction methods are widely used to extract three-dimensional information from scanning electron microscope (SEM) images. This paper presents a new hybrid reconstruction method that combines stereoscopic reconstruction with shape-from-shading calculations to generate highly-detailed elevation maps from SEM image pairs. The method makes use of an imaged glass sphere to determine the quantitative relationship between observed intensity and angles between the beam and surface normal, and the detector and surface normal. Two specific equations are derived to make use of image intensity information in creating the final elevation map. The equations are used together, one making use of intensities in the two images, the other making use of intensities within a single image. The method is specifically designed for SEM images captured with a single secondary electron detector, and is optimized to capture maximum detail from complex natural surfaces. The method is illustrated with a complex structured abrasive material, and a rough natural sand grain. Results show that the method is capable of capturing details such as angular surface features, varying surface roughness, and surface striations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Geochemical Survey of Pernambuco

    International Nuclear Information System (INIS)

    Horowitz, A.; Duarte, P.J.; Almeida, M.G. de; Medeiros, M.O.

    1988-01-01

    The area studied i this work is located in a triangle formed by the Sibiro and Boca da Mata Sugar-Mills and Serinhaem country. In the Cabo Formation the search determinated conglomerates, arcos and clays. Although the highest geochemical activity have been done in the decomposed crystalin, and the values from Cabo Formation don't be encourager, this formation has lithology compatible with uranium mineralization. The Cabo Formation's sediments presents lithologic variations very expressives, with conglomerates, arcoses and clay silts, which determinate the choise of the area. This area presented favorable to uranium prospecting and to others elements interesting to ragional geochemistry. The atomic absorption analysis, fluorimetry and spectrometry were done for the following elements: Zn, V, Ti, Ni, Pb, Mn, Ga, Cu, Co, Bi, Ag, B, Mo, and U. (C.D.G.) [pt

  18. Use of polyamfolit complexes of ethyl-amino-crotonate/acrylic acid with surface-active materials for radionuclide extraction

    International Nuclear Information System (INIS)

    Kabdyrakova, A.M.; Artem'ev, O.I.; Protskij, A.V.; Bimendina, L.A.; Yashkarova, M.G.; Orazzhanova, L.K.

    2005-01-01

    Pentifylline of betaine structure was synthesised on the basis of 3-aminocrotonate and acrylic acid. Polyamfolit composition and its complexes with anionic surface-active material (lauryl sulfate of sodium) were determined. It is revealed that complex formation occurs with [polyamfolit]:[surface active material]=1:1 ratio and is accompanied by significant reduce of system characteristics viscosity. The paper presents results of [polyamfolit]:[surface active material] complex apply experimental investigation for radionuclide directed migration in soil. (author)

  19. Geochemical tracing of As pollution in the Orbiel Valley (southern France): 87Sr/86Sr as a tracer of the anthropogenic arsenic in surface and groundwater.

    Science.gov (United States)

    Khaska, Mahmoud; Le Gal La Salle, Corinnne; Lancelot, Joël; Verdoux, Patrick; Boutin, René

    2014-05-01

    The environmental impacts of arsenic mining activities and their effects on ecosystem and human health are observed in many stream waters and groundwater. The aim of this study is to identify the origin of As content in a mining environment using Sr isotopes. At the Salsigne gold mine, before the closure in 2004, high arsenic content has been observed in surface water and groundwater in the Orbiel valley. At the site, immobilization of As, in As rich leachate, is carried out by adding CaO. High contrast in 87Sr/86Sr between Arsenic rich minerals associated with Variscan metamorphic rocks (0.714888-0.718835), together with rich As waste water (0.713463-715477), and the CaO (0.707593) allows as to trace the origin of anthropogenic As. In 2012, Orbiel stream waters were sampled monthly upstream and downstream from the ancient ore processing site and once after an important rainy event (117mm). The upstream valley samples showed low and relatively constant As content with natural regional background of 3.6 and 5.6 μg/L. The rainy event induced only a slight increase in the As content up to 6.3 μg/L. High 87Sr/86Sr ratios suggested an influence of radiogenic Sr issued from the Variscan metamorphic basement. Downstream from the area, the As content was at least10 time as high. In the wet season, stream water As content clearly increased to 13.9-24 μg/L, reaching 120.5 μg/L during the rainy event. Associated 87Sr/86Sr ratio showed to be less radiogenic (0.712276-0.714002). The anti correlation observed between As and 87Sr/86Sr suggest that As issued from a natural origin is characterised by a high 87Sr/86Sr compared to As derived from the CaO treatement used on site and characterized by a low 87Sr/86Sr ratio. During the dry season, increase in As content was observed reaching 110 μg/L. These highlights the contribution of alluvial groundwater to base flow, probably associated with As reach leachate from the site. Contribution from the alluvial aquifer is confirmed by

  20. Surface glycosylation of polysulfone membrane towards a novel complexing membrane for boron removal.

    Science.gov (United States)

    Meng, Jianqiang; Yuan, Jing; Kang, Yinlin; Zhang, Yufeng; Du, Qiyun

    2012-02-15

    In this study, a novel complexing membrane was synthesized for boron removal from aqueous solution. A glycopolymer, poly(2-gluconamidoethyl methacrylate) (PGAMA), was grafted onto the chloromethylated polysulfone (CMPSF) microporous membrane via surface-initiated ATRP (SIATRP). The glycosylated PSF (GlyPSF) membrane was characterized by attenuated total refection-Flourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM). It was demonstrated that PGAMA was successfully anchored onto the membrane surface and the grafting yield can be tuned in a wide range up to 5.9 mg/cm(2) by varying the polymerization time. The complexing membrane can adsorb boron rapidly with the equilibrium reached within 2h and has a remarkable high boron adsorption capacity higher than 2.0 mmol/g at optimized conditions. Freundlich, Langmuir, and Dubinin-Radushkevich adsorption isotherms were applied, and the data were best described by Langmuir model. Kinetic data were analyzed, and the data fitted very well to the pseudo-second-order rate expression. The optimal pH for boron uptake is in a wide range of 6-9, and the optimal initial boron concentration is over 300 mg/L. Studies of ionic strength effects indicated the formation of inner-sphere surface complexes. The complexed boron can be leached quantitatively under acid condition. Copyright © 2011 Elsevier Inc. All rights reserved.

  1. Design Process Control for Improved Surface Finish of Metal Additive Manufactured Parts of Complex Build Geometry

    Directory of Open Access Journals (Sweden)

    Mikdam Jamal

    2017-12-01

    Full Text Available Metal additive manufacturing (AM is increasingly used to create complex 3D components at near net shape. However, the surface finish (SF of the metal AM part is uneven, with surface roughness being variable over the facets of the design. Standard post-processing methods such as grinding and linishing often meet with major challenges in finishing parts of complex shape. This paper reports on research that demonstrated that mass finishing (MF processes are able to deliver high-quality surface finishes (Ra and Sa on AM-generated parts of a relatively complex geometry (both internal features and external facets under select conditions. Four processes were studied in this work: stream finishing, high-energy (HE centrifuge, drag finishing and disc finishing. Optimisation of the drag finishing process was then studied using a structured design of experiments (DOE. The effects of a range of finishing parameters were evaluated and optimal parameters and conditions were determined. The study established that the proposed method can be successfully applied in drag finishing to optimise the surface roughness in an industrial application and that it is an economical way of obtaining the maximum amount of information in a short period of time with a small number of tests. The study has also provided an important step in helping understand the requirements of MF to deliver AM-generated parts to a target quality finish and cycle time.

  2. The PSA-2 glycoprotein complex of Leishmania major is a glycosylphosphatidylinositol-linked promastigote surface antigen.

    Science.gov (United States)

    Murray, P J; Spithill, T W; Handman, E

    1989-12-15

    Polyclonal rabbit antiserum to the Triton X-114 phase material of Leishmania major, which comprises the surface and internal integral membrane proteins of the parasite, was used to screen a lambda gt11 genomic expression library. A recombinant clone producing a Mr 123,000 beta-galactosidase fusion protein was isolated. Antibodies affinity-purified on this fusion protein recognized a complex of three surface-oriented proteins of promastigotes of L. major of Mr 94,000, 90,000, and 80,000 that we have termed the promastigote surface Ag 2 (PSA-2) complex. The DNA sequence of the insert in this clone predicted the 3' end of an open reading frame encoding a hydrophobic C-terminus. The inferred C-terminal sequence was suggestive of a glycosylphosphatidyl-inositol membrane anchoring mechanism. Phosphatidylinositol-specific phospholipase C treatment of the native PSA-2 proteins caused a shift in their electrophoretic mobility with an apparent reduction in the molecular weight of the PSA-2 complex. After phospholipase C treatment these proteins also displayed the cryptic cross-reacting determinant recognized by antibodies to the Trypanosoma brucei variant surface Ag. Moreover, PSA-2, which previously partitioned in the detergent phase after Triton X-114 phase separation, became water-soluble after phospholipase C treatment. Immunoprecipitation of the PSA-2 proteins with sera directed to lectin-binding proteins indicated that these polypeptides may be differentially glycosylated. Finally, these PSA-2 proteins were recognized by sera from some patients with cutaneous leishmaniasis.

  3. Incorporating classic adsorption isotherms into modern surface complexation models: implications for sorption of radionuclides

    International Nuclear Information System (INIS)

    Kulik, D.A.

    2005-01-01

    Full text of publication follows: Computer-aided surface complexation models (SCM) tend to replace the classic adsorption isotherm (AI) analysis in describing mineral-water interface reactions such as radionuclide sorption onto (hydr) oxides and clays. Any site-binding SCM based on the mole balance of surface sites, in fact, reproduces the (competitive) Langmuir isotherm, optionally amended with electrostatic Coulomb's non-ideal term. In most SCM implementations, it is difficult to incorporate real-surface phenomena (site heterogeneity, lateral interactions, surface condensation) described in classic AI approaches other than Langmuir's. Thermodynamic relations between SCMs and AIs that remained obscure in the past have been recently clarified using new definitions of standard and reference states of surface species [1,2]. On this basis, a method for separating the Langmuir AI into ideal (linear) and non-ideal parts [2] was applied to multi-dentate Langmuir, Frumkin, and BET isotherms. The aim of this work was to obtain the surface activity coefficient terms that make the SCM site mole balance constraints obsolete and, in this way, extend thermodynamic SCMs to cover sorption phenomena described by the respective AIs. The multi-dentate Langmuir term accounts for the site saturation with n-dentate surface species, as illustrated on modeling bi-dentate U VI complexes on goethite or SiO 2 surfaces. The Frumkin term corrects for the lateral interactions of the mono-dentate surface species; in particular, it has the same form as the Coulombic term of the constant-capacitance EDL combined with the Langmuir term. The BET term (three parameters) accounts for more than a monolayer adsorption up to the surface condensation; it can potentially describe the surface precipitation of nickel and other cations on hydroxides and clay minerals. All three non-ideal terms (in GEM SCMs implementation [1,2]) by now are used for non-competing surface species only. Upon 'surface dilution

  4. Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation

    Energy Technology Data Exchange (ETDEWEB)

    Veselská, Veronika, E-mail: veselskav@fzp.czu.cz [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Fajgar, Radek [Department of Analytical and Material Chemistry, Institute of Chemical Process Fundamentals of the CAS, v.v.i., Rozvojová 135/1, CZ-16502, Prague (Czech Republic); Číhalová, Sylva [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Bolanz, Ralph M. [Institute of Geosciences, Friedrich-Schiller-University Jena, Carl-Zeiss-Promenade 10, DE-07745, Jena (Germany); Göttlicher, Jörg; Steininger, Ralph [ANKA Synchrotron Radiation Facility, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, DE-76344, Eggenstein-Leopoldshafen (Germany); Siddique, Jamal A.; Komárek, Michael [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic)

    2016-11-15

    Highlights: • Study of Cr(VI) adsorption on soil minerals over a large range of conditions. • Combined surface complexation modeling and spectroscopic techniques. • Diffuse-layer and triple-layer models used to obtain fits to experimental data. • Speciation of Cr(VI) and Cr(III) was assessed. - Abstract: This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3–10), ionic strengths (0.001–0.1 M KNO{sub 3}), sorbate concentrations (10{sup −4}, 10{sup −5}, and 10{sup −6} M Cr(VI)), and sorbate/sorbent ratios (50–500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes.

  5. Surface complexation modeling of Cu(II adsorption on mixtures of hydrous ferric oxide and kaolinite

    Directory of Open Access Journals (Sweden)

    Schaller Melinda S

    2008-09-01

    Full Text Available Abstract Background The application of surface complexation models (SCMs to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO, pure kaolinite (from two sources and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples.

  6. Geochemical and hydrodynamic phosphorus retention mechanisms in lowland catchments

    NARCIS (Netherlands)

    van der Grift, B.|info:eu-repo/dai/nl/373433484

    2017-01-01

    The release of phosphorus (P) to surface water from heavily fertilised agricultural fields is of major importance for surface water quality. The research reported in this thesis examined the role of geochemical and hydrodynamic processes controlling P speciation and transport in lowland catchments

  7. Surface complexation modeling calculation of Pb(II) adsorption onto the calcined diatomite

    Science.gov (United States)

    Ma, Shu-Cui; Zhang, Ji-Lin; Sun, De-Hui; Liu, Gui-Xia

    2015-12-01

    Removal of noxious heavy metal ions (e.g. Pb(II)) by surface adsorption of minerals (e.g. diatomite) is an important means in the environmental aqueous pollution control. Thus, it is very essential to understand the surface adsorptive behavior and mechanism. In this work, the Pb(II) apparent surface complexation reaction equilibrium constants on the calcined diatomite and distributions of Pb(II) surface species were investigated through modeling calculations of Pb(II) based on diffuse double layer model (DLM) with three amphoteric sites. Batch experiments were used to study the adsorption of Pb(II) onto the calcined diatomite as a function of pH (3.0-7.0) and different ionic strengths (0.05 and 0.1 mol L-1 NaCl) under ambient atmosphere. Adsorption of Pb(II) can be well described by Freundlich isotherm models. The apparent surface complexation equilibrium constants (log K) were obtained by fitting the batch experimental data using the PEST 13.0 together with PHREEQC 3.1.2 codes and there is good agreement between measured and predicted data. Distribution of Pb(II) surface species on the diatomite calculated by PHREEQC 3.1.2 program indicates that the impurity cations (e.g. Al3+, Fe3+, etc.) in the diatomite play a leading role in the Pb(II) adsorption and dominant formation of complexes and additional electrostatic interaction are the main adsorption mechanism of Pb(II) on the diatomite under weak acidic conditions.

  8. Riemann surfaces of complex classical trajectories and tunnelling splitting in one-dimensional systems

    Science.gov (United States)

    Harada, Hiromitsu; Mouchet, Amaury; Shudo, Akira

    2017-10-01

    The topology of complex classical paths is investigated to discuss quantum tunnelling splittings in one-dimensional systems. Here the Hamiltonian is assumed to be given as polynomial functions, so the fundamental group for the Riemann surface provides complete information on the topology of complex paths, which allows us to enumerate all the possible candidates contributing to the semiclassical sum formula for tunnelling splittings. This naturally leads to action relations among classically disjoined regions, revealing entirely non-local nature in the quantization condition. The importance of the proper treatment of Stokes phenomena is also discussed in Hamiltonians in the normal form.

  9. Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

    Directory of Open Access Journals (Sweden)

    Akinori Honda

    2016-10-01

    Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

  10. Evaluating polymer degradation with complex mixtures using a simplified surface area method.

    Science.gov (United States)

    Steele, Kandace M; Pelham, Todd; Phalen, Robert N

    2017-09-01

    Chemical-resistant gloves, designed to protect workers from chemical hazards, are made from a variety of polymer materials such as plastic, rubber, and synthetic rubber. One material does not provide protection against all chemicals, thus proper polymer selection is critical. Standardized testing, such as chemical degradation tests, are used to aid in the selection process. The current methods of degradation ratings based on changes in weight or tensile properties can be expensive and data often do not exist for complex chemical mixtures. There are hundreds of thousands of chemical products on the market that do not have chemical resistance data for polymer selection. The method described in this study provides an inexpensive alternative to gravimetric analysis. This method uses surface area change to evaluate degradation of a polymer material. Degradation tests for 5 polymer types against 50 complex mixtures were conducted using both gravimetric and surface area methods. The percent change data were compared between the two methods. The resulting regression line was y = 0.48x + 0.019, in units of percent, and the Pearson correlation coefficient was r = 0.9537 (p ≤ 0.05), which indicated a strong correlation between percent weight change and percent surface area change. On average, the percent change for surface area was about half that of the weight change. Using this information, an equivalent rating system was developed for determining the chemical degradation of polymer gloves using surface area.

  11. Application of the complex cepstrum to the location of acoustic sources near reflective surfaces

    Science.gov (United States)

    Fuller, C. R.; Tavakkoli, S.; Elliott, K. B.; Hurst, C. J.; Obrien, W. F.

    1987-01-01

    The complex cepstrum is used to correct bearing estimations of acoustic sources in the presence of a reflective surface. An automated liftering procedure is used which zeros out a block portion of the cepstrum including the echo information. The problem of the resulting distortion is alleviated by applying a coherence criterion to the recovered direct signals at each microphone. Thus to a large degree the interactive nature of cepstral processing is overcome for this application. For the test signals and geometries considered the cepstrum is shown to accurately correct for bearing errors in acoustic signals contaminated with reflections from nearby surfaces.

  12. Modeling and simulation for fewer-axis grinding of complex surface

    Science.gov (United States)

    Li, Zhengjian; Peng, Xiaoqiang; Song, Ci

    2017-10-01

    As the basis of fewer-axis grinding of complex surface, the grinding mathematical model is of great importance. A mathematical model of the grinding wheel was established, and then coordinate and normal vector of the wheel profile could be calculated. Through normal vector matching at the cutter contact point and the coordinate system transformation, the grinding mathematical model was established to work out the coordinate of the cutter location point. Based on the model, interference analysis was simulated to find out the right position and posture of workpiece for grinding. Then positioning errors of the workpiece including the translation positioning error and the rotation positioning error were analyzed respectively, and the main locating datum was obtained. According to the analysis results, the grinding tool path was planned and generated to grind the complex surface, and good form accuracy was obtained. The grinding mathematical model is simple, feasible and can be widely applied.

  13. Effect of glutamic acid on copper sorption onto kaolinite. Batch experiments and surface complexation modeling

    International Nuclear Information System (INIS)

    Karimzadeh, Lotfallah; Barthen, Robert; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna; Stockmann, Madlen

    2017-01-01

    In this work, we study the mobility behavior of Cu(II) under conditions related to an alternative, neutrophile biohydrometallurgical Cu(II) leaching approach. Sorption of copper onto kaolinite influenced by glutamic acid (Glu) was investigated in the presence of 0.01 M NaClO 4 by means of binary and ternary batch adsorption measurements over a pH range of 4 to 9 and surface complexation modeling.

  14. Integrating Sound Scattering Measurements in the Design of Complex Architectural Surfaces

    DEFF Research Database (Denmark)

    Peters, Brady

    2010-01-01

    Digital tools present the opportunity for incorporating performance analysis into the architectural design process. Acoustic performance is an important criterion for architectural design. There is much known about sound absorption but little about sound scattering, even though scattering...... is recognized to be one of the most important factors in predicting the computational prediction of acoustic performance. This paper proposes a workflow for the design of complex architectural surfaces and the prediction of their sound scattering properties. This workflow includes the development...

  15. Effect of glutamic acid on copper sorption onto kaolinite. Batch experiments and surface complexation modeling

    Energy Technology Data Exchange (ETDEWEB)

    Karimzadeh, Lotfallah; Barthen, Robert; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Reactive Transport; Stockmann, Madlen [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes

    2017-06-01

    In this work, we study the mobility behavior of Cu(II) under conditions related to an alternative, neutrophile biohydrometallurgical Cu(II) leaching approach. Sorption of copper onto kaolinite influenced by glutamic acid (Glu) was investigated in the presence of 0.01 M NaClO{sub 4} by means of binary and ternary batch adsorption measurements over a pH range of 4 to 9 and surface complexation modeling.

  16. A novel Pfs38 protein complex on the surface of Plasmodium falciparum blood-stage merozoites

    DEFF Research Database (Denmark)

    Paul, Gourab; Deshmukh, Arunaditya; Kaur, Inderjeet

    2017-01-01

    BACKGROUND: The Plasmodium genome encodes for a number of 6-Cys proteins that contain a module of six cysteine residues forming three intramolecular disulphide bonds. These proteins have been well characterized at transmission as well as hepatic stages of the parasite life cycle. In the present...... the development of a multi-sub-unit malaria vaccine based on some of these protein complexes on merozoite surface....

  17. Potential energy surface and rovibrational energy levels of the H2-CS van der Waals complex.

    Science.gov (United States)

    Denis-Alpizar, Otoniel; Stoecklin, Thierry; Halvick, Philippe; Dubernet, Marie-Lise; Marinakis, Sarantos

    2012-12-21

    Owing to its large dipole, astrophysicists use carbon monosulfide (CS) as a tracer of molecular gas in the interstellar medium, often in regions where H(2) is the most abundant collider. Predictions of the rovibrational energy levels of the weakly bound complex CS-H(2) (not yet observed) and also of rate coefficients for rotational transitions of CS in collision with H(2) should help to interpret the observed spectra. This paper deals with the first goal, i.e., the calculation of the rovibrational energy levels. A new four-dimensional intermolecular potential energy surface for the H(2)-CS complex is presented. Ab initio potential energy calculations were carried out at the coupled-cluster level with single and double excitations and a perturbative treatment of triple excitations, using a quadruple-zeta basis set and midbond functions. The potential energy surface was obtained by an analytic fit of the ab initio data. The equilibrium structure of the H(2)-CS complex is found to be linear with the carbon pointing toward H(2) at the intermolecular separation of 8.6 a(o). The corresponding well depth is -173 cm(-1). The potential was used to calculate the rovibrational energy levels of the para-H(2)-CS and ortho-H(2)-CS complexes. The present work provides the first theoretical predictions of these levels. The calculated dissociation energies are found to be 35.9 cm(-1) and 49.9 cm(-1), respectively, for the para and ortho complexes. The second virial coefficient for the H(2)-CS pair has also been calculated for a large range of temperature. These results could be used to assign future experimental spectra and to check the accuracy of the potential energy surface.

  18. Surface complexation modeling of uranyl adsorption on corrensite from the Waste Isolation Pilot Plant Site

    International Nuclear Information System (INIS)

    Park, Sang-Won; Leckie, J.O.; Siegel, M.D.

    1995-09-01

    Corrensite is the dominant clay mineral in the Culebra Dolomite at the Waste Isolation Pilot Plant. The surface characteristics of corrensite, a mixed chlorite/smectite clay mineral, have been studied. Zeta potential measurements and titration experiments suggest that the corrensite surface contains a mixture of permanent charge sites on the basal plane and SiOH and AlOH sites with a net pH-dependent charge at the edge of the clay platelets. Triple-layer model parameters were determined by the double extrapolation technique for use in chemical speciation calculations of adsorption reactions using the computer program HYDRAQL. Batch adsorption studies showed that corrensite is an effective adsorbent for uranyl. The pH-dependent adsorption behavior indicates that adsorption occurs at the edge sites. Adsorption studies were also conducted in the presence of competing cations and complexing ligands. The cations did not affect uranyl adsorption in the range studied. This observation lends support to the hypothesis that uranyl adsorption occurs at the edge sites. Uranyl adsorption was significantly hindered by carbonate. It is proposed that the formation of carbonate uranyl complexes inhibits uranyl adsorption and that only the carbonate-free species adsorb to the corrensite surface. The presence of the organic complexing agents EDTA and oxine also inhibits uranyl sorption

  19. New strategy for chemically attachment of Schiff base complexes on Multiwalled Carbon Nanotubes surfaces

    Directory of Open Access Journals (Sweden)

    Leila Moradi

    2014-06-01

    Full Text Available Chemically attachment of Schiff base complexes on multiwalled carbon nanotubes (MWCNTs surfaces through a convenient and simple method was studied. In the first step of this method, we present a new method for preparation of aminated MWCNTs in order to attachment of (new chlorinated salen Schiff bases. Amination of multiwalled carbon nanotubes performed under microwave (MW irradiation through a one pot two step reaction. The chemically attachment of salen Schiff bases on functionalized MWCNTs (salen@MWCNTs performed under a facile simple nucleophilic substitution reaction and complexation of attached salen Schiff bases (salen complex@MWCNTs in last step, have been occurred with reaction of transition metal salts and salen@MWCNTs. The obtained products were characterized in detail, using FTIR, XRD, UV-Vis absorption, SEM and EDX methods.

  20. Modelling the closure-related geochemical evolution of groundwater at a former uranium mine.

    Science.gov (United States)

    Bain, J G; Mayer, K U; Blowes, D W; Frind, E O; Molson, J W; Kahnt, R; Jenk, U

    2001-11-01

    A newly developed reactive transport model was used to evaluate the potential effects of mine closure on the geochemical evolution in the aquifer downgradient from a mine site. The simulations were conducted for the Königstein uranium mine located in Saxony, Germany. During decades of operation, uranium at the former mine site had been extracted by in situ acid leaching of the ore underground, while the mine was maintained in a dewatered condition. One option for decommissioning is to allow the groundwater level to rise to its natural level, flooding the mine workings. As a result, pore water containing high concentrations of dissolved metals, radionuclides, and sulfate may be released. Additional contamination may arise due to the dissolution of minerals contained in the aquifer downgradient of the mine. On the other hand, dissolved metals may be attenuated by reactions within the aquifer. The geochemical processes and interactions involved are highly non-linear and their impact on the quality of the groundwater and surface water downstream of the mine is not always intuitive. The multicomponent reactive transport model MIN3P, which can describe mineral dissolution-precipitation reactions, aqueous complexation, and oxidation-reduction reactions, is shown to be a powerful tool for investigating these processes. The predictive capabilities of the model are, however, limited by the availability of key geochemical parameters such as the presence and quantities of primary and secondary mineral phases. Under these conditions, the model can provide valuable insight by means of sensitivity analyses.

  1. Statistical interpretation of geochemical data

    International Nuclear Information System (INIS)

    Carambula, M.

    1990-01-01

    Statistical results have been obtained from a geochemical research from the following four aerial photographies Zapican, Carape, Las Canias, Alferez. They have been studied 3020 samples in total, to 22 chemical elements using plasma emission spectrometry methods.

  2. Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption

    Science.gov (United States)

    Padhi, S.; Tokunaga, T.

    2017-12-01

    Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

  3. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    Science.gov (United States)

    Bertolino, María Candelaria; Granados, Alejandro Manuel

    2016-10-01

    In this work we present a detailed study of classic reactions such as ;click reaction; and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV-vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  4. Surface and Subsurface Geochemical Monitoring of an EOR-CO2 Field: Buracica, Brazil Monitoring géochimique en surface et sub-surface d’un gisement en production par récupération assistée et injection de CO2 : le champ de Buracica, Brésil

    Directory of Open Access Journals (Sweden)

    Magnier C.

    2012-04-01

    Full Text Available This paper presents a surface and subsurface geochemical survey of the Buracica EOR-CO2 field onshore Brazil. We adopted a methodology coupling the stable isotopes of carbon with noble gases to investigate the adequacy of geochemical monitoring to track deep fluid leakage at the surface. Three campaigns of CO2 flux and concentration in soils were performed to understand the CO2 variability across the field. The distribution of the CO2 soil contents between 0.8 and 14% is in great part controlled by the properties of the soil, with a first-order topographic dependency. These results, together with a δ13CCO2 between –15 and –23‰, suggest that the bulk of the soil CO2 flux is biological. The gas injected and produced at numerous wells across the field showed a great spatial and somewhat temporal heterogeneity with respect to molecular, δ13CCO2 and noble gas compositions. This heterogeneity is a consequence of the EOR-induced sweeping of the petroleum fluids by the injected CO2, producing a heterogeneous mixing controlled by the production scheme and the distribution in reservoir permeability. In light of the δ13CCO2 found in the reservoir, the stable isotopic composition of carbon was insufficient to track CO2 leaks at the surface. We demonstrate how noble gases may be powerful leak discriminators, even for CO2 abundances in soils in the bottom range of the biological baseline (~1%. The results presented in this study show the potential of geochemical monitoring techniques, involving stable isotopes and noble gases at the reservoir and soil levels, for tracing CO2 in CCS projects. Le monitoring géochimique du gisement de Buracica, qui produit des hydrocarbures par récupération assistée et injection de dioxyde de carbone, est présenté dans cet article. Une méthodologie permettant de coupler l’utilisation des isotopes stables du carbone et des isotopes des gaz rares pour étudier la faisabilité de traçage d’une fuite de CO2 du r

  5. GEOCHEMICAL CONTROLS ON NUCLEAR MAGNETIC RESONANCE MEASUREMENTS

    International Nuclear Information System (INIS)

    Knight, Rosemary

    2008-01-01

    Proton nuclear magnetic resonance (NMR) is used in the Earth Sciences as a means of obtaining information about the molecular-scale environment of fluids in porous geological materials. Laboratory experiments were conducted to advance our fundamental understanding of the link between the NMR response and the geochemical properties of geological materials. In the first part of this research project, we studied the impact of both the surface-area-to-volume ratio (S/V) of the pore space and the surface relaxivity on the NMR response of fluids in sand-clay mixtures. This study highlighted the way in which these two parameters control our ability to use NMR measurements to detect and quantify fluid saturation in multiphase saturated systems. The second part of the project was designed to explore the way in which the mineralogic form of iron, as opposed to simply the concentration of iron, affects the surface relaxation rate and, more generally, the NMR response of porous materials. We found that the magnitude of the surface relaxation rate was different for the various iron-oxide minerals because of changes in both the surface-area-to-volume ratio of the pore space, and the surface relaxivity. Of particular significance from this study was the finding of an anomalously large surface relaxivity of magnetite compared to that of the other iron minerals. Differences in the NMR response of iron minerals were seen in column experiments during the reaction of ferrihydrite-coated quartz sand with aqueous Fe(II) solutions to form goethite, lepidocrocite and magnetite; indicating the potential use of NMR as a means of monitoring geochemical reactions. The final part of the research project investigated the impact of heterogeneity, at the pore-scale, on the NMR response. This work highlighted the way in which the geochemistry, by controlling the surface relaxivity, has a significant impact on the link between NMR data and the microgeometry of the pore space.

  6. Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

    Science.gov (United States)

    Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

    2014-03-01

    Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

  7. A dynamic duo: pairing click chemistry and postpolymerization modification to design complex surfaces.

    Science.gov (United States)

    Arnold, Rachelle M; Patton, Derek L; Popik, Vladimir V; Locklin, Jason

    2014-10-21

    Advances in key 21st century technologies such as biosensors, biomedical implants, and organic light-emitting diodes rely heavily on our ability to imagine, design, and understand spatially complex interfaces. Polymer-based thin films provide many advantages in this regard, but the direct synthesis of polymers with incompatible functional groups is extremely difficult. Using postpolymerization modification in conjunction with click chemistry can circumvent this limitation and result in multicomponent surfaces that are otherwise unattainable. The two methods used to form polymer thin films include physisorption and chemisorption. Physisorbed polymers suffer from instability because of the weak intermolecular forces between the film and the substrate, which can lead to dewetting, delamination, desorption, or displacement. Covalent immobilization of polymers to surfaces through either a "grafting to" or "grafting from" approach provides thin films that are more robust and less prone to degradation. The grafting to technique consists of adsorbing a polymer containing at least one reactive group along the backbone to form a covalent bond with a complementary surface functionality. Grafting from involves polymerization directly from the surface, in which the polymer chains deviate from their native conformation in solution and stretch away from the surface because of the high density of chains. Postpolymerization modification (PPM) is a strategy used by our groups over the past several years to immobilize two or more different chemical functionalities onto substrates that contain covalently grafted polymer films. PPM exploits monomers with reactive pendant groups that are stable under the polymerization conditions but are readily modified via covalent attachment of the desired functionality. "Click-like" reactions are the most common type of reactions used for PPM because they are orthogonal, high-yielding, and rapid. Some of these reactions include thiol-based additions

  8. Spectroscopic evidence for ternary surface complexes in the lead(II)-malonic acid-hematite system

    Science.gov (United States)

    Lenhart, J.J.; Bargar, J.R.; Davis, J.A.

    2001-01-01

    Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb LIII-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 A??, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. ?? 2001 Academic Press.

  9. Synthesis of INERIS works in 2006-2008 on the issue: gaseous phase geochemical monitoring at the surface and in the intermediate roofing of storage sites. CO2 capture and storage 2005 ANR program - Geo-carbon Monitoring Convention ANR-05-CO2-008-05. Investigation report

    International Nuclear Information System (INIS)

    Pokryszka, Zbigniew; Charmoille, Arnaud; Bentivegna, Gaetan

    2008-01-01

    Within the frame of the project of CO 2 capture and storage as a way to struggle against the greenhouse effect, this report proposes a synthesis of works performed by the INERIS in the field of gaseous phase geochemical monitoring, and more particularly on some parts of a larger programme, i.e. leakage detection in storage roofing and aquifers, leakage detection at the surface and at its vicinity (development of means of detection and direct measurement of CO 2 flows at the soil/atmosphere interface, assessment of leakages at the surface on the basis of point measurements), and testing of methods of direct measurement of CO 2 flows on sites

  10. Geochemical Trends are a Window on the Processes that Generate Volcano Fields

    Science.gov (United States)

    Smith, I. E.; McGee, L.; Brenna, M.

    2009-12-01

    A first order determinant of the nature of a magmatic system is magma flux rate. Small scale basaltic volcanic systems are characterized by low rates of magma production and dispersed plumbing leading to their expression at the surface as fields of small ‘monogenetic’ volcanoes. Because of the very small magma volumes and rapid ascent rates involved there is little interaction with conduit surroundings and this means that the chemical composition of magmas that reach the surface carry the signature of the deep seated process that formed them. Detailed sampling through the stratigraphic sequence in some monogenetic cones of the Auckland Volcanic Field in northern New Zealand and on Jeju Island in Korea has revealed systematic compositional variations that reflect fractionation process acting on magma bodies close to their source. We observe simple trends indicating unitary processes in some volcanoes while in others there are multiple trends suggesting two or more discrete magma batches, fractionation processes in a range of pressures and mixing of magmas. There is also evidence that some ‘monogenetic’ cones have produced eruptions of compositionally distinct magma in temporally discrete episodes separated by years or decades suggesting separate but linked melting events. In some volcanic sequences eruptions begin with relatively primitive compositions and in others evolved compositions precede the eruption of more primitive compositions. Clearly there exists a spectrum between a simple compositional trend in a monogenetic cone and the often chaotic geochemical patterns of large complex volcanoes. This reflects increasingly complex plumbing systems through which larger and larger magma volumes transit the lithospheric mantle and crust. Magmatic systems in which the plumbing system is re-used over significant time periods will show thermal evolution and ultimately geochemical evolution which is reflected in increasingly complicated petrographic and

  11. Modules based on the geochemical model PHREEQC for use in scripting and programming languages

    Science.gov (United States)

    Charlton, Scott R.; Parkhurst, David L.

    2011-01-01

    The geochemical model PHREEQC is capable of simulating a wide range of equilibrium reactions between water and minerals, ion exchangers, surface complexes, solid solutions, and gases. It also has a general kinetic formulation that allows modeling of nonequilibrium mineral dissolution and precipitation, microbial reactions, decomposition of organic compounds, and other kinetic reactions. To facilitate use of these reaction capabilities in scripting languages and other models, PHREEQC has been implemented in modules that easily interface with other software. A Microsoft COM (component object model) has been implemented, which allows PHREEQC to be used by any software that can interface with a COM server—for example, Excel®, Visual Basic®, Python, or MATLAB". PHREEQC has been converted to a C++ class, which can be included in programs written in C++. The class also has been compiled in libraries for Linux and Windows that allow PHREEQC to be called from C++, C, and Fortran. A limited set of methods implements the full reaction capabilities of PHREEQC for each module. Input methods use strings or files to define reaction calculations in exactly the same formats used by PHREEQC. Output methods provide a table of user-selected model results, such as concentrations, activities, saturation indices, and densities. The PHREEQC module can add geochemical reaction capabilities to surface-water, groundwater, and watershed transport models. It is possible to store and manipulate solution compositions and reaction information for many cells within the module. In addition, the object-oriented nature of the PHREEQC modules simplifies implementation of parallel processing for reactive-transport models. The PHREEQC COM module may be used in scripting languages to fit parameters; to plot PHREEQC results for field, laboratory, or theoretical investigations; or to develop new models that include simple or complex geochemical calculations.

  12. Development of thermodynamic databases for geochemical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Arthur, R.C. [Monitor Scientific, L.L.C., Denver, Colorado (United States); Sasamoto, Hiroshi; Shibata, Masahiro; Yui, Mikazu [Japan Nuclear Cycle Development Inst., Tokai, Ibaraki (Japan); Neyama, Atsushi [Computer Software Development Corp., Tokyo (Japan)

    1999-09-01

    Two thermodynamic databases for geochemical calculations supporting research and development on geological disposal concepts for high level radioactive waste are described in this report. One, SPRONS.JNC, is compatible with thermodynamic relations comprising the SUPCRT model and software, which permits calculation of the standard molal and partial molal thermodynamic properties of minerals, gases, aqueous species and reactions from 1 to 5000 bars and 0 to 1000degC. This database includes standard molal Gibbs free energies and enthalpies of formation, standard molal entropies and volumes, and Maier-Kelly heat capacity coefficients at the reference pressure (1 bar) and temperature (25degC) for 195 minerals and 16 gases. It also includes standard partial molal Gibbs free energies and enthalpies of formation, standard partial molal entropies, and Helgeson, Kirkham and Flowers (HKF) equation-of-state coefficients at the reference pressure and temperature for 1147 inorganic and organic aqueous ions and complexes. SPRONS.JNC extends similar databases described elsewhere by incorporating new and revised data published in the peer-reviewed literature since 1991. The other database, PHREEQE.JNC, is compatible with the PHREEQE series of geochemical modeling codes. It includes equilibrium constants at 25degC and l bar for mineral-dissolution, gas-solubility, aqueous-association and oxidation-reduction reactions. Reaction enthalpies, or coefficients in an empirical log K(T) function, are also included in this database, which permits calculation of equilibrium constants between 0 and 100degC at 1 bar. All equilibrium constants, reaction enthalpies, and log K(T) coefficients in PHREEQE.JNC are calculated using SUPCRT and SPRONS.JNC, which ensures that these two databases are mutually consistent. They are also internally consistent insofar as all the data are compatible with basic thermodynamic definitions and functional relations in the SUPCRT model, and because primary

  13. The surface chemistry of divalent metal carbonate minerals; a critical assessment of surface charge and potential data using the charge distribution multi-site ion complexation model

    NARCIS (Netherlands)

    Wolthers, M.; Charlet, L.; Van Cappellen, P.

    2008-01-01

    The Charge Distribution MUltiSite Ion Complexation or CD–MUSIC modeling approach is used to describe the chemical structure of carbonate mineralaqueous solution interfaces. The new model extends existing surface complexation models of carbonate minerals, by including atomic scale information on

  14. Stability of nano-metric colloidal dispersions of titanium: effect of surface complexation

    International Nuclear Information System (INIS)

    Peyre, Veronique

    1996-01-01

    This research thesis reports the study of the adsorption of small organic molecules at the surface of nano-particles of mineral oxides (zirconia), and of its effects on the stability of the colloidal dispersion. Adsorption has been quantified by adsorption isotherms and surface titrations. Processes and mechanisms are thus discussed with respect to pH. The influence of various protecting molecules (acetyl acetone, but also acetic acid, citric acid and diethanolamine) has been studied, and notably highlighted the role of the outer face of the complexing agent in the assessment of reactions between particles which govern the compression and re-dispersability properties of protected dispersions. This study is performed by osmotic pressure measurements and by X-ray diffusion at small angles, completed by statistical mechanics calculations [fr

  15. Ultrasonic detection technology based on joint robot on composite component with complex surface

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Juan; Xu, Chunguang; Zhang, Lan [School of Mechanical Engineering, Beijing Institute of Technology, Beijing (China)

    2014-02-18

    Some components have complex surface, such as the airplane wing and the shell of a pressure vessel etc. The quality of these components determines the reliability and safety of related equipment. Ultrasonic nondestructive detection is one of the main methods used for testing material defects at present. In order to improve the testing precision, the acoustic axis of the ultrasonic transducer should be consistent with the normal direction of the measured points. When we use joint robots, automatic ultrasonic scan along the component surface normal direction can be realized by motion trajectory planning and coordinate transformation etc. In order to express the defects accurately and truly, the robot position and the signal of the ultrasonic transducer should be synchronized.

  16. Formal Killing fields for minimal Lagrangian surfaces in complex space forms

    Science.gov (United States)

    Wang, Joe S.

    2017-04-01

    The differential system for minimal Lagrangian surfaces in a 2C-dimensional, non-flat, complex space form is an elliptic integrable system defined on the Grassmann bundle of oriented Lagrangian 2-planes. This is a 6-symmetric space associated with the Lie group SL(3 , C) , and the minimal Lagrangian surfaces arise as the primitive maps. Utilizing this property, we derive the inductive differential algebraic formulas for a pair of the formal loop algebra sl(3 , C) [ [ λ ] ] -valued canonical formal Killing fields. For applications, (a) we give a complete classification of the (pseudo) Jacobi fields for the minimal Lagrangian system, (b) we obtain an infinite sequence of conservation laws from the components of the canonical formal Killing fields.

  17. Surface Complexation Modeling in Variable Charge Soils: Prediction of Cadmium Adsorption

    Directory of Open Access Journals (Sweden)

    Giuliano Marchi

    2015-10-01

    Full Text Available ABSTRACT Intrinsic equilibrium constants for 22 representative Brazilian Oxisols were estimated from a cadmium adsorption experiment. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. Intrinsic equilibrium constants were optimized by FITEQL and by hand calculation using Visual MINTEQ in sweep mode, and Excel spreadsheets. Data from both models were incorporated into Visual MINTEQ. Constants estimated by FITEQL and incorporated in Visual MINTEQ software failed to predict observed data accurately. However, FITEQL raw output data rendered good results when predicted values were directly compared with observed values, instead of incorporating the estimated constants into Visual MINTEQ. Intrinsic equilibrium constants optimized by hand calculation and incorporated in Visual MINTEQ reliably predicted Cd adsorption reactions on soil surfaces under changing environmental conditions.

  18. Acid-base surface chemistry and sorption of some lanthanides on K +-saturated Marblehead illite: II. a multisite-surface complexation modeling

    Science.gov (United States)

    Kulik, Dmitrii A.; Aja, Stephen U.; Sinitsyn, Vasilii A.; Wood, Scott A.

    2000-01-01

    The surface reactivity and sorption of Nd and Eu onto K +-saturated Marblehead illite at 25°C, measured in aqueous 0.01, 0.1, and 1.0 M KCl solutions, were interpreted with a multi-site-surface complexation model. Model potentiometric titration and sorption curves (computed using the Gibbs free energy minimization code, Selektor-A) resolve into reactions on variable-charge amphoteric sites on edge surfaces and on permanent-charge siloxane surfaces (φ x). Standard partial molal Gibbs free energy of formation from elements (g 2980) for surface complexes were derived from oxide (SiO 2,am and γ-Al 2O 3) surface deprotonation KA10, KA20 and electrolyte adsorption constants KCl0, KNa0. Because surface complexation reactions on siloxane basal surfaces are negligible in 1 M KCl, models of surface charge and adsorption edges of Nd and Eu presumed that C 1 is equal to 1.6 Fm -2 for amphoteric site types, and a maximum site density of 1.2 ± 0.2 sites nm -2 for the outer-sphere species, (Al>OH 2+Cl -). To obtain values of g 2980 for exchangeable cations and charged X ˜REE complexes, ion exchange sites were assumed to be fully deprotonated in 1.0 M KCl solutions (pH > 2.7). Proton release and REE 3+ uptake on ion exchange sites were then simulated (pH 4.0) from initial values of 20 to 48%. The application of Gibbs free energy minimization to sorption processes is innovative in that simultaneous treatment of surface complexation reactions and minerals stability is feasible in any system without introducing mass-balance constraints particular to surface species.

  19. Geochemical computer codes. A review

    International Nuclear Information System (INIS)

    Andersson, K.

    1987-01-01

    In this report a review of available codes is performed and some code intercomparisons are also discussed. The number of codes treating natural waters (groundwater, lake water, sea water) is large. Most geochemical computer codes treat equilibrium conditions, although some codes with kinetic capability are available. A geochemical equilibrium model consists of a computer code, solving a set of equations by some numerical method and a data base, consisting of thermodynamic data required for the calculations. There are some codes which treat coupled geochemical and transport modeling. Some of these codes solve the equilibrium and transport equations simultaneously while other solve the equations separately from each other. The coupled codes require a large computer capacity and have thus as yet limited use. Three code intercomparisons have been found in literature. It may be concluded that there are many codes available for geochemical calculations but most of them require a user that us quite familiar with the code. The user also has to know the geochemical system in order to judge the reliability of the results. A high quality data base is necessary to obtain a reliable result. The best results may be expected for the major species of natural waters. For more complicated problems, including trace elements, precipitation/dissolution, adsorption, etc., the results seem to be less reliable. (With 44 refs.) (author)

  20. A Simple and Universal Aerosol Retrieval Algorithm for Landsat Series Images Over Complex Surfaces

    Science.gov (United States)

    Wei, Jing; Huang, Bo; Sun, Lin; Zhang, Zhaoyang; Wang, Lunche; Bilal, Muhammad

    2017-12-01

    Operational aerosol optical depth (AOD) products are available at coarse spatial resolutions from several to tens of kilometers. These resolutions limit the application of these products for monitoring atmospheric pollutants at the city level. Therefore, a simple, universal, and high-resolution (30 m) Landsat aerosol retrieval algorithm over complex urban surfaces is developed. The surface reflectance is estimated from a combination of top of atmosphere reflectance at short-wave infrared (2.22 μm) and Landsat 4-7 surface reflectance climate data records over densely vegetated areas and bright areas. The aerosol type is determined using the historical aerosol optical properties derived from the local urban Aerosol Robotic Network (AERONET) site (Beijing). AERONET ground-based sun photometer AOD measurements from five sites located in urban and rural areas are obtained to validate the AOD retrievals. Terra MODerate resolution Imaging Spectrometer Collection (C) 6 AOD products (MOD04) including the dark target (DT), the deep blue (DB), and the combined DT and DB (DT&DB) retrievals at 10 km spatial resolution are obtained for comparison purposes. Validation results show that the Landsat AOD retrievals at a 30 m resolution are well correlated with the AERONET AOD measurements (R2 = 0.932) and that approximately 77.46% of the retrievals fall within the expected error with a low mean absolute error of 0.090 and a root-mean-square error of 0.126. Comparison results show that Landsat AOD retrievals are overall better and less biased than MOD04 AOD products, indicating that the new algorithm is robust and performs well in AOD retrieval over complex surfaces. The new algorithm can provide continuous and detailed spatial distributions of AOD during both low and high aerosol loadings.

  1. Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

    Science.gov (United States)

    Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

    2017-12-01

    We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

  2. Effects of complex terrain on net surface longwave radiation in China

    Science.gov (United States)

    Zhu, Xiaochen; Qiu, Xinfa; Zeng, Yan; Ren, Wei; Tao, Bo; Gao, Jiaqi; Liu, Haobo; Tan, Yunjuan

    2017-09-01

    Net surface longwave radiation (NSLR) is one of key meteorological factors and is strongly influenced by cloud cover, surface temperature, humidity, and local micrometeorological conditions as well as terrain conditions. Realistically estimating NSLR is vitally important for understanding surface radiation balance and investigating micrometeorological factors of air pollution dispersion, especially in regions with complicated terrain. In this study, we proposed a distributed model for estimating NSLR by considering effects of complex local terrain conditions in China. Meteorological data (including mean temperature, relative humidity, and sunshine percentage) and observed NSLR data from 1993 to 2001 together with the digital elevation model data were used to parametrize the model and account for the effects of atmospheric factors and surface terrain factors according to the isotropic principle. The monthly NSLR during 1961-2000 was estimated at a spatial resolution of 1 km. Topographic analysis suggests that the distribution characteristics of NSLR with elevation or slope are consistent with those of field observations. In particular, the estimated NSLR is favorably comparable with site-level observations on the Tibetan Plateau (average relative error < 11%). Our results indicate that this model can describe microscale distribution features in mountainous areas in detail and that this improved approach can be used for NSLR spatial estimation in other regions with complicated terrain.

  3. Biodiversity of benthic microbial communities in bioturbated coastal sediments is controlled by geochemical microniches.

    Science.gov (United States)

    Bertics, Victoria J; Ziebis, Wiebke

    2009-11-01

    We used a combination of field and laboratory approaches to address how the bioturbation activity of two crustaceans, the ghost shrimp Neotrypaea californiensis and the fiddler crab Uca crenulata, affects the microbial diversity in the seabed of a coastal lagoon (Catalina Harbor, Santa Catalina Island, CA, USA). Detailed geochemical analyses, including oxygen microsensor measurements, were performed to characterize environmental parameters. We used a whole-assemblage fingerprinting approach (ARISA: amplified ribosomal intergenic spacer analysis) to compare bacterial diversity along geochemical gradients and in relation to subsurface microniches. The two crustaceans have different burrowing behaviors. The ghost shrimp maintains complex, deep-reaching burrows and permanently lives subterranean, supplying its burrow with oxygen-rich water. In contrast, the fiddler crab constructs simpler, J-shaped burrows, which it does not inhabit permanently and does not actively ventilate. Our goal was to address how varying environmental parameters affect benthic microbial communities. An important question in benthic microbial ecology has been whether burrows support similar or unique communities compared with the sediment surface. Our results showed that sediment surface microbial communities are distinct from subsurface assemblages and that different burrow types support diverse bacterial taxa. Statistical comparisons by canonical correspondence analysis indicated that the availability of oxidants (oxygen, nitrate, ferric iron) play a key role in determining the presence and abundance of different taxa. When geochemical parameters were alike, microbial communities associated with burrows showed significant similarity to sediment surface communities. Our study provides implications on the community structure of microbial communities in marine sediments and the factors controlling their distribution.

  4. Investigations of surface-tension effects due to small-scale complex boundaries

    Science.gov (United States)

    Feng, Jiansheng

    these two different types of surfaces differed by about 50° ˜ 60°, with the low-adhesion surfaces at about 120° ˜ 130° and the high-adhesion surfaces at about 70° ˜ 80°. Characterizations of both the microscopic structures and macroscopic wetting properties of these product surfaces allowed us to pinpoint the structural features responsible for specific wetting properties. It is found that the advancing contact angle was mainly determined by the primary structures while the receding contact angle is largely affected by the side-wall slope of the secondary features. This study established a platform for further exploration of the structure aspects of surface wettability. In the third and final project (Chapter 4), we demonstrated a new type of microfluidic channel that enable asymmetric wicking of wetting fluids based on structure-induced direction-dependent surface-tension effect. By decorating the side-walls of open microfluidic channels with tilted fins, we were able to experimentally demonstrate preferential wicking behaviors of various IPA-water mixtures with a range of contact angles in these channels. A simplified 2D model was established to explain the wicking asymmetry, and a complete 3D model was developed to provide more accurate quantitative predictions. The design principles developed in this study provide an additional scheme for controlling the spreading of fluids. The research presented in this dissertation spreads out across a wide range of physical phenomena (wicking, wetting, and capillarity), and involves a number of computational and experimental techniques, yet all of these projects are intrinsically united under a common theme: we want to better understand how simple fluids respond to small-scale complex surface structures as manifestations of surface-tension effects. We hope our findings can serve as building blocks for a larger scale endeavor of scientific research and engineering development. After all, the pursue of knowledge is most

  5. Basic principles of forward and inverse geochemical modelization

    International Nuclear Information System (INIS)

    Gimeno, M.J.; Pena, J.

    1994-01-01

    Geochemical modeling consists in the application of thermodynamic and physicochemical principles in the hydrogeochemical systems interpretation. It has been developed following two different approaches: a) inverse modeling (or mass balance calculations), which uses observed chemical and isotopic data from waters and rocks to identify geochemical reactions responsible of them, in a quantitative way; and b) forward modeling, which attempts to predict water compositions and mass transfer that can result from hypothesized reactions, from observed initial conditions on water-rock system compositions. Both of them have intrinsic uses and limitations which drive to their use in specific problems. For systems with adequate chemical, isotopic, and mineralogic data, the inverse modeling approach of speciation and mass-balance modeling provides the most direct means of determining quantitative geochemical reaction models. In contrast, for systems with missing or inadequate data, reaction-path modeling provides an a priori method of predicting geochemical reactions. In some cases it is useful to combine forward modeling with the results from inverse models. The mass-balance results determine the net mass transfer along the flow path, but these results are only partially constrained by thermodynamics. The forward modeling can be used both, to prove thermodynamic consistency for them, and to predict water quality at points where there are no enough data. Recent advances in geochemical modeling are focused on finding the most efficient numerical procedures for coupling geochemical reactions (both equilibrium and kinetic) with the hydrodynamic transport equations in compositionally-complex systems, on uncertainty analysis, and on model validation for actual geochemical systems

  6. Formation mechanism of a silane-PVA/PVAc complex film on a glass fiber surface.

    Science.gov (United States)

    Repovsky, Daniel; Jane, Eduard; Palszegi, Tibor; Slobodnik, Marek; Velic, Dusan

    2013-10-21

    Mechanical properties of glass fiber reinforced composite materials are affected by fiber sizing. A complex film formation, based on a silane film and PVA/PVAc (polyvinyl alcohol/polyvinyl acetate) microspheres on a glass fiber surface is determined at 1) the nanoscale by using atomic force microscopy (AFM), and 2) the macroscale by using the zeta potential. Silane groups strongly bind through the Si-O-Si bond to the glass surface, which provides the attachment mechanism as a coupling agent. The silane groups form islands, a homogeneous film, as well as empty sites. The average roughness of the silanized surface is 6.5 nm, whereas it is only 0.6 nm for the non-silanized surface. The silane film vertically penetrates in a honeycomb fashion from the glass surface through the deposited PVA/PVAc microspheres to form a hexagonal close pack structure. The silane film not only penetrates, but also deforms the PVA/PVAc microspheres from the spherical shape in a dispersion to a ellipsoidal shape on the surface with average dimensions of 300/600 nm. The surface area value Sa represents an area of PVA/PVAc microspheres that are not affected by the silane penetration. The areas are found to be 0.2, 0.08, and 0.03 μm(2) if the ellipsoid sizes are 320/570, 300/610, and 270/620 nm for silane concentrations of 0, 3.8, and 7.2 μg mL(-1), respectively. The silane film also moves PVA/PVAc microspheres in the process of complex film formation, from the low silane concentration areas to the complex film area providing enough silane groups to stabilize the structure. The values for the residual silane honeycomb structure heights (Ha ) are 6.5, 7, and 12 nm for silane concentrations of 3.8, 7.2, and 14.3 μg mL(-1), respectively. The pH-dependent zeta-potential results suggest a specific role of the silane groups with effects on the glass fiber surface and also on the PVA/PVAc microspheres. The non-silanized glass fiber surface and the silane film have similar zeta potentials ranging

  7. Transmission X-ray scattering as a probe for complex liquid-surface structures

    Energy Technology Data Exchange (ETDEWEB)

    Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; Kuzmenko, Ivan

    2016-01-28

    The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibility of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.

  8. On the relationship between enamel band complexity and occlusal surface area in Equids (Mammalia, Perissodactyla

    Directory of Open Access Journals (Sweden)

    Nicholas A. Famoso

    2016-07-01

    Full Text Available Enamel patterns on the occlusal surfaces of equid teeth are asserted to have tribal-level differences. The most notable example compares the Equini and Hipparionini, where Equini have higher crowned teeth with less enamel-band complexity and less total occlusal enamel than Hipparionini. Whereas previous work has successfully quantified differences in enamel band shape by dividing the length of enamel band by the square root of the occlusal surface area (Occlusal Enamel Index, OEI, it was clear that OEI only partially removes the effect of body size. Because enamel band length scales allometrically, body size still has an influence on OEI, with larger individuals having relatively longer enamel bands than smaller individuals. Fractal dimensionality (D can be scaled to any level, so we have used it to quantify occlusal enamel complexity in a way that allows us to get at an accurate representation of the relationship between complexity and body size. To test the hypothesis of tribal-level complexity differences between Equini and Hipparionini, we digitally traced a sample of 98 teeth, one tooth per individual; 31 Hipparionini and 67 Equini. We restricted our sampling to the P3-M2 to reduce the effect of tooth position. After calculating the D of these teeth with the fractal box method which uses the number of boxes of various sizes to calculate the D of a line, we performed a t-test on the individual values of D for each specimen, comparing the means between the two tribes, and a phylogenetically informed generalized least squares regression (PGLS for each tribe with occlusal surface area as the independent variable and D as the dependent variable. The slopes of both PGLS analyses were compared using a t-test to determine if the same linear relationship existed between the two tribes. The t-test between tribes was significant (p < 0.0001, suggesting different D populations for each lineage. The PGLS for Hipparionini was a positive but not

  9. Get a grip on chaos: Tailored measures for complex systems on surfaces

    Science.gov (United States)

    Firle, Sascha Oliver

    Complex systems are ubiquitous in physics, biology and mathematics. This thesis is concerned with describing and understanding complex systems. Some new concepts about how large systems can be viewed in a lower dimensional framework are proposed. The systems presented are examples from ecology and chemistry. In both cases we have a large amount of interacting units that can be understood by The predator-prey system investigated consists of ground beetles, Pterostichus cuprens L. (Coleoptera: Carabidae), that feeds on bird-cherry oat aphids. The beetles' movement can consistently be described by a combined model of surface diffusion and biased random walk. This allows conclusions about how fast and in which fashion the beetle covers its habitat. Movement is dependent on aphid densities and predation, in turn modifies aphid distributions locally. The presented generalized functional response theory describes predation rates in the presence of spatial heterogeneity. A single measure for fragmentation captures all essential features of the prey aggregation and allows the estimation of outbreak densities and distributions. The chemical example is the catalytic oxidation of CO on a Pt(110) single crystal surface. Unstable periodic orbits reconstructed from experimental data are used to reveal the topology of the attractor, underlying the time series dynamics. The found braid supports an orbit which implies that the time series is chaotic. The system is simulated numerically by a set of partial differential equations for surface coverage in one space dimension. The bifurcation diagram of the corresponding traveling wave ODE reveals the homoclinic and heteroclinic orbits that organize the phase space and mediate the transition to chaos. Studies in the PDE- framework relate this to the stability and to the interaction of pulse-like solutions.

  10. The interaction of streptococcal enolase with canine plasminogen: the role of surfaces in complex formation.

    Directory of Open Access Journals (Sweden)

    Vinod Balhara

    Full Text Available The enolase from Streptococcus pyogenes (Str enolase F137L/E363G is a homo-octamer shaped like a donut. Plasminogen (Pgn is a monomeric protein composed of seven discrete separated domains organized into a lock washer. The enolase is known to bind Pgn. In past work we searched for conditions in which the two proteins would bind to one another. The two native proteins in solution would not bind under any of the tried conditions. We found that if the structures were perturbed binding would occur. We stated that only the non-native Str enolase or Pgn would interact such that we could detect binding. We report here the results of a series of dual polarization interferometry (DPI experiments coupled with atomic force microscopy (AFM, isothermal titration calorimetry (ITC, dynamic light scattering (DLS, and fluorescence. We show that the critical condition for forming stable complexes of the two native proteins involves Str enolase binding to a surface. Surfaces that attract Str enolase are a sufficient condition for binding Pgn. Under certain conditions, Pgn adsorbed to a surface will bind Str enolase.

  11. Additive surface complexation modeling of uranium(VI) adsorption onto quartz-sand dominated sediments.

    Science.gov (United States)

    Dong, Wenming; Wan, Jiamin

    2014-06-17

    Many aquifers contaminated by U(VI)-containing acidic plumes are composed predominantly of quartz-sand sediments. The F-Area of the Savannah River Site (SRS) in South Carolina (USA) is an example. To predict U(VI) mobility and natural attenuation, we conducted U(VI) adsorption experiments using the F-Area plume sediments and reference quartz, goethite, and kaolinite. The sediments are composed of ∼96% quartz-sand and 3-4% fine fractions of kaolinite and goethite. We developed a new humic acid adsorption method for determining the relative surface area abundances of goethite and kaolinite in the fine fractions. This method is expected to be applicable to many other binary mineral pairs, and allows successful application of the component additivity (CA) approach based surface complexation modeling (SCM) at the SRS F-Area and other similar aquifers. Our experimental results indicate that quartz has stronger U(VI) adsorption ability per unit surface area than goethite and kaolinite at pH ≤ 4.0. Our modeling results indicate that the binary (goethite/kaolinite) CA-SCM under-predicts U(VI) adsorption to the quartz-sand dominated sediments at pH ≤ 4.0. The new ternary (quartz/goethite/kaolinite) CA-SCM provides excellent predictions. The contributions of quartz-sand, kaolinite, and goethite to U(VI) adsorption and the potential influences of dissolved Al, Si, and Fe are also discussed.

  12. NOAA and MMS Marine Minerals Geochemical Database

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — The Marine Minerals Geochemical Database was created by NGDC as a part of a project to construct a comprehensive computerized bibliography and geochemical database...

  13. Development of a Composite Non-Electrostatic Surface Complexation Model Describing Plutonium Sorption to Aluminosilicates

    Energy Technology Data Exchange (ETDEWEB)

    Powell, B A; Kersting, A; Zavarin, M; Zhao, P

    2008-10-28

    Due to their ubiquity in nature and chemical reactivity, aluminosilicate minerals play an important role in retarding actinide subsurface migration. However, very few studies have examined Pu interaction with clay minerals in sufficient detail to produce a credible mechanistic model of its behavior. In this work, Pu(IV) and Pu(V) interactions with silica, gibbsite (Aloxide), and Na-montmorillonite (smectite clay) were examined as a function of time and pH. Sorption of Pu(IV) and Pu(V) to gibbsite and silica increased with pH (4 to 10). The Pu(V) sorption edge shifted to lower pH values over time and approached that of Pu(IV). This behavior is apparently due to surface mediated reduction of Pu(V) to Pu(IV). Surface complexation constants describing Pu(IV)/Pu(V) sorption to aluminol and silanol groups were developed from the silica and gibbsite sorption experiments and applied to the montmorillonite dataset. The model provided an acceptable fit to the montmorillonite sorption data for Pu(V). In order to accurately predict Pu(IV) sorption to montmorillonite, the model required inclusion of ion exchange. The objective of this work is to measure the sorption of Pu(IV) and Pu(V) to silica, gibbsite, and smectite (montmorillonite). Aluminosilicate minerals are ubiquitous at the Nevada National Security Site and improving our understanding of Pu sorption to aluminosilicates (smectite clays in particular) is essential to the accurate prediction of Pu transport rates. These data will improve the mechanistic approach for modeling the hydrologic source term (HST) and provide sorption Kd parameters for use in CAU models. In both alluvium and tuff, aluminosilicates have been found to play a dominant role in the radionuclide retardation because their abundance is typically more than an order of magnitude greater than other potential sorbing minerals such as iron and manganese oxides (e.g. Vaniman et al., 1996). The sorption database used in recent HST models (Carle et al., 2006

  14. Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

    Science.gov (United States)

    Davis, J.A.; Meece, D.E.; Kohler, M.; Curtis, G.P.

    2004-01-01

    Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of

  15. Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.

    Science.gov (United States)

    Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

    2009-04-15

    A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength.

  16. Method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation in conjunction with mass spectrometric analysis

    Science.gov (United States)

    Laskin, Julia [Richland, WA; Futrell, Jean H [Richland, WA

    2008-04-29

    The invention relates to a method and apparatus for enhanced sequencing of complex molecules using surface-induced dissociation (SID) in conjunction with mass spectrometric analysis. Results demonstrate formation of a wide distribution of structure-specific fragments having wide sequence coverage useful for sequencing and identifying the complex molecules.

  17. Oak Ridge Geochemical Reconnaissance Program

    International Nuclear Information System (INIS)

    Arendt, J.W.

    1977-03-01

    The Oak Ridge reconnaissance program is responsible for the geochemical survey in a 12-state area covering Texas, Oklahoma, Kansas, Nebraska, South Dakota, North Dakota, Minnesota, Wisconsin, Michigan, Iowa, Indiana, and Illinois as part of the National Uranium Resource Evaluation Program. The program concept is outlined and the planning and organization of the program is discussed

  18. Ab initio treatment of the chemical reaction precursor complex Br(2P)-HCN. 1. Adiabatic and diabatic potential surfaces

    NARCIS (Netherlands)

    Fishchuk, A.V.; Merritt, J.M.; Avoird, A. van der

    2007-01-01

    The three adiabatic potential surfaces of the Br(P-2)-HCN complex that correlate to the P-2 ground state of the Br atom were calculated ab initio. With the aid of a geometry-dependent diabatic mixing angle, also calculated ab initio, these adiabatic potential surfaces were transformed into a set of

  19. Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

    Science.gov (United States)

    Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; Davis, J. A.

    2018-01-01

    The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonite edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites ('spillover' effect). A series of U(VI) - Na-montmorillonite batch adsorption experiments was conducted as a function of pH, with variable U(VI), Ca, and dissolved carbonate concentrations. Based on the experimental data, a new type of surface complexation model (SCM) was developed for montmorillonite, that specifically accounts for the spillover effect using the edge surface speciation model by Tournassat et al. (2016a). The SCM allows for a prediction of U(VI) adsorption under varying chemical conditions with a minimum number of fitting parameters, not only for our own experimental results, but also for a number of published data sets. The model agreed well with many of these datasets without introducing a second site type or including the formation of ternary U(VI)-carbonato surface complexes. The model predictions were greatly impacted by utilizing analytical measurements of dissolved inorganic carbon (DIC) concentrations in individual sample solutions rather than assuming solution equilibration with a specific partial pressure of CO2, even when the gas phase was

  20. Areal Measurements of Ozone, Water, and Heat Fluxes Over Land With Different Surface Complexity, Using Aircraft

    International Nuclear Information System (INIS)

    Hicks, Bruce B.

    2001-01-01

    Contemporary models addressing issues of air quality and/or atmospheric deposition continue to exploit air-surface exchange formulations originating from single-tower studies. In reality,these expressions describe situations that are rare in the real world - nearly flat and spatially homogeneous. There have been several theoretical suggestions about how to extend from single-point understanding to areal descriptions, but so far the capability to address the problem experimentally has been limited. In recent years, however, developments in sensing technology have permitted adaptation of eddy-correlation methods to low-flying aircraft in a far more cost-effective manner than previously. A series of field experiments has been conducted, ranging from flat farmland to rolling countryside, employing a recently modified research aircraft operated by the US NationalOceanic and Atmospheric Administration (NOAA). The results demonstrate the complexity of the spatial heterogeneity question,especially for pollutants (ozone in particular). In general, the uncertainty associated with the adoption of any single-point formulation when describing areal averages is likely to be in the range 10% to 40%. In the case of sensible and latent heat fluxes, the overall behavior is controlled by the amount of energy available. For pollutant deposition, there is no constraint equivalent to the net radiation limitation on convective heat exchange. Consequently, dry deposition rates and air-surface exchange of trace gases in general are especially vulnerable to errors in spatial extrapolation. The results indicate that the susceptibility of dry deposition formulations to terrain complexity depends on the deposition velocity itself. For readily transferred pollutants (such as HNO 3 ), a factor of two error could be involved

  1. Surface expression of protein A on magnetosomes and capture of pathogenic bacteria by magnetosome/ antibody complexes

    Directory of Open Access Journals (Sweden)

    Jun eXu

    2014-04-01

    Full Text Available Magnetosomes are membrane-enclosed magnetite nanocrystals synthesized by magnetotactic bacteria (MTB. They display chemical purity, narrow size ranges, and species-specific crystal morphologies. Specific transmembrane proteins are sorted to the magnetosome membrane (MM. MamC is the most abundant MM protein of Magnetospirillum gryphiswaldense strain MSR-1. MamF is the second most abundant MM protein of MSR-1 and forms stable oligomers. We expressed staphylococcal protein A (SPA, an immunoglobulin-binding protein from the cell wall of Staphylococcus aureus, on MSR-1 magnetosomes by fusion with MamC or MamF. The resulting recombinant magnetosomes were capable of self-assembly with the Fc region of mammalian antibodies (Abs and were therefore useful for functionalization of magnetosomes. Recombinant plasmids pBBR-mamC-spa and pBBR-mamF-spa were constructed by fusing spa (the gene that encodes SPA with mamC and mamF, respectively. Recombinant magnetosomes with surface expression of SPA were generated by introduction of these fusion genes into wild-type MSR-1 or a mamF mutant strain. Studies with a Zeta Potential Analyzer showed that the recombinant magnetosomes had hydrated radii significantly smaller than those of WT magnetosomes and zeta potentials less than -30 mV, indicating that the magnetosome colloids were relatively stable. Observed conjugation efficiencies were as high as 71.24 µg Ab per mg recombinant magnetosomes, and the conjugated Abs retained most of their activity. Numbers of Vibrio parahaemolyticus (a common pathogenic bacterium in seafood captured by recombinant magnetosome/ Ab complexes were measured by real-time fluorescence-based quantitative PCR. One mg of complex was capable of capturing as many as 1.74×107 Vibrio cells. The surface expression system described here will be useful for design of functionalized magnetosomes from MSR-1 and other MTB.

  2. Is formamide a geochemically plausible prebiotic solvent?

    Science.gov (United States)

    Bada, Jeffrey L; Chalmers, John H; Cleaves, H James

    2016-07-27

    From a geochemical perspective, significant amounts of pure formamide (HCONH2) would have likely been rare on the early Earth. There may have been mixed formamide-water solutions, but even in the presence of catalyst, solutions with >20 weight% water in formamide would not have produced significant amounts of prebiotic compounds. It might be feasible to produce relatively pure formamide by a rare occurrence of freezing formamide/water mixtures at temperatures lower than formamide's freezing point (2.55 °C) but greater than the freezing point of water. Because of the high density of formamide ice it would have sunk and accumulated at the bottom of the solution. If the remaining water froze on the surface of this ice, and was then removed by a sublimation-ablation process, a small amount of pure formamide ice might have been produced. In addition a recent report suggested that ∼85 weight% formamide could be prepared by a geochemical type of fractional distillation process, offering another possible route for prebiotic formamide production.

  3. Diazonium salt derivatives of osmium bipyridine complexes: Electrochemical grafting and characterisation of modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, David J. [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Jenkins, Peter [School of Chemistry, National University of Ireland, Galway (Ireland); Polson, Matthew I.J. [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Leech, Donal [School of Chemistry, National University of Ireland, Galway (Ireland); Baronian, Keith H.R. [School of Biological Sciences, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Downard, Alison J., E-mail: alison.downard@canterbury.ac.n [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand)

    2011-02-01

    Osmium bipyridine complexes were directly grafted to carbon electrodes through electroreduction of the diazonium salts [Os(bpy-ph-N{sub 2}{sup +}){sub 3}](PF{sub 6}){sub 5} (1) and [Os(bpy-ph-N{sub 2}{sup +}){sub 2}Cl{sub 2}](PF{sub 6}){sub 2} (2). Growth of the films was not self-limiting as is usually found for grafting from diazonium salts. It appears that electron hopping through the bipyridine ligands of the immobilised complexes enables film growth to continue at a constant rate during grafting by potential cycling. The surface concentrations of deposited films were measured electrochemically and the film thicknesses were measured by depth-profiling using the atomic force microscope. Films up to 42 nm thick were prepared with no evidence for slowing of film growth. The grafted films exhibited high stability when repetitively cycled through the Os{sup 2+/3+} couple and electron transfer rate constants of 11.4 s{sup -1} and 35.4 s{sup -1} were measured in ACN and PBS, respectively, for the Os{sup 2+/3+} couple of the film grafted from 1.

  4. Effect of glutamic acid on copper sorption onto kaolinite - Batch experiments and surface complexation modeling.

    Science.gov (United States)

    Karimzadeh, Lotfollah; Barthen, Robert; Stockmann, Madlen; Gruendig, Marion; Franke, Karsten; Lippmann-Pipke, Johanna

    2017-07-01

    High carbonate content of the European Kupferschiefer ore deposits is a challenge for acid copper leaching (pH ≤ 2). Therefore investigating the mobility behavior of Cu(II) under conditions related to an alternative, neutrophil biohydrometallurgical Cu(II) leaching approach is of interest. As glutamic acid (Glu) might be present as a component in the growth media, we studied its effects on the adsorption of Cu(II) onto kaolinite. The binary and ternary batch sorption measurements of Cu(II) and Glu onto kaolinite were performed in the presence of 10 mM NaClO 4 as background electrolyte and at a pH range from 4 to 9. Sorption experiments were modeled by the charge-distribution multi-site ion complexation (CD-MUSIC) model by using single sorption site (≡SOH) and monodentate surface complexation reactions. Glu sorption on kaolinite is weak (kaolinite mimics the Freundlich model. The proposed CD-MUSIC model provides a close fit to the experimental data and predicts the sorption of Cu(II), Cu(II)-Glu and Glu onto kaolinite as well as the effect of Glu on Cu(II) mobility. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Using Google Earth Surface Metrics to Predict Plant Species Richness in a Complex Landscape

    Directory of Open Access Journals (Sweden)

    Sebastián Block

    2016-10-01

    Full Text Available Google Earth provides a freely available, global mosaic of high-resolution imagery from different sensors that has become popular in environmental and ecological studies. However, such imagery lacks the near-infrared band often used in studying vegetation, thus its potential for estimating vegetation properties remains unclear. In this study, we assess the potential of Google Earth imagery to describe and predict vegetation attributes. Further, we compare it to the potential of SPOT imagery, which has additional spectral information. We measured basal area, vegetation height, crown cover, density of individuals, and species richness in 60 plots in the oak forests of a complex volcanic landscape in central Mexico. We modelled each vegetation attribute as a function of surface metrics derived from Google Earth and SPOT images, and selected the best-supported linear models from each source. Total species richness was the best-described and predicted variable: the best Google Earth-based model explained nearly as much variation in species richness as its SPOT counterpart (R2 = 0.44 and 0.51, respectively. However, Google Earth metrics emerged as poor predictors of all remaining vegetation attributes, whilst SPOT metrics showed potential for predicting vegetation height. We conclude that Google Earth imagery can be used to estimate species richness in complex landscapes. As it is freely available, Google Earth can broaden the use of remote sensing by researchers and managers in low-income tropical countries where most biodiversity hotspots are found.

  6. Dynamics of Defects and Dopants in Complex Systems: Si and Oxide Surfaces and Interfaces

    Science.gov (United States)

    Kirichenko, Taras; Yu, Decai; Banarjee, Sanjay; Hwang, Gyeong

    2004-10-01

    Fabrication of forthcoming nanometer scale electronic devices faces many difficulties including formation of extremely shallow and highly doped junctions. At present, ultra-low-energy ion implantation followed by high-temperature thermal annealing is most widely used to fabricate such ultra-shallow junctions. In the process, a great challenge lies in achieving precise control of redistribution and electrical activation of dopant impurities. Native defects (such as vacancies and interstitials) generated during implantation are known to be mainly responsible for the TED and also influence significantly the electrical activation/deactivation. Defect-dopant dynamics is rather well understood in crystalline Si and SiO2. However, little is known about their diffusion and annihilation (or precipitation) at the surfaces and interfaces, despite its growing importance in determining junction profiles as device dimensions get smaller. In this talk, we will present our density functional theory calculation results on the atomic and electronic structure and dynamical behavior of native defects and dopant-defect complexes in disordered/strained Si and oxide systems, such as i) clean and absorbent-modified Si(100) surface and subsurface layers, ii) amorphous-crystalline Si interfaces and iii) amorphous SiO2/Si interfaces. The fundamental understanding and data is essential in developing a comprehensive kinetic model for junction formation, which would contribute greatly in improving current process technologies.

  7. B lymphocytes confer immune tolerance via cell surface GARP-TGF-β complex.

    Science.gov (United States)

    Wallace, Caroline H; Wu, Bill X; Salem, Mohammad; Ansa-Addo, Ephraim A; Metelli, Alessandra; Sun, Shaoli; Gilkeson, Gary; Shlomchik, Mark J; Liu, Bei; Li, Zihai

    2018-04-05

    GARP, a cell surface docking receptor for binding and activating latent TGF-β, is highly expressed by platelets and activated Tregs. While GARP is implicated in immune invasion in cancer, the roles of the GARP-TGF-β axis in systemic autoimmune diseases are unknown. Although B cells do not express GARP at baseline, we found that the GARP-TGF-β complex is induced on activated human and mouse B cells by ligands for multiple TLRs, including TLR4, TLR7, and TLR9. GARP overexpression on B cells inhibited their proliferation, induced IgA class-switching, and dampened T cell-independent antibody production. In contrast, B cell-specific deletion of GARP-encoding gene Lrrc32 in mice led to development of systemic autoimmune diseases spontaneously as well as worsening of pristane-induced lupus-like disease. Canonical TGF-β signaling more readily upregulates GARP in Peyer patch B cells than in splenic B cells. Furthermore, we demonstrated that B cells are required for the induction of oral tolerance of T cell-dependent antigens via GARP. Our studies reveal for the first time to our knowledge that cell surface GARP-TGF-β is an important checkpoint for regulating B cell peripheral tolerance, highlighting a mechanism of autoimmune disease pathogenesis.

  8. Petroleum-collecting and dispersing complexes based on oleic acid and nitrogenous compounds as surface-active agents for removing thin petroleum films from water surface.

    Science.gov (United States)

    Asadov, Ziyafaddin H; Tantawy, Ahmed H; Zarbaliyeva, Ilhama A; Rahimov, Ravan A

    2012-01-01

    Petroleum-collecting and dispersing complexes were synthesized on the basis of oleic acid and nitrogen-containing compounds. Surface-active properties (interfacial tension) of the obtained complexes were investigated by stalagmometric method. Petroleum-collecting and dispersing properties of the oleic acid complexes in diluted (5% wt. water or alcoholic solution) and undiluted form have been studied in waters of varying salinity (distilled, fresh and sea waters). Some of physico-chemical indices of the prepared compounds such as solubility, acid and amine numbers as well as electrical conductivity have been determined. The ability of oleic acid complex with ethylenediamine as petro-collecting and dispersing agent towards different types of petroleum has been studied. The influence of thickness and "age" of the petroleum slick on collecting and dispersing capacity of this complex has been clarified. Surface properties studied included critical micelle concentration (CMC), maximum surface excess (Γ(max)), and minimum surface area (A(min)). Free energies of micellization (ΔG°(mic)) and adsorption (ΔG°(ads)) were calculated.

  9. Engineering yeast consortia for surface-display of complex cellulosome structures

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wilfred [University of Delaware

    2014-03-31

    As our society marches toward a more technologically advanced future, energy and environmental sustainability are some of the most challenging problems we face today. Biomass is one of the most abundant renewable-feedstock for sustainable production of biofuels. However, the main technological obstacle to more widespread uses of this resource is the lack of low-cost technologies to overcome the recalcitrant nature of the cellulosic structure, especially the hydrolysis step on highly ordered celluloses. In this proposal, we successfully engineered several efficient and inexpensive whole-cell biocatalysts in an effort to produce economically compatible and sustainable biofuels, namely cellulosic ethanol. Our approach was to display of a highly efficient cellulolytic enzyme complex, named cellulosome, on the surface of a historical ethanol producer Saccharomyces cerevisiae for the simultaneous and synergistic saccharification and fermentation of cellulose to ethanol. We first demonstrated the feasibility of assembling a mini-cellulosome by incubating E. coli lysates expressing three different cellulases. Resting cells displaying mini-cellulosomes produced 4-fold more ethanol from phosphoric acid-swollen cellulose (PASC) than cultures with only added enzymes. The flexibility to assemble the mini-cellulosome structure was further demonstrated using a synthetic yeast consortium through intracellular complementation. Direct ethanol production from PASC was demonstrated with resting cell cultures. To create a microorganism suitable for a more cost-effective process, called consolidated bioprocessing (CBP), a synthetic consortium capable of displaying mini-cellulosomes on the cell surface via intercellular complementation was created. To further improve the efficiency, a new adaptive strategy of employing anchoring and adaptor scaffoldins to amplify the number of enzymatic subunits was developed, resulting in the creation of an artificial tetravalent cellulosome on the

  10. Towards a consistent geochemical model for prediction of uranium(VI) removal from groundwater by ferrihydrite

    International Nuclear Information System (INIS)

    Gustafsson, Jon Petter; Daessman, Ellinor; Baeckstroem, Mattias

    2009-01-01

    Uranium(VI), which is often elevated in granitoidic groundwaters, is known to adsorb strongly to Fe (hydr)oxides under certain conditions. This process can be used in water treatment to remove U(VI). To develop a consistent geochemical model for U(VI) adsorption to ferrihydrite, batch experiments were performed and previous data sets reviewed to optimize a set of surface complexation constants using the 3-plane CD-MUSIC model. To consider the effect of dissolved organic matter (DOM) on U(VI) speciation, new parameters for the Stockholm Humic Model (SHM) were optimized using previously published data. The model, which was constrained from available X-ray absorption fine structure (EXAFS) spectroscopy evidence, fitted the data well when the surface sites were divided into low- and high-affinity binding sites. Application of the model concept to other published data sets revealed differences in the reactivity of different ferrihydrites towards U(VI). Use of the optimized SHM parameters for U(VI)-DOM complexation showed that this process is important for U(VI) speciation at low pH. However in neutral to alkaline waters with substantial carbonate present, Ca-U-CO 3 complexes predominate. The calibrated geochemical model was used to simulate U(VI) adsorption to ferrihydrite for a hypothetical groundwater in the presence of several competitive ions. The results showed that U(VI) adsorption was strong between pH 5 and 8. Also near the calcite saturation limit, where U(VI) adsorption was weakest according to the model, the adsorption percentage was predicted to be >80%. Hence U(VI) adsorption to ferrihydrite-containing sorbents may be used as a method to bring down U(VI) concentrations to acceptable levels in groundwater

  11. Mathematical Optimal Sequence Model Development to Process Planes and Other Interconnected Surfaces of Complex Body Parts

    Directory of Open Access Journals (Sweden)

    I. I. Kravchenko

    2016-01-01

    Full Text Available Experience in application of multi-operational machines CNC (MOM CNC shows that they are efficient only in case of significantly increasing productivity and dramatically reducing time-to-market cycle of new products. Most full technological MOM capabilities are revealed when processing the complex body parts. The more complex is a part design and the more is its number of machined surfaces, the more tools are necessary for its processing and positioning, the more is an efficiency of their application. At the same time, the case history of using these machines in industry shows that MOM CNC are, virtually, used mostly for technological processes of universal equipment, which is absolutely unacceptable. One way to improve the processing performance on MOM CNC is to reduce nonproductive machine time through reducing the mutual idle movements of the working machine. This problem is solved using dynamic programming methods, one of which is the solution of the traveling salesman problem (Bellman's method. With a known plan for treatment of all elementary surfaces of the body part, i.e. the known number of performed transitions, each transition is represented as a vertex of some graph, while technological links between the vertices are its edges. A mathematical model is developed on the Bellman principle, which is adapted to technological tasks to minimize the idle time of mutual idle movements of the working machine to perform all transitions in the optimal sequence. The initial data to fill matrix of time expenditures are time consumed by the hardware after executing the i-th transition, and necessary to complete the j-transition. The programmer fills in matrix cells according to known routing body part taking into account the time for part and table positioning, tool exchange, spindle and table approach to the working zone, and the time of table rotation, etc. The mathematical model was tested when machining the body part with 36 transitions on the

  12. Determination of B-complex vitamins in pharmaceutical formulations by surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Junior, Benedito Roberto Alvarenga; Soares, Frederico Luis Felipe; Ardila, Jorge Armando; Durango, Luis Guillermo Cuadrado; Forim, Moacir Rossi; Carneiro, Renato Lajarim

    2018-01-01

    The aim of this work was to quantify B-complex vitamins in pharmaceutical samples by surface enhanced Raman spectroscopy technique using gold colloid substrate. Synthesis of gold nanoparticles was performed according to an adapted Turkevich method. Initial essays were able to suggest the orientation of molecules on gold nanoparticles surface. Central Composite design was performed to obtain the highest SERS signal for nicotinamide and riboflavin. The evaluated parameters in the experimental design were volume of AuNPs, concentration of vitamins and sodium chloride concentration. The best condition for nicotinamide was NaCl 2.3 × 10- 3 mol L- 1 and 700 μL of AuNPs colloid and this same condition showed to be adequate to quantify thiamine. The experimental design for riboflavin shows the best condition at NaCl 1.15 × 10- 2 mol L- 1 and 2.8 mL of AuNPs colloid. It was possible to quantify thiamine and nicotinamide in presence of others vitamins and excipients in two solid multivitamin formulations using the standard addition procedure. The standard addition curve presented a R2 higher than 0.96 for both nicotinamide and thiamine, at orders of magnitude 10- 7 and 10- 8 mol L- 1, respectively. The nicotinamide content in a cosmetic gel sample was also quantified by direct analysis presenting R2 0.98. The t-student test presented no significant difference regarding HPLC method. Despite the experimental design performed for riboflavin, it was not possible its quantification in the commercial samples.

  13. The Leishmania promastigote surface antigen 2 complex is differentially expressed during the parasite life cycle.

    Science.gov (United States)

    Handman, E; Osborn, A H; Symons, F; van Driel, R; Cappai, R

    1995-11-01

    The promastigote surface antigen 2 (PSA-2) complex comprises a family of antigenically similar polypeptides of M(r) 96,000, 80,000 and 50,000, anchored to the membrane with glycosylphosphatidylinositol. Although PSA-2 was initially detected only in promastigotes, Northern blot analysis indicated that mRNA transcripts are also present in amastigotes. Unlike the situation in promastigotes, where at least four major transcripts (2.6-5.3 kb) were detected, only one major (2.6 kb) and two minor transcripts were present in amastigotes. A cDNA clone encoding a member of the PSA-2 family expressed in amastigotes was isolated using DNA probes. The predicted protein sequence of M(r) 40,000 is distinct from promastigote sequences, but shows significant similarity to previously described members of the family from L major and L amazonensis. Antibodies to the carboxyl terminal sequence conserved in all L major PSA-2 studied to date, as well as antibodies affinity purified on the amastigote cDNA-derived polypeptide recognized a major M(r) 50,000 amastigote polypeptide. Immuno-electron microscopy localized both promastigote and amastigote PSA-2 to the cell surface. The expression of PSA-2 polypeptides during the transformation of amastigotes into promastigotes was ordered in a time-dependent manner, with the promastigote M(r) 80000 polypeptide appearing first, followed by the M(r) 96000 polypeptide. In contrast to the glycosylphosphatidylinositol anchor of promastigote PSA-2, which could be hydrolysed by phosphatidylinositol-specific phospholipase C, the amastigote form was resistant to this enzyme.

  14. Noncontact Surface Roughness Estimation Using 2D Complex Wavelet Enhanced ResNet for Intelligent Evaluation of Milled Metal Surface Quality

    Directory of Open Access Journals (Sweden)

    Weifang Sun

    2018-03-01

    Full Text Available Machined surfaces are rough from a microscopic perspective no matter how finely they are finished. Surface roughness is an important factor to consider during production quality control. Using modern techniques, surface roughness measurements are beneficial for improving machining quality. With optical imaging of machined surfaces as input, a convolutional neural network (CNN can be utilized as an effective way to characterize hierarchical features without prior knowledge. In this paper, a novel method based on CNN is proposed for making intelligent surface roughness identifications. The technical scheme incorporates there elements: texture skew correction, image filtering, and intelligent neural network learning. Firstly, a texture skew correction algorithm, based on an improved Sobel operator and Hough transform, is applied such that surface texture directions can be adjusted. Secondly, two-dimensional (2D dual tree complex wavelet transform (DTCWT is employed to retrieve surface topology information, which is more effective for feature classifications. In addition, residual network (ResNet is utilized to ensure automatic recognition of the filtered texture features. The proposed method has verified its feasibility as well as its effectiveness in actual surface roughness estimation experiments using the material of spheroidal graphite cast iron 500-7 in an agricultural machinery manufacturing company. Testing results demonstrate the proposed method has achieved high-precision surface roughness estimation.

  15. Effect of source integration on the geochemical fluxes from springs

    International Nuclear Information System (INIS)

    Frisbee, Marty D.; Phillips, Fred M.; White, Art F.; Campbell, Andrew R.; Liu, Fengjing

    2013-01-01

    Geochemical fluxes from watersheds are typically defined using mass-balance methods that essentially lump all weathering processes operative in a watershed into a single flux of solute mass measured in streamflow at the watershed outlet. However, it is important that we understand how weathering processes in different hydrological zones of a watershed (i.e., surface, unsaturated, and saturated zones) contribute to the total geochemical flux from the watershed. This capability will improve understanding of how geochemical fluxes from these different zones may change in response to climate change. Here, the geochemical flux from weathering processes occurring solely in the saturated zone is investigated. This task, however, remains exceedingly difficult due to the sparsity of subsurface sampling points, especially in large, remote, and/or undeveloped watersheds. In such cases, springflow is often assumed to be a proxy for groundwater (defined as water residing in fully saturated geologic formations). However, springflow generation may integrate different sources of water including, but not limited to, groundwater. The authors’ hypothesis is that long-term estimates of geochemical fluxes from groundwater using springflow proxies will be too large due to the integrative nature of springflow generation. Two conceptual models of springflow generation are tested using endmember mixing analyses (EMMA) on observations of spring chemistries and stable isotopic compositions in a large alpine watershed in the San Juan Mountains of southwestern Colorado. In the “total springflow” conceptual model, springflow is assumed to be 100% groundwater. In the “fractional springflow” conceptual model, springflow is assumed to be an integration of different sources of water (e.g., groundwater, unsaturated flow, preferential flow in the soil, etc.) and groundwater is only a fractional component. The results indicate that groundwater contributions in springflow range from 2% to 100

  16. Validation of the WATEQ4 geochemical model for uranium

    International Nuclear Information System (INIS)

    Krupka, K.M.; Jenne, E.A.; Deutsch, W.J.

    1983-09-01

    As part of the Geochemical Modeling and Nuclide/Rock/Groundwater Interactions Studies Program, a study was conducted to partially validate the WATEQ4 aqueous speciation-solubility geochemical model for uranium. The solubility controls determined with the WATEQ4 geochemical model were in excellent agreement with those laboratory studies in which the solids schoepite [UO 2 (OH) 2 . H 2 O], UO 2 (OH) 2 , and rutherfordine ((UO 2 CO 3 ) were identified as actual solubility controls for uranium. The results of modeling solution analyses from laboratory studies of uranyl phosphate solids, however, identified possible errors in the characterization of solids in the original solubility experiments. As part of this study, significant deficiencies in the WATEQ4 thermodynamic data base for uranium solutes and solids were corrected. Revisions included recalculation of selected uranium reactions. Additionally, thermodynamic data for the hydroxyl complexes of U(VI), including anionic (VI) species, were evaluated (to the extent permitted by the available data). Vanadium reactions were also added to the thermodynamic data base because uranium-vanadium solids can exist in natural ground-water systems. This study is only a partial validation of the WATEQ4 geochemical model because the available laboratory solubility studies do not cover the range of solid phases, alkaline pH values, and concentrations of inorganic complexing ligands needed to evaluate the potential solubility of uranium in ground waters associated with various proposed nuclear waste repositories. Further validation of this or other geochemical models for uranium will require careful determinations of uraninite solubility over the pH range of 7 to 10 under highly reducing conditions and of uranyl hydroxide and phosphate solubilities over the pH range of 7 to 10 under oxygenated conditions

  17. Evaluation of one-dimensional potential energy surfaces for prediction of spectroscopic properties of hydrogen bonds in linear bonded complexes.

    Science.gov (United States)

    Jouypazadeh, Hamidreza; Farrokhpour, Hossein; Solimannejad, Mohammad

    2017-05-01

    This work evaluated the reliability of the one-dimensional potential energy surface for calculating the spectroscopic properties (rovibrational constants and rotational line energies) of hydrogen bonds in linear bonded complexes by comparing theoretical results with the corresponding experimental results. For this purpose, two hydrogen bonded complexes were selected: the HCN···HCN homodimer and the HCN···HF heterodimer. The one-dimensional potential energy surfaces related to the hydrogen bonds in these complexes were calculated using different computational methods and basis sets. The calculated potential curve of each complex was fitted to an analytical one-dimensional potential function to obtain the potential parameters. The obtained analytical potential function of each complex was used in a two-particle Schrödinger equation to obtain the rovibrational energy levels of the hydrogen bond. Using the calculated rovibrational levels, the rovibrational spectra and constants of each complex were calculated and compared with experimental data available from the literature. Compared with experimental data, the calculated one-dimensional potential energy surface at the QCISD/aug-cc-pVDZ level of theory was found to predict the spectroscopic properties of hydrogen bonds better than the potential curves obtained using other computational methods, especially for the HCN···HCN homodimer complex. Generally, the results obtained for the HCN···HCN homodimer complex were closer to experimental data than those obtained for the HCN···HF heterodimer complex. The investigation performed in this work showed that the one-dimensional potential curve related to the hydrogen bond between two linear molecules can be used to predict the spectroscopic constants of hydrogen bonds. Graphical abstract Potential energy curves of HCN···HCN and HCN···HF complexes calculated at the different computational levels.

  18. Geochemical Investigations of Groundwater Stability

    Energy Technology Data Exchange (ETDEWEB)

    Bath, Adrian [Intellisci Ltd., Loughborough (United Kingdom)

    2006-05-15

    The report describes geochemical parameters and methods that provide information about the hydrodynamic stability of groundwaters in low permeability fractured rocks that are potential hosts for radioactive waste repositories. Hydrodynamic stability describes the propensity for changes in groundwater flows over long timescales, in terms of flow rates and flow directions. Hydrodynamic changes may also cause changes in water compositions, but the related issue of geochemical stability of a potential repository host rock system is outside the scope of this report. The main approaches to assessing groundwater stability are numerical modelling, measurement and interpretation of geochemical indicators in groundwater compositions, and analyses and interpretations of secondary minerals and fluid inclusions in these minerals. This report covers the latter two topics, with emphasis on geochemical indicators. The extent to which palaeohydrogeology and geochemical stability indicators have been used in past safety cases is reviewed. It has been very variable, both in terms of the scenarios considered, the stability indicators considered and the extent to which the information was explicitly or implicitly used in assessing FEPs and scenarios in the safety cases. Geochemical indicators of hydrodynamic stability provide various categories of information that are of hydrogeological relevance. Information about groundwater mixing, flows and water sources is potentially provided by the total salinity of groundwaters, their contents of specific non-reactive solutes (principally chloride) and possibly of other solutes, the stable isotopic ratio of water, and certain characteristics of secondary minerals and fluid inclusions. Information pertaining directly to groundwater ages and the timing of water and solute movements is provided by isotopic systems including tritium, carbon-14, chlorine-36, stable oxygen and hydrogen isotopes, uranium isotopes and dissolved mobile gases in

  19. Surface complexation modelling: Experiments on the sorption of nickel on quartz

    International Nuclear Information System (INIS)

    Puukko, E.; Hakanen, M.

    1995-10-01

    Assessing the safety of a final repository for nuclear wastes requires knowledge concerning the way in which the radionuclides released are retarded in the geosphere. The aim of the work is to aquire knowledge of empirical methods repeating the experiments on the sorption of nickel on quartz described in the reports published by the British Geological Survey (BGS). The experimental results were modelled with computer models at the Technical Research Centre of Finland (VTT Chemical Technology). The results showed that the experimental knowledge of the sorption of Ni on quartz have been acheved by repeating the experiments of BGS. Experiments made with the two quartz types, Min-U-Sil 5 (MUS) and Nilsiae, showed the difference in sorption of Ni in the low ionic strength solution (0.001 M NaNO 3 ). The sorption of Ni on MUS was higher than predicted by the Surface Complexation Model (SCM). The phenomenon was also observed by the BGS, and may be due to the different amounts of inpurities in the MUS and in the NLS. In other respects, the results of the sorption experiments fitted quite well with those predicted by the SCM model. (8 refs., 8 figs., 11 tabs.)

  20. Direct protein quantification in complex sample solutions by surface-engineered nanorod probes

    KAUST Repository

    Schrittwieser, Stefan

    2017-06-30

    Detecting biomarkers from complex sample solutions is the key objective of molecular diagnostics. Being able to do so in a simple approach that does not require laborious sample preparation, sophisticated equipment and trained staff is vital for point-of-care applications. Here, we report on the specific detection of the breast cancer biomarker sHER2 directly from serum and saliva samples by a nanorod-based homogeneous biosensing approach, which is easy to operate as it only requires mixing of the samples with the nanorod probes. By careful nanorod surface engineering and homogeneous assay design, we demonstrate that the formation of a protein corona around the nanoparticles does not limit the applicability of our detection method, but on the contrary enables us to conduct in-situ reference measurements, thus further strengthening the point-of-care applicability of our method. Making use of sandwich assays on top of the nanorods, we obtain a limit of detection of 110 pM and 470 pM in 10-fold diluted spiked saliva and serum samples, respectively. In conclusion, our results open up numerous applications in direct protein biomarker quantification, specifically in point-of-care settings where resources are limited and ease-of-use is of essence.

  1. Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity.

    Science.gov (United States)

    Shang, Jianying; Liu, Chongxuan; Wang, Zheming; Zachara, John M

    2011-07-15

    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.

  2. Detection of biomolecules in complex media using surface plasmon resonance sensors

    Science.gov (United States)

    Malone, Michael R.; Masson, Jean-Francois; Barhnart, Margaret; Beaudoin, Stephen; Booksh, Karl S.

    2005-11-01

    Detection of multiple biologically relevant molecules was accomplished at sub-ng/mL levels in highly fouling media using fiber- optic based surface plasmon resonance sensors. Myocardial infarction markers, myoglobin and cTnI, were quantified in full serum with limits of detection below 1 ng/mL. Biologically relevant levels are between 15-30 ng/mL and 1-5 ng/mL for myoglobin and cTnI respectively. Cytokines involved in chronic wound healing, Interleukin 1, Interleukin 6, and tumor necrosis factor α, were detected at around 1 ng/mL in cell culture media. Preliminary results in monitoring these cytokines in cell cultures expressing the cytokines were obtained. The protein diagnostic of spinal muscular atrophy, survival motor neuron protein, was quantified from cell lysate. To obtain such results in complex media, the sensor's stability to non-specific protein adsorption had to be optimized. A layer of the N-hydroxysuccinimide ester of 16-mercaptohexadecanoic acid is attached to the sensor. This layer optimizes the antibody attachment to the sensor while minimizing the non-specific signal from serum proteins.

  3. From LIDAR Scanning to 3d FEM Analysis for Complex Surface and Underground Excavations

    Science.gov (United States)

    Chun, K.; Kemeny, J.

    2017-12-01

    Light detection and ranging (LIDAR) has been a prevalent remote-sensing technology applied in the geological fields due to its high precision and ease to use. One of the major applications is to use the detailed geometrical information of underground structures as a basis for the generation of three-dimensional numerical model that can be used in FEM analysis. To date, however, straightforward techniques in reconstructing numerical model from the scanned data of underground structures have not been well established or tested. In this paper, we propose a comprehensive approach integrating from LIDAR scanning to finite element numerical analysis, specifically converting LIDAR 3D point clouds of object containing complex surface geometry into finite element model. This methodology has been applied to the Kartchner Caverns in Arizona for the stability analysis. Numerical simulations were performed using the finite element code ABAQUS. The results indicate that the highlights of our technologies obtained from LIDAR is effective and provide reference for other similar engineering project in practice.

  4. A new ab initio potential energy surface for the NH-He complex

    Science.gov (United States)

    Ramachandran, R.; Kłos, J.; Lique, F.

    2018-02-01

    We present a new three-dimensional potential energy surface (PES) for the NH(X3Σ-)-He van der Waals system, which explicitly takes into account the NH vibrational motion. The NH-He PES was obtained using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations. The augmented correlation-consistent aug-cc-pVXZ (X = Q, 5, 6) basis sets were employed, and the energies obtained were then extrapolated to the complete basis set limit. Using this new PES, we have studied the spectroscopy of the NH-He complex and we have determined a new rotational constant that agrees well with the available experimental data. Collisional excitation of NH(X3Σ-) by He was also studied at the close-coupling level. Calculations of the collisional excitation cross sections of the fine-structure levels of NH by He were performed for energies up to 3500 cm-1, which yield, after thermal average, rate coefficients up to 350 K. The calculated rate coefficients are compared with available experimental measurements at room temperature, and a reasonably good agreement is found between experimental and theoretical data.

  5. PhreeqcRM: A reaction module for transport simulators based on the geochemical model PHREEQC

    Science.gov (United States)

    Parkhurst, David L.; Wissmeier, Laurin

    2015-09-01

    PhreeqcRM is a geochemical reaction module designed specifically to perform equilibrium and kinetic reaction calculations for reactive transport simulators that use an operator-splitting approach. The basic function of the reaction module is to take component concentrations from the model cells of the transport simulator, run geochemical reactions, and return updated component concentrations to the transport simulator. If multicomponent diffusion is modeled (e.g., Nernst-Planck equation), then aqueous species concentrations can be used instead of component concentrations. The reaction capabilities are a complete implementation of the reaction capabilities of PHREEQC. In each cell, the reaction module maintains the composition of all of the reactants, which may include minerals, exchangers, surface complexers, gas phases, solid solutions, and user-defined kinetic reactants. PhreeqcRM assigns initial and boundary conditions for model cells based on standard PHREEQC input definitions (files or strings) of chemical compositions of solutions and reactants. Additional PhreeqcRM capabilities include methods to eliminate reaction calculations for inactive parts of a model domain, transfer concentrations and other model properties, and retrieve selected results. The module demonstrates good scalability for parallel processing by using multiprocessing with MPI (message passing interface) on distributed memory systems, and limited scalability using multithreading with OpenMP on shared memory systems. PhreeqcRM is written in C++, but interfaces allow methods to be called from C or Fortran. By using the PhreeqcRM reaction module, an existing multicomponent transport simulator can be extended to simulate a wide range of geochemical reactions. Results of the implementation of PhreeqcRM as the reaction engine for transport simulators PHAST and FEFLOW are shown by using an analytical solution and the reactive transport benchmark of MoMaS.

  6. Surface-Active Mononuclear and Dinuclear Ru(II) Complexes based on Thio-substituted Terpyridines Bearing Cyclodextrin Recognition Units

    OpenAIRE

    Pikramenou, Zoe; Unwin, Patrick R

    2007-01-01

    Abstract Ruthenium(II) surface active complexes based on a tpySH ligand have been prepared and characterised, (1) [Ru(tpyada)(tpySH)](PF6)2, (2) [Ru(biptpy)(tpySH)](PF6)2 and (3) [Ru(pm-?-CD(ttp))(tpySH)](PF6)2. The complexes bear a surface active thiol group and a recognition unit which is either a ?-cyclodextrin or a hydrophobic tail (admantyl- or biphenyl) in order to utilise cyclodextrin recognition for the formation of supramolecular wires using bottom up approaches. Monolaye...

  7. GeoComplexity and scale: surface processes and remote sensing of geosystems. GeoComplexity and scale: surface processes and remote sensing of geosystems

    Science.gov (United States)

    Muller, Jan-Peter

    2015-04-01

    Understanding the role of scaling in different planetary surface processes within our Solar System is one of the fundamental goals of planetary and solid earth scientific research. There has been a revolution in planetary surface observations over the past decade for the Earth, Mars and the Moon, especially in 3D imaging of surface shape (from the planetary scale down to resolutions of 75cm). I will examine three areas that I have been active in over the last 25 years giving examples of newly processed global datasets ripe for scaling analysis: topography, BRDF/albedo and imaging. For understanding scaling in terrestrial land surface topography we now have global 30m digital elevation models (DEMs) from different types of sensors (InSAR and stereo-optical) along with laser altimeter data to provide global reference models (to better than 1m in cross-over areas) and airborne laser altimeter data over small areas at resolutions better than 1m and height accuracies better than 10-15cm. We also have an increasing number of sub-surface observations from long wavelength SAR in arid regions, which will allow us to look at the true surface rather than the one buried by sand. We also still have a major limitation of these DEMs in that they represent an unknown observable surface with C-band InSAR DEMs representing being somewhere near the top of the canopy and X-band InSAR and stereo near the top of the canopy but only P-band representing the true understorey surface. I will present some of the recent highlights of topography on Mars including 3D modelling of surface shape from the ESA Mars Express HRSC (High Resolution Stereo Camera), see [1], [2] at 30-100m grid-spacing; and then co-registered to HRSC using a resolution cascade of 20m DTMs from NASA MRO stereo-CTX and 0.75m digital terrain models (as there is no land cover on Mars) DTMs from MRO stereo-HiRISE [3]. Comparable DTMs now exist for the Moon from 100m up to 1m. I will show examples of these DEM/DTM datasets

  8. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

    OpenAIRE

    Stumpel, Jelle E.; Marco, Saccone; Valentina, Dichiarante; Ossi, Lehtonen; Matti, Virkki; Pierangelo, Metrangolo; Arri, Priimagi

    2017-01-01

    In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, a...

  9. Structure and reactivity of heterogeneous surfaces and study of the geometry of surface complexes. Progress report, January 1, 1984-December 31, 1984

    International Nuclear Information System (INIS)

    Landman, U.

    1984-01-01

    Since the beginning of this project, our group has been involved in theoretical studies of surface phenomena and processes, aimed toward increasing our understanding of fundamental processes which govern the properties of material surfaces. Our studies cover a wide spectrum of surface phenomena: surface reactivity, surface crystallography, electronic and vibrational structure, dynamical processes, phase transformations and phase change, the properties of interfaces and investigations of material processing and novel materials preparation techniques. In these investigations we develop and employ analytical and novel numerical, simulation, methods for the study of complex surface phenomena. Our recent surface molecular dynamics studies and simulations of laser annealing phenomena opened new avenues for the investigation of the microscopic dynamics and evolution of equilibrium and non-equilibrium processes at surfaces and interfaces. Our current studies of metallic glasses using a new langrangian formulation which includes all components of the total energy (density dependent electron gas, single particle and pair interactions) of the system, represents a novel approach for theoretical studies of this important class of systems

  10. Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

    Science.gov (United States)

    Glynn, P.D.

    2003-01-01

    One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the

  11. Engineering the cell surface display of cohesins for assembly of cellulosome-inspired enzyme complexes on Lactococcus lactis

    Directory of Open Access Journals (Sweden)

    Wieczorek Andrew S

    2010-09-01

    Full Text Available Abstract Background The assembly and spatial organization of enzymes in naturally occurring multi-protein complexes is of paramount importance for the efficient degradation of complex polymers and biosynthesis of valuable products. The degradation of cellulose into fermentable sugars by Clostridium thermocellum is achieved by means of a multi-protein "cellulosome" complex. Assembled via dockerin-cohesin interactions, the cellulosome is associated with the cell surface during cellulose hydrolysis, forming ternary cellulose-enzyme-microbe complexes for enhanced activity and synergy. The assembly of recombinant cell surface displayed cellulosome-inspired complexes in surrogate microbes is highly desirable. The model organism Lactococcus lactis is of particular interest as it has been metabolically engineered to produce a variety of commodity chemicals including lactic acid and bioactive compounds, and can efficiently secrete an array of recombinant proteins and enzymes of varying sizes. Results Fragments of the scaffoldin protein CipA were functionally displayed on the cell surface of Lactococcus lactis. Scaffolds were engineered to contain a single cohesin module, two cohesin modules, one cohesin and a cellulose-binding module, or only a cellulose-binding module. Cell toxicity from over-expression of the proteins was circumvented by use of the nisA inducible promoter, and incorporation of the C-terminal anchor motif of the streptococcal M6 protein resulted in the successful surface-display of the scaffolds. The facilitated detection of successfully secreted scaffolds was achieved by fusion with the export-specific reporter staphylococcal nuclease (NucA. Scaffolds retained their ability to associate in vivo with an engineered hybrid reporter enzyme, E. coli β-glucuronidase fused to the type 1 dockerin motif of the cellulosomal enzyme CelS. Surface-anchored complexes exhibited dual enzyme activities (nuclease and β-glucuronidase, and were

  12. Baseline Geochemical Data for Medical Researchers in Kentucky

    Science.gov (United States)

    Anderson, W.

    2017-12-01

    According to the Centers for Disease Control, Kentucky has the highest cancer incidence and death rates in the country. New efforts by geochemists and medical researchers are examining ways to diagnose the origin and sources of carcinogenesis. In an effort to determine if naturally occurring geochemical or mineral elements contributes to the cancer causation, the Kentucky Geological Survey has established a Minerals and Geochemical Database that is available to medical researchers for examination of baseline geochemistry and determine if naturally occurring mineral or chemical elements contribute to the high rate of cancers in the state. Cancer causation is complex, so if natural sources can be accounted for, then researchers can focus on the true causation. Naturally occurring minerals, metals and elements occur in many parts of the state, and their presence is valuable for evaluating causation. For example, some data in the database contain maps showing (a) statewide elemental geochemistry, (b) areas of black shale oxidation occurrence, which releases metals in soil and surface waters, (c) some clay deposits in the state that can contain high content of rare earth elements, and (d) site-specific uranium occurrences. Knowing the locations of major ore deposits in the state can also provide information related to mineral and chemical anomalies, such as for base metals and mercury. Radionuclide data in soil and water analyses are limited, so future research may involve obtaining more analyses to determine radon potential. This database also contains information on faulting and geology in the state. Although the metals content of trees may not seem relevant, the ash and humus content of degraded trees affects soil, stream sediment and water geochemistry. Many rural homes heat with wood, releasing metals into the surrounding biosphere. Stressed vegetation techniques can be used to explore for ore deposits and look for high metal contents in soils and rocks. These

  13. Immune evasion proteins of murine cytomegalovirus preferentially affect cell surface display of recently generated peptide presentation complexes.

    Science.gov (United States)

    Lemmermann, Niels A W; Gergely, Kerstin; Böhm, Verena; Deegen, Petra; Däubner, Torsten; Reddehase, Matthias J

    2010-02-01

    For recognition of infected cells by CD8 T cells, antigenic peptides are presented at the cell surface, bound to major histocompatibility complex class I (MHC-I) molecules. Downmodulation of cell surface MHC-I molecules is regarded as a hallmark function of cytomegalovirus-encoded immunoevasins. The molecular mechanisms by which immunoevasins interfere with the MHC-I pathway suggest, however, that this downmodulation may be secondary to an interruption of turnover replenishment and that hindrance of the vesicular transport of recently generated peptide-MHC (pMHC) complexes to the cell surface is the actual function of immunoevasins. Here we have used the model of murine cytomegalovirus (mCMV) infection to provide experimental evidence for this hypothesis. To quantitate pMHC complexes at the cell surface after infection in the presence and absence of immunoevasins, we generated the recombinant viruses mCMV-SIINFEKL and mCMV-Deltam06m152-SIINFEKL, respectively, expressing the K(b)-presented peptide SIINFEKL with early-phase kinetics in place of an immunodominant peptide of the viral carrier protein gp36.5/m164. The data revealed approximately 10,000 K(b) molecules presenting SIINFEKL in the absence of immunoevasins, which is an occupancy of approximately 10% of all cell surface K(b) molecules, whereas immunoevasins reduced this number to almost the detection limit. To selectively evaluate their effect on preexisting pMHC complexes, cells were exogenously loaded with SIINFEKL peptide shortly after infection with mCMV-SIINFEKA, in which endogenous presentation is prevented by an L174A mutation of the C-terminal MHC-I anchor residue. The data suggest that pMHC complexes present at the cell surface in advance of immunoevasin gene expression are downmodulated due to constitutive turnover in the absence of resupply.

  14. Geochemical modelling of bentonite porewater in high-level waste repositories

    Science.gov (United States)

    Wersin, Paul

    2003-03-01

    The description of the geochemical properties of the bentonite backfill that serves as engineered barrier for nuclear repositories is a central issue for perfomance assessment since these play a large role in determining the fate of contaminants released from the waste. In this study the porewater chemistry of bentonite was assessed with a thermodynamic modelling approach that includes ion exchange, surface complexation and mineral equilibrium reactions. The focus was to identify the geochemical reactions controlling the major ion chemistry and acid-base properties and to explore parameter uncertainties specifically at high compaction degrees. First, the adequacy of the approach was tested with two distinct surface complexation models by describing recent experimental data performed at highly varying solid/liquid ratios and ionic strengths. The results indicate adequate prediction of the entire experimental data set. Second, the modelling was extended to repository conditions, taking as an example the current Swiss concept for high-level waste where the compacted bentonite backfill is surrounded by argillaceous rock. The main reactions controlling major ion chemistry were found to be calcite equilibrium and concurrent Na-Ca exchange reactions and de-protonation of functional surface groups. Third, a sensitivity analysis of the main model parameters was performed. The results thereof indicate a remarkable robustness of the model with regard to parameter uncertainties. The bentonite system is characterised by a large acid-base buffering capacity which leads to stable pH-conditions. The uncertainty in pH was found to be mainly induced by the pCO 2 of the surrounding host rock. The results of a simple diffusion-reaction model indicate only minor changes of porewater composition with time, which is primarily due to the geochemical similarities of the bentonite and the argillaceous host rock. Overall, the results show the usefulness of simple thermodynamic models to

  15. Arsenic mobilization in an oxidizing alkaline groundwater: Experimental studies, comparison and optimization of geochemical modeling parameters

    International Nuclear Information System (INIS)

    Hafeznezami, Saeedreza; Lam, Jacquelyn R.; Xiang, Yang; Reynolds, Matthew D.; Davis, James A.; Lin, Tiffany; Jay, Jennifer A.

    2016-01-01

    Arsenic (As) mobilization and contamination of groundwater affects millions of people worldwide. Progress in developing effective in-situ remediation schemes requires the incorporation of data from laboratory experiments and field samples into calibrated geochemical models. In an oxidizing aquifer where leaching of high pH industrial waste from unlined surface impoundments led to mobilization of naturally occurring As up to 2 mg L −1 , sequential extractions of solid phase As as well as, batch sediment microcosm experiments were conducted to understand As partitioning and solid-phase sorptive and buffering capacity. These data were combined with field data to create a series of geochemical models of the system with modeling programs PHREEQC and FITEQL. Different surface complexation modeling approaches, including component additivity (CA), generalized composite (GC), and a hybrid method were developed, compared and fitted to data from batch acidification experiments to simulate potential remediation scenarios. Several parameters strongly influence the concentration of dissolved As including pH, presence of competing ions (particularly phosphate) and the number of available sorption sites on the aquifer solids. Lowering the pH of groundwater to 7 was found to have a variable, but limited impact (<63%) on decreasing the concentration of dissolved As. The models indicate that in addition to lowering pH, decreasing the concentration of dissolved phosphate and/or increasing the number of available sorption sites could significantly decrease the As solubility to levels below 10 μg L −1 . The hybrid and GC modeling results fit the experimental data well (NRMSE<10%) with reasonable effort and can be implemented in further studies for validation. - Highlights: • Samples were collected from an oxidizing aquifer where high pH waste has led to mobilization of naturally occurring As. • Three surface complexation modeling approaches were used in modeling adsorption

  16. Field Analytical Techniques for Geochemical Surveys

    OpenAIRE

    Lemière, Bruno

    2015-01-01

    International audience; Obtaining geochemical results in the field has been a persistent dream for exploration geologists in the last century, and a few practical geochemical? tests were developed, but shipping samples to faraway labs and waiting weeks for results was the rule. This remained a dream until around 1990, when technology developments of portable instruments allowed on-site measurement of the first key metals in solids. This development progressed rapidly and by 2010, most geochem...

  17. Application of a surface complexation model to the interactions of Pu and Am with Esk Estuary sediments

    International Nuclear Information System (INIS)

    Turner, D.R.; Knox, S.; Titley, J.G.; Hamilton-Taylor, J.; Kelly, M.; Williams, G.

    1990-10-01

    Previous work has shown that Pu is remobilised from Esk sediments at low salinities of overlying water. A constant capacitance surface complexation model has been developed in order to understand and model the chemical processes occurring. The model is based on detailed chemical characterisation of sediment samples from the estuary. The following measurements were carried out to provide input parameters for the model: specific surface area; total surface sites (tritium exchange); proton and major ion exchange (potentiometric titration); and actinide (Pu and Am) partition coefficient as a function of pH and salinity at sediment and actinide concentrations typical of the Esk. (author)

  18. Analytical modeling provides new insight into complex mutual coupling between surface loops at ultrahigh fields.

    Science.gov (United States)

    Avdievich, N I; Pfrommer, A; Giapitzakis, I A; Henning, A

    2017-10-01

    Ultrahigh-field (UHF) (≥7 T) transmit (Tx) human head surface loop phased arrays improve both the Tx efficiency (B 1 + /√P) and homogeneity in comparison with single-channel quadrature Tx volume coils. For multi-channel arrays, decoupling becomes one of the major problems during the design process. Further insight into the coupling between array elements and its dependence on various factors can facilitate array development. The evaluation of the entire impedance matrix Z for an array loaded with a realistic voxel model or phantom is a time-consuming procedure when performed using electromagnetic (EM) solvers. This motivates the development of an analytical model, which could provide a quick assessment of the Z-matrix. In this work, an analytical model based on dyadic Green's functions was developed and validated using an EM solver and bench measurements. The model evaluates the complex coupling, including both the electric (mutual resistance) and magnetic (mutual inductance) coupling. Validation demonstrated that the model does well to describe the coupling at lower fields (≤3 T). At UHFs, the model also performs well for a practical case of low magnetic coupling. Based on the modeling, the geometry of a 400-MHz, two-loop transceiver array was optimized, such that, by simply overlapping the loops, both the mutual inductance and the mutual resistance were compensated at the same time. As a result, excellent decoupling (below -40 dB) was obtained without any additional decoupling circuits. An overlapped array prototype was compared (signal-to-noise ratio, Tx efficiency) favorably to a gapped array, a geometry which has been utilized previously in designs of UHF Tx arrays. Copyright © 2017 John Wiley & Sons, Ltd.

  19. Titanium biomaterials with complex surfaces induced aberrant peripheral circadian rhythms in bone marrow mesenchymal stromal cells.

    Science.gov (United States)

    Hassan, Nathaniel; McCarville, Kirstin; Morinaga, Kenzo; Mengatto, Cristiane M; Langfelder, Peter; Hokugo, Akishige; Tahara, Yu; Colwell, Christopher S; Nishimura, Ichiro

    2017-01-01

    Circadian rhythms maintain a high level of homeostasis through internal feed-forward and -backward regulation by core molecules. In this study, we report the highly unusual peripheral circadian rhythm of bone marrow mesenchymal stromal cells (BMSCs) induced by titanium-based biomaterials with complex surface modifications (Ti biomaterial) commonly used for dental and orthopedic implants. When cultured on Ti biomaterials, human BMSCs suppressed circadian PER1 expression patterns, while NPAS2 was uniquely upregulated. The Ti biomaterials, which reduced Per1 expression and upregulated Npas2, were further examined with BMSCs harvested from Per1::luc transgenic rats. Next, we addressed the regulatory relationship between Per1 and Npas2 using BMSCs from Npas2 knockout mice. The Npas2 knockout mutation did not rescue the Ti biomaterial-induced Per1 suppression and did not affect Per2, Per3, Bmal1 and Clock expression, suggesting that the Ti biomaterial-induced Npas2 overexpression was likely an independent phenomenon. Previously, vitamin D deficiency was reported to interfere with Ti biomaterial osseointegration. The present study demonstrated that vitamin D supplementation significantly increased Per1::luc expression in BMSCs, though the presence of Ti biomaterials only moderately affected the suppressed Per1::luc expression. Available in vivo microarray data from femurs exposed to Ti biomaterials in vitamin D-deficient rats were evaluated by weighted gene co-expression network analysis. A large co-expression network containing Npas2, Bmal1, and Vdr was observed to form with the Ti biomaterials, which was disintegrated by vitamin D deficiency. Thus, the aberrant BMSC peripheral circadian rhythm may be essential for the integration of Ti biomaterials into bone.

  20. Assessment of land surface complexity in relation to information capacity and NDVI in different landform regions using landsat data

    Science.gov (United States)

    Wang, Xuhong; Zhang, Zhe; Cao, Mingming; Qin, Huijie; Cao, Yakun

    2014-05-01

    Information capacity is a grayscale digital image quality evaluation model based on multi-dimensional histogram. As local region characteristics of pixels are taken into account in the calculation, it can objectively and effectively characterize the structural feature information of these ground objects. Information capacity is related to image gray levels, while gray levels of remote sensing imagery reflect the complexity of surface landscape. Information capacity is firstly used in geo-science research in this paper, and spatial variation of information capacity in different landform areas is discussed. The results show that spatial the variation of information capacity is closely related to complexity of regional surface structure in different landform types. Generally, information capacity of mountain is the largest, information capacity of hills and plain is followed in order. Moreover, information capacity is sensitive to the change rate of vegetation coverage of different land covers. There are strong correlation between information capacity and NDVI standard deviation, and the correlation coefficient respectively is 0.8347 or 0.8648 in different experimental areas. This study shows that information capacity can effectively characterize the complexity of the regional surface structure and have great significance for quantitative research of surface feature complexity.

  1. Adsorption of a metalorganic complex at a metal surface: A density functional theory study vs. model description

    Energy Technology Data Exchange (ETDEWEB)

    Kostyrko, T., E-mail: tkos@amu.edu.pl; Ślusarski, T. [Faculty of Physics, A. Mickiewicz University, ul. Umultowska 85, 61-614 Poznań (Poland)

    2015-01-21

    A modification of the electronic and magnetic structure of a metalorganic complex by chemisorption at a metallic surface is addressed. The density functional theory (DFT) is applied to investigate a simplified form of a copper-dioxolene complex in a free state and connected to Au(111) surface with alkanethiol linkers. A systematic study of the dependence of the system electronic structure on the linker length is performed. It is found that the electronic structure of the complex is well preserved during the adsorption process. The magnetic moment of the Cu-dioxolene functional group is shown to be strictly correlated with the amount of the charge residing at the complex. On the basis of the DFT results, a model Hamiltonian of the adsorbed metalorganic system is proposed. The model is an extension of the Sandorfy's model of the alkanes and includes explicitly Coulomb interaction between electrons both within the alkane's backbone and the end group. We show that the latter feature is necessary to understand the evolution of the system's properties with the length of the linkers. The advantage of this approach is that it not only reproduces the main results of our DFT analysis but also provides a simple common basis to analyse a wide class of metal complexes bound to metal surfaces with alkanethiol linkers.

  2. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    Energy Technology Data Exchange (ETDEWEB)

    Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J., E-mail: fwilliams@qi.fcen.uba.ar [INQUIMAE-CONICET, Departamento de Química Inorgánica, Analítica y Química-Física, Facultad Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires C1428EHA (Argentina)

    2015-11-14

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  3. Estimation of surface energy fluxes under complex terrain of Mt. Qomolangma over the Tibetan Plateau

    NARCIS (Netherlands)

    Chen, Xuelong; Su, Zhongbo; Ma, Y.; Yang, K.; Wang, B.

    2013-01-01

    Surface solar radiation is an important parameter in surface energy balance models and in estimation of evapotranspiration. This study developed a DEM based radiation model to estimate instantaneous clear sky solar radiation for surface energy balance system to obtain accurate energy absorbed by the

  4. Risk evaluation of uranium mining: A geochemical inverse modelling approach

    Science.gov (United States)

    Rillard, J.; Zuddas, P.; Scislewski, A.

    2011-12-01

    It is well known that uranium extraction operations can increase risks linked to radiation exposure. The toxicity of uranium and associated heavy metals is the main environmental concern regarding exploitation and processing of U-ore. In areas where U mining is planned, a careful assessment of toxic and radioactive element concentrations is recommended before the start of mining activities. A background evaluation of harmful elements is important in order to prevent and/or quantify future water contamination resulting from possible migration of toxic metals coming from ore and waste water interaction. Controlled leaching experiments were carried out to investigate processes of ore and waste (leached ore) degradation, using samples from the uranium exploitation site located in Caetité-Bahia, Brazil. In experiments in which the reaction of waste with water was tested, we found that the water had low pH and high levels of sulphates and aluminium. On the other hand, in experiments in which ore was tested, the water had a chemical composition comparable to natural water found in the region of Caetité. On the basis of our experiments, we suggest that waste resulting from sulphuric acid treatment can induce acidification and salinization of surface and ground water. For this reason proper storage of waste is imperative. As a tool to evaluate the risks, a geochemical inverse modelling approach was developed to estimate the water-mineral interaction involving the presence of toxic elements. We used a method earlier described by Scislewski and Zuddas 2010 (Geochim. Cosmochim. Acta 74, 6996-7007) in which the reactive surface area of mineral dissolution can be estimated. We found that the reactive surface area of rock parent minerals is not constant during time but varies according to several orders of magnitude in only two months of interaction. We propose that parent mineral heterogeneity and particularly, neogenic phase formation may explain the observed variation of the

  5. Geochemical and geo-electrical study of mud pools at the Mutnovsky volcano (South Kamchatka, Russia): Behavior of elements, structures of feeding channels and a model of origin

    International Nuclear Information System (INIS)

    Bessonova, E.P.; Bortnikova, S.B.; Gora, M.P.; Manstein, Yu.A.; Shevko, A.Ya.; Panin, G.L.; Manstein, A.K.

    2012-01-01

    This study presents data on the geochemical composition of boiling mud pools at the Mutnovsky volcano. The physicochemical characteristics of the pools and the concentrations of major, minor and trace elements in pool solutions vary widely. A comparison of the geochemical compositions of host rocks and solutions indicates that leaching from rocks is not the only source of chemicals in thermal solutions. Geophysical studies reveal the inner structure of thermal fields, which reflect the shapes of the underground reservoirs and feed channels. Using geophysical methods (electrical resistivity tomography and frequency domain investigations), it was shown that the vertical structure and complex geochemical zonation of the feed channels leads to a high contrast in the compositions of the mud solutions. These findings answer questions about the origin and composition of surface manifestations. To elucidate the mechanisms of solution formation, an attempt was made to describe the magmatic fluid evolution and the resulting mixing of waters by physical and mathematical models. The model illustrates fluid migration from a magma chamber to the surface. It is shown that the formation of brines corresponding to the mud pool composition is possible during secondary boiling.

  6. Crystal structure, Hirshfeld surfaces and DNA cleavage investigation of two copper(II) complexes containing polypyridine and salicylide ligands.

    Science.gov (United States)

    Luo, Yang-Hui; Sun, Bai-Wang

    2014-05-21

    Two copper complexes 1 [Cu2(phen)2(salicylaldehyde)2(ClO4)2] and 2 [Cu2 (2,2'-dipyridyl)2(salicylaldehyde)2(ClO4)2] have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. These two complexes were display binuclear structure with Cu(II) ions in distorted octahedral environment but antipodal orientation of the binuclear units between them. Molecular Hirshfeld surfaces revealed that the crystal structures of 1 and 2 were supported mainly by H-H, C-H⋯π, π⋯π (C-C), and C-H⋯O intermolecular interactions. DNA cleavage experiments of complexes 1 and 2 revealed that these complexes can intercalation with DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Planification de trajectoires pour placement automatise de fibres sur surfaces de geometries complexes

    Science.gov (United States)

    Hely, Clement

    During the past 50 years, the use of composite materials drastically increase, mainly thanks to the interest of aeronautical industries for these strong and lightweight materials. To improve the productivity of composite materials manufacturing some of the largest aeronautics companies began to develop automated processes such as Automated Fibre Placement (AFP). The AFP workcells currently used by the industry were mainly developed for production of large, nearly flat, plates with low curvatures such as aircraft fuselages. However, the fields of aeronautics and sport goods production begin nowadays to show an interest for manufacturing of smaller and more complex parts. The aim of the project in which this research takes place is to design a new AFP workcell and to develop new techniques allowing production of parts with small size and complex geometry. The work presented in this thesis focuses on the path planning on multi-axial revolution surfaces, e.g. Y-shaped tubes of constant circular cross section. Several path planning algorithms will be presented aiming at the exhaustive coverage of a mandrel with pre-impregnated (prepreg) composite tape. The methodology used in two of these algorithms is to individually cover each branch of the Y-shaped part with paths deriving from a helix. In the first one, the helix will be cut at the boundary between a branch and the junction region (algorithm HD) while in the second (algorithm HA) the pseudo-helix path can be adjusted to follow this boundary. These two methods were shown to have some drawbacks compromising their practical use and possibly leading to parts with diminished mechanical properties. To avoid these drawbacks, two others algorithms were developed with a new methodology. With them, the aim is to cover two branches of the Y-shape with a continuous course (i.e. without cut). The first one uses a well known strategy which defines plies with a constant fibre orientation. Parallel paths are then computed to

  8. Proceedings of the workshop on geochemical modeling

    International Nuclear Information System (INIS)

    1986-01-01

    The following collection of papers was presented at a workshop on geochemical modeling that was sponsored by the Office of Civilian Radioactive Waste Management Program at the Lawrence Livermore National Laboratory (LLNL). The LLNL Waste Management Program sponsored this conference based on their belief that geochemical modeling is particularly important to the radioactive waste disposal project because of the need to predict the consequences of long-term water-rock interactions at the proposed repository site. The papers included in this volume represent a subset of the papers presented at the Fallen Leaf Lake Conference and cover a broad spectrum of detail and breadth in a subject that reflects the diverse research interests of the conference participants. These papers provide an insightful look into the current status of geochemical modeling and illustrate how various geochemical modeling codes have been applied to problems of geochemical interest. The emphasis of these papers includes traditional geochemical modeling studies of individual geochemical systems, the mathematical and theoretical development and refinement of new modeling capabilities, and enhancements of data bases on which the computations are based. The papers in this proceedings volume have been organized into the following four areas: Geochemical Model Development, Hydrothermal and Geothermal Systems, Sedimentary and Low Temperature Environments, and Data Base Development. The participants of this symposium and a complete list of the talks presented are listed in the appendices

  9. Geochemical mapping in polluted floodplains using handheld XRF, geophysical imaging, and geostatistics

    Science.gov (United States)

    Hošek, Michal; Matys Grygar, Tomáš; Popelka, Jan; Kiss, Timea; Elznicová, Jitka; Faměra, Martin

    2017-04-01

    In the recent years researchers have enjoyed noticeable improvements of portable analytical and geophysical methods, which allow studying floodplain architecture and deciphering pollutant distribution more easily than ever before. Our area of interest was floodplain of the Ploučnice River, particularly a pollution hotspot in Boreček, severely impacted by U mining between the 1970s and late 1980s, in particular a "radioactive flood" in 1981. In the area, we used hand drill coring and in situ (field) analysis of so acquired sediments by handheld X-ray fluorescence spectrometer (XRF), which gave us information about depth profiles of pollutants (Ba, U, Zn) and the Al/Si and Zr/Rb ratios, i.e., proxies for sediment lithology. We found that spatial distribution of pollutants (control by depth and position in the floodplain) is apparently complex and discontinuous. In some places, contamination is buried by a couple decimetres of less polluted sediments, while in other places the peak pollution is near surface, apparently without a straightforward connection with the surface topography and the distance to the river channel. We thus examined the floodplain architecture, the internal structure of the floodplain using two geophysical methods. First of them, dipole electromagnetic profiling (DEMP, also denoted EMP, MP, or Slingram) quickly acquires average electric resistivity in top strata in selected areas, which was actually top 3 m with our particular instrument. Second, electric resistivity tomography (ERT) produces much more detailed information on resistivity with depth resolution of ca 0.5 m to the depth of ca 5 m in selected lines. ERT thus allows identifying boundaries of electric resistivity domains (sediment bodies) and DEMP their spatial distribution. Based on the obtained data, we divided the floodplain to five segments with specific topography, pollution characteristics, and electric resistivity. We suppose that those segments are lithogenetic floodplain

  10. One-level modeling for diagnosing surface winds over complex terrain. II - Applicability to short-range forecasting

    Science.gov (United States)

    Alpert, P.; Getenio, B.; Zak-Rosenthal, R.

    1988-01-01

    The Alpert and Getenio (1988) modification of the Mass and Dempsey (1985) one-level sigma-surface model was used to study four synoptic events that included two winter cases (a Cyprus low and a Siberian high) and two summer cases. Results of statistical verification showed that the model is not only capable of diagnosing many details of surface mesoscale flow, but might also be useful for various applications which require operative short-range prediction of the diurnal changes of high-resolution surface flow over complex terrain, for example, in locating wildland fires, determining the dispersion of air pollutants, and predicting changes in wind energy or of surface wind for low-level air flights.

  11. Investigate the complex process in particle-fluid based surface generation technology using reactive molecular dynamics method

    Science.gov (United States)

    Han, Xuesong; Li, Haiyan; Zhao, Fu

    2017-07-01

    Particle-fluid based surface generation process has already become one of the most important materials processing technology for many advanced materials such as optical crystal, ceramics and so on. Most of the particle-fluid based surface generation technology involves two key process: chemical reaction which is responsible for surface softening; physical behavior which is responsible for materials removal/deformation. Presently, researchers cannot give a reasonable explanation about the complex process in the particle-fluid based surface generation technology because of the small temporal-spatial scale and the concurrent influence of physical-chemical process. Molecular dynamics (MD) method has already been proved to be a promising approach for constructing effective model of atomic scale phenomenon and can serve as a predicting simulation tool in analyzing the complex surface generation mechanism and is employed in this research to study the essence of surface generation. The deformation and piles of water molecule is induced with the feeding of abrasive particle which justifies the property mutation of water at nanometer scale. There are little silica molecule aggregation or materials removal because the water-layer greatly reduce the strength of mechanical interaction between particle and materials surface and minimize the stress concentration. Furthermore, chemical effect is also observed at the interface: stable chemical bond is generated between water and silica which lead to the formation of silconl and the reaction rate changes with the amount of water molecules in the local environment. Novel ring structure is observed in the silica surface and it is justified to be favored of chemical reaction with water molecule. The siloxane bond formation process quickly strengthened across the interface with the feeding of abrasive particle because of the compressive stress resulted by the impacting behavior.

  12. Investigate the complex process in particle-fluid based surface generation technology using reactive molecular dynamics method

    Directory of Open Access Journals (Sweden)

    Xuesong Han

    2017-07-01

    Full Text Available Particle-fluid based surface generation process has already become one of the most important materials processing technology for many advanced materials such as optical crystal, ceramics and so on. Most of the particle-fluid based surface generation technology involves two key process: chemical reaction which is responsible for surface softening; physical behavior which is responsible for materials removal/deformation. Presently, researchers cannot give a reasonable explanation about the complex process in the particle-fluid based surface generation technology because of the small temporal-spatial scale and the concurrent influence of physical-chemical process. Molecular dynamics (MD method has already been proved to be a promising approach for constructing effective model of atomic scale phenomenon and can serve as a predicting simulation tool in analyzing the complex surface generation mechanism and is employed in this research to study the essence of surface generation. The deformation and piles of water molecule is induced with the feeding of abrasive particle which justifies the property mutation of water at nanometer scale. There are little silica molecule aggregation or materials removal because the water-layer greatly reduce the strength of mechanical interaction between particle and materials surface and minimize the stress concentration. Furthermore, chemical effect is also observed at the interface: stable chemical bond is generated between water and silica which lead to the formation of silconl and the reaction rate changes with the amount of water molecules in the local environment. Novel ring structure is observed in the silica surface and it is justified to be favored of chemical reaction with water molecule. The siloxane bond formation process quickly strengthened across the interface with the feeding of abrasive particle because of the compressive stress resulted by the impacting behavior.

  13. ACCURACY EVALUATION FOR THE NON-CONTACT DEFECT AREA MEASUREMENT AT THE COMPLEX-SHAPE SURFACES UNDER VIDEOENDOSCOPIC CONTROL

    Directory of Open Access Journals (Sweden)

    A. V. Gorevoy

    2014-07-01

    Full Text Available The problem of non-contact surface defect area measurement at complex-shape objects under videoendoscopic control is considered. Major factors contributing to the measurement uncertainty are analyzed for the first time. The proposed method of accuracy analysis is based on the evaluation of 3D coordinates of surface points from 2D projections under assumption of projective camera model and Mahalanobis distance minimization in the image plane. Expressions for area measurement error caused by sum-of-triangles approximation are obtained analytically for practically important cases of cylindrical and spherical surfaces. It is shown that the magnitude of this error component for a single triangle does not exceed 1% for the real values of parameters of the endoscopic imaging system. Expressions are derived for area measurement uncertainty evaluation on arbitrary shape surfaces, caused by measurement errors of 3D coordinates of individual points with and without a priori information about surface shape. Verification of the obtained expressions with real experiment data showed that area measurement error for a complex figure, given by a set of points, is mainly caused by ignoring the fact that these points belong to the surface. It is proved that the use of a priori information about investigated surface shape, which is often available from the design documentation, in many cases would radically improve the accuracy of surface defects area measurement. The presented results are valid for stereoscopic, shadow and phase methods of video endoscopic measurements and can be effectively used in development of new non-contact measuring endoscopic systems and modernization of existing ones.

  14. Chemodynamics of Soft Nanoparticulate Metal Complexes: From the Local Particle/Medium Interface to a Macroscopic Sensor Surface.

    Science.gov (United States)

    Town, Raewyn M; Pinheiro, José Paulo; van Leeuwen, Herman P

    2017-01-17

    The lability of a complex species between a metal ion M and a binding site S, MS, is conventionally defined with respect to an ongoing process at a reactive interface, for example, the conversion or accumulation of the free metal ion M by a sensor. In the case of soft charged multisite nanoparticulate complexes, the chemodynamic features that are operative within the micro environment of the particle body generally differ substantially from those for dissolved similar single-site complexes in the same medium. Here we develop a conceptual framework for the chemodynamics and the ensuing lability of soft (3D) nanoparticulate metal complexes. The approach considers the dynamic features of MS at the intraparticulate level and their impact on the overall reactivity of free metal ions at the surface of a macroscopic sensing interface. Chemodynamics at the intraparticulate level is shown to involve a local reaction layer at the particle/medium interface, while at the macroscopic sensor level an operational reaction layer is invoked. Under a certain window of conditions, volume exclusion of the nanoparticle body near the medium/sensor interface is substantial and affects the properties of the reaction layer and the overall lability of the nanoparticulate MS complex toward the reactive surface.

  15. Surface-Relief Gratings in Halogen-Bonded Polymer–Azobenzene Complexes: A Concentration-Dependence Study

    Directory of Open Access Journals (Sweden)

    Jelle E. Stumpel

    2017-10-01

    Full Text Available In recent years, supramolecular complexes comprising a poly(4-vinylpyridine backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs. The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer–azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer–azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer–azobenzene complexes.

  16. Surface-Relief Gratings in Halogen-Bonded Polymer-Azobenzene Complexes: A Concentration-Dependence Study.

    Science.gov (United States)

    Stumpel, Jelle E; Saccone, Marco; Dichiarante, Valentina; Lehtonen, Ossi; Virkki, Matti; Metrangolo, Pierangelo; Priimagi, Arri

    2017-10-28

    In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer-azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer-azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation using two halogen-bond-donating azobenzene derivatives, one functionalized with a tetrafluoroiodophenyl and the other with an iodoethynylphenyl group. Both have been previously identified as efficient molecules in driving the SRG formation. We cover a broad concentration range, starting from 10 mol % azobenzene content and going all the way up to equimolar degree of complexation. The complexes are studied as spin-coated thin films, and analyzed by optical microscopy, atomic force microscopy, and optical diffraction arising during the SRG formation. We obtained diffraction efficiencies as high as 35%, and modulation depths close to 400 nm, which are significantly higher than the values previously reported for halogen-bonded polymer-azobenzene complexes.

  17. Comparison of surface extraction techniques performance in computed tomography for 3D complex micro-geometry dimensional measurements

    DEFF Research Database (Denmark)

    Torralba, Marta; Jiménez, Roberto; Yagüe-Fabra, José A.

    2018-01-01

    micro-geometries as well (i.e., in the sub-mm dimensional range). However, there are different factors that may influence the CT process performance, being one of them the surface extraction technique used. In this paper, two different extraction techniques are applied to measure a complex miniaturized...... Canny algorithm. This algorithm has proven to provide accurate results in parts with simple geometries, but its suitability for 3D complex geometries has not been proven so far. To verify the measurement results and compare both techniques, reference measurements are performed on an optical coordinate...

  18. Surface-Enhanced Raman Scattering of the Complexes of Silver with Adenine and dAMP

    NARCIS (Netherlands)

    Otto, Cornelis; Hoeben, F.P.; Hoeben, F.P.; Greve, Jan

    1991-01-01

    The behaviour of adenine and 2'-deoxyadenosine-5'-monophosphate (dAMP) at positive surface potentials of a silver working electrode was investigated using surface-enhanced Raman scattering (SERS). The use of positive potentials in the presence of adenine or dAMP leads to a rapid accumulation of an

  19. Effective surface passivation of multi-shelled InP quantum dots through a simple complexing with titanium species

    Science.gov (United States)

    Jo, Jung-Ho; Kim, Min-Seok; Han, Chang-Yeol; Jang, Eun-Pyo; Do, Young Rag; Yang, Heesun

    2018-01-01

    Fluorescent efficiency of various visible quantum dots (QDs) has been incessantly improved to meet industrially high standard mainly through the advance in core/shell heterostructural design, however, their stability against degradable environments appears still lacking. The most viable strategy to cope with this issue was to exploit chemically inert oxide phases to passivate QD surface in the form of either individual overcoating or matrix embedding. Herein, we report a simple but effective means to passivate QD surface by complexing its organic ligands with a metal alkoxide of titanium isopropoxide (Ti(i-PrO)4). For this, highly efficient red-emitting InP QDs with a multi-shell structure of ZnSeS intermediate plus ZnS outer shell are first synthesized and then the surface of resulting InP/ZnSeS/ZnS QDs is in-situ decorated with Ti(i-PrO)4. The presence of Tisbnd O species from Ti(i-PrO)4 on QD surface is verified by x-ray photoelectron and Fourier transform infrared spectroscopic analyses. Two comparative dispersions of pristine versus Ti(i-PrO)4-complexed QDs are exposed for certain periods of time to UV photon and heat and their temporal changes in photoluminescence are monitored, resulting in a huge improvement in QD stability from the latter ones through Ti(i-PrO)4-mediated better surface passivation.

  20. Geochemical Fate and Transport of Sildenafil and Vardenafil

    Science.gov (United States)

    Richter, L.; Boudinot, G.; Vulava, V. M.; Cory, W. C.

    2015-12-01

    The geochemical fate of pharmaceuticals and their degradation products is a developing environmental field. The geologic, chemical, and biological fate of these pollutants has become very relevant with the increase in human population and the resulting increase in pollutant concentrations in the environment. In this study, we focus on sildenafil (SDF) and vardenafil (VDF), active compounds in Viagra and Levitra, respectively, two commonly used erectile dysfunction drugs. The main objective is to determine the sorption potential and transport behavior of these two compounds in natural soils. Both SDF and VDF are complex organic molecules with multiple amine functional groups in their structures. Two types of natural acidic soils (pH≈4.5), an organic-rich soil (7.6% OM) and clay-rich soil (5.1% clay) were used in this study to determine which soil components influence sorption behavior of both compounds. Sorption isotherms measured using batch reactors were nearly linear, but sorption was stronger in soil that contained higher clay content. Both compounds have multiple pKas due to the amine functional groups, the relevant pKas of SDF are 5.97 and 7.27, and those of VDF's are 4.72 and 6.21. These values indicate that these compounds likely behave as cations in soil suspensions and hence were strongly sorbed to negatively-charged clay minerals present in both soils. The clay composition in both soils is predominantly kaolinite with smaller amount of montmorillonite, both of which have a predominantly negative surface charge. Transport experiments using glass chromatography columns indicated that both compounds were more strongly retarded in the clay-rich soils. Breakthrough curves from the transport experiments were modeled using convection-dispersion transport equations. The organic matter in the soil seemed to play a less dominant role in the geochemistry in this study, but is likely to transform both compounds into derivative compounds as seen in other studies.

  1. Direct Imaging of DNA/Lipid Complexes Interacting with Liposome Surfaces and Fibroblasts

    Science.gov (United States)

    Lin, Alison J.; Idziak, Stefan H. J.; Rädler, Joachim; George, Cyril X.; Safinya, Cyrus R.; Samuel, Charles E.

    1996-03-01

    Video-enhanced light microscopy techniques (phase contrast, differential interference contrast, and fluorescence) were used for direct imaging of the structure and dynamics of nucleic acid-cationic liposome complexes both on liposomes (a model cell) and within the cytoplasm of Mouse L929 Fibroblasts. The experiments are designed to enable us to correlate the complex's structure to the transfection efficiencies (i.e. the uptake and expression of nucleic acid) in animal cells. The ultimate goal of the project is to design an optimal non-viral vector (carrier of nucleic acids). Fluorescence labeling of both the lipid and nucleic acid components is used for visualization experiments at the level of single complexes interacting with a single cell (e.g. a giant liposome or an isolated mammalian cell). This allows us to follow the temporal path of a complex. Direct motion versus random Brownian diffusion are readily distinguished. Micropipettes were used for placement of cells and microinjection into cells.

  2. Composition and structure of Si-doped NiTi with a complex surface profile

    Science.gov (United States)

    Slabodchikov, Vladimir A.; Ovchinnikov, Stanislav V.; Kuznetsov, Vladimir M.

    2017-12-01

    The paper presents Auger spectroscopy and electron microscopy data on the elemental composition and structure of NiTi specimens with blind holes doped with Si through plasma immersion ion implantation. The data demonstrate how silicon is distributed through the depth of NiTi from its front surface and along the side of its hole. The upper layer formed upon treatment is shown to be amorphous, and its thickness measuring several tens of nanometers is about two times larger on the side surface of the hole than on the front surface.

  3. Final Report: Optimal Model Complexity in Geological Carbon Sequestration: A Response Surface Uncertainty Analysis

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ye [Univ. of Wyoming, Laramie, WY (United States)

    2018-01-17

    The critical component of a risk assessment study in evaluating GCS is an analysis of uncertainty in CO2 modeling. In such analyses, direct numerical simulation of CO2 flow and leakage requires many time-consuming model runs. Alternatively, analytical methods have been developed which allow fast and efficient estimation of CO2 storage and leakage, although restrictive assumptions on formation rock and fluid properties are employed. In this study, an intermediate approach is proposed based on the Design of Experiment and Response Surface methodology, which consists of using a limited number of numerical simulations to estimate a prediction outcome as a combination of the most influential uncertain site properties. The methodology can be implemented within a Monte Carlo framework to efficiently assess parameter and prediction uncertainty while honoring the accuracy of numerical simulations. The choice of the uncertain properties is flexible and can include geologic parameters that influence reservoir heterogeneity, engineering parameters that influence gas trapping and migration, and reactive parameters that influence the extent of fluid/rock reactions. The method was tested and verified on modeling long-term CO2 flow, non-isothermal heat transport, and CO2 dissolution storage by coupling two-phase flow with explicit miscibility calculation using an accurate equation of state that gives rise to convective mixing of formation brine variably saturated with CO2. All simulations were performed using three-dimensional high-resolution models including a target deep saline aquifer, overlying caprock, and a shallow aquifer. To evaluate the uncertainty in representing reservoir permeability, sediment hierarchy of a heterogeneous digital stratigraphy was mapped to create multiple irregularly shape stratigraphic models of decreasing geologic resolutions: heterogeneous (reference), lithofacies, depositional environment, and a (homogeneous) geologic formation. To ensure model

  4. Curvature Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Curvature was calculated from the bathymetry surface for each raster cell using the ArcGIS 3D Analyst "Curvature" Tool. Curvature describes the rate of change of...

  5. Rugosity Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Rugosity was calculated from the bathymetry surface for each cell using the "Rugosity" function in the Benthic Terrain Modeler toolbox (Jenness 2002, 2004; Wright et...

  6. Profile Curvature Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Profile curvature was calculated from the bathymetry surface for each raster cell using the ArcGIS 3D Analyst "Curvature" Tool. Profile curvature describes the rate...

  7. Slope Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Slope was calculated from the bathymetry surface for each raster cell using ArcGIS's Spatial Analyst 'Slope' Tool. Slope describes the maximum steepness of a terrain...

  8. Bipodal surface organometallic complexes with surface N-donor ligands and application to the catalytic cleavage of C-H and C-C bonds in n -Butane

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2013-11-27

    We present a new generation of "true vicinal" functions well-distributed on the inner surface of SBA15: [(Sî - Si-NH 2)(≡Si-OH)] (1) and [(≡Si-NH2)2] (2). From these amine-modified SBA15s, two new well-defined surface organometallic species [(≡Si-NH-)(≡Si-O-)]Zr(CH2tBu) 2 (3) and [(≡Si-NH-)2]Zr(CH2tBu) 2 (4) have been obtained by reaction with Zr(CH2tBu) 4. The surfaces were characterized with 2D multiple-quantum 1H-1H NMR and infrared spectroscopies. Energy-filtered transmission electron microscopy (EFTEM), mass balance, and elemental analysis unambiguously proved that Zr(CH2tBu)4 reacts with these vicinal amine-modified surfaces to give mainly bipodal bis(neopentyl)zirconium complexes (3) and (4), uniformly distributed in the channels of SBA15. (3) and (4) react with hydrogen to give the homologous hydrides (5) and (6). Hydrogenolysis of n-butane catalyzed by these hydrides was carried out at low temperature (100 C) and low pressure (1 atm). While (6) exhibits a bis(silylamido)zirconium bishydride, [(≡Si-NH-)2]Zr(H) 2 (6a) (60%), and a bis(silylamido)silyloxozirconium monohydride, [(≡Si-NH-)2(≡Si-O-)]ZrH (6b) (40%), (5) displays a new surface organometallic complex characterized by an 1H NMR signal at 14.46 ppm. The latter is assigned to a (silylimido)(silyloxo)zirconium monohydride, [(≡Si-Nî)(≡Si-O-)]ZrH (5b) (30%), coexistent with a (silylamido)(silyloxo)zirconium bishydride, [(≡Si-NH-)(≡Si-O-)] Zr(H)2 (5a) (45%), and a silylamidobis(silyloxo)zirconium monohydride, [(≡Si-NH-)(≡Si-O-)2]ZrH (5c) (25%). Surprisingly, nitrogen surface ligands possess catalytic properties already encountered with silicon oxide surfaces, but interestingly, catalyst (5) with chelating [N,O] shows better activity than (6) with chelating [N,N]. © 2013 American Chemical Society.

  9. Final Technical Report: Metal—Organic Surface Catalyst for Low-temperature Methane Oxidation: Bi-functional Union of Metal—Organic Complex and Chemically Complementary Surface

    Energy Technology Data Exchange (ETDEWEB)

    Tait, Steven L. [Indiana Univ., Bloomington, IN (United States)

    2016-10-01

    Stabilization and chemical control of transition metal centers is a critical problem in the advancement of heterogeneous catalysts to next-generation catalysts that exhibit high levels of selectivity, while maintaining strong activity and facile catalyst recycling. Supported metal nanoparticle catalysts typically suffer from having a wide range of metal sites with different coordination numbers and varying chemistry. This project is exploring new possibilities in catalysis by combining features of homogeneous catalysts with those of heterogeneous catalysts to develop new, bi-functional systems. The systems are more complex than traditional heterogeneous catalysts in that they utilize sequential active sites to accomplish the desired overall reaction. The interaction of metal—organic catalysts with surface supports and their interactions with reactants to enable the catalysis of critical reactions at lower temperatures are at the focus of this study. Our work targets key fundamental chemistry problems. How do the metal—organic complexes interact with the surface? Can those metal center sites be tuned for selectivity and activity as they are in the homogeneous system by ligand design? What steps are necessary to enable a cooperative chemistry to occur and open opportunities for bi-functional catalyst systems? Study of these systems will develop the concept of bringing together the advantages of heterogeneous catalysis with those of homogeneous catalysis, and take this a step further by pursuing the objective of a bi-functional system. The use of metal-organic complexes in surface catalysts is therefore of interest to create well-defined and highly regular single-site centers. While these are not likely to be stable in the high temperature environments (> 300 °C) typical of industrial heterogeneous catalysts, they could be applied in moderate temperature reactions (100-300 °C), made feasible by lowering reaction temperatures by better catalyst control. They also

  10. Modeling the Excess Cell Surface Stored in a Complex Morphology of Bleb-Like Protrusions.

    Directory of Open Access Journals (Sweden)

    Maryna Kapustina

    2016-03-01

    Full Text Available Cells transition from spread to rounded morphologies in diverse physiological contexts including mitosis and mesenchymal-to-amoeboid transitions. When these drastic shape changes occur rapidly, cell volume and surface area are approximately conserved. Consequently, the rounded cells are suddenly presented with a several-fold excess of cell surface whose area far exceeds that of a smooth sphere enclosing the cell volume. This excess is stored in a population of bleb-like protrusions (BLiPs, whose size distribution is shown by electron micrographs to be skewed. We introduce three complementary models of rounded cell morphologies with a prescribed excess surface area. A 2D Hamiltonian model provides a mechanistic description of how discrete attachment points between the cell surface and cortex together with surface bending energy can generate a morphology that satisfies a prescribed excess area and BLiP number density. A 3D random seed-and-growth model simulates efficient packing of BLiPs over a primary rounded shape, demonstrating a pathway for skewed BLiP size distributions that recapitulate 3D morphologies. Finally, a phase field model (2D and 3D posits energy-based constitutive laws for the cell membrane, nematic F-actin cortex, interior cytosol, and external aqueous medium. The cell surface is equipped with a spontaneous curvature function, a proxy for the cell surface-cortex couple, that is a priori unknown, which the model "learns" from the thin section transmission electron micrograph image (2D or the "seed and growth" model image (3D. Converged phase field simulations predict self-consistent amplitudes and spatial localization of pressure and stress throughout the cell for any posited stationary morphology target and cell compartment constitutive properties. The models form a general framework for future studies of cell morphological dynamics in a variety of biological contexts.

  11. A preliminary investigation of the applicability of surface complexation modeling to the understanding of transportation cask weeping

    International Nuclear Information System (INIS)

    Granstaff, V.E.; Chambers, W.B.; Doughty, D.H.

    1994-01-01

    A new application for surface complexation modeling is described. These models, which describe chemical equilibria among aqueous and adsorbed species, have typically been used for predicting groundwater transport of contaminants by modeling the natural adsorbents as various metal oxides. Our experiments suggest that this type of modeling can also explain stainless steel surface contamination and decontamination mechanisms. Stainless steel transportation casks, when submerged in a spent fuel storage pool at nuclear power stations, can become contaminated with radionuclides such as 137 Cs, 134 Cs, and 60 Co. Subsequent release or desorption of these contaminants under varying environmental conditions occasionally results in the phenomenon known as open-quotes cask weeping.close quotes We have postulated that contaminants in the storage pool adsorb onto the hydrous metal oxide surface of the passivated stainless steel and are subsequently released (by conversion from a fixed to a removable form) during transportation, due to varying environmental factors, such as humidity, road salt, dirt, and acid rain. It is well known that 304 stainless steel has a chromium enriched passive surface layer; thus its adsorption behavior should be similar to that of a mixed chromium/iron oxide. To help us interpret our studies of reversible binding of dissolved metals on stainless steel surfaces, we have studied the adsorption of Co +2 on Cr 2 O 3 . The data are interpreted using electrostatic surface complexation models. The FITEQL computer program was used to obtain the model binding constants and site densities from the experimental data. The MINTEQA2 computer speciation model was used, with the fitted constants, in an attempt to validate this approach

  12. Directed assembly of functional light harvesting antenna complexes onto chemically patterned surfaces

    International Nuclear Information System (INIS)

    Escalante, Maryana; Maury, Pascale; Bruinink, Christiaan M; Werf, Kees van der; Olsen, John D; Timney, John A; Huskens, Jurriaan; Hunter, C Neil; Subramaniam, Vinod; Otto, Cees

    2008-01-01

    We report the directed assembly of the photosynthetic membrane proteins LH1 and LH2 isolated from the purple bacterium Rhodobacter sphaeroides onto chemically patterned substrates. Nanoimprint lithography was used to pattern discrete regions of amino- and fluoro-terminated or poly(ethylene glycol) self-assembled monolayers onto a glass substrate. Densely packed layers of assembled protein complexes were observed with atomic force microscopy. The protein complexes attached selectively to the amino-terminated regions by electrostatic interactions. Spectral images generated with a hybrid scanning probe and fluorescence microscope confirmed that the patterned proteins retained their native optical signatures

  13. Compilation of kinetic data for geochemical calculations

    International Nuclear Information System (INIS)

    Arthur, R.C.; Savage, D.; Sasamoto, Hiroshi; Shibata, Masahiro; Yui, Mikazu

    2000-01-01

    Kinetic data, including rate constants, reaction orders and activation energies, are compiled for 34 hydrolysis reactions involving feldspars, sheet silicates, zeolites, oxides, pyroxenes and amphiboles, and for similar reactions involving calcite and pyrite. The data are compatible with a rate law consistent with surface reaction control and transition-state theory, which is incorporated in the geochemical software package EQ3/6 and GWB. Kinetic data for the reactions noted above are strictly compatible with the transition-state rate law only under far-from-equilibrium conditions. It is possible that the data are conceptually consistent with this rate law under both far-from-equilibrium and near-to-equilibrium conditions, but this should be confirmed whenever possible through analysis of original experimental results. Due to limitations in the availability of kinetic data for mine-water reactions, and in order to simplify evaluations of geochemical models of groundwater evolution, it is convenient to assume local-equilibrium in such models whenever possible. To assess whether this assumption is reasonable, a modeling approach accounting for couple fluid flow and water-rock interaction is described that can be use to estimate spatial and temporal scale of local equilibrium. The approach is demonstrated for conditions involving groundwater flow in fractures at JNC's Kamaishi in-situ tests site, and is also used to estimate the travel time necessary for oxidizing surface waters to migrate to the level of a HLW repository in crystalline rock. The question of whether local equilibrium is a reasonable assumption must be addressed using an appropriate modeling approach. To be appropriate for conditions at the Kamaishi site using the modeling approach noted above, the fracture fill must closely approximate a porous mine, groundwater flow must be purely advective and diffusion of solutes across the fracture-host rock boundary must not occur. Moreover, the mineralogical and

  14. Compilation of kinetic data for geochemical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Arthur, R.C. [Monitor Scientific, LLC., Denver, Colorado (United States); Savage, D. [Quintessa, Ltd., Nottingham (United Kingdom); Sasamoto, Hiroshi; Shibata, Masahiro; Yui, Mikazu [Japan Nuclear Cycle Development Inst., Tokai, Ibaraki (Japan). Tokai Works

    2000-01-01

    Kinetic data, including rate constants, reaction orders and activation energies, are compiled for 34 hydrolysis reactions involving feldspars, sheet silicates, zeolites, oxides, pyroxenes and amphiboles, and for similar reactions involving calcite and pyrite. The data are compatible with a rate law consistent with surface reaction control and transition-state theory, which is incorporated in the geochemical software package EQ3/6 and GWB. Kinetic data for the reactions noted above are strictly compatible with the transition-state rate law only under far-from-equilibrium conditions. It is possible that the data are conceptually consistent with this rate law under both far-from-equilibrium and near-to-equilibrium conditions, but this should be confirmed whenever possible through analysis of original experimental results. Due to limitations in the availability of kinetic data for mine-water reactions, and in order to simplify evaluations of geochemical models of groundwater evolution, it is convenient to assume local-equilibrium in such models whenever possible. To assess whether this assumption is reasonable, a modeling approach accounting for couple fluid flow and water-rock interaction is described that can be use to estimate spatial and temporal scale of local equilibrium. The approach is demonstrated for conditions involving groundwater flow in fractures at JNC's Kamaishi in-situ tests site, and is also used to estimate the travel time necessary for oxidizing surface waters to migrate to the level of a HLW repository in crystalline rock. The question of whether local equilibrium is a reasonable assumption must be addressed using an appropriate modeling approach. To be appropriate for conditions at the Kamaishi site using the modeling approach noted above, the fracture fill must closely approximate a porous mine, groundwater flow must be purely advective and diffusion of solutes across the fracture-host rock boundary must not occur. Moreover, the

  15. LASL approach to uranium geochemical reconnaissance

    Energy Technology Data Exchange (ETDEWEB)

    Sharp, R.R. Jr.

    1977-01-01

    The US ERDA, as part of the NURE program, has initiated a nationwide Hydrogeochemical and Stream Sediment Reconnaissance (HSSR). The aims of the NURE program are to provide data on which to base more accurate estimates of US uranium reserves for long-range planning and to aid in meeting the nation's projected uranium demands into the next century. The HSSR objective is to complete, by 1980, a reconnaissance of the nation's surface waters, ground waters, and stream and lake sediments, to aid in assessment of uranium reserves and identification of areas of interest for exploration. Patterned after extensive uranium reconnaissance done in many other countries, the LASL project is comprised of the following five components: (1) organization and planning, which includes management, design, and execution; (2) field sampling, which includes orientation studies, generation of specifications, and contracting and inspection of field work; (3) sample receiving and analysis, which includes development of methods and hardware, quality assurance, and archival storage; (4) data handling and presentation, including verification, storage, output, and plotting; and (5) data evaluation and publication, which incorporates geochemical, geological, statistical, and empirical evaluation and report writing. The LASL approach to each component and the current status in each state are described.

  16. LASL approach to uranium geochemical reconnaissance

    International Nuclear Information System (INIS)

    Sharp, R.R. Jr.

    1977-01-01

    The US ERDA, as part of the NURE program, has initiated a nationwide Hydrogeochemical and Stream Sediment Reconnaissance (HSSR). The aims of the NURE program are to provide data on which to base more accurate estimates of US uranium reserves for long-range planning and to aid in meeting the nation's projected uranium demands into the next century. The HSSR objective is to complete, by 1980, a reconnaissance of the nation's surface waters, ground waters, and stream and lake sediments, to aid in assessment of uranium reserves and identification of areas of interest for exploration. Patterned after extensive uranium reconnaissance done in many other countries, the LASL project is comprised of the following five components: (1) organization and planning, which includes management, design, and execution; (2) field sampling, which includes orientation studies, generation of specifications, and contracting and inspection of field work; (3) sample receiving and analysis, which includes development of methods and hardware, quality assurance, and archival storage; (4) data handling and presentation, including verification, storage, output, and plotting; and (5) data evaluation and publication, which incorporates geochemical, geological, statistical, and empirical evaluation and report writing. The LASL approach to each component and the current status in each state are described

  17. Sorption and speciation of iodine in groundwater system: The roles of organic matter and organic-mineral complexes

    Science.gov (United States)

    Li, Junxia; Zhou, Hailing; Wang, Yanxin; Xie, Xianjun; Qian, Kun

    2017-06-01

    Characterizing the properties of main host of iodine in soil/sediment and the geochemical behaviors of iodine species are critical to understand the mechanisms of iodine mobilization in groundwater systems. Four surface soil and six subsurface sediment samples were collected from the iodine-affected area of Datong basin in northern China to conduct batch experiments and to evaluate the effects of NOM and/or organic-mineral complexes on iodide/iodate geochemical behaviors. The results showed that both iodine contents and kf-iodate values had positive correlations with solid TOC contents, implying the potential host of NOM for iodine in soil/sediment samples. The results of chemical removal of easily extracted NOM indicated that the NOM of surface soils is mainly composed of surface embedded organic matter, while sediment NOM mainly occurs in the form of organic-mineral complexes. After the removal of surface sorbed NOM, the decrease in kf-iodate value of treated surface soils indicates that surface sorbed NOM enhances iodate adsorption onto surface soil. By contrast, kf-iodate value increases in several H2O2-treated sediment samples, which was considered to result from exposed rod-like minerals rich in Fe/Al oxyhydroxide/oxides. After chemical removal of organic-mineral complexes, the lowest kf-iodate value for both treated surface soils and sediments suggests the dominant role of organic-mineral complexes on controlling the iodate geochemical behavior. In comparison with iodate, iodide exhibited lower affinities on all (un)treated soil/sediment samples. The understanding of different geochemical behaviors of iodine species helps to explain the occurrence of high iodine groundwater with iodate and iodide as the main species in shallow (oxidizing conditions) and deep (reducing conditions) groundwater.

  18. Sorption and speciation of iodine in groundwater system: The roles of organic matter and organic-mineral complexes.

    Science.gov (United States)

    Li, Junxia; Zhou, Hailing; Wang, Yanxin; Xie, Xianjun; Qian, Kun

    2017-06-01

    Characterizing the properties of main host of iodine in soil/sediment and the geochemical behaviors of iodine species are critical to understand the mechanisms of iodine mobilization in groundwater systems. Four surface soil and six subsurface sediment samples were collected from the iodine-affected area of Datong basin in northern China to conduct batch experiments and to evaluate the effects of NOM and/or organic-mineral complexes on iodide/iodate geochemical behaviors. The results showed that both iodine contents and k f -iodate values had positive correlations with solid TOC contents, implying the potential host of NOM for iodine in soil/sediment samples. The results of chemical removal of easily extracted NOM indicated that the NOM of surface soils is mainly composed of surface embedded organic matter, while sediment NOM mainly occurs in the form of organic-mineral complexes. After the removal of surface sorbed NOM, the decrease in k f -iodate value of treated surface soils indicates that surface sorbed NOM enhances iodate adsorption onto surface soil. By contrast, k f -iodate value increases in several H 2 O 2 -treated sediment samples, which was considered to result from exposed rod-like minerals rich in Fe/Al oxyhydroxide/oxides. After chemical removal of organic-mineral complexes, the lowest k f -iodate value for both treated surface soils and sediments suggests the dominant role of organic-mineral complexes on controlling the iodate geochemical behavior. In comparison with iodate, iodide exhibited lower affinities on all (un)treated soil/sediment samples. The understanding of different geochemical behaviors of iodine species helps to explain the occurrence of high iodine groundwater with iodate and iodide as the main species in shallow (oxidizing conditions) and deep (reducing conditions) groundwater. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Wear of carbide inserts with complex surface treatment when milling nickel alloy

    Science.gov (United States)

    Fedorov, Sergey; Swe, Min Htet; Kapitanov, Alexey; Egorov, Sergey

    2018-03-01

    One of the effective ways of strengthening hard alloys is the creating structure layers on their surface with the gradient distribution of physical and mechanical properties between the wear-resistant coating and the base material. The article discusses the influence of the near-surface layer which is modified by low-energy high-current electron-beam alloying and the upper anti-friction layer in a multi-component coating on the wear mechanism of the replaceable multifaceted plates in the dry milling of the difficult to machine nickel alloys.

  20. PHAST Version 2-A Program for Simulating Groundwater Flow, Solute Transport, and Multicomponent Geochemical Reactions

    Science.gov (United States)

    Parkhurst, David L.; Kipp, Kenneth L.; Charlton, Scott R.

    2010-01-01

    The computer program PHAST (PHREEQC And HST3D) simulates multicomponent, reactive solute transport in three-dimensional saturated groundwater flow systems. PHAST is a versatile groundwater flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. Major enhancements in PHAST Version 2 allow spatial data to be defined in a combination of map and grid coordinate systems, independent of a specific model grid (without node-by-node input). At run time, aquifer properties are interpolated from the spatial data to the model grid; regridding requires only redefinition of the grid without modification of the spatial data. PHAST is applicable to the study of natural and contaminated groundwater systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock/water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, or density-dependent flow. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux (specified-flux), and leaky (head-dependent) conditions, as well as the special cases of rivers, drains, and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association or Pitzer specific interaction thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, ion exchange sites, surface complexation sites, solid solutions, and gases; and

  1. Validation of solar radiation surfaces from MODIS and reanalysis data over topographically complex terrain

    Science.gov (United States)

    Todd A. Schroeder; Robbie Hember; Nicholas C. Coops; Shunlin Liang

    2009-01-01

    The magnitude and distribution of incoming shortwave solar radiation (SW) has significant influence on the productive capacity of forest vegetation. Models that estimate forest productivity require accurate and spatially explicit radiation surfaces that resolve both long- and short-term temporal climatic patterns and that account for topographic variability of the land...

  2. The complex dispersion relation of surface plasmon polaritons at gold/para-hexaphenylene interfaces

    DEFF Research Database (Denmark)

    Lemke, Christoph; Leißner, Till; Klick, Alwin

    2014-01-01

    Two-photon photoemission electron microscopy (2P-PEEM) is used to measure the real and imaginary part of the dispersion relation of surface plasmon polaritons at different interface systems. A comparison of calculated and measured dispersion data for a gold/vacuum interface demonstrates...

  3. Carborane–β-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

    NARCIS (Netherlands)

    Neirynck, Pauline; Neirynck, P.; Schimer, J.; Jonkheijm, Pascal; Milroy, L.G.; Cigler, P.; Brunsveld, Luc

    2015-01-01

    Supramolecular chemistry provides an attractive entry to generate dynamic and well-controlled bioactive surfaces. Novel host–guest systems are urgently needed to provide a broader affinity and applicability portfolio. A synthetic strategy to carborane–peptide bioconjugates was therefore developed to

  4. Geochemical prospecting for rare earth elements using termite mound materials

    Science.gov (United States)

    Horiuchi, Yu; Ohno, Tetsuji; Hoshino, Mihoko; Shin, Ki-Cheol; Murakami, Hiroyasu; Tsunematsu, Maiko; Watanabe, Yasushi

    2014-12-01

    The Blockspruit fluorite prospect, located in North West State of the Republic of South Africa, occurs within an actinolite rock zone that was emplaced into the Kenkelbos-type granite of Proterozoic age. There are a large number of termite mounds in the prospect. For geochemical prospecting for rare earth elements (REEs), in total, 200 samples of termite mound material were collected from actinolite rock and granite zones in the prospect. Geochemical analyses of these termite mound materials were conducted by two methods: portable X-ray fluorescence (XRF) spectrometry and inductively coupled plasma-mass spectrometry (ICP-MS). Comparison of the two methods broadly indicates positive correlations of REEs (La, Ce, Pr, Nd, and Y), in particular Y and La having a strong correlation. As the result of modal abundance analyses, the actinolite rock at surface mainly consists of ferro-actinolite (89.89 wt%) and includes xenotime (0.26 wt%) and monazite (0.21 wt%) grains as REE minerals. Termite mound materials from actinolite rock also contain xenotime (0.27 wt%) and monazite (0.41 wt%) grains. In addition, termite mound materials from the actinolite rock zone have high hematite and Fe silicate contents compared to those from granite zone. These relationships suggest that REE minerals in termite mound materials originate form actinolite rock. Geochemical anomaly maps of Y, La, and Fe concentrations drawn based on the result of the portable XRF analyses show that high concentrations of these elements trend from SW to NE which broadly correspond to occurrences of actinolite body. These results indicate that termite mounds are an effective tool for REE geochemical prospection in the study area for both light REEs and Y, but a more detailed survey is required to establish the distribution of the actinolite rock body.

  5. Petrographic features, geochemical trends and mass balance ...

    African Journals Online (AJOL)

    Petrographic features, geochemical trends and mass balance computation, in relation to the evolution of anatectic migmatites in the granulite facies terrain of the Manalur area, Tamil Nadu, south India.

  6. Proceedings of 2. Brazilian Geochemical Congress

    International Nuclear Information System (INIS)

    1989-01-01

    Some works about geochemistry are presented, including themes about geochemical exploration, lithogeochemistry and isotope geochemistry, environmental geochemistry, analytical geochemistry, geochemistry of carbonatites and rare earth elements and organic geochemistry. (C.G.C.) [pt

  7. Collected radiochemical and geochemical procedures

    Energy Technology Data Exchange (ETDEWEB)

    Kleinberg, J [comp.

    1990-05-01

    This revision of LA-1721, 4th Ed., Collected Radiochemical Procedures, reflects the activities of two groups in the Isotope and Nuclear Chemistry Division of the Los Alamos National Laboratory: INC-11, Nuclear and radiochemistry; and INC-7, Isotope Geochemistry. The procedures fall into five categories: I. Separation of Radionuclides from Uranium, Fission-Product Solutions, and Nuclear Debris; II. Separation of Products from Irradiated Targets; III. Preparation of Samples for Mass Spectrometric Analysis; IV. Dissolution Procedures; and V. Geochemical Procedures. With one exception, the first category of procedures is ordered by the positions of the elements in the Periodic Table, with separate parts on the Representative Elements (the A groups); the d-Transition Elements (the B groups and the Transition Triads); and the Lanthanides (Rare Earths) and Actinides (the 4f- and 5f-Transition Elements). The members of Group IIIB-- scandium, yttrium, and lanthanum--are included with the lanthanides, elements they resemble closely in chemistry and with which they occur in nature. The procedures dealing with the isolation of products from irradiated targets are arranged by target element.

  8. Coupling of transport and geochemical models

    International Nuclear Information System (INIS)

    Noy, D.J.

    1986-01-01

    This report considers mass transport in the far-field of a radioactive waste repository, and detailed geochemical modelling of the ground-water in the near-field. A parallel approach to this problem of coupling transport and geochemical codes is the subject of another CEC report (ref. EUR 10226). Both studies were carried out in the framework of the CEC project MIRAGE. (Migration of radionuclides in the geosphere)

  9. On the source inversion of fugitive surface layer releases. Part II. Complex sources

    Science.gov (United States)

    Sanfélix, V.; Escrig, A.; López-Lilao, A.; Celades, I.; Monfort, E.

    2017-06-01

    The experimental measurement of fugitive emissions of particulate matter entails inherent complexity because they are usually discontinuous, of short duration, may be mobile, and are affected by weather conditions. Owing to this complexity, instead of experimental measurements, emission factors are used to inventory such emissions. Unfortunately, emission factor datasets are still very limited at present and are insufficient to identify problematic operations and appropriately select control measures. To extend these datasets, a source inversion methodology (described in Part I of this work) was applied to field campaigns in which operation-specific fugitive particulate matter emission factors were determined for several complex fugitive sources, some of which were mobile. Mobile sources were treated as a superposition of instantaneous sources. The experimental campaigns were conducted at ports (bulk solids terminals), aggregate quarries, and cement factories, encompassing powder handling operations and vehicle circulation on paved and unpaved roads. Emission factors were derived for the operations and materials involved in these scenarios and compared with those available in the emission factor compilations. Significant differences were observed between the emission factors obtained in the studied handling operations. These differences call into question the use of generic emission factors and highlight the need for more detailed studies in this field.

  10. The National Geochemical Survey; database and documentation

    Science.gov (United States)

    ,

    2004-01-01

    The USGS, in collaboration with other federal and state government agencies, industry, and academia, is conducting the National Geochemical Survey (NGS) to produce a body of geochemical data for the United States based primarily on stream sediments, analyzed using a consistent set of methods. These data will compose a complete, national-scale geochemical coverage of the US, and will enable construction of geochemical maps, refine estimates of baseline concentrations of chemical elements in the sampled media, and provide context for a wide variety of studies in the geological and environmental sciences. The goal of the NGS is to analyze at least one stream-sediment sample in every 289 km2 area by a single set of analytical methods across the entire nation, with other solid sample media substituted where necessary. The NGS incorporates geochemical data from a variety of sources, including existing analyses in USGS databases, reanalyses of samples in USGS archives, and analyses of newly collected samples. At the present time, the NGS includes data covering ~71% of the land area of the US, including samples in all 50 states. This version of the online report provides complete access to NGS data, describes the history of the project, the methodology used, and presents preliminary geochemical maps for all analyzed elements. Future editions of this and other related reports will include the results of analysis of variance studies, as well as interpretive products related to the NGS data.

  11. Carborane-beta-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

    Czech Academy of Sciences Publication Activity Database

    Neirynck, P.; Schimer, Jiří; Jonkheijm, P.; Milroy, L. G.; Cígler, Petr; Brunsveld, L.

    2015-01-01

    Roč. 3, č. 4 (2015), s. 539-545 ISSN 2050-750X R&D Projects: GA MŠk(CZ) LH11027 Institutional support: RVO:61388963 Keywords : beta-cyclodextrine/carborane host-guest system * supramolecular chemistry * bioactive surfaces Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.872, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/tb/c4tb01489h

  12. Complex surface deformation of Akutan volcano, Alaska revealed from InSAR time series

    Science.gov (United States)

    Wang, Teng; DeGrandpre, Kimberly; Lu, Zhong; Freymueller, Jeffrey T.

    2018-02-01

    Akutan volcano is one of the most active volcanoes in the Aleutian arc. An intense swarm of volcano-tectonic earthquakes occurred across the island in 1996. Surface deformation after the 1996 earthquake sequence has been studied using Interferometric Synthetic Aperture Radar (InSAR), yet it is hard to determine the detailed temporal behavior and spatial extent of the deformation due to decorrelation and the sparse temporal sampling of SAR data. Atmospheric delay anomalies over Akutan volcano are also strong, bringing additional technical challenges. Here we present a time series InSAR analysis from 2003 to 2016 to reveal the surface deformation in more detail. Four tracks of Envisat data acquired from 2003 to 2010 and one track of TerraSAR-X data acquired from 2010 to 2016 are processed to produce high-resolution surface deformation, with a focus on studying two transient episodes of inflation in 2008 and 2014. For the TerraSAR-X data, the atmospheric delay is estimated and removed using the common-master stacking method. These derived deformation maps show a consistently uplifting area on the northeastern flank of the volcano. From the TerraSAR-X data, we quantify the velocity of the subsidence inside the caldera to be as high as 10 mm/year, and identify another subsidence area near the ground cracks created during the 1996 swarm.

  13. Downscaling Land Surface Temperature in Complex Regions by Using Multiple Scale Factors with Adaptive Thresholds.

    Science.gov (United States)

    Yang, Yingbao; Li, Xiaolong; Pan, Xin; Zhang, Yong; Cao, Chen

    2017-04-01

    Many downscaling algorithms have been proposed to address the issue of coarse-resolution land surface temperature (LST) derived from available satellite-borne sensors. However, few studies have focused on improving LST downscaling in urban areas with several mixed surface types. In this study, LST was downscaled by a multiple linear regression model between LST and multiple scale factors in mixed areas with three or four surface types. The correlation coefficients (CCs) between LST and the scale factors were used to assess the importance of the scale factors within a moving window. CC thresholds determined which factors participated in the fitting of the regression equation. The proposed downscaling approach, which involves an adaptive selection of the scale factors, was evaluated using the LST derived from four Landsat 8 thermal imageries of Nanjing City in different seasons. Results of the visual and quantitative analyses show that the proposed approach achieves relatively satisfactory downscaling results on 11 August, with coefficient of determination and root-mean-square error of 0.87 and 1.13 °C, respectively. Relative to other approaches, our approach shows the similar accuracy and the availability in all seasons. The best (worst) availability occurred in the region of vegetation (water). Thus, the approach is an efficient and reliable LST downscaling method. Future tasks include reliable LST downscaling in challenging regions and the application of our model in middle and low spatial resolutions.

  14. Analysis of progression of fatigue conditions in biceps brachii muscles using surface electromyography signals and complexity based features.

    Science.gov (United States)

    Karthick, P A; Makaram, Navaneethakrishna; Ramakrishnan, S

    2014-01-01

    Muscle fatigue is a neuromuscular condition where muscle performance decreases due to sustained or intense contraction. It is experienced by both normal and abnormal subjects. In this work, an attempt has been made to analyze the progression of muscle fatigue in biceps brachii muscles using surface electromyography (sEMG) signals. The sEMG signals are recorded from fifty healthy volunteers during dynamic contractions under well defined protocol. The acquired signals are preprocessed and segmented in to six equal parts for further analysis. The features, such as activity, mobility, complexity, sample entropy and spectral entropy are extracted from all six zones. The results are found showing that the extracted features except complexity feature have significant variations in differentiating non-fatigue and fatigue zone respectively. Thus, it appears that, these features are useful in automated analysis of various neuromuscular activities in normal and pathological conditions.

  15. The NO-carbon reaction: the influence of potassium and CO on reactivity and populations of oxygen surface complexes

    Energy Technology Data Exchange (ETDEWEB)

    Diana Lopez; Joseph Calo [Brown University, Providence, RI (United States). Division of Engineering

    2007-08-15

    Results on the effects of a metal catalyst and the role of CO as a reducing agent are reported for a resin char and a Wyodak coal char, as well as demineralized samples of the latter. The effect of an active metal catalyst, such as potassium in the current work, is to significantly increase the reactivity both by increasing the number of reaction sites via the catalyst dispersion and reducing the activation energy and by increasing CO{sub 2} production. The latter is a beneficial result because it means that less carbon is consumed per molecule of NO reduced. Additional CO in the gas phase 'catalyzes' NO reduction via the creation of more labile surface complexes and facilitation of desorption of other oxygen complexes. This effect decreases with an increasing temperature and disappears by about 1123 K. The activation energy of this reaction is comparable to that induced by the metal catalyst. 21 refs., 9 figs., 2 tabs.

  16. A coupled remote sensing and the Surface Energy Balance with Topography Algorithm (SEBTA) to estimate actual evapotranspiration under complex terrain

    Science.gov (United States)

    Gao, Z. Q.; Liu, C. S.; Gao, W.; Chang, N. B.

    2010-07-01

    Evapotranspiration (ET) may be used as an ecological indicator to address the ecosystem complexity. The accurate measurement of ET is of great significance for studying environmental sustainability, global climate changes, and biodiversity. Remote sensing technologies are capable of monitoring both energy and water fluxes on the surface of the Earth. With this advancement, existing models, such as SEBAL, S_SEBI and SEBS, enable us to estimate the regional ET with limited temporal and spatial scales. This paper extends the existing modeling efforts with the inclusion of new components for ET estimation at varying temporal and spatial scales under complex terrain. Following a coupled remote sensing and surface energy balance approach, this study emphasizes the structure and function of the Surface Energy Balance with Topography Algorithm (SEBTA). With the aid of the elevation and landscape information, such as slope and aspect parameters derived from the digital elevation model (DEM), and the vegetation cover derived from satellite images, the SEBTA can fully account for the dynamic impacts of complex terrain and changing land cover in concert with some varying kinetic parameters (i.e., roughness and zero-plane displacement) over time. Besides, the dry and wet pixels can be recognized automatically and dynamically in image processing thereby making the SEBTA more sensitive to derive the sensible heat flux for ET estimation. To prove the application potential, the SEBTA was carried out to present the robust estimates of 24 h solar radiation over time, which leads to the smooth simulation of the ET over seasons in northern China where the regional climate and vegetation cover in different seasons compound the ET calculations. The SEBTA was validated by the measured data at the ground level. During validation, it shows that the consistency index reached 0.92 and the correlation coefficient was 0.87.

  17. Phosphorescence quenching of fac-tris(2-phenylpyridyl)iridium(iii) complexes in thin films on dielectric surfaces.

    Science.gov (United States)

    Ribierre, J C; Ruseckas, A; Staton, S V; Knights, K; Cumpstey, N; Burn, P L; Samuel, I D W

    2016-02-07

    We study the influence of the film thickness on the time-resolved phosphorescence and the luminescence quantum yield of fac-tris(2-phenylpyridyl)iridium(iii) [Ir(ppy)3]-cored dendrimers deposited on dielectric substrates. A correlation is observed between the surface quenching velocity and the quenching rate by intermolecular interactions in the bulk film, which suggests that both processes are controlled by dipole-dipole interactions between Ir(ppy)3 complexes at the core of the dendrimers. It is also found that the surface quenching velocity decreases as the refractive index of the substrate is increased. This can be explained by partial screening of dipole-dipole interactions by the dielectric environment.

  18. The monothiocyanate complexes of chromium ion(III) on the silver electrode by the surface enhanced Raman scattering

    Science.gov (United States)

    Wang, Huanru; Wu, Guozhen

    2005-11-01

    Two adsorbate forms of the monothiocyanate complex of chromium ion on the silver electrode are identified in the surface enhanced Raman scattering. The spectroscopic, especially the electronic, properties of these two forms under different applied voltages on the electrode and under both 632.8 and 514.5 nm excitations are studied by the bond force constants (bond orders) and the bond polarizability derivatives which are retrieved from the Raman intensities by an algorithm developed by Wu and co-workers [B. Tian, G. Wu, G. Liu, J. Chem. Phys. 87 (1987) 7300]. The work shows the potential of this approach to the surface enhanced Raman scattering and other fields like resonance Raman that involve vibronic coupling.

  19. Surface complexation modeling of U(VI) sorption on GMZ bentonite in the presence of fulvic acid

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Jie [Lanzhou Univ. (China). Radiochemistry Laboratory; Ministry of Industry and Information Technology, Guangzhou (China). The 5th Electronics Research Inst.; Luo, Daojun [Ministry of Industry and Information Technology, Guangzhou (China). The 5th Electronics Research Inst.; Qiao, Yahua; Wang, Liang; Zhang, Chunming [Ministry of Environmental Protection, Beijing (China). Nuclear and Radiation Safety Center; Wu, Wangsuo [Lanzhou Univ. (China). Radiochemistry Laboratory; Ye, Yuanlv [Ministry of Environmental Protection, Beijing (China). Nuclear and Radiation Safety Center; Lanzhou Univ. (China). Radiochemistry Laboratory

    2017-03-01

    In this work, experiments and modeling for the interactions between uranyl ion and GMZ bentonite in the presence of fulvic acid are presented. The results demonstrated that FA is strongly bound to GMZ bentonite, and these molecules have a very large effect on the U(VI) sorption. The results also demonstrated that U(VI) sorption to GMZ bentonite in the presence and absence of sorbed FA can be well predicted by combining SHM and DLM. According to the model calculations, the nature of the interactions between FA with U(VI) at GMZ bentonite surface is mainly surface complex. The first attempt to simulate clay interaction with humus by the SHM model.

  20. A simple method for the preparation of difficult 99mTc complexes using surface adsorbed stannous ions

    International Nuclear Information System (INIS)

    Maddalena, D.J.; Snowdon, G.M.; Pojer, P.M.

    1987-01-01

    A simple new technique where stannous tin is adsorbed on the inner surface of plastic tubing and used to reduce ( 99m Tc) pertechnetate prior to labelling radiopharmaceuticals, has been evaluated, using some lipophillic and metal containing ligands. Complexes formed using the technique had good labelling efficiency and behaved the same in rat biodistribution studies as those prepared using conventional labelling methods. The labelling efficiency of the ligands was not related to their lipophillicity suggesting that this technique may be useful for labelling lipophillic and other difficult ligands such as those containing metals, which are incompatible with free stannous ions in solution. (M.E.L.) [es

  1. Development of thermodynamic databases and geochemical/transport models for prediction of long-term radionuclide migration (Germany)

    International Nuclear Information System (INIS)

    Kienzler, B.

    2000-01-01

    The isolation capacity of a repository system for radionuclides is described by geochemical modeling. The models for interpretation of experimental findings and for long-term extrapolation of experimental results are based on thermodynamic approaches. The geochemical models include dissolution reactions of waste forms, the evolution of the geochemical milieu, interactions of radionuclides with constituents of the groundwater (brines) and the precipitation of new solid phases. Reliable thermodynamic data, understanding of radionuclide complexation in aqueous multi-electrolyte solutions at the relevant ionic strength and knowledge on the formation of pure and mixed solids and on sorption processes are urgently needed for such model calculations. (author)

  2. Discrete complexes immobilized onto click-SBA-15 silica: controllable loadings and the impact of surface coverage on catalysis.

    Science.gov (United States)

    Nakazawa, Jun; Smith, Brian J; Stack, T Daniel P

    2012-02-08

    Azidopropyl functionalized mesoporous silica SBA-15 were prepared with variable azide loadings of 0.03-0.7 mmol g(-1) (~2-50% of maximal surface coverage) through a direct synthesis, co-condensation approach. These materials are functionalized selectively with ethynylated organic moieties through a copper-catalyzed azide alkyne cycloaddition (CuAAC) or "click" reaction. Specific loading within a material can be regulated by either the azide loading or limiting the alkyne reagent relative to the azide loading. The immobilization of ferrocene, pyrene, tris(pyridylmethyl)amine (TPA), and iron porphyrin (FeTPP) demonstrates the robust nature and reproducibility of this two-step synthetic attachment strategy. Loading-sensitive pyrene fluorescence correlates with a theoretically random surface distribution, rather than a uniform one; site-isolation of tethered moieties ~15 Å in length occurs at loadings less than 0.02 mmol g(-1). The effect of surface loading on reactivity is observed in the oxygenation of SBA-15-[Cu(I)(TPA)]. SBA-15-[Mn(II)(TPA)]-catalyzed epoxidation exhibits a systematic dependence on surface loading. A comparison of homogeneous, site-isolated and site-dense complexes provides insight into catalyst speciation and ligand activity.

  3. Geochemical Characteristics of Overbank Deposits after a Flood Event in a Small, Mountainous River System in the Oregon Coast Range, USA

    Science.gov (United States)

    Guerrero, F. J.; Hatten, J. A.; Goni, M. A.; Gray, A. B.; Pasternack, G. B.

    2014-12-01

    The geochemical characteristics of particulate organic matter (POM) transported by rivers has broad implications in our understanding of aquatic nutrient dynamics, the fate of contaminants, environmental change in watersheds, and carbon export to depositional environments. The major fraction of this POM is mobilized during storms, especially in small mountainous river systems (SMRS) producing complex spatial-temporal POM patterns poorly documented due to logistical difficulties. In this study, we examine the use of overbank flood deposits as a surrogate of a quasi-Lagrangian POM sampling scheme to supplement the conventional Eulerian sampling scheme for POM. We report on the geochemical characteristics of 11 overbank deposits created after a significant flood (10 X mean discharge) along 80 km in the Alsea River, a SMRS in the Oregon Coast Range. We measure organic carbon, nitrogen, stable isotopes, and biomarkers such as lignin-derived phenols as well as particle size distribution and surface area of the deposited sediments. We compared those characteristics with the POM sampled during several storms at a fixed location. Our results suggest that despite the differences in local depositional conditions inferred from particle size distributions and texture, the geochemical properties of overbank deposits resemble the properties of the material in transport, mainly derived from a terrestrial source with a clear signal of gymnosperm wood. Furthermore, the normalized ranges of the geochemical indicators measured across space for one single event are comparable to, or even higher than, the normalized range of the same indicators measured along time at the fixed location. The implications of the amount and quality of the additional information offered by the overbank deposits in POM dynamics in watershed is discussed.

  4. The geochemical behavior of protactinium 231 and its chosen geochemical analogue thorium in the biosphere

    International Nuclear Information System (INIS)

    Gillberg-Wickman, M.

    1983-03-01

    To be able to judge whether protactinium 231 might represent a major contribution to the human radiation risk from high level radioactive waste a literature study of the geochemical behavior of protactinium has been made. The interest in protactinium determinations has, as far, been in the field of marine geochemistry and geochronology. These investigations show that thorium may be used as a chemical analogue. The content of protactinium 231 is determined by the 235 U content and consequently the occurrence of protactinium in nature is directly associated to the geochemistry of uranium. The pronounced hydrolytic tendency of protactinium and its great sorption and coprecipitation capacity ought to prevent or at least appreciably delay its transport from a back-filled nuclear waste vault to the uppermost surface of the earth. It also has a tendency to form colloids or particulates which may be strongly fixed on a rock surface. In adsorption and desorption processes kinetics must play an important role. Our knowledge in this field is quite limited. Under the physico-chemical conditions in the sea, protactinium is rapidly scavenged from the water column by particulates. It accumulates in the sediments. (author)

  5. Excitation of multipolar surface plasmon resonance in plasmonic nanoparticles by complex accelerating beams

    International Nuclear Information System (INIS)

    Yang, Yang; Li, Jiafang; Li, Zhi-Yuan; Chen, Yue-Gang

    2015-01-01

    In this paper, through a vector-spherical harmonics approach, we investigate the optical spectra of plasmonic Au nanoparticles excited by two special accelerating beams: a non-paraxial Airy beam and a Bessel beam. We systematically analyze the impacts of the beam profile, phase, and helical wave front of the electromagnetic fields on the optical spectrum and the excitation of the surface plasmon resonance (SPR). We find that the high-order phase in the Airy beam would result in strong plasmonic oscillations in the optical spectra, while the cone angle and orbital angular momentum carried by the Bessel beam could be employed to engineer the plasmon modes excited in Au nanoparticles. Furthermore, the optical spectrum excited by a combined Airy–Bessel–Gauss beam is discussed. The study could help to deeply explore new ways to manipulate SPR in metal nanoparticles via the wave front engineering of optical beams for enhancing light–matter interaction and optical sensing performance. (paper)

  6. Advantage of Chernobyl radionuclides at modelling of geochemical landscape

    International Nuclear Information System (INIS)

    Samsonenka, I.P.

    2002-01-01

    Any human activity causes a chemical alteration of environment. It occurs as a result of both the immediate emission of pollutants, and of violation of the ecosystems homeostasis. Under technogenic effect a geochemical field becomes still more variegated. This phenomenon is formed by subjective processes. In this case the unconditional application of statistical methods is not correct. Efficiently a contamination patchiness is scrutinised by method of a radioactive label, as some pollutants are allocated on a surface similarly artificial radionuclides. During 10 years the radioecological investigation like this was carried out in the moderate contamination area of Chernobyl zone. Nuclide 137Cs predominant on this terrain was used as a tracer. It turned out that the pollution field heterogeneity is depended on structure of landscape most intimately. The modelling of 137Cs allocation allowed to establish the attitude of background and anomalous zone. Principal premise of beginnings of an anomaly is the interplay of migration streams with geochemical barriers. Combination of these factors determines the radiological and geochemical parameters. The behaviour of other pollutants (Sr, Pb, Cu, Zn, Ni, Cr, Co) in discrete segments of elementary landscape also rather differs. Within test area six types of positive going local geochemical anomalies are being discovered. The detailed analysis of them has resulted in creation of new technique of account of pollutants total inventory. This parameter is computed with the use of correction for a natural patchiness. For example the stoichiometric relationship show that an average of 0.73 % of the total 137Cs inventory was involved in the processes of secondary redistribution. More than on third of this value (0.26 %) was fixed at local geochemical barriers within eluvial landscapes and formed radiogeochemical anomalies at the intra facies level. The other portion of 137Cs inventory (0.47 %) was removed outside the boundaries of

  7. Uncertainty in reactive transport geochemical modelling

    International Nuclear Information System (INIS)

    Oedegaard-Jensen, A.; Ekberg, C.

    2005-01-01

    Full text of publication follows: Geochemical modelling is one way of predicting the transport of i.e. radionuclides in a rock formation. In a rock formation there will be fractures in which water and dissolved species can be transported. The composition of the water and the rock can either increase or decrease the mobility of the transported entities. When doing simulations on the mobility or transport of different species one has to know the exact water composition, the exact flow rates in the fracture and in the surrounding rock, the porosity and which minerals the rock is composed of. The problem with simulations on rocks is that the rock itself it not uniform i.e. larger fractures in some areas and smaller in other areas which can give different water flows. The rock composition can be different in different areas. In additions to this variance in the rock there are also problems with measuring the physical parameters used in a simulation. All measurements will perturb the rock and this perturbation will results in more or less correct values of the interesting parameters. The analytical methods used are also encumbered with uncertainties which in this case are added to the uncertainty from the perturbation of the analysed parameters. When doing simulation the effect of the uncertainties must be taken into account. As the computers are getting faster and faster the complexity of simulated systems are increased which also increase the uncertainty in the results from the simulations. In this paper we will show how the uncertainty in the different parameters will effect the solubility and mobility of different species. Small uncertainties in the input parameters can result in large uncertainties in the end. (authors)

  8. Archean cherts: field, petrographic and geochemical criteria to determine their origin

    Science.gov (United States)

    Ledevin, Morgane; Arndt, Nicholas T.; Simionovici, Alexandre

    2013-04-01

    Archean cherts provide valuable information about conditions on the sea floor during the early history of Earth. We conducted field, petrological and geochemical studies on examples from different environments in the Barberton Greenstone Belt (3.2-3.5 Ga), South Africa, with the aim of improving our understanding of these enigmatic rocks. We distinguish three different origins for cherts: direct precipitation from seawater (C-cherts); precipitation in fractures from silica-rich fluids (F-cherts); and replacement of preexisting rocks (silicification) either at or near the surface (S-cherts). The three types were distinguished using a combination of sedimentary and deformation structures, petrological observations (RAMAN, electron microprobe, X-Ray microfluorescence, cathodoluminescence) and geochemical data. C-cherts best record the composition and physical conditions in primitive oceans and the depositional environment because they precipitated from seawater. Based on sedimentary structures, we show that the silica was deposited as a siliceous ooze or amorphous gel on the seafloor, with variable precipitation rates that depend on the amount and nature of co-precipitated phases (called here the "contaminant"), such as detrital grains, carbonates, carbonaceous matter and oxides. We observe a complex rheology of C-cherts, which show both ductile to brittle deformation structures, sometimes in the same layer. We infer that the cherts underwent extremely rapid diagenetic induration at or near the surface, a process that proceeded faster when contaminants are lacking. Geochemical data (ICP-MS/ICP-AES) indicate that whole rock chemistries are dominated by the contaminant phases. Detrital grains with continental signatures dominate the compositions of cherts in the turbidite sequence of the Komati River whereas carbonates preserving modern, seawater-like compositions control the compositions of cherts of Fig Tree Fm in the Barite Valley. The silica minerals do not

  9. Chirality of weakly bound complexes: The potential energy surfaces for the hydrogen-peroxide−noble-gas interactions

    Energy Technology Data Exchange (ETDEWEB)

    Roncaratti, L. F., E-mail: lz@fis.unb.br; Leal, L. A.; Silva, G. M. de [Instituto de Física, Universidade de Brasília, 70910 Brasília (Brazil); Pirani, F. [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Aquilanti, V. [Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Instituto de Física, Universidade Federal da Bahia, 40210 Salvador (Brazil); Gargano, R. [Instituto de Física, Universidade de Brasília, 70910 Brasília (Brazil); Departments of Chemistry and Physics, University of Florida, Quantum Theory Project, Gainesville, Florida 32611 (United States)

    2014-10-07

    We consider the analytical representation of the potential energy surfaces of relevance for the intermolecular dynamics of weakly bound complexes of chiral molecules. In this paper we study the H{sub 2}O{sub 2}−Ng (Ng=He, Ne, Ar, Kr, and Xe) systems providing the radial and the angular dependence of the potential energy surface on the relative position of the Ng atom. We accomplish this by introducing an analytical representation which is able to fit the ab initio energies of these complexes in a wide range of geometries. Our analysis sheds light on the role that the enantiomeric forms and the symmetry of the H{sub 2}O{sub 2} molecule play on the resulting barriers and equilibrium geometries. The proposed theoretical framework is useful to study the dynamics of the H{sub 2}O{sub 2} molecule, or other systems involving O–O and S–S bonds, interacting by non-covalent forces with atoms or molecules and to understand how the relative orientation of the O–H bonds changes along collisional events that may lead to a hydrogen bond formation or even to selectivity in chemical reactions.

  10. Geochemical Treasure Hunt for Primary School Children

    Science.gov (United States)

    Tesmer, Maja; Frick, Daniel; Gerrits, Ruben; des GFZ-GeoWunderWerkstatt, Schülerlabor

    2017-04-01

    How can you inspire school children for geochemistry, and scientific exploratory urge? The key is to raise their curiosity and make learning new things a hands-on experience. The Fellows of the European Marie Curie Initial Training Network IsoNose designed and established a "Geochemical Treasure Hunt" to excite children for scientific investigations. This workshop explains primary school children the research and scientific methods of isotopic geochemistry, and their use to understand processes on the Earth's surface. From obtaining 'samples', performing various experiments, the school children gather clues leading them to the hidden treasure on the Telegrafenberg (campus of the GFZ Potsdam). The course was designed for school children to learn hands-on the meaning of elements, atoms and isotopes. In small groups the children conduct experiments of simplified methods being indispensable to any isotope geochemist. However, prior to working in any laboratory environment, a security briefing is necessary. For the course, two stages were implemented; firstly the use of harmful substances and dangerous equipment was minimised, and secondly children were equipped with size-matched personal protective equipment (lab coats, gloves, and safety googles). The purification of elements prior to isotopic analysis was visualised using colour chromatography. However, instead of using delicate mass spectrometers for the isotope ratio measurements, the pupils applied flame spectroscopy to analyse their dissolved and purified mineral solutions. Depending on the specific element present, a different colour was observed in the flame. The children plotted their colours of the flame spectroscopy onto a map and by interpreting the emerging colour patterns they localized the treasure on the map. In small teams they swarmed out on the Telegrafenberg to recover the hidden treasure. The project leading to this outreach activity has received funding from the People Programme (Marie Curie

  11. Coal weathering and the geochemical carbon cycle

    Science.gov (United States)

    Chang, Soobum; Berner, Robert A.

    1999-10-01

    The weathering rate of sedimentary organic matter in the continental surficial environment is poorly constrained despite its importance to the geochemical carbon cycle. During this weathering, complete oxidation to carbon dioxide is normally assumed, but there is little proof that this actually occurs. Knowledge of the rate and mechanisms of sedimentary organic matter weathering is important because it is one of the major controls on atmospheric oxygen level through geologic time. We have determined the aqueous oxidation rates of pyrite-free bituminous coal at 24° and 50°C by using a dual-cell flow-through method. Coal was used as an example of sedimentary organic matter because of the difficulty in obtaining pyrite-free kerogen for laboratory study. The aqueous oxidation rate obtained in the present study for air-saturated water (270 μM O2) was found to be on the order of 2 × 10-12 mol O2/m2/s at 25°C, which is fast compared to other geologic processes such as tectonic uplift and exposure through erosion. The reaction order with respect to oxygen level is 0.5 on a several thousand hour time scale for both 24° and 50°C experiments. Activation energies, determined under 24° and 50°C conditions, were ≈40 kJ/mol O2 indicating that the oxidation reaction is surface reaction controlled. The oxygen consumption rate obtained in this study is two to three orders of magnitude smaller than that for pyrite oxidation in water, but still rapid on a geologic time scale. Aqueous coal oxidation results in the formation of dissolved CO2, dissolved organic carbon (DOC), and solid oxidation products, which are all quantitatively significant reaction products.

  12. Geochemical factors influencing vault design and layout

    International Nuclear Information System (INIS)

    Gascoyne, M.; Stroes-Gascoyne, S.; Sargent, F.P.

    1995-01-01

    The design and construction of a vault for used nuclear fuel in crystalline rock may be influenced by a number of geochemical factors. During the siting stage, information is needed regarding the rock type, heterogeneities in its composition and the mineralogy of permeable zones because these will cause variations in thermal conductivity, strength and radionuclide sorptive properties of the rock. These factors may affect decisions regarding depth of vault construction, tunnel dimensions and spacing of panels and waste containers. The decision on whether groundwaters are allowed to flow freely into a planned excavation may depend on measurements of their chemical compositions, microbiological contents and presence of hazardous or corrosive constituents. During site characterization, borehole drilling from the surface and subsequent hydraulic testing will introduce both chemical and microbiological contaminants that may further influence this decision. During vault construction, the geochemistry of the rock may cause changes to the characterization, design and construction of the vault. For example, high salinity fluids in micropores in the rock could prevent the use of radar surveys to detect fractures in the surrounding rock. High rock salinity may also cause unacceptably high total dissolved solids loadings in water discharged from the facility. Again, the presence of toxic, corrosive or radioactive constituents in inflowing groundwater may require grouting or, if inflow is needed for service operations, development of treatment facilities both above and below ground. In addition, the use of explosives will cause high organic and nitrate loadings in service water as well as the possible impregnation of these chemicals in the damaged wall-rock surrounding an excavation. These chemicals may remain despite cleaning efforts and act as nutrients to promote microbial activity in the post-closure phase. In the operational phase, further design and construction, changes

  13. Surface stabilized GMR nanorods of silver coated CrO2 synthesized via a polymer complex at ambient pressure

    International Nuclear Information System (INIS)

    Biswas, S.; Singh, G.P.; Ram, S.; Fecht, H.-J.

    2013-01-01

    Stable anisotropic nanorods of surface modified CrO 2 (∼18 nm diameter) with a correlated diamagnetic layer (2–3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr 4+ ions by Ag atoms on the CrO 2 surface (topotactic surface layer) via an etching reaction of a CrO 2 -polymer complex with Ag + ions in hot water followed by heating the dried sample at 300–400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO 2 such that it no longer converts to Cr 2 O 3 in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO 2 structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d 5/2 and 3d 3/2 X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (−) 7.6% at 77 K, than reported values in compacted CrO 2 powders or composites. Such a large MR-value in the Coulomb blockade regime ( 2 nanorods. - Highlights: • Synthesis and structural studies of a novel GMR material of Ag coated CrO 2 . • Tailoring useful GMR property in CrO 2 nanorods of controlled shape and anisotropy. • Enhanced GMR is explained in correlation to the surface structure of CrO 2 nanorods

  14. The complex dynamics of the seasonal component of USA's surface temperature

    Directory of Open Access Journals (Sweden)

    A. Vecchio

    2010-10-01

    Full Text Available The dynamics of the climate system has been investigated by analyzing the complex seasonal oscillation of monthly averaged temperatures recorded at 1167 stations covering the whole USA. We found the presence of an orbit-climate relationship on time scales remarkably shorter than the Milankovitch period {related to the nutational forcing}. The relationship manifests itself through occasional destabilization of the phase of the seasonal component due to the local changing of balance between direct insolation and the net energy received by the Earth. Quite surprisingly, we found that the local intermittent dynamics is modulated by a periodic component of about 18.6 yr due to the nutation of the Earth, which represents the main modulation of the Earth's precession. The global effect in the last century results in a cumulative phase-shift of about 1.74 days towards earlier seasons, in agreement with the phase shift expected from the Earth's precession. The climate dynamics of the seasonal cycle can be described through a nonlinear circle-map, indicating that the destabilization process can be associated to intermittent transitions from quasi-periodicity to chaos.

  15. The geochemical atlas of Alaska, 2016

    Science.gov (United States)

    Lee, Gregory K.; Yager, Douglas B.; Mauk, Jeffrey L.; Granitto, Matthew; Denning, Paul; Wang, Bronwen; Werdon, Melanie B.

    2016-06-21

    A rich legacy of geochemical data produced since the early 1960s covers the great expanse of Alaska; careful treatment of such data may provide significant and revealing geochemical maps that may be used for landscape geochemistry, mineral resource exploration, and geoenvironmental investigations over large areas. To maximize the spatial density and extent of data coverage for statewide mapping of element distributions, we compiled and integrated analyses of more than 175,000 sediment and soil samples from three major, separate sources: the U.S. Geological Survey, the National Uranium Resource Evaluation program, and the Alaska Division of Geological & Geophysical Surveys geochemical databases. Various types of heterogeneity and deficiencies in these data presented major challenges to our development of coherently integrated datasets for modeling and mapping of element distributions. Researchers from many different organizations and disparate scientific studies collected samples that were analyzed using highly variable methods throughout a time period of more than 50 years, during which many changes in analytical techniques were developed and applied. Despite these challenges, the U.S. Geological Survey has produced a new systematically integrated compilation of sediment and soil geochemical data with an average sample site density of approximately 1 locality per 10 square kilometers (km2) for the entire State of Alaska, although density varies considerably among different areas. From that compilation, we have modeled and mapped the distributions of 68 elements, thus creating an updated geochemical atlas for the State.

  16. Formation, surface characterization, and electrocatalytic application of self-assembled monolayer films of tetra-substituted manganese, iron, and cobalt benzylthio phthalocyanine complexes

    CSIR Research Space (South Africa)

    Akinbulu, IA

    2011-10-01

    Full Text Available Molecular thin films of manganese (SAM-2), iron (SAM-3), and cobalt (SAM-4) phthalocyanine complexes, non-peripherally tetra-substituted with benzylmercapto, were formed on polycrystalline gold disc electrode by selfassembly technique. Surface...

  17. Surface complexation modeling of groundwater arsenic mobility: Results of a forced gradient experiment in a Red River flood plain aquifer, Vietnam

    DEFF Research Database (Denmark)

    Jessen, Søren; Postma, Dieke; Larsen, Flemming

    2012-01-01

    Three surface complexation models (SCMs) developed for, respectively, ferrihydrite, goethite and sorption data for a Pleistocene oxidized aquifer sediment from Bangladesh were used to explore the effect of multicomponent adsorption processes on As mobility in a reduced Holocene floodplain aquifer...

  18. Adaptive Robust Online Constructive Fuzzy Control of a Complex Surface Vehicle System.

    Science.gov (United States)

    Wang, Ning; Er, Meng Joo; Sun, Jing-Chao; Liu, Yan-Cheng

    2016-07-01

    In this paper, a novel adaptive robust online constructive fuzzy control (AR-OCFC) scheme, employing an online constructive fuzzy approximator (OCFA), to deal with tracking surface vehicles with uncertainties and unknown disturbances is proposed. Significant contributions of this paper are as follows: 1) unlike previous self-organizing fuzzy neural networks, the OCFA employs decoupled distance measure to dynamically allocate discriminable and sparse fuzzy sets in each dimension and is able to parsimoniously self-construct high interpretable T-S fuzzy rules; 2) an OCFA-based dominant adaptive controller (DAC) is designed by employing the improved projection-based adaptive laws derived from the Lyapunov synthesis which can guarantee reasonable fuzzy partitions; 3) closed-loop system stability and robustness are ensured by stable cancelation and decoupled adaptive compensation, respectively, thereby contributing to an auxiliary robust controller (ARC); and 4) global asymptotic closed-loop system can be guaranteed by AR-OCFC consisting of DAC and ARC and all signals are bounded. Simulation studies and comprehensive comparisons with state-of-the-arts fixed- and dynamic-structure adaptive control schemes demonstrate superior performance of the AR-OCFC in terms of tracking and approximation accuracy.

  19. Conformational Explosion: Understanding the Complexity of the Para-Dialkylbenzene Potential Energy Surfaces

    Science.gov (United States)

    Mishra, Piyush; Hewett, Daniel M.; Zwier, Timothy S.

    2017-06-01

    This talk focuses on the single-conformation spectroscopy of small-chain para-dialkylbenzenes. This work builds on previous studies from our group on long-chain n-alkylbenzenes that identified the first folded structure in octylbenzene. The dialkylbenzenes are representative of a class of molecules that are common components of coal and aviation fuel and are known to be present in vehicle exhaust. We bring the molecules para-diethylbenzene, para-dipropylbenzene and para-dibutylbenzene into the gas phase and cool the molecules in a supersonic expansion. The jet-cooled molecules are then interrogated using laser-induced fluorescence excitation, fluorescence dip IR spectroscopy (FDIRS) and dispersed fluorescence. The LIF spectra in the S_{0}-S_{1} origin region show dramatic increases in the number of resolved transitions with increasing length of alkyl chains, reflecting an explosion in the number of unique low-energy conformations formed when two independent alkyl chains are present. Since the barriers to isomerization of the alkyl chain are similar in size, this results in an 'egg carton' shape to the potential energy surface. We use a combination of electronic frequency shift and alkyl CH stretch infrared spectra to generate a consistent set of conformational assignments.

  20. Efficient near-real-time monitoring of 3D surface displacements in complex landslide scenarios

    Science.gov (United States)

    Allasia, Paolo; Manconi, Andrea; Giordan, Daniele; Baldo, Marco; Lollino, Giorgio

    2013-04-01

    Ground deformation measurements play a key role in monitoring activities of landslides. A wide spectrum of instruments and methods is nowadays available, going from in-situ to remote sensing approaches. In emergency scenarios, monitoring is often based on automated instruments capable to achieve accurate measurements, possibly with a very high temporal resolution, in order to achieve the best information about the evolution of the landslide in near-real-time, aiming at early warning purposes. However, the available tools for a rapid and efficient exploitation, understanding and interpretation of the retrieved measurements is still a challenge. This issue is particularly relevant in contexts where monitoring is fundamental to support early warning systems aimed at ensuring safety to people and/or infrastructures. Furthermore, in many cases the results obtained might be of difficult reading and divulgation, especially when people of different backgrounds are involved (e.g. scientists, authorities, civil protection operators, decision makers, etc.). In this work, we extend the concept of automatic and near real time from the acquisition of measurements to the data processing and divulgation, in order to achieve an efficient monitoring of surface displacements in landslide scenarios. We developed an algorithm that allows to go automatically and in near-real-time from the acquisition of 3D displacements on a landslide area to the efficient divulgation of the monitoring results via WEB. This set of straightforward procedures is called ADVICE (ADVanced dIsplaCement monitoring system for Early warning), and has been already successfully applied in several emergency scenarios. The algorithm includes: (i) data acquisition and transfer protocols; (ii) data collection, filtering, and validation; (iii) data analysis and restitution through a set of dedicated software, such as ©3DA [1]; (iv) recognition of displacement/velocity threshold and early warning (v) short term

  1. Complex Indigenous Organic Matter Embedded in Apollo 17 Volcanic Black Glass Surface Deposits

    Science.gov (United States)

    Thomas-Keprta, Kathie L.; Clemett, S. J.; Ross, D. K.; Le, L.; Rahman, Z.; Gonzalez, C.; McKay, D. S.; Gibson, E. K.

    2013-01-01

    Papers presented at the first Lunar Science Conference [1] and those published in the subsequent Science Moon Issue [2] reported the C content of Apollo II soils, breccias, and igneous rocks as rang-ing from approx.50 to 250 parts per million (ppm). Later Fegley & Swindle [3] summarized the C content of bulk soils from all the Apollo missions as ranging from 2.5 (Apollo 15) to 280 ppm (Apollo 16) with an overall average of 124+/- 45 ppm. These values are unexpectedly low given that multiple processes should have contributed (and in some cases continue to contribute) to the lunar C inventory. These include exogenous accretion of cometary and asteroidal dust, solar wind implantation, and synthesis of C-bearing species during early lunar volcanism. We estimate the contribution of C from exogenous sources alone is approx.500 ppm, which is approx.4x greater than the reported average. While the assessm ent of indigenous organic matter (OM) in returned lunar samples was one of the primary scientific goals of the Apollo program, extensive analysis of Apollo samples yielded no evidence of any significant indigenous organic species. Furthermore, with such low concentrations of OM reported, the importance of discriminating indigenous OM from terrestrial contamination (e.g., lunar module exhaust, sample processing and handling) became a formidable task. After more than 40 years, with the exception of CH4 [5-7], the presence of indigenous lunar organics still remains a subject of considerable debate. We report for the first time the identification of arguably indigenous OM present within surface deposits of black glass grains collected on the rim of Shorty crater during the Apollo 17 mission by astronauts Eugene Cernan and Harrison Schmitt.

  2. Geochemical information and isotopic ratios in pinpointing the rates of contamination processes generated at mine sites

    Science.gov (United States)

    Turunen, Kaisa; Kittilä, Anniina; Backnäs, Soile; Pasanen, Antti; Hendriksson, Nina

    2015-04-01

    The isotopic composition of water is an important fingerprinting method for tracing recharge sources, distribution processes and possible hydraulic connections of mine waters. However, since, the isotopes alone do not indicate the contamination derived from mining activities; also a set of geochemical analysis of harmful substance in water is acquired. This complex approach will allow a detailed insight in migration of potentially harmful substances, their reactions, mixing and dilution in ground and surface waters. The data can be applied also when comparing geogenic and anthropogenic emissions. Isotopic methods are rather new approach to estimate mining related emissions in Finland and thus, a novel approach of isotopic methods for investigation and monitoring of migration of harmful substances from mine sites are tested in two mine sites in Finland. The aim of this study is to assess the emission sources, flow paths and interaction between mine waters, groundwater and surface waters. A set of isotopic data, including S, Li, Mg, U, Sr, Pb, O, and H, will be combined with chemical information and physical parameters of water in order to assess the source and extent of possible contamination as well as the rates of processes that generate or at best attenuate the contamination. The results obtained from water analyses and field measurements will be used in hydrogeochemical modelling for the prediction of chemical transformation and long-term impacts of mining at study site and its surroundings.

  3. Geochemical indicators for use in the computation of critical loads and dynamic risk assessments

    NARCIS (Netherlands)

    Vries, de W.; Posch, M.; Sverdrup, H.U.; Larssen, T.; Wit, H.A.; Bobbink, R.; Hettelingh, J.P.

    2015-01-01

    This chapter provides an overview of geochemical indicators for nitrogen (N), acidity, and metals in soil and water (soil solution, ground water and surface water) in view of their impacts on different endpoints (tree growth/health, human health, soil biodiversity etc.). Relevant indicators for N

  4. Geochemical investigation of iron transport into bentonite as steel corrodes

    International Nuclear Information System (INIS)

    Hunter, Fiona; Bate, Fiona; Heath, Tim; Hoch, Andrew

    2007-09-01

    some experiments. Using the experimental data as a guide, a modelling investigation has been carried out. The objectives of the modelling investigation were: To develop a geochemical model of the transport of iron into bentonite based on the clear experimental evidence of the penetration of iron into bentonite. To improve our understanding of the desaturation of the bentonite as water is consumed during the corrosion process and the resultant gas(es) escapes. The production of iron from the corroding source was modelled using a rate of gas evolution that had been fitted. It was shown that ion exchange and surface complexation processes do not provide sufficient sorption to predict the high amount of iron observed in the solid phase. Therefore alternative processes, such as iron-containing mineral formation or mineral transformations, were also suggested to account for the amount of iron observed within the bentonite phase. Magnetite was identified as the most thermodynamically stable solubility limiting phase under the experimental conditions. A one-dimensional transport model was constructed to include all relevant processes. The simulations considered the diffusive transport of Fe 2+ ions away from a corroding source, using the rate of gas evolution resulting from the corrosion process. Ion exchange and surface complexation processes were allowed within the bentonite which would provide sorption of iron onto and within the bentonite solid. The pH was buffered by allowing protonation and deprotonation of the surface sites of the bentonite solid. In addition, saturation of iron-containing minerals was permitted. The base case model suggests that about 4.4 wt % of iron could form in the bentonite if the formation of magnetite was allowed. However, the maximum theoretical amount of iron available from the source term is limited to 4.5 wt % of iron by the cumulative gas evolution rate, which is lower than the observed amount of iron in the bulk bentonite (6.6 wt %). A

  5. The Nasca and Palpa geoglyphs: geophysical and geochemical data

    Science.gov (United States)

    Hartsch, Kerstin; Weller, Andreas; Rosas, Silvia; Reppchen, Gunter

    2009-10-01

    The Nasca geoglyphs in the stone desert in southern Peru are part of our world cultural heritage. These remarkable drawings have roused the interest of scientists from different disciplines. Here we report the results of integrated geophysical, petrophysical, mineralogical, and geochemical investigations of the geoglyphs at six test sites in the stone desert around Nasca and Palpa. The geomagnetic measurements revealed clear indications of subsurface structures that differ from the visible surface geoglyphs. The high-resolution geoelectrical images show unexpected resistivity anomalies underneath the geoglyphs down to a depth of about 2 m. Remarkable structures were revealed in both vertical and lateral directions. No evidence was found of geochemical or mineralogical alterations of the natural geogenic materials (desert pavement environment versus geoglyphs). Neither salts nor other mineral materials were used by the Nasca people to alter or prepare the surfaces of geoglyphs. This supports the hypothesis that the Nasca people simply removed stone material down to the natural hard pan horizon to create the geoglyphs.

  6. Uranium exploration data and global geochemical baselines: The need for co-ordinated action

    International Nuclear Information System (INIS)

    Darnley, A.G.

    1997-01-01

    Public concern about environmental problems continues. In order to assess the magnitude of potential problems it is necessary to have comprehensive information. The absence of quantitative geochemical data to map the surface composition of the earth is one of the major information gaps in present day environmental science. An IAEA Technical Committee meeting held in November 1993 reviewed the uses of uranium exploration data for environmental purposes. Most attention was focussed on data involving radiation measurements. Uranium exploration programmes conducted since 1970 in many countries collected a considerable amount of geochemical survey data, providing information about the distribution of non-radioactive elements in the natural environment. Canada is one of several countries where such data provided the foundation for national geochemical mapping; other countries could benefit from similar actions. Increasing importance is being attached by governments to the need to enact effective environmental legislation concerning ''safe levels'' of many chemical substances. Such legislation requires geochemical variations in the natural environment. It is becoming necessary to make quantitative comparisons of element abundances across national boundaries, and from continent to continent. In 1995 the IAEA, with other organizations, supported UNESCO to publish a report concerned with the establishment of a Global Geochemical Reference Network. This is designed to provide a framework to connect all types of geochemical survey, to move towards international compatibility of data. The report contains recommendations relating to the standardization of field and laboratory methods; the use of the most sensitive analytical techniques; and standardization of data management. Ground and airborne gamma ray spectrometry, and nuclear laboratory techniques are all discussed. Following the publication of the report, the International Union of Geological Sciences has now established a

  7. Surface stabilized GMR nanorods of silver coated CrO2 synthesized via a polymer complex at ambient pressure

    Science.gov (United States)

    Biswas, S.; Singh, G. P.; Ram, S.; Fecht, H.-J.

    2013-08-01

    Stable anisotropic nanorods of surface modified CrO2 (˜18 nm diameter) with a correlated diamagnetic layer (2-3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr4+ ions by Ag atoms on the CrO2 surface (topotactic surface layer) via an etching reaction of a CrO2-polymer complex with Ag+ ions in hot water followed by heating the dried sample at 300-400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO2 such that it no longer converts to Cr2O3 in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO2 structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d5/2 and 3d3/2 X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (-) 7.6% at 77 K, than reported values in compacted CrO2 powders or composites. Such a large MR-value in the Coulomb blockade regime (<100 K) arises not only due to the suppressed spin flipping at low temperature but also from a spin dependent co-tunneling through an interlinked structure of silver and silver coated CrO2 nanorods.

  8. Hydrologic Regulation of Global Geochemical Cycles

    Science.gov (United States)

    Maher, K.

    2015-12-01

    Earth's temperature is thought to be regulated by a negative feedback between atmospheric CO2 levels and chemical weathering of silicate rocks. However, direct evidence for the operation of this feedback over million-year timescales is difficult to obtain. For example, weathering fluxes over the last 20 million years of the Cenozoic Era, calculated using marine isotopic proxies (i.e. 87Sr/86Sr, δ7Li, and 187Os/188Os), appear inconsistent with past atmospheric CO2 levels and carbon mass balance. Similarly, observations from modern catchments suggest that chemical weathering fluxes are strongly correlated with erosion rates and only weakly correlated with temperature. As an alternative approach to evaluating the operation of a negative feedback, we use the major surface reservoirs of carbon to determine the imbalance in the geologic carbon cycle and the required silicate weathering flux over the Cenozoic. A miniscule (0.5-1%) increase in silicate weathering is necessary to explain the long-term decline in CO2 levels over the Cenozoic, providing evidence for a strong negative feedback between silicate weathering and climate. Rather than an appreciable increase in the silicate weathering flux, the long-term decrease in CO2levels may be due to an increase in the strength of the silicate weathering feedback. To explain the observed variations in the strength of the weathering feedback during the Cenozoic, we present a model for silicate weathering where hydrologic processes regulate climatic and tectonic forcings due to the presence of a thermodynamic limit to weathering fluxes. Climate regulation by silicate weathering is thus strongest when global topography is elevated, similar to today, and lowest when global topography is more subdued, allowing planetary temperatures to vary depending on the global distribution of topography and mountain belts. These results also motivate several key outstanding challenges in earth surface processes, including the need to

  9. Robust statistics and geochemical data analysis

    International Nuclear Information System (INIS)

    Di, Z.

    1987-01-01

    Advantages of robust procedures over ordinary least-squares procedures in geochemical data analysis is demonstrated using NURE data from the Hot Springs Quadrangle, South Dakota, USA. Robust principal components analysis with 5% multivariate trimming successfully guarded the analysis against perturbations by outliers and increased the number of interpretable factors. Regression with SINE estimates significantly increased the goodness-of-fit of the regression and improved the correspondence of delineated anomalies with known uranium prospects. Because of the ubiquitous existence of outliers in geochemical data, robust statistical procedures are suggested as routine procedures to replace ordinary least-squares procedures

  10. Coupling of transport and geochemical models

    International Nuclear Information System (INIS)

    Noy, D.J.

    1985-01-01

    This contract stipulated separate pieces of work to consider mass transport in the far-field of a repository, and more detailed geochemical modelling of the groundwater in the near-field. It was envisaged that the far-field problem would be tackled by numerical solutions to the classical advection-diffusion equation obtained by the finite element method. For the near-field problem the feasibility of coupling existing geochemical equilibrium codes to the three dimensional groundwater flow codes was to be investigated. This report is divided into two sections with one part devoted to each aspect of this contract. (author)

  11. Uncertainty Analysis of Geochemical Parameters Related To CO2 Leakage into an Unconfined Limestone Aquifer

    Science.gov (United States)

    Bacon, D. H.; Keating, E. H.; Viswanathan, H. S.; Dai, Z.

    2011-12-01

    Accurate prediction of the impact of leaking CO2 on groundwater quality is limited by the complexity of subsurface aquifers and the geochemical reactions that control drinking water compositions. As a result there is a high uncertainty associated with any predictions, hampering monitoring plans, interpretation of the monitoring results, and mitigation plans for a given site. Many physical and geochemical characteristics will dictate a drinking water aquifer's response to a CO2 leak. As a part of the National Risk Assessment Program (NRAP), funded by the U.S. Department of Energy, scientists at Pacific Northwest National Laboratory (PNNL) and Los Alamos National Laboratory (LANL) have collaborated on the development of a 3D heterogeneous model of the Edwards Aquifer in Texas to examine the impacts of CO2 leakage into an unconfined, carbonate aquifer. Using the same base case model, LANL has focused on uncertainty quantification (UQ) of the aquifer's hydraulic properties, whereas PNNL has examined the impact of uncertainty related to geochemical parameters. This abstract describes PNNL's work on geochemical UQ. The uncertainty analysis looks at the impact on several model outputs, including CO2 leakage rate from the water table, mean pH value, and pHdisordered dolomite. We also examine the impact on drinking water quality, specifically TDS, from leakage of brine from the underlying formation, forced upwards by increased pressure due to CO2 injection. To conduct these simulations we use STOMP-CO2-R, which is a multiphase flow simulator, coupled with the reactive transport module ECKEChem, developed at PNNL to simulate CO2 sequestration in deep saline formations and the associated reactions with formation minerals. For uncertainty quantification, we use the PSUADE code. The user defines a range and/or distribution of key input parameters. PSUADE then generates a number of parameter files containing sample points from prescribed sampling method (i.e. Latin hypercube

  12. PHAST--a program for simulating ground-water flow, solute transport, and multicomponent geochemical reactions

    Science.gov (United States)

    Parkhurst, David L.; Kipp, Kenneth L.; Engesgaard, Peter; Charlton, Scott R.

    2004-01-01

    The computer program PHAST simulates multi-component, reactive solute transport in three-dimensional saturated ground-water flow systems. PHAST is a versatile ground-water flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. PHAST is applicable to the study of natural and contaminated ground-water systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock-water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, density-dependent flow, or waters with high ionic strengths. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux, and leaky conditions, as well as the special cases of rivers and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, gases, surface complexation sites, ion exchange sites, and solid solutions; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, gases, exchangers, surfaces, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a

  13. Accurate prediction of complex free surface flow around a high speed craft using a single-phase level set method

    Science.gov (United States)

    Broglia, Riccardo; Durante, Danilo

    2017-11-01

    This paper focuses on the analysis of a challenging free surface flow problem involving a surface vessel moving at high speeds, or planing. The investigation is performed using a general purpose high Reynolds free surface solver developed at CNR-INSEAN. The methodology is based on a second order finite volume discretization of the unsteady Reynolds-averaged Navier-Stokes equations (Di Mascio et al. in A second order Godunov—type scheme for naval hydrodynamics, Kluwer Academic/Plenum Publishers, Dordrecht, pp 253-261, 2001; Proceedings of 16th international offshore and polar engineering conference, San Francisco, CA, USA, 2006; J Mar Sci Technol 14:19-29, 2009); air/water interface dynamics is accurately modeled by a non standard level set approach (Di Mascio et al. in Comput Fluids 36(5):868-886, 2007a), known as the single-phase level set method. In this algorithm the governing equations are solved only in the water phase, whereas the numerical domain in the air phase is used for a suitable extension of the fluid dynamic variables. The level set function is used to track the free surface evolution; dynamic boundary conditions are enforced directly on the interface. This approach allows to accurately predict the evolution of the free surface even in the presence of violent breaking waves phenomena, maintaining the interface sharp, without any need to smear out the fluid properties across the two phases. This paper is aimed at the prediction of the complex free-surface flow field generated by a deep-V planing boat at medium and high Froude numbers (from 0.6 up to 1.2). In the present work, the planing hull is treated as a two-degree-of-freedom rigid object. Flow field is characterized by the presence of thin water sheets, several energetic breaking waves and plungings. The computational results include convergence of the trim angle, sinkage and resistance under grid refinement; high-quality experimental data are used for the purposes of validation, allowing to

  14. Inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    NARCIS (Netherlands)

    Ridley, M.K.; Hiemstra, T.; Riemsdijk, van W.H.; Machesky, M.L.

    2009-01-01

    Acid–base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in

  15. Complex trend of magnetic order in Fe clusters on 4d transition-metal surfaces. I. Experimental evidence and Monte Carlo simulations

    Czech Academy of Sciences Publication Activity Database

    Sessi, V.; Otte, F.; Krotzky, S.; Tieg, C.; Wasniowska, M.; Ferriani, P.; Heinze, S.; Honolka, Jan; Kern, K.

    2014-01-01

    Roč. 89, č. 20 (2014), "205425-1"-"205425-6" ISSN 1098-0121 Institutional support: RVO:68378271 Keywords : iron atoms on 4d metal surfaces * surface magnetism * complex spin order * indirect exchange interactions Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.736, year: 2014

  16. Surface-enhanced Raman scattering and density functional theory study of 1,4-benzenedithiol and its silver complexes.

    Science.gov (United States)

    Shao, Yangfan; Li, Chongyang; Feng, Yuanming; Lin, Wang

    2013-12-01

    This paper experimentally and theoretically investigated Raman and surface-enhanced Raman scattering (SERS) of 1,4-benzenedithiol (1,4-BDT). Density functional theory methods were used to study Raman scattering spectra of isolated 1,4-BDT and 1,4-BDT-Agn (n=2,4,6) complexes with B3LYP/6-311+g(d)(C,H,S)/Lanl2dz(Ag) basis set. A full assignment of the Raman spectrum of 1,4-BDT has been made based on the DFT analysis. The calculated data showed good agreement with experimental observations. The adsorption sites, metal cluster size, and HOMO-LUMO energies are discussed to give insight in the SERS mechanisms for 1,4-BDT molecules. Copyright © 2013 Elsevier B.V. All rights reserved.

  17. Assessing the contributions of surface waves and complex rays to far-field Mie scattering by use of the Debye series

    Science.gov (United States)

    Hovenac, Edward A.; Lock, James A.

    1991-01-01

    The contributions of complex rays and the secondary radiation shed by surface waves to scattering by a dielectric sphere are calculated in the context of the Debye series expansion of the Mie scattering amplitudes. Also, the contributions of geometrical rays are reviewed and compared with the Debye series. Interference effects between surface waves, complex waves, and geometrical waves are calculated, and the possibility of observing these interference effects is discussed. Experimental data supporting the observation of a surface wave-geometrical pattern is presented.

  18. Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

    Science.gov (United States)

    Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

    2018-04-01

    Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

  19. An integrated geochemical and geoelectrical Investigation of an ...

    African Journals Online (AJOL)

    Ife Journal of Science ... Geochemical analysis of borehole soil samples for Total Petroleum Hydrocarbon (TPH), geoelectrical imaging and geotechnical sieve analysis were used to assess the ... Keywords: Geochemical Analysis, Geoelectric Imaging, Borehole Sampling, TPH Concentrations, Oil Spill, Contamination ...

  20. Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex

    Energy Technology Data Exchange (ETDEWEB)

    Nasri, Sameh; Ajili, Yosra [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France); Jaidane, Nejm-Eddine [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Kalugina, Yulia N. [Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation); Halvick, Philippe; Stoecklin, Thierry [Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex (France); Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr [Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

    2015-05-07

    Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is mapped along the intermonomer coordinates. An analytic fit of this 4D-PES is performed. Our extensive computations confirm that the most stable form corresponds to a T-shape structure where the nitrogen molecule points towards the carbon atom of CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} dissociation limit. This 4D-PES is flat and strongly anisotropic along the intermonomer coordinates. This results in the possibility of the occurrence of large amplitude motions within the complex, such as the inversion of N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

  1. Phthalocyaninato complexes with peripheral alkylthio chains: disk-like adsorbate species for the vertical anchoring of ligands on gold surfaces.

    Science.gov (United States)

    Siemeling, Ulrich; Schirrmacher, Christian; Glebe, Ulrich; Bruhn, Clemens; Baio, Joe E; Arnadóttir, Líney; Castner, David G; Weidner, Tobias

    2011-08-01

    Thin metalorganic films were prepared on gold by self-assembly of thioether-functionalised phthalocyaninato complexes from solution. The phthalocyaninato ligands used contain eight peripheral, β-positioned, alkylthio substituents SR (1a: R = n-C(8)H(17), 1b: R = n-C(12)H(25)), which serve as headgroups for surface binding and promote lateral assembly, while the disk-like phthalocyaninato core offers the scope for the attachment of axial ligands to the adsorbed molecules. This process was mimicked by coordination of pyridine (Py) to [Zn(1a)] and [Zn(1b)], respectively. The crystal structures of the products [Zn(1a)(Py)] and [Zn(1b)(Py)] were determined. The crystal structures of 4,5-bis(octylthio)phthalodinitrile and 4,5-bis(dodecylthio)phthalodinitrile were also determined. The films fabricated from [Mn(1a)Cl] and [Mn(1b)Cl] on gold were characterised by XPS, ToF-SIMS and NEXAFS spectroscopy, which revealed the presence of well-defined and homogeneous self-assembled monolayers (SAMs), whose constituents are bound to the substrate by thioether-gold linkages. The orientation of the macrocycles is predominantly parallel to the surface. Strong electronic interaction of the manganese(III) centre with the substrate leads to Cl loss upon adsorption and its reduction to Mn(II).

  2. Synthesis, structural characterization, Hirshfeld surface analysis and spectroscopic studies of cadmium (II) chloride complex with 4-hydroxy-1-methylpiperidine

    Energy Technology Data Exchange (ETDEWEB)

    Soudani, S. [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna (Tunisia); Ferretti, V. [Department of Chemical and Pharmaceutical Sciences and Center for Structural Diffractometry, via Fossato di Mortara 17, I-44121 Ferrara (Italy); Jelsch, C. [CRM2, CNRS, Institut Jean Barriol, Université de Lorraine, Vandoeuvre les Nancy CEDEX (France); Lefebvre, F. [Laboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie Physique Electronique, 69626 Villeurbanne Cedex (France); Nasr, C. Ben, E-mail: cherif_bennasr@yahoo.fr [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna (Tunisia)

    2016-05-15

    The chemical preparation, crystal structure, Hirshfeld surface analysis and spectroscopic characterization of the novel cadmium (II) 4-hydroxy-1-methylpiperidine complex, Cd{sub 4}Cl{sub 10}(C{sub 6}H{sub 14}NO){sub 2}·2H{sub 2}O, have been reported. The atomic arrangement can be described as built up by an anionic framework, formed by edge sharing CdCl{sub 6} and CdCl{sub 5}O octahedral linear chains spreading along the a-axis. These chains are interconnected by water molecules via O–H⋯Cl and O–H⋯O hydrogen bonds to form layers parallel to (011) plane. The organic cations are inserted between layers through C–H⋯Cl hydrogen bonds. Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the H{sub C}⋯Cl and H{sub C}⋯H{sub C} intermolecular interactions are the most abundant contacts of the organic cation in the crystal packing. The statistical analysis of crystal contacts reveals the driving forces in the packing formation. The {sup 13}C and {sup 15}N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks and of the IR bands.

  3. Low-coverage surface diffusion in complex periodic energy landscapes. II. Analytical solution for systems with asymmetric hops

    Science.gov (United States)

    Gosálvez, Miguel A.; Otrokov, Mikhail M.; Ferrando, Nestor; Ryabishchenkova, Anastasia G.; Ayuela, Andres; Echenique, Pedro M.; Chulkov, Evgueni V.

    2016-05-01

    This is part II in a series of two papers that introduce a general expression for the tracer diffusivity in complex, periodic energy landscapes with M distinct hop rates in one-, two-, and three-dimensional diluted systems (low coverage, single-tracer limit). While Part I [Gosálvez et al., Phys. Rev. B 93, 075429 (2016), 10.1103/PhysRevB.93.075429] focuses on the analysis of diffusion in systems where the end sites of the hops are located symmetrically with respect to the hop origins (symmetric hops), as encountered in many ideal surfaces and bulk materials, this report (Part II) presents a more general approach to determining the tracer diffusivity in systems where the end sites can be located asymmetrically with respect to the hop origins (asymmetric hops), as observed in reconstructed and/or chemically modified surfaces and/or bulk materials. The obtained diffusivity formulas for numerous systems are validated against kinetic Monte Carlo simulations and previously reported analytical expressions based on the continuous-time random walk (CTRW) method. The proposed method corrects some of the CTRW formulas and provides new expressions for difficult cases that have not been solved earlier. This demonstrates the ability of the proposed formalism to describe tracer diffusion.

  4. Surface stabilized GMR nanorods of silver coated CrO{sub 2} synthesized via a polymer complex at ambient pressure

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, S., E-mail: drsomnathbiswas@gmail.com [The LNM Institute of Information Technology, Jaipur-302031 (India); Singh, G.P. [Centre for Nanotechnology, Central University of Jharkhand, Ranchi-835205 (India); Ram, S. [Materials Science Centre, Indian Institute of Technology, Kharagpur-721302 (India); Fecht, H.-J. [Insitut für Micro-und Nanomaterialien, Universität Ulm, Albert Einstein Allee-47, Ulm, D-89081, and Forschungszentrum Karlsruhe, Institute of Nanotechnology, Karlsruhe, D-76021 (Germany)

    2013-08-15

    Stable anisotropic nanorods of surface modified CrO{sub 2} (∼18 nm diameter) with a correlated diamagnetic layer (2–3 nm thickness) of silver efficiently tailors useful magnetic and magnetoresistance (MR) properties. Essentially, it involves a core-shell structure that is developed by displacing part of Cr{sup 4+} ions by Ag atoms on the CrO{sub 2} surface (topotactic surface layer) via an etching reaction of a CrO{sub 2}-polymer complex with Ag{sup +} ions in hot water followed by heating the dried sample at 300–400 °C in air. The stable Ag-layer so obtained in the form of a shell protects CrO{sub 2} such that it no longer converts to Cr{sub 2}O{sub 3} in ambient pressure during the processing. X-ray diffractogram of the Rutile type tetragonal CrO{sub 2} structure (lattice parameters a=0.4429 nm and c=0.2950 nm) includes weak peaks of a minority phase of an fcc-Ag (a=0.4086 nm). The silver surface layer, which manifests itself in a doublet of the 3d{sub 5/2} and 3d{sub 3/2} X-ray photoelectron bands of binding energies 368.46 eV and 374.48 eV, respectively, suppresses almost all Cr bands to appear in a measurable intensity. The sample exhibits a distinctly enhanced MR-value, e.g., (−) 7.6% at 77 K, than reported values in compacted CrO{sub 2} powders or composites. Such a large MR-value in the Coulomb blockade regime (<100 K) arises not only due to the suppressed spin flipping at low temperature but also from a spin dependent co-tunneling through an interlinked structure of silver and silver coated CrO{sub 2} nanorods. - Highlights: • Synthesis and structural studies of a novel GMR material of Ag coated CrO{sub 2}. • Tailoring useful GMR property in CrO{sub 2} nanorods of controlled shape and anisotropy. • Enhanced GMR is explained in correlation to the surface structure of CrO{sub 2} nanorods.

  5. An integrated geophysical and geochemical exploration of critical zone weathering on opposing montane hillslope

    Science.gov (United States)

    Singha, K.; Navarre-Sitchler, A.; Bandler, A.; Pommer, R. E.; Novitsky, C. G.; Holbrook, S.; Moore, J.

    2017-12-01

    Quantifying coupled geochemical and hydrological properties and processes that operate in the critical zone is key to predicting rock weathering and subsequent transmission and storage of water in the shallow subsurface. Geophysical data have the potential to elucidate geochemical and hydrologic processes across landscapes over large spatial scales that are difficult to achieve with point measurements alone. Here, we explore the connections between weathering and fracturing, as measured from integrated geochemical and geophysical borehole data and seismic velocities on north- and south-facing aspects within one watershed in the Boulder Creek Critical Zone Observatory. We drilled eight boreholes up to 13 m deep on north- and south-facing aspects within Upper Gordon Gulch, and surface seismic refraction data were collected near these wells to explore depths of regolith and bedrock, as well as anisotropic characteristics of the subsurface material due to fracturing. Optical televiewer data were collected in these wells to infer the dominant direction of fracturing and fracture density in the near surface to corroborate with the seismic data. Geochemical samples were collected from four of these wells and a series of shallow soil pits for bulk chemistry, clay fraction, and exchangeable cation concentrations to identify depths of chemically altered saprolite. Seismic data show that depth to unweathered bedrock, as defined by p-wave seismic velocity, is slightly thicker on the north-facing slopes. Geochemical data suggest that the depth to the base of saprolite ranges from 3-5 m, consistent with a p-wave velocity value of 1200 m/s. Based on magnitude and anisotropy of p-wave velocities together with optical televiewer data, regolith on north-facing slopes is thought to be more fractured than south-facing slopes, while geochemical data indicate that position on the landscape is another important characteristic in determining depths of weathering. We explore the importance

  6. Non-invasive identification of metal-oxalate complexes on polychrome artwork surfaces by reflection mid-infrared spectroscopy.

    Science.gov (United States)

    Monico, Letizia; Rosi, Francesca; Miliani, Costanza; Daveri, Alessia; Brunetti, Brunetto G

    2013-12-01

    In this work a reflection mid-infrared spectroscopy study of twelve metal-oxalate complexes, of interest in art conservation science as alteration compounds, was performed. Spectra of the reference materials highlighted the presence of derivative-like and/or inverted features for the fundamental vibrational modes as result of the main contribution from the surface component of the reflected light. In order to provide insights in the interpretation of theses spectral distortions, reflection spectra were compared with conventional transmission ones. The Kramers-Kronig (KK) algorithm, employed to correct for the surface reflection distortions, worked properly only for the derivative-like bands. Therefore, to pay attention to the use of this algorithm when interpreting the reflection spectra is recommended. The outcome of this investigation was exploited to discriminate among different oxalates on thirteen polychrome artworks analyzed in situ by reflection mid-infrared spectroscopy. The visualization of the νs(CO) modes (1400-1200 cm(-1)) and low wavenumber bands (below 900 cm(-1)) in the raw reflection profiles allowed Ca, Cu and Zn oxalates to be identified. Further information about the speciation of different hydration forms of calcium oxalates were obtained by using the KK transform. The work proves reflection mid-infrared spectroscopy to be a reliable and sensitive spectro-analytical method for identifying and mapping different metal-oxalate alteration compounds on the surface of artworks, thus providing conservation scientists with a non-invasive tool to obtain information on the state of conservation and causes of alteration of artworks. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Effect of pullulan nanoparticle surface charges on HSA complexation and drug release behavior of HSA-bound nanoparticles.

    Directory of Open Access Journals (Sweden)

    Xiaojun Tao

    Full Text Available Nanoparticle (NP compositions such as hydrophobicity and surface charge are vital to determine the presence and amount of human serum albumin (HSA binding. The HSA binding influences drug release, biocompatibility, biodistribution, and intercellular trafficking of nanoparticles (NPs. Here, we prepared 2 kinds of nanomaterials to investigate HSA binding and evaluated drug release of HSA-bound NPs. Polysaccharides (pullulan carboxyethylated to provide ionic derivatives were then conjugated to cholesterol groups to obtain cholesterol-modified carboxyethyl pullulan (CHCP. Cholesterol-modified pullulan (CHP conjugate was synthesized with a similar degree of substitution of cholesterol moiety to CHCP. CHCP formed self-aggregated NPs in aqueous solution with a spherical structure and zeta potential of -19.9 ± 0.23 mV, in contrast to -1.21 ± 0.12 mV of CHP NPs. NPs could quench albumin fluorescence intensity with maximum emission intensity gradually decreasing up to a plateau at 9 to 12 h. Binding constants were 1.12 × 10(5 M(-1 and 0.70 × 10(5 M(-1 to CHP and CHCP, respectively, as determined by Stern-Volmer analysis. The complexation between HSA and NPs was a gradual process driven by hydrophobic force and inhibited by NP surface charge and shell-core structure. HSA conformation was altered by NPs with reduction of α-helical content, depending on interaction time and particle surface charges. These NPs could represent a sustained release carrier for mitoxantrone in vitro, and the bound HSA assisted in enhancing sustained drug release.

  8. Appliance of geochemical engineering in radioactive waste disposal

    International Nuclear Information System (INIS)

    Li Shuang; Zhang Chengjiang; Ni Shijun; Li Kuanliang

    2008-01-01

    The basic foundation of applying geochemical engineering to control environment, common engineering models of disposal radioactive waste and the functions of the engineering barriers are introduced in this paper. The authors take the geochemical engineering barrier materiel research of a radioactive waste repository as an example to explain the appliance of geochemical engineering in the disposal of radioactive waste. And the results show that it can enhance the security of the nuclear waste repository if we use geochemical engineering barrier. (authors)

  9. Geochemical assessment of fluoride enrichment and nitrate ...

    Indian Academy of Sciences (India)

    62

    minerals. By reducing the consumption of fertilizer and stress over groundwater, the water quality can be improved. Key Word- Hydro-geochemistry, Fluoride, ... source (industries effluent, fertilizer industry and fertilizer used in agriculture field) influences ...... groundwater of the Taiyuan basin, Northern China; J. Geochem.

  10. Geochemical modelling baseline compositions of groundwater

    DEFF Research Database (Denmark)

    Postma, Diederik Jan; Kjøller, Claus; Andersen, Martin Søgaard

    2008-01-01

    dissolution (East Midlands, Valreas and Aveiro). Reactive transport models, employing the code PHREEQC, which included these geochemical processes and one-dimensional solute transport were able to duplicate the observed patterns in water quality. These models may provide a quantitative understanding...

  11. Geochemical fingerprints and pebbles zircon geochronology

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Earth System Science; Volume 125; Issue 7. Geochemical fingerprints and pebbles zircon geochronology: Implications for the provenance and tectonic setting of Lower Cretaceous sediments in the Zhucheng Basin (Jiaodong peninsula, North China). Jin-Long Ni Jun-Lai Liu Xiao-Ling Tang ...

  12. Kriging - a challenge in geochemical mapping

    Czech Academy of Sciences Publication Activity Database

    Štojdl, J.; Matys Grygar, Tomáš; Elznicová, J.; Popelka, J.; Váchová, T.; Hošek, Michal

    2017-01-01

    Roč. 19, APR (2017) ISSN 1607-7962. [EGU General Assembly 2017. 23.04.2017-28.04.2017, Vienna] Institutional support: RVO:61388980 Keywords : kriging * geochemical mapping Subject RIV: DD - Geochemistry http://meetingorganizer. copernicus .org/EGU2017/EGU2017-3615.pdf

  13. Discriminating four tectonic settings: Five new geochemical ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Earth System Science; Volume 115; Issue 5. Discriminating four tectonic settings: Five new geochemical diagrams for basic and ultrabasic volcanic rocks based on log–ratio transformation of major-element data. Surendra P Verma Mirna Guevara Salil Agrawal. Volume 115 Issue 5 October 2006 ...

  14. Association between physical and geochemical characteristics of ...

    African Journals Online (AJOL)

    ... as well as in waters relatively rich in uranium, rubidium, vanadium and manganese. It was clear that the occurrence of algae coincided with specific geological formations. These algae could act as indicator species of geology and heavy metals. Keywords: thermal springs, Limpopo Province, algae, diversity, geochemical ...

  15. Implementation and Testing of Advanced Surface Boundary Conditions Over Complex Terrain in A Semi-idealized Model

    Science.gov (United States)

    Li, Y.; Epifanio, C.

    2017-12-01

    In numerical prediction models, the interaction between the Earth's surface and the atmosphere is typically accounted for in terms of surface layer parameterizations, whose main job is to specify turbulent fluxes of heat, moisture and momentum across the lower boundary of the model domain. In the case of a domain with complex geometry, implementing the flux conditions (particularly the tensor stress condition) at the boundary can be somewhat subtle, and there has been a notable history of confusion in the CFD community over how to formulate and impose such conditions generally. In the atmospheric case, modelers have largely been able to avoid these complications, at least until recently, by assuming that the terrain resolved at typical model resolutions is fairly gentle, in the sense of having relatively shallow slopes. This in turn allows the flux conditions to be imposed as if the lower boundary were essentially flat. Unfortunately, while this flat-boundary assumption is acceptable for coarse resolutions, as grids become more refined and the geometry of the resolved terrain becomes more complex, the appproach is less justified. With this in mind, the goal of our present study is to explore the implementation and usage of the full, unapproximated version of the turbulent flux/stress conditions in atmospheric models, thus taking full account of the complex geometry of the resolved terrain. We propose to implement the conditions using a semi-idealized model developed by Epifanio (2007), in which the discretized boundary conditions are reduced to a large, sparse-matrix problem. The emphasis will be on fluxes of momentum, as the tensor nature of this flux makes the associated stress condition more difficult to impose, although the flux conditions for heat and moisture will be considered as well. With the resulotion of 90 meters, some of the results show that the typical differences between flat-boundary cases and full/stress cases are on the order of 10%, with extreme

  16. Study of solid/liquid and solid/gas interfaces in Cu–isoleucine complex by surface X-ray diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Ferrer, Pilar, E-mail: ferreres@esrf.fr [SpLine Spanish CRG Beamline at the ESRF, 38000 Grenoble (France); Instituto de Ciencia de Materiales de Madrid, 28049 Madrid (Spain); Rubio-Zuazo, Juan; Castro, German R. [SpLine Spanish CRG Beamline at the ESRF, 38000 Grenoble (France); Instituto de Ciencia de Materiales de Madrid, 28049 Madrid (Spain)

    2013-02-15

    The enzymes could be understood like structures formed by amino acids bonded with metals, which act as active sites. The research on the coordination of metal–amino acid complexes will bring light on the behavior of metal enzymes, due to the close relation existing between the atomic structure and the functionality. The Cu–isoleucine bond is considered as a good model system to attain a better insight into the characteristics of naturally occurring copper metalloproteins. The surface structure of metal–amino acid complex could be considered as a more realistic model for real systems under biologic working conditions, since the molecular packing is decreased. In the surface, the structural constrains are reduced, keeping the structural capability of surface complex to change as a function of the surrounding environment. In this work, we present a surface X-ray diffraction study on Cu–isoleucine complex under different ambient conditions. Cu(Ile){sub 2} crystals of about 5 mm × 5 mm × 1 mm have been growth, by seeding method in a supersaturated solution, presenting a surface of high quality. The sample for the surface diffraction study was mounted on a cell specially designed for solid/liquid or solid/gas interface analysis. The Cu–isoleucine crystal was measured under a protective dry N{sub 2} gas flow and in contact with a saturated metal amino acid solution. The bulk and the surface signals were compared, showing different atomic structures. In both cases, from surface diffraction data, it is observed that the atomic structure of the top layer undergoes a clear structural deformation. A non-uniform surface relaxation is observed producing an inhomogeneous displacement of the surface atoms towards the surface normal.

  17. Effect of surface conditioning modalities on the repair bond strength of resin composite to the zirconia core / veneering ceramic complex.

    Science.gov (United States)

    Ozcan, Mutlu; Valandro, Luiz Felipe; Pereira, Sarina Maciel; Amaral, Regina; Bottino, Marco Antonio; Pekkan, Gurel

    2013-06-01

    This study evaluated the effect of different surface conditioning protocols on the repair strength of resin composite to the zirconia core / veneering ceramic complex, simulating the clinical chipping phenomenon. Forty disk-shaped zirconia core (Lava Zirconia, 3M ESPE) (diameter: 3 mm) specimens were veneered circumferentially with a feldspathic veneering ceramic (VM7, Vita Zahnfabrik) (thickness: 2 mm) using a split metal mold. They were then embedded in autopolymerizing acrylic with the bonding surfaces exposed. Specimens were randomly assigned to one of the following surface conditioning protocols (n = 10 per group): group 1, veneer: 4% hydrofluoric acid (HF) (Porcelain Etch) + core: aluminum trioxide (50-µm Al2O3) + core + veneer: silane (ESPE-Sil); group 2: core: Al2O3 (50 µm) + veneer: HF + core + veneer: silane; group 3: veneer: HF + core: 30 µm aluminum trioxide particles coated with silica (30 µm SiO2) + core + veneer: silane; group 4: core: 30 µm SiO2 + veneer: HF + core + veneer: silane. Core and veneer ceramic were conditioned individually but no attempt was made to avoid cross contamination of conditioning, simulating the clinical intraoral repair situation. Adhesive resin (VisioBond) was applied to both the core and the veneer ceramic, and resin composite (Quadrant Posterior) was bonded onto both substrates using polyethylene molds and photopolymerized. After thermocycling (6000 cycles, 5°C-55°C), the specimens were subjected to shear bond testing using a universal testing machine (1 mm/min). Failure modes were identified using an optical microscope, and scanning electron microscope images were obtained. Bond strength data (MPa) were analyzed statistically using the non-parametric Kruskal-Wallis test followed by the Wilcoxon rank-sum test and the Bonferroni Holm correction (α = 0.05). Group 3 demonstrated significantly higher values (MPa) (8.6 ± 2.7) than those of the other groups (3.2 ± 3.1, 3.2 ± 3, and 3.1 ± 3.5 for groups 1, 2, and 4

  18. Proceedings of 13. International Geochemical Exploration Symposium. 2. Brazilian Geochemical Congress

    International Nuclear Information System (INIS)

    1989-01-01

    Some works about geochemistry are presented, including themes about geochemical exploration, lithogeochemistry and isotope geochemistry, environmental geochemistry, analyical geochemistry, geochemistry of carbonatites and rare earth elements and organic geochemistry. (C.G.C.) [pt

  19. Alaska Geochemical Database (AGDB)-Geochemical data for rock, sediment, soil, mineral, and concentrate sample media

    Science.gov (United States)

    Granitto, Matthew; Bailey, Elizabeth A.; Schmidt, Jeanine M.; Shew, Nora B.; Gamble, Bruce M.; Labay, Keith A.

    2011-01-01

    The Alaska Geochemical Database (AGDB) was created and designed to compile and integrate geochemical data from Alaska in order to facilitate geologic mapping, petrologic studies, mineral resource assessments, definition of geochemical baseline values and statistics, environmental impact assessments, and studies in medical geology. This Microsoft Access database serves as a data archive in support of present and future Alaskan geologic and geochemical projects, and contains data tables describing historical and new quantitative and qualitative geochemical analyses. The analytical results were determined by 85 laboratory and field analytical methods on 264,095 rock, sediment, soil, mineral and heavy-mineral concentrate samples. Most samples were collected by U.S. Geological Survey (USGS) personnel and analyzed in USGS laboratories or, under contracts, in commercial analytical laboratories. These data represent analyses of samples collected as part of various USGS programs and projects from 1962 to 2009. In addition, mineralogical data from 18,138 nonmagnetic heavy mineral concentrate samples are included in this database. The AGDB includes historical geochemical data originally archived in the USGS Rock Analysis Storage System (RASS) database, used from the mid-1960s through the late 1980s and the USGS PLUTO database used from the mid-1970s through the mid-1990s. All of these data are currently maintained in the Oracle-based National Geochemical Database (NGDB). Retrievals from the NGDB were used to generate most of the AGDB data set. These data were checked for accuracy regarding sample location, sample media type, and analytical methods used. This arduous process of reviewing, verifying and, where necessary, editing all USGS geochemical data resulted in a significantly improved Alaska geochemical dataset. USGS data that were not previously in the NGDB because the data predate the earliest USGS geochemical databases, or were once excluded for programmatic reasons

  20. Geochemical databases. Part 1. Pmatch: a program to manage thermochemical data. Part 2. The experimental validation of geochemical computer models

    International Nuclear Information System (INIS)

    Pearson, F.J. Jr.; Avis, J.D.; Nilsson, K.; Skytte Jensen, B.

    1993-01-01

    This work is carried out under cost-sharing contract with European Atomic Energy Community in the framework of its programme on Management and Storage of Radioactive Wastes. Part 1: PMATCH, A Program to Manage Thermochemical Data, describes the development and use of a computer program, by means of which new thermodynamic data from literature may be referenced to a common frame and thereby become internally consistent with an existing database. The report presents the relevant thermodynamic expressions and their use in the program is discussed. When there is not sufficient thermodynamic data available to describe a species behaviour under all conceivable conditions, the problems arising are thoroughly discussed and the available data is handled by approximating expressions. Part II: The Experimental Validation of Geochemical Computer models are the results of experimental investigations of the equilibria established in aqueous suspensions of mixtures of carbonate minerals (Calcium, magnesium, manganese and europium carbonates) compared with theoretical calculations made by means of the geochemical JENSEN program. The study revealed that the geochemical computer program worked well, and that its database was of sufficient validity. However, it was observed that experimental difficulties could hardly be avoided, when as here a gaseous component took part in the equilibria. Whereas the magnesium and calcium carbonates did not demonstrate mutual solid solubility, this produced abnormal effects when manganese and calcium carbonates were mixed resulting in a diminished solubility of both manganese and calcium. With tracer amounts of europium added to a suspension of calcite in sodium carbonate solutions long term experiments revealed a transition after 1-2 months, whereby the tracer became more strongly adsorbed onto calcite. The transition is interpreted as the nucleation and formation of a surface phase incorporating the 'species' NaEu(Co 3 ) 2

  1. Geochemical evolution of magmatism in Archean granite-greenstone terrains

    Science.gov (United States)

    Samsonov, A. V.; Larionova, Yu. O.

    2006-05-01

    Evolution of Archean magmatism is one of the key problems concerning the early formation stages of the Earth crust and biosphere, because that evolution exactly controlled variable concentrations of chemical elements in the World Ocean, which are important for metabolism. Geochemical evolution of magmatism between 3.5 and 2.7 Ga is considered based on database characterizing volcanic and intrusive rock complexes of granite-greenstone terrains (GGT) studied most comprehensively in the Karelian (2.9-2.7 Ga) and Kaapvaal (3.5-2.9 Ga) cratons and in the Pilbara block (3.5-2.9 Ga). Trends of magmatic geochemical evolution in the mentioned GGTs were similar in general. At the early stage of their development, tholeiitic magmas were considerably enriched in chalcophile and siderophile elements Fe2O3, MgO, Cr, Ni, Co, V, Cu, and Zn. At the next stage, calc-alkaline volcanics of greenstone belts and syntectonic TTG granitoids were enriched in lithophile elements Rb, Cs, Ba, Th, U, Pb, Nb, La, Sr, Be and others. Elevated concentrations of both the “crustal” and “mantle-derived” elements represented a distinctive feature of predominantly intrusive rocks of granitoid composition, which were characteristic of the terminal stage of continental crust formation in the GGTs, because older silicic rocks and lithospheric mantle were jointly involved into processes of magma generation. On the other hand, the GGTs different in age reveal specific trends in geochemical evolution of rock associations close in composition and geological position. First, the geochemical cycle of GGT evolution was of a longer duration in the Paleoarchean than in the Meso-and Neoarchean. Second, the Paleoarche an tholeiitic associations had higher concentrations of LREE and HFSE (Zr, Ti, Th, Nb, Ta, Hf) than their Meso-and Neoarchean counterparts. Third, the Y and Yb concentrations in Paleoarchean calc-alkaline rock associations are systematically higher than in Neoarchean rocks of the same type

  2. Geochemical characteristics and organic carbon sources within the ...

    Indian Academy of Sciences (India)

    This paper uses C isotopic methods coupled with other geochemical parameters to investigate differences in the geochemical characteristics and sources of organic C within the Nanpan and Beipan rivers, two upstream tributaries to the Xi River. 2. Geographic, hydrologic, and geochemical setting. The Nanpan and Beipan ...

  3. Geochemical baseline studies of soil in Finland

    Science.gov (United States)

    Pihlaja, Jouni

    2017-04-01

    The soil element concentrations regionally vary a lot in Finland. Mostly this is caused by the different bedrock types, which are reflected in the soil qualities. Geological Survey of Finland (GTK) is carrying out geochemical baseline studies in Finland. In the previous phase, the research is focusing on urban areas and mine environments. The information can, for example, be used to determine the need for soil remediation, to assess environmental impacts or to measure the natural state of soil in industrial areas or mine districts. The field work is done by taking soil samples, typically at depth between 0-10 cm. Sampling sites are chosen to represent the most vulnerable areas when thinking of human impacts by possible toxic soil element contents: playgrounds, day-care centers, schools, parks and residential areas. In the mine districts the samples are taken from the areas locating outside the airborne dust effected areas. Element contents of the soil samples are then analyzed with ICP-AES and ICP-MS, Hg with CV-AAS. The results of the geochemical baseline studies are published in the Finnish national geochemical baseline database (TAPIR). The geochemical baseline map service is free for all users via internet browser. Through this map service it is possible to calculate regional soil baseline values using geochemical data stored in the map service database. Baseline data for 17 elements in total is provided in the map service and it can be viewed on the GTK's web pages (http://gtkdata.gtk.fi/Tapir/indexEN.html).

  4. Geochemical Signature of Amazon Tropical Rainforest Soils

    Directory of Open Access Journals (Sweden)

    José João Lelis Leal de Souza

    2018-02-01

    Full Text Available ABSTRACT: Evaluating soil geochemical diversity in the Amazon Basin has been a challenge largely because most study sites have been at the edge of the basin and it is difficult to get samples in such a region. Here we show that even among the most weathered soils, physicochemical soil properties express lithology. Our results are based on topsoil samples collected from different locations in minimally disturbed areas in the state of Amazonas, Brazil. Soil properties were measured using methods which are suitable for highly developed soils. The Chemical Index Alteration and Weathering Index of Parker was calculated based on the content of metal(loids in soils determined by X-ray fluorescence. Descriptive statistics, Pearson correlation, and Principal Component Analysis (PCA were performed on data. In general, Amazon rainforest soils are more deeply weathered than soils in other Brazilian biomes and tropical rainforests in Asia and Africa. The high coefficient of variation of metal(loid contents express pedogenesis and parent material diversity. Correlation analysis indicated that the tri-pentavalent elements are strongly associated with Al and Fe contents in the topsoil. In contrast, mono-divalent elements are correlated with sand and silt fractions. According to PCA, five soil groups with defined geochemical compositions and degrees of weathering could be identified: i acidic sandy podzolized soils; ii acidic loamy ferralitic soils with the highest content of tri-pentavalent ions; iii acidic clayey kaolinitic soils with low metal(loid contents; iv acidic loamy kaolinitic soils with low metal(loid contents; and v silty neutral 2:1 clay soils. This study is the first effort to analyze the geochemical diversity in Amazon rainforest soils. These data are extremely valuable in determining the geochemical background for these soil types and this region. Geochemical variability can be predicted to some extent by lithology and pedogenesis, which can be

  5. Alligator Rivers Analogue project. Geochemical Data Bases

    International Nuclear Information System (INIS)

    Bennett, D.G.; Read, D.

    1992-01-01

    The Koongarra uranium deposit in the Northern Territory of Australia is being studied to evaluate the processes involved in the geochemical alteration of the ore body and the formation of the uranium dispersion fan. A broad range of research is being undertaken into the geochemistry and hydrology of the site with the aim of understanding the transport of radionuclides through the system. During the project a range of geochemical and hydrogeochemical models have been developed to account for measured data from the site and with which to predict site evolution. The majority of these models are based on the premise of thermodynamic chemical equilibrium and employ fundamental thermodynamic data to characterise the chemistry of the system. From the differences which exist between the thermodynamic data bases (Appendices I and II) it is possible to gain a view of the level of uncertainty associated with thermodynamic data in each set of calculations. This report gives a brief introduction to the geochemical processes underlying the models, and details the equations used to quantify the more common of these processes (e.g. aqueous speciation and mineral solubility). A description is given of the computer codes (EQ3/6, PHREEQE, MINTEQ) most commonly used during the project for geochemical modelling. Their key features are highlighted and comparisons made. It is concluded that the degree of uncertainty in geochemical modelling studies arising as a result of using one code rather than another is relatively insignificant when compared to that related to differences in the underlying data bases. 73 refs., 3 figs

  6. Chemical functionalization of crystalline silicon surface with complexes of type (M3 (Dpa) 4X2) for the development of electronic devices

    International Nuclear Information System (INIS)

    Sanchez Zamora, Maria Alejandra

    2012-01-01

    New surfaces on crystalline silicon (100) diamines have been developed. The diamines 4-aminopyridine, 4-aminomethylpyridine and 1,12-dodecildiame, and self-assembled surfaces Si-diamine-metallic complexes, with cooper (II) acetate and trimetal Cu 3 (dpa) 4 CI 2 were studied. These surfaces are characterized with X-ray photoelectron spectroscopy (XPS), chemical force microscopy (CFM), by contact angle and cyclic voltammetry (CV). The XPS has suggested the formation of diamines monolayers with covalent binding to crystalline silicon, and modification of these surfaces, with metal complexes by coordination chemistry. The CFM has confirmed that surfaces are modified with diamines and cooper (II) acetate, and that were determined different chemical forces according to the change. The contact angle has been suggested that the functionalized surface with 4-aminomethylpyridine has had similar basicity to 1,12-dodecildiame, and more than 4-aminopyridine. This implies that the coordination with metallics complexes is benefited with 4-aminopyridine, which in turn is reflected with electrochemical data. Cyclic voltammetry analysis have showed that silicon surfaces with 4-aminomethylpyridine and 4-aminopyridine with cooper (II) acetate and trimetal have been electrochemically active. Thus, the surfaces could to have interesting applications in molecular electronics. (author) [es

  7. Preliminary study of volcano monitoring using geochemical composition of lichen

    Science.gov (United States)

    KUAN, S.

    2012-12-01

    Taipei City, the capital of Taiwan, is bounded with Tatun Volcano Group (TVG), which is not active since 200 ka. However, some evidences indicate that the latest explosion of volcanic ash was dated to 5-6 ka as well as TVG is so close to metropolis. The monitoring on TVG is crucial for crisis management. For monitoring TVG, changes of geochemical signal in some volcanic gases and hot springs are currently assessed by monthly sampling. The geochemistry of volcanic gas and hot spring represents a short-term condition on sampling time and is highly controlled by temperature and precipitation on the surface. A long-term average geochemistry will be very helpful to be compared with the results of volcanic gas and hot spring. A bioindicator not only has the ability to store geochemical compositions in their tissues but also has a wide geographical distribution. It is very suitable in this kind of study and lichen is one of the best bioindicators mainly because lichens grow slowly and have a large-scale dependence upon the environment for their nutrition, In TVG, the high SO2 content in the atmosphere results in the absence of fruticose lichen. On the contrary, crustos lichen is the most common species in the study area. For the preliminary analysis, one fruticose, four foliose and four crustos lichens were collected around the major emission centers of volcanic gas. According to the results of ICP-MS analysis, the abundances of heavy metals are generally in the order of Zn, Fe, Mn, Cu, Cr, Pb, Cd, Ni, V, Co and U. Factor analysis (FA) demonstrates that most of the metals show very high loadings in the first factor. This means that the fractionation of metals among different lichen species is minor and the geochemical compositions of lichen are possibly controlled by the same source (atmosphere). The second factor of FA includes Mn, Sr and Ba, which share the same oxidation state of +2 in acidic environment. This factor can describe the variation of Mn, Sr and Ba in the

  8. Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

    Science.gov (United States)

    Fernandes, M Marques; Scheinost, A C; Baeyens, B

    2016-08-01

    The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one

  9. Uranium(VI) transport modeling: geochemical data and submodels

    International Nuclear Information System (INIS)

    Tripathi, V.S.

    1984-01-01

    Understanding the geochemical mobility of U(VI) and modeling its transport is important in several contexts including ore genesis, uranium exploration, nuclear and mill-tailings waste management, and solution mining of uranium ores. Adsorption is a major control on partitioning of solutes at the mineral/solution interface. The effect of carbonate, fluoride, and phosphate complexing on adsorption of uranium was investigated. A critical compilation of stability constants of inorganic complexes and solid compounds of U(VI) necessary for proper design of experiment and for modeling transport of uranium was prepared. The general features of U(VI) adsorption in ligand-free systems are similar to those characteristic of other hydrolyzable metal ions. The adsorption processes studied were found to be reversible. The adsorption model developed in ligand-free systems, when solution complexing is taken into account, proved remarkably successful in describing adsorption of uranium in the presence of carbonate and fluoride. The presence of phosphate caused a much smaller decrease in the extent of adsorption than expected; however, a critical reassessment of the stability of UO 2 2+ .HPO 4 2- complexes, showed that phosphato complexes, if any, are extremely weak under experimental conditions. Removal of uranium may have occurred due to precipitation of sodium uranyl phosphates in addition to adsorption

  10. Geochemical engineering problem identification and program description. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Crane, C.H.; Kenkeremath, D.C.

    1981-05-01

    The Geochemical Engineering Program has as its goal the improvement of geochemical fluid management techniques. This document presents the strategy and status of the Geochemical Engineering Program. The magnitude and scope of geochemical-related problems constraining geothermal industry productivity are described. The goals and objectives of the DGE Geochemical Engineering Program are defined. The rationale and strategy of the program are described. The structure, priorities, funding, and management of specific elements within the program are delineated, and the status of the overall program is presented.

  11. Crustal seismicity associated to rpid surface uplift at Laguna del Maule Volcanic Complex, Southern Volcanic Zone of the Andes

    Science.gov (United States)

    Cardona, Carlos; Tassara, Andrés; Gil-Cruz, Fernando; Lara, Luis; Morales, Sergio; Kohler, Paulina; Franco, Luis

    2018-03-01

    Laguna del Maule Volcanic Complex (LMVC, Southern Andes of Chile) has been experiencing large rates (ca. 30 cm/yr) of surface uplift as detected since 2008 by satellite geodetic measurements. Previous works have modeled the source of this deformation as an inflating rectangular sub-horizontal sill underlying LMVC at 5 km depth, which is supposedly related to an active process of magmatic replenishment of a shallow silicic reservoir. However little is known about the tectonic context on which this activity is taking place, particularly its relation with crustal seismicity that could help understanding and monitoring the current deformation process. Here we present the first detailed characterization of the seismic activity taking place at LMVC and integrate it with structural data acquired in the field in order to illuminate the possible connection between the ongoing process of surface uplift and the activation of crustal faults. Our main finding is the recognition of repetitive volcano-tectonic (VT) seismic swarms that occur periodically between 2011 and 2014 near the SW corner of the sill modeled by InSAR studies. A cross-correlation analysis of the waveforms recorded for these VT events allows identifying three different seismic families. Families F1 and F3 share some common features in the stacked waveform and its locations, which markedly differ from those of family F2. Swarms belonging to this later family are more energetic and its energy was increasing since 2011 to a peak in January 2013, which coincide with maximum vertical velocities detected by local GPS stations. This points to a common process relating both phenomena. The location of VT seismic swarms roughly coincides with the intersection of a NE-SW lineament with a WNW-ESE lineament. The former shows clear field evidences of dextral strike-slip that are fully consistent with one nodal plane of focal mechanism for well-recorded F2 events. The conjugate nodal plane of these focal mechanisms could

  12. Remarkable fluorescence enhancement versus complex formation of cationic porphyrins on the surface of ZnO nanoparticles

    KAUST Repository

    Aly, Shawkat Mohammede

    2014-06-12

    Fluorescence enhancement of organic fluorophores shows tremendous potential to improve image contrast in fluorescence-based bioimaging. Here, we present an experimental study of the interaction of two cationic porphyrins, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride (TMPyP) and meso-tetrakis(4-N,N,N-trimethylanilinium)porphyrin chloride (TMAP), with cationic surfactant-stabilized zinc oxide nanoparticles (ZnO NPs) based on several steady-state and time-resolved techniques. We show the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic porphyrins. For TMPyP, we observe a sixfold increase in the fluorescence intensity of TMPyP upon addition of ZnO NPs. Our experimental results indicate that the electrostatic binding of TMPyP with the surface of ZnO NPs increases the symmetry of the porphyrin macrocycle. This electronic communication hinders the rotational relaxation of the meso unit and/or decreases the intramolecular CT character between the cavity and the meso substituent of the porphyrin, resulting in the enhancement of the intensity of the fluorescence. For TMAP, on the other hand, the different type and nature of the positive charge resulting in the development of the CT band arise from the interaction with the surface of ZnO NPs. This observation is confirmed by the femtosecond transient absorption spectroscopy, which provides clear spectroscopic signatures of photoinduced electron transfer from TMAP to ZnO NPs. © 2014 American Chemical Society.

  13. Estimation of Supraglacial Dust and Debris Geochemical Composition via Satellite Reflectance and Emissivity

    Directory of Open Access Journals (Sweden)

    Kimberly Casey

    2012-09-01

    Full Text Available We demonstrate spectral estimation of supraglacial dust, debris, ash and tephra geochemical composition from glaciers and ice fields in Iceland, Nepal, New Zealand and Switzerland. Surface glacier material was collected and analyzed via X-ray fluorescence spectroscopy (XRF and X-ray diffraction (XRD for geochemical composition and mineralogy. In situ data was used as ground truth for comparison with satellite derived geochemical results. Supraglacial debris spectral response patterns and emissivity-derived silica weight percent are presented. Qualitative spectral response patterns agreed well with XRF elemental abundances. Quantitative emissivity estimates of supraglacial SiO2 in continental areas were 67% (Switzerland and 68% (Nepal, while volcanic supraglacial SiO2 averages were 58% (Iceland and 56% (New Zealand, yielding general agreement. Ablation season supraglacial temperature variation due to differing dust and debris type and coverage was also investigated, with surface debris temperatures ranging from 5.9 to 26.6 C in the study regions. Applications of the supraglacial geochemical reflective and emissive characterization methods include glacier areal extent mapping, debris source identification, glacier kinematics and glacier energy balance considerations.

  14. Application of cluster analysis to geochemical compositional data for identifying ore-related geochemical anomalies

    Science.gov (United States)

    Zhou, Shuguang; Zhou, Kefa; Wang, Jinlin; Yang, Genfang; Wang, Shanshan

    2017-12-01

    Cluster analysis is a well-known technique that is used to analyze various types of data. In this study, cluster analysis is applied to geochemical data that describe 1444 stream sediment samples collected in northwestern Xinjiang with a sample spacing of approximately 2 km. Three algorithms (the hierarchical, k-means, and fuzzy c-means algorithms) and six data transformation methods (the z-score standardization, ZST; the logarithmic transformation, LT; the additive log-ratio transformation, ALT; the centered log-ratio transformation, CLT; the isometric log-ratio transformation, ILT; and no transformation, NT) are compared in terms of their effects on the cluster analysis of the geochemical compositional data. The study shows that, on the one hand, the ZST does not affect the results of column- or variable-based (R-type) cluster analysis, whereas the other methods, including the LT, the ALT, and the CLT, have substantial effects on the results. On the other hand, the results of the row- or observation-based (Q-type) cluster analysis obtained from the geochemical data after applying NT and the ZST are relatively poor. However, we derive some improved results from the geochemical data after applying the CLT, the ILT, the LT, and the ALT. Moreover, the k-means and fuzzy c-means clustering algorithms are more reliable than the hierarchical algorithm when they are used to cluster the geochemical data. We apply cluster analysis to the geochemical data to explore for Au deposits within the study area, and we obtain a good correlation between the results retrieved by combining the CLT or the ILT with the k-means or fuzzy c-means algorithms and the potential zones of Au mineralization. Therefore, we suggest that the combination of the CLT or the ILT with the k-means or fuzzy c-means algorithms is an effective tool to identify potential zones of mineralization from geochemical data.

  15. Applying a modified Donnan model to describe the surface complexation of chromate to iron oxyhydroxide agglomerates with heteromorphous pores.

    Science.gov (United States)

    Wei, Zongsu; Semiat, Raphael

    2017-11-15

    In this study, a modified Donnan model (mDM) is incorporated into surface complexation model (SCM) to better understand the physicochemical processes for adsorption of hexavalent chromium, Cr(VI), on porous iron oxyhydroxide agglomerates (IOAs). The mDM includes a chemical potential term μ att to account for ionic transport and electrostatic interaction in micropores (d mi 2nm) demonstrating high Cr(VI) adsorption in a broad range of ionic strengths. The batch data was then fitted with Donnan model in PHREEQC to obtain Stern (ψ S ) and Donnan (ψ D ) potentials used for μ att calculation. The decreasing μ att values with ionic strength indicated obstructing effect of electrolyte ions on Cr(VI) uptake in micropores. Finally, the ionic activity coefficients and reaction constants were corrected using Pitzer model due to the high level electrolytes accumulated in the Donnan layer through osmotic and electrostatic attraction. Results of this study have captured the effects of inner structure of IOAs on Cr(VI) uptake and quantitatively discerned the contribution of micropores and macropores for adsorption reactions at different ionic strengths. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Geochemical prospecting in Morrinhos area - Ceara

    International Nuclear Information System (INIS)

    Andrade, V.A. de; Campos, M. de; Braga, A. de P.G.

    1982-01-01

    Morrinhos ring-shaped structure has been considered by several authors as reflecting a non-rising pluton, related to the regional uranium mineralization. NUCLEBRAS carried out a geochemical prospecting in the area, (through soil and stream samples), to better understand the relationship between the structure and the ore bodies. The 229 samples were all analysed for 33 trace-elements, using optical spectrography and X-ray fluorescence methods. (Author) [pt

  17. Summary report on geochemical barrier special study

    International Nuclear Information System (INIS)

    1988-12-01

    Long-term management of uranium mill tailings must provide assurance that soluble contaminants will not migrate beyond the Point of Compliance. Conventional management alternatives provide containment through the use of physical barriers which are designed to prevent migration of water through the tailings pile. An alternative is to geochemically modify the tailings to immobilize the contaminants. This investigation examined three potential geochemical modifiers to determine their ability to immobilize inorganic groundwater contaminants found in uranium mill tailings. These modifiers were hydrated lime (Ca(OH) 2 ), limestone (CaCO 3 ), and a sphaegnum peat moss. This investigation focused on both the geochemical interactions between the tailings and the modifiers, and the effects the modifiers had on the physical strength of the tailings. The geochemical investigations began with characterization of the tailings by X-ray diffraction and scanning electron microscopy. This was followed by batch leaching experiments in which various concentrations of each modifier were added to tailings in shaker flasks and allowed to come to equilibrium. Finally, column experiments were conducted to simulate flow through a tailings pile. The results show that all of the modifiers were at least moderately effective at immobilizing most of the groundwater contaminants of concern at uranium mill tailings sites. Hydrated lime was able to achieve 90 percent concentration reduction of arsenic, cadmium, selenium, uranium, and sulfate when added at a two percent concentration. Limestone was somewhat less effective and peat removed greater than 90 percent of arsenic, lead, uranium, and sulfate at a one percent concentration. The column tests showed that kinetic and/or mass transfer limitations are important and that sufficient time must be allowed for the immobilization reactions to occur

  18. Geochemical characterization of surface water and spring water in ...

    Indian Academy of Sciences (India)

    Water samples from precipitation, glacier melt, snow melt, glacial lake, streams and karst springs were collected across SE of Kashmir Valley, to understand the hydrogeochemical processes governing the evolution of the water in a natural and non-industrial area of western Himalayas. The time series data on solute ...

  19. A Fast Independent Component Analysis Algorithm for Geochemical Anomaly Detection and Its Application to Soil Geochemistry Data Processing

    Directory of Open Access Journals (Sweden)

    Bin Liu

    2014-01-01

    Full Text Available A fast independent component analysis algorithm (FICAA is introduced to process geochemical data for anomaly detection. In geochemical data processing, the geological significance of separated geochemical elements must be explicit. This requires that correlation coefficients be used to overcome the limitation of indeterminacy for the sequences of decomposed signals by the FICAA, so that the sequences of the decomposed signals can be correctly reflected. Meanwhile, the problem of indeterminacy in the scaling of the decomposed signals by the FICAA can be solved by the cumulative frequency method (CFM. To classify surface geochemical samples into true anomalies and false anomalies, assays of the 1 : 10 000 soil geochemical data in the area of Dachaidan in the Qinghai province of China are processed. The CFM and FICAA are used to detect the anomalies of Cu and Au. The results of this research demonstrate that the FICAA can demultiplex the mixed signals and achieve results similar to actual mineralization when 85%, 95%, and 98% are chosen as three levels of anomaly delineation. However, the traditional CFM failed to produce realistic results and has no significant use for prospecting indication. It is shown that application of the FICAA to geochemical data processing is effective.

  20. Hydrogeological and geochemical studies in the Perch Lake basin

    International Nuclear Information System (INIS)

    Barry, P.J.

    1979-08-01

    The Perch Lake basin is a small drainage system along the Ottawa River about 200 km west of Ottawa on the Canadian Shield. Since 1975, groups of scientists from several Canadian universities and government departments have been studying the hydrological, geological and geochemical properties of the basin. The object of these studies is to develop and test simulation models used to describe the time-dependent mass flow rates of water and dissolved and suspended substances through the basin. To review progress, a symposium/workshop was held at Chalk Rier in 1978 April. This report contains 24 extended summaries of the material presented verbally at the workshop. Subject matters include atmospheric sources and sinks, mass flows through the surface and subsurface regimes in the drainage basins and interactions occurring in the lake. (author)

  1. The 'glass earth' - geochemical frontiers in exploration through cover

    International Nuclear Information System (INIS)

    Carr, G.; Denton, G.; Giblin, A.; Korsch, M.; Andrew, A.; Whitford, D.

    1999-01-01

    'Glass Earth' represents a number of current and planned projects within CSIRO aimed at making 'transparent' the top 1000 m of the Earth's crust It builds upon current technologies developed within a number of CSIRO divisions as well as the Australian Mineral Exploration Technologies CRC (AMET CRC), the Australian Geodynamics CRC (AG CRC) and the CRC for Landscape Evolution and Mineral Exploration (CRC LEME). New geophysical and geochemical technologies will be developed to complement these, together with new capabilities in modelling, data integration and visualisation, including hydrogeochemistry, hydrogeology, surface geochemistry and isotope geochemistry, modelling of chemical, fluid and heat flows in rock and regolith, advanced visualisation and data fusion. This paper describes some recent work in the field of isotope geochemistry, with the principal aim of 'seeing through' cover to understand basement geology and detect hidden ore systems

  2. Sharp fronts within geochemical transport problems

    International Nuclear Information System (INIS)

    Grindrod, P.

    1995-01-01

    The authors consider some reactive geochemical transport problems in groundwater systems. When incoming fluid is in disequilibrium with the mineralogy sharp transition fronts may develop. They show that this is a generic property for a class of systems where the timescales associated with reaction and diffusion phenomena are much shorter than those associated with advective transport. Such multiple timescale problems are relevant to a variety of processes in natural systems: mathematically methods of singular perturbation theory reduce the dimension of the problems to be solved locally. Furthermore, they consider how spatial heterogeneous mineralogy can impact upon the propagation of sharp geochemical fronts. The authors developed an asymptotic approach in which they solve equations for the evolving geometry of the front and indicate how the non-smooth perturbations due to natural heterogeneity of the mineralogy on underlying ground water flow field are balanced against the smoothing effect of diffusion/dispersive processes. Fronts are curvature damped, and the results here indicate the generic nature of separate front propagation within both model (idealized) and natural (heterogeneous) geochemical systems

  3. Exploring inclusion complexes of ionic liquids with α- and β- cyclodextrin by NMR, IR, mass, density, viscosity, surface tension and conductance study

    Science.gov (United States)

    Barman, Biraj Kumar; Rajbanshi, Biplab; Yasmin, Ananya; Roy, Mahendra Nath

    2018-05-01

    The formation of the host-guest inclusion complexes of ionic liquids namely [BMIm]Cl and [HMIm]Cl with α-CD and β-CD were studied by means of physicochemical and spectroscopic methods. Conductivity and surface tension study were in good agreement with the 1H NMR and FT-IR studies which confirm the formation of the inclusion complexes. The Density and viscosity study also supported the formation of the ICs. Further the stoichiometry was determined 1:1 for each case and the association constants and thermodynamic parameters derived supported the most feasible formation of the [BMIm]Cl- β-CD inclusion complex.

  4. A Geochemical Reaction Model for Titration of Contaminated Soil and Groundwater at the Oak Ridge Reservation

    Science.gov (United States)

    Zhang, F.; Parker, J. C.; Gu, B.; Luo, W.; Brooks, S. C.; Spalding, B. P.; Jardine, P. M.; Watson, D. B.

    2007-12-01

    This study investigates geochemical reactions during titration of contaminated soil and groundwater at the Oak Ridge Reservation in eastern Tennessee. The soils and groundwater exhibits low pH and high concentrations of aluminum, calcium, magnesium, manganese, various trace metals such as nickel and cobalt, and radionuclides such as uranium and technetium. The mobility of many of the contaminant species diminishes with increasing pH. However, base additions to increase pH are strongly buffered by various precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior and associated geochemical effects is thus critical to evaluate remediation performance of pH manipulation strategies. This study was undertaken to develop a practical but generally applicable geochemical model to predict aqueous and solid-phase speciation during soil and groundwater titration. To model titration in the presence of aquifer solids, an approach proposed by Spalding and Spalding (2001) was utilized, which treats aquifer solids as a polyprotic acid. Previous studies have shown that Fe and Al-oxyhydroxides strongly sorb dissolved Ni, U and Tc species. In this study, since the total Fe concentration is much smaller than that of Al, only ion exchange reactions associated with Al hydroxides are considered. An equilibrium reaction model that includes aqueous complexation, precipitation, ion exchange, and soil buffering reactions was developed and implemented in the code HydroGeoChem 5.0 (HGC5). Comparison of model results with experimental titration curves for contaminated groundwater alone and for soil- water systems indicated close agreement. This study is expected to facilitate field-scale modeling of geochemical processes under conditions with highly variable pH to develop practical methods to control contaminant mobility at geochemically complex sites.

  5. Refined ab initio intermolecular ground-state potential energy surface for the He-C2H2 van der Waals complex

    DEFF Research Database (Denmark)

    Fernández, Berta; Henriksen, Christian; Farrelly, David

    2013-01-01

    A refined CCSD(T) intermolecular potential energy surface is developed for the He-C2H2 van der Waals complex. For this, 206 points on the intermolecular potential energy surface, evaluated using the CCSD(T) method and the aug-cc-pVQZ basis set extended with a set of 3s3p2d1f1g midbond functions...... previously by Munteanu and Fernández (J. Chem. Phys., 123, 014309, 2005) but differs notably at short range. The improved potential energy surface should, therefore, be particularly useful for computations of collision line broadening. Dynamical calculations of a number of rovibrational bound state energies...

  6. Diethylenetriamine/diamines/copper (II complexes [Cu(dien(NN]Br2: Synthesis, solvatochromism, thermal, electrochemistry, single crystal, Hirshfeld surface analysis and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Fatima Abu Saleemh

    2017-09-01

    Full Text Available Two dicationic water soluble mixed triamine/diamine copper (II complexes, of general formula [Cu(dienNN]Br2 (1–2 [dien = diethelenetriamine and NN is en = ethylenediamine or Me4en = N,N′,N,N′-tetramethylethylenediamine] were prepared under ultrasonic mode with a relatively high yield. These complexes were characterized by elemental microanalysis, UV visible IR spectroscopy, and thermal and electrochemical techniques. In addition, complex 2 structure was solved by X-ray single crystal and Hirshfeld surface analysis. The complex exhibits a distorted square pyramidal coordination environment around Cu(II centre. The solvatochromism of the desired complexes was investigated in water and other suitable organic solvents. The results show that the Guttmann’s DN parameter values of the solvents have mainly contributed to the shift of the d–d absorption band towards the linear increase in the wavelength of the absorption maxima of the complexes. The complex 1 showed higher antibacterial activity against the studied microorganisms compared to complex 2. Both complexes revealed promising antibacterial activities.

  7. inner-sphere complexation of cations at the rutile-water interface: A concise surface structural interpretation with the CD and MUSIC model

    Energy Technology Data Exchange (ETDEWEB)

    Ridley, Mora K. [Texas Tech University, Lubbock; Hiemstra, T [Oak Ridge National Laboratory (ORNL); Van Riemsdijk, Willem H. [Wageningen University and Research Centre, The Netherlands; Machesky, Michael L. [Illinois State Water Survey, Champaign, IL

    2009-01-01

    Acid base reactivity and ion-interaction between mineral surfaces and aqueous solutions is most frequently investigated at the macroscopic scale as a function of pH. Experimental data are then rationalized by a variety of surface complexation models. These models are thermodynamically based which in principle does not require a molecular picture. The models are typically calibrated to relatively simple solid-electrolyte solution pairs and may provide poor descriptions of complex multicomponent mineral aqueous solutions, including those found in natural environments. Surface complexation models may be improved by incorporating molecular-scale surface structural information to constrain the modeling efforts. Here, we apply a concise, molecularly-constrained surface complexation model to a diverse suite of surface titration data for rutile and thereby begin to address the complexity of multi-component systems. Primary surface charging curves in NaCl, KCl, and RbCl electrolyte media were fit simultaneously using a charge distribution (CD) and multisite complexation (MUSIC) model [Hiemstra T. and Van Riemsdijk W. H. (1996) A surface structural approach to ion adsorption: the charge distribution (CD) model. J. Colloid Interf. Sci. 179, 488 508], coupled with a Basic Stern layer description of the electric double layer. In addition, data for the specific interaction of Ca2+ and Sr2+ with rutile, in NaCl and RbCl media, were modeled. In recent developments, spectroscopy, quantum calculations, and molecular simulations have shown that electrolyte and divalent cations are principally adsorbed in various inner-sphere configurations on the rutile 110 surface [Zhang Z., Fenter P., Cheng L., Sturchio N. C., Bedzyk M. J., Pr edota M., Bandura A., Kubicki J., Lvov S. N., Cummings P. T., Chialvo A. A., Ridley M. K., Be ne zeth P., Anovitz L., Palmer D. A., Machesky M. L. and Wesolowski D. J. (2004) Ion adsorption at the rutile water interface: linking molecular and macroscopic

  8. Bacterial communities associated with subsurface geochemical processes in continental serpentinite springs.

    Science.gov (United States)

    Brazelton, William J; Morrill, Penny L; Szponar, Natalie; Schrenk, Matthew O

    2013-07-01

    Reactions associated with the geochemical process of serpentinization can generate copious quantities of hydrogen and low-molecular-weight organic carbon compounds, which may provide energy and nutrients to sustain subsurface microbial communities independently of the photosynthetically supported surface biosphere. Previous microbial ecology studies have tested this hypothesis in deep sea hydrothermal vents, such as the Lost City hydrothermal field. This study applied similar methods, including molecular fingerprinting and tag sequencing of the 16S rRNA gene, to ultrabasic continental springs emanating from serpentinizing ultramafic rocks. These molecular surveys were linked with geochemical measurements of the fluids in an interdisciplinary approach designed to distinguish potential subsurface organisms from those derived from surface habitats. The betaproteobacterial genus Hydrogenophaga was identified as a likely inhabitant of transition zones where hydrogen-enriched subsurface fluids mix with oxygenated surface water. The Firmicutes genus Erysipelothrix was most strongly correlated with geochemical factors indicative of subsurface fluids and was identified as the most likely inhabitant of a serpentinization-powered subsurface biosphere. Both of these taxa have been identified in multiple hydrogen-enriched subsurface habitats worldwide, and the results of this study contribute to an emerging biogeographic pattern in which Betaproteobacteria occur in near-surface mixing zones and Firmicutes are present in deeper, anoxic subsurface habitats.

  9. A geostatistical method applied to the geochemical study of the Chichinautzin Volcanic Field in Mexico

    Science.gov (United States)

    Robidoux, P.; Roberge, J.; Urbina Oviedo, C. A.

    2011-12-01

    The origin of magmatism and the role of the subducted Coco's Plate in the Chichinautzin volcanic field (CVF), Mexico is still a subject of debate. It has been established that mafic magmas of alkali type (subduction) and calc-alkali type (OIB) are produced in the CVF and both groups cannot be related by simple fractional crystallization. Therefore, many geochemical studies have been done, and many models have been proposed. The main goal of the work present here is to provide a new tool for the visualization and interpretation of geochemical data using geostatistics and geospatial analysis techniques. It contains a complete geodatabase built from referred samples over the 2500 km2 area of CVF and its neighbour stratovolcanoes (Popocatepetl, Iztaccihuatl and Nevado de Toluca). From this database, map of different geochemical markers were done to visualise geochemical signature in a geographical manner, to test the statistic distribution with a cartographic technique and highlight any spatial correlations. The distribution and regionalization of the geochemical signatures can be viewed in a two-dimensional space using a specific spatial analysis tools from a Geographic Information System (GIS). The model of spatial distribution is tested with Linear Decrease (LD) and Inverse Distance Weight (IDW) interpolation technique because they best represent the geostatistical characteristics of the geodatabase. We found that ratio of Ba/Nb, Nb/Ta, Th/Nb show first order tendency, which means visible spatial variation over a large scale area. Monogenetic volcanoes in the center of the CVF have distinct values compare to those of the Popocatepetl-Iztaccihuatl polygenetic complex which are spatially well defined. Inside the Valley of Mexico, a large quantity of monogenetic cone in the eastern portion of CVF has ratios similar to the Iztaccihuatl and Popocatepetl complex. Other ratios like alkalis vs SiO2, V/Ti, La/Yb, Zr/Y show different spatial tendencies. In that case, second

  10. Using skin surface temperature to differentiate between complex regional pain syndrome type 1 patients after a fracture and control patients with various complaints after a fracture

    NARCIS (Netherlands)

    S.P. Niehof (Sjoerd); A. Beerthuizen (Annemerle); F.J.P.M. Huygen (Frank); F.J. Zijlstra (Freek)

    2008-01-01

    textabstractOBJECTIVE: In this study, we assessed the validity of skin surface temperature recordings, based on various calculation methods applied to the thermographic data, to diagnose acute complex regional pain syndrome type 1 (CRPS1) fracture patients. METHODS: Thermographic recordings of the

  11. TOUGHREACT User's Guide: A Simulation Program for Non-isothermal Multiphase Reactive geochemical Transport in Variably Saturated Geologic Media

    International Nuclear Information System (INIS)

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2004-01-01

    Coupled modeling of subsurface multiphase fluid and heat flow, solute transport and chemical reactions can be used for the assessment of mineral alteration in hydrothermal systems, waste disposal sites, acid mine drainage remediation, contaminant transport, and groundwater quality. A comprehensive non-isothermal multi-component reactive fluid flow and geochemical transport simulator, TOUGHREACT, has been developed. A wide range of subsurface thermo-physical-chemical processes is considered under various thermohydrological and geochemical conditions of pressure, temperature, water saturation, and ionic strength. The program can be applied to one-, two- or three-dimensional porous and fractured media with physical and chemical heterogeneity. The model can accommodate any number of chemical species present in liquid, gas and solid phases. A variety of equilibrium chemical reactions are considered, such as aqueous complexation, gas dissolution/exsolution, and cation exchange. Mineral dissolution/precipitation can proceed either subject to local equilibrium or kinetic conditions. Changes in porosity and permeability due to mineral dissolution and precipitation can be considered. Linear adsorption and decay can be included. For the purpose of future extensions, surface complexation by double layer model is coded in the program. Xu and Pruess (1998) developed a first version of a non-isothermal reactive geochemical transport model, TOUGHREACT, by introducing reactive geochemistry into the framework of the existing multi-phase fluid and heat flow code TOUGH2 (Pruess, 1991). Xu, Pruess, and their colleagues have applied the program to a variety of problems such as: (1) supergene copper enrichment (Xu et al, 2001), (2) caprock mineral alteration in a hydrothermal system (Xu and Pruess, 2001a), and (3) mineral trapping for CO 2 disposal in deep saline aquifers (Xu et al, 2003b and 2004a). For modeling the coupled thermal, hydrological, and chemical processes during heater

  12. Studies of surface complexation of H+, NpO2+, Co2+, Th4+ onto TiO2 and H+, UO22+ onto alumina

    International Nuclear Information System (INIS)

    Jakobsson, Anna-Maria; Albinsson, Yngve

    1998-11-01

    This report describes the determination of surface complexation reactions of some radionuclides on mineral oxides from sorption experiments and potentiometric titrations. The surface acidity constants of the mineral oxide have been determined using potentiometric titrations. A description and discussion of the extrapolation method used is included as well as the calibration method which is of uttermost importance for calculating the constants. In this report it is shown that the data close to pH pzc can not be used to calculate the apparent equilibrium constants since the assumption that either the positive or negative sites dominate gives rise to a pK app that approach infinity. Furthermore it is shown that it is a fair estimation to assume a linear relationship between the inner surface charge and the potential since pure titanium dioxide gives a pK app that has a linear dependence on the inner surface charge. Besides the surface acidity constants, the capacitance of the inner layer has been calculated from this linear dependence. The values of these agree well with other proposed in the literature. The sorption of cobalt, thorium and neptunyl ions onto titanium dioxide and uranyl ions onto alumina from aqueous solution was studied as a function of pH and ionic strength in a C0 2 free environment at moderate radionuclide concentrations. Two different experimental methods were employed; an on-line method in which samples withdrawn at a specific pH are separated and measured, and a batch method. There is no significant difference between the average results from the two methods, however the on-line method provides less scatter. Also, using this method we were able to study the desorption easily and thus the reversibility of the reactions. There is no difference in sorption between the different ionic strengths for Np, Th, Co and U ions. This indicates the formation of inner sphere complexes with the surface. Neptunyl ion forms a neutral complex with the titanium

  13. Geochemical modelling of groundwater chemistry in the Tono area

    International Nuclear Information System (INIS)

    Arthur, R.C.

    2003-03-01

    This report summarizes the research result about geochemical modelling of the groundwater during H14 financial year. JNC-TGC have built the geochemical conceptual models of groundwater by using the chemical data of the groundwater of the Mizunami group and Toki granite. Although this models are extremely useful as interpretive tools, they lack the quantitative basis necessary to evaluate coupled processes of fluid-flow and water-rock interaction driving the chemical evolution of groundwater systems. In this research, the following three items have been considered for the purpose of construction of the geochemical model which can express the chemical reaction in groundwater correctly. Evaluation of the quality of the previous analytical data in the Tono region. Grasp of the chemical character of groundwaters. Consideration about the influence between Eh, pH and CO 2 (g) parameter, and which the change has. Evaluation of the quality of the previous analytical data are important because deficiencies in sampling technique, sample-preservation procedures or analytical method may adversely affect the overall quality of groundwater chemical and isotopic analysis. In addition, the effects of borehole drilling and logging, hydraulic testing inappropriate sampling strategies or inadequate sampling tools may perturb groundwater compositions to such an extent that they are unrepresentative of in-situ conditions. The quality of water analysis is indicated by its charge balance. The charge balance of many of the analysis lies within the strictly acceptable range of 0±5%, but charge imbalances exceeding these limits are calculated for many other samples. These reasons are examined in the following. Analytical errors (e.q., of alkalinity). Errors arising from the use of IC values that are unrepresentative because CO 2 was gained by or lost from the sample during storage and (or) analysis. Errors arising from the invalid assumption that non-carbonate contributions to the

  14. Evaluation of geochemical mobility of heavy metals in the dump mine rocks Western Donbass

    Directory of Open Access Journals (Sweden)

    Yatsechko N.Y.

    2014-12-01

    Full Text Available Typification of turn mine rocks of Western Donbas is conducted after a size acid-lye the index of water-soluble complex. It is set that exactly rocks with the low value of it an index characterized the most sizes of middle content of water-soluble forms of heavy metals. It is well-proven that exactly mine dumps are the generating source of contamination of objects of environment of this region by heavy metals. The significant impact on the environment inflicted not only directly in the process of coal mining, but for many years after its completion. The source of contamination of environmental objects are dumps that occupy large areas of fertile land. Every year in the dumps is stored about 40 million. m3 moldboard mine rock. Most of the waste coal industry have potential toxic and mutagenic properties as containing a significant amount of heavy metals, which are practically not biodegradable in the environment and is therefore especially dangerous for living organisms paramount importance score geochemical mobility of heavy metals, ie their property to move from solid to liquid phase, migrate to the natural landscape and absorbed by vegetation. This applies particularly to water-soluble forms of metals, as in warehousing surface mine dump piles of rocks, the priority factor that regulates the processes of migration of heavy metals are leaching precipitation of solid phase wastes. It is the existence and content of heavy metals in water-soluble complex characterized by their solubility and migration activity and can be used to assess the real extent of possible contamination of the hydrosphere.

  15. Stepwise magnetic-geochemical approach for efficient assessment of heavy metal polluted sites

    Science.gov (United States)

    Appel, E.; Rösler, W.; Ojha, G.

    2012-04-01

    Previous studies have shown that magnetometry can outline the distribution of fly ash deposition in the surroundings of coal-burning power plants and steel industries. Especially the easy-to-measure magnetic susceptibility (MS) is capable to act as a proxy for heavy metal (HM) pollution caused by such kind of point source pollution. Here we present a demonstration project around the coal-burning power plant complex "Schwarze Pumpe" in eastern Germany. Before reunification of West and East Germany huge amounts of HM pollutants were emitted from the "Schwarze Pumpe" into the environment by both fly ash emission and dumped clinker. The project has been conducted as part of the TASK Centre of Competence which aims at bringing new innovative techniques closer to the market. Our project combines in situ and laboratory MS measurements and HM analyses in order to demonstrate the efficiency of a stepwise approach for site assessment of HM pollution around point sources of fly-ash emission and deposition into soil. The following scenario is played through: We assume that the "true" spatial distribution of HM pollution (given by the pollution load index PLI comprising Fe, Zn, Pb, and Cu) is represented by our entire set of 85 measured samples (XRF analyses) from forest sites around the "Schwarze Pumpe". Surface MS data (collected with a Bartington MS2D) and in situ vertical MS sections (logged by an SM400 instrument) are used to determine a qualitative overview of potentially higher and lower polluted areas. A suite of spatial HM distribution maps obtained by random selections of 30 out of the 85 analysed sites is compared to the HM map obtained from a targeted 30-sites-selection based on pre-information from the MS results. The PLI distribution map obtained from the targeted 30-sites-selection shows all essential details of the "true" pollution map, while the different random 30-sites-selections miss important features. This comparison shows that, for the same cost

  16. Understanding sediment sources in a peri-urban Mediterranean catchment using geochemical tracers

    Science.gov (United States)

    Ferreira, Carla; Walsh, Rory; Kikuchi, Ryunosuke; Blake, Will

    2016-04-01

    One of the main physical environmental impacts of urbanization is an increase in suspended sediment concentrations and loads, particularly in the constructional phase. Impacts in peri-urban catchments characterized by a mosaic of urban and non-urban landscape elements with varying roles in acting as sources and sinks of overland flow and slope wash have received little attention, particularly in Mediterranean environments. The present study uses a sediment 'fingerprinting' approach to determine the main sediment sources in the peri-urban Ribeira dos Covões catchment (6.2km2) in Portugal and how they change during storm events following contrasting antecedent weather. The catchment, rural until 1972, underwent discontinuous urbanization in 1973-1993, followed by an urban consolidation phase. Currently, its land-use is a complex mosaic of woodland (56%), urban (40%) and agricultural (4%) land parcels. Distinct urban patterns include some well-defined urban residential centres, but also areas of discontinuous urban sprawl. Since 2010, a major road was built and an enterprise park has been under construction, covering 1% and 5% of the catchment, respectively. The catchment has a Mediterranean climate. The geology comprises sandstone (56%), limestone (41%) and alluvial deposits (3%). Soils are generally deep (>3.0m), but shallow (road surface immediately it entered the stream network. The elemental composition (40 elements) of each size fraction was assessed using a Niton X-ray fluorescence elemental analyser. Results show that rock type has a profound influence on the geochemical properties of bed-sediments. Catchment outlet sediment collected after the summer and a storm of high rainfall intensity following dry weather displayed geochemical properties closer to those of sediment from sandstone sub-catchments, and in particularly sediment from the enterprise park under construction. After the storm that followed very wet weather, however, limestone areas became of

  17. Uruguay mining inventory. Geochemical prospecting results of the Las Flores aerial map

    International Nuclear Information System (INIS)

    Zeegers, H.; Bonnefoy, D.; Garau, M.; Spangenberg, J.

    1981-01-01

    In the context of the Uruguay mining inventory, the aerial photography map Las Flores had been covered by a specific strategic which included geochemical prospecting elements. The surface covered has the 550 km2, and 1042 samples which they have been analized in Orleans France. 22 elements by plasma spectroscopy and gold by atomic absorption and for uranium laser spectroscopy . They have been evidenced the following anomalies: gold, Pb, Pb-Ba-Cu, Ba and Ni-Cr

  18. Integrated Geochemical-Petrographic Insights on Neoproterozoic Ocean Oxygenation

    Science.gov (United States)

    Hood, A.; Planavsky, N.; Wallace, M. W.; Wang, X.; Gueguen, B.

    2015-12-01

    Novel isotope systems have the potential to provide new insights into biogeochemical cycling in Earth's evolving oceans. However, much recent paleo-redox work has been done without extensive consideration of sample preservation or paleoenvironmental setting. Neoproterozoic reef complexes from South Australia provide a perfect setting to test geochemical redox proxies (e.g. uranium isotopes and trace metal chemistry) within a well-defined sedimentological and petrographic context. These reefs developed significant frameworks over ~1km of steep platform relief from the seafloor, and contain a variety of carbonate components including primary dolomite marine cements. Analysis of a variety of components within these reefs reveals significant variation in uranium isotope composition and trace metal chemistry between components, even within a single sample. Marine cements, which precipitated directly from seawater, have much lower contamination element concentrations (e.g. Al, Zr, Th) than depositional micrites, and appear to represent the best archive of ancient ocean conditions. These cements have high levels of Fe, Mn in shallow and deep reef facies (e.g. 2-3wt% Fe), but only Fe-oxide inclusions in peritidal settings. This distribution suggests ferruginous conditions under a surficial chemocline in this Neoproterozoic seawater. Uranium isotopes from pristine marine cements have relatively heavy values compared to modern seawater (median = -0.22 δ238U). These values are essentially unfractionated from riverine inputs, which we interpret as tracking extensive near quantitative low-T reduction of U(VI) to U(IV) by abundant soluble iron in seawater. Depositional components and late stage cements have a much lighter and more variable U isotope compositions (-0.71 to -0.08 δ238U). This work highlights the need for fundamental petrographic constraints on the preservation of depositional geochemical signatures in the future use and development of sedimentary redox proxies.

  19. Landscape-geochemical factors of deposit formation

    International Nuclear Information System (INIS)

    Batulin, S.G.

    1980-01-01

    Effect of landscape-geochemical factors on hydrogenic formation of uranium ores is considered. The primary attention is paid to finding reasons for hydrogeochemical background increase in the regions of arid climate. Problems of uranium distribution in alluvial landscapes, hydrogeochemical regime of ground waters, reflecting the effect of waters of the zone of aeration are revealed. Chemical composition of porous solutions in the zone of aeration, as well as historical geochemindstry of landscape a its role from the view point of uranium solution formation in the arid zone are considered [ru

  20. sedimentological and geochemical characteristics of outcrop ...

    African Journals Online (AJOL)

    USER

    0.17. 0.70. 1.13. 1.37. -. CIA (%). 73.00. 76.00. 74.00. 85.00. 99.00. 95.00. 98.00. 90.00. 96.00. 77.00. 99.00. 96.00. 94.00. -. CIW (%). 78.00. 87.00. 83.00. 97.00. 100.00. 99.00. 100. 99.00. 99.00. 86.00. 00. 99.00. 100.00. -. Nton and Adamolekun: Sedimentological and Geochemical Characteristics of Outcrop Sediments ...

  1. DNA-based methods of geochemical prospecting

    Energy Technology Data Exchange (ETDEWEB)

    Ashby, Matthew [Mill Valley, CA

    2011-12-06

    The present invention relates to methods for performing surveys of the genetic diversity of a population. The invention also relates to methods for performing genetic analyses of a population. The invention further relates to methods for the creation of databases comprising the survey information and the databases created by these methods. The invention also relates to methods for analyzing the information to correlate the presence of nucleic acid markers with desired parameters in a sample. These methods have application in the fields of geochemical exploration, agriculture, bioremediation, environmental analysis, clinical microbiology, forensic science and medicine.

  2. Kriging - a challenge in geochemical mapping

    Science.gov (United States)

    Stojdl, Jiri; Matys Grygar, Tomas; Elznicova, Jitka; Popelka, Jan; Vachova, Tatina; Hosek, Michal

    2017-04-01

    Geochemists can easily provide datasets for contamination mapping thanks to recent advances in geographical information systems (GIS) and portable chemical-analytical instrumentation. Kriging is commonly used to visualise the results of such mapping. It is understandable, as kriging is a well-established method of spatial interpolation. It was created in 1950's for geochemical data processing to estimate the most likely distribution of gold based on samples from a few boreholes. However, kriging is based on the assumption of continuous spatial distribution of numeric data that is not realistic in environmental geochemistry. The use of kriging is correct when the data density is sufficient with respect to heterogeneity of the spatial distribution of the geochemical parameters. However, if anomalous geochemical values are focused in hotspots of which boundaries are insufficiently densely sampled, kriging could provide misleading maps with the real contours of hotspots blurred by data smoothing and levelling out individual (isolated) but relevant anomalous values. The data smoothing can thus it results in underestimation of geochemical extremes, which may in fact be of the greatest importance in mapping projects. In our study we characterised hotspots of contamination by uranium and zinc in the floodplain of the Ploučnice River. The first objective of our study was to compare three methods of sampling: random (based on stochastic generation of sampling points), systematic (square grid) and judgemental sampling (based on judgement stemming from principles of fluvial deposition) as the basis for pollution maps. The first detected problem in production of the maps was the reduction of the smoothing effect of kriging using appropriate function of empirical semivariogram and setting the variation of at microscales smaller than the sampling distances to minimum (the "nugget" parameter of semivariogram). Exact interpolators such as Inverse Distance Weighting (IDW) or Radial

  3. SURVEY, REPRESENTATION AND ANALYSIS OF A WAR I COMPLEX SYSTEM OF SURFACE AND UNDERGROUND FORTIFICATIONS IN THE GRESTA VALLEY, ITALY

    Directory of Open Access Journals (Sweden)

    I. Salvador

    2012-09-01

    Full Text Available This work is part of a research on the use of terrestrial laser scanner, integrated with total station and GPS, for the documentation and comprehension of complex architectures in up-land sites. The research is performed in the framework of the project "Ambiente e Paesaggi dei siti di Altura Trentini" – APSAT (Environment and landscape of hill-top sites in Trentino, a multidisciplinary project focused on the evolution of hill-top anthropic system in the Trentino region, Italy. The study area is located in the Gresta Valley and this work concerns on the Nagià Grom site, fortified by the Austria-Hungarian Army during the World War I. The site has been interested by a significant restore operation of a large series of entrenches paths and fortifications in the last decade. The survey herein described has involved an area once interested by military barracks with Officers' Mess, water provision and by one of the biggest field kitchens discovered in the Trentino region. A second survey involved the tunnel connecting the ammunition depot to the artillery stations. The nature of such complex architectures, characterized by an irregular and composite 3D span leads, in general, to necessary simple surveys and representations and somehow to simplified studies too. The 3D point cloud, once filtered by the massive presence of dense vegetation, eventually constitutes a rich data set for further analyses on the spatial, geological, architectural and historical properties of the site. The analysis has been carried out on two different scales. At the architectural-scale, the comparison to historic photos has allowed to understand how the original structure of the barracks was made and to find building characters that now are lost. The on-site observation of the underground stratigraphic splices and their analysis in the 3D point cloud, e.g., spatial extension and slope, have permitted the understanding of the special excavation process guided by the

  4. Effect of partial or complete elimination of light-harvesting complexes on the surface electric properties and the functions of cyanobacterial photosynthetic membranes.

    Science.gov (United States)

    Dobrikova, Anelia G; Domonkos, Ildikó; Sözer, Özge; Laczkó-Dobos, Hajnalka; Kis, Mihály; Párducz, Árpád; Gombos, Zoltán; Apostolova, Emilia L

    2013-02-01

    Influence of the modification of the cyanobacterial light-harvesting complex [i.e. phycobilisomes (PBS)] on the surface electric properties and the functions of photosynthetic membranes was investigated. We used four PBS mutant strains of Synechocystis sp. PCC6803 as follows: PAL (PBS-less), CK (phycocyanin-less), BE (PSII-PBS-less) and PSI-less/apcE(-) (PSI-less with detached PBS). Modifications of the PBS content lead to changes in the cell morphology and surface electric properties of the thylakoid membranes as well as in their functions, such as photosynthetic oxygen-evolving activity, P700 kinetics and energy transfer between the pigment-protein complexes. Data reveal that the complete elimination of PBS in the PAL mutant causes a slight decrease in the electric dipole moments of the thylakoid membranes, whereas significant perturbations of the surface charges were registered in the membranes without assembled PBS-PSII macrocomplex (BE mutant) or PSI complex (PSI-less mutant). These observations correlate with the detected alterations in the membrane structural organization. Using a polarographic oxygen rate electrode, we showed that the ratio of the fast to the slow oxygen-evolving PSII centers depends on the partial or complete elimination of light-harvesting complexes, as the slow operating PSII centers dominate in the PBS-less mutant and in the mutant with detached PBS. Copyright © Physiologia Plantarum 2012.

  5. Use of Alternatives to Air-Fluidized Support Surfaces in the Care of Complex Wounds in Postflap and Postgraft Patients

    OpenAIRE

    Fleck, Cynthia A.; Rappl, Laurie M.; Simman, Richard; Titterington, Virginia; Conwill, Jill; Koerner, Cathy; Locke, Pam; Bechtold, Dawn; Papantonio, Cathie; Gray, Deborah P.; Lawrence, Kathleen

    2010-01-01

    Air-fluidized support surface therapy has many drawbacks, such as dehydration, in an already difficult recovery for those wound patients who have undergone flap and graft surgery. In addition, patient care and handling are also problematic. Patients complain of discomfort, and the instability of the surface interferes with patient stability in side lying and semi-Fowler's positions. Alternative support surfaces can be considered for postflap or postgraft patients. Such technologies as alterna...

  6. Evidence for Milankovitch periodicities in Cenomanian-Turonian lithologic and geochemical cycles, western interior U.S.A.

    Science.gov (United States)

    Sageman, B.B.; Rich, J.; Arthur, M.A.; Birchfield, G.E.; Dean, W.E.

    1997-01-01

    The limestone/marlstone bedding couplets of the Bridge Creek Limestone Member, Cenomanian-Turonian Greenhorn Formation, were analyzed by applying spectral techniques to high-resolution lithologic and geochemical data from a core. The results suggest that the Bridge Creek contains a complex record of orbital cyclicity. The dominant signal appears to be obliquity, but signals corresponding to precession and eccentricity were also observed. The development of the bedding couplets is interpreted to have resulted from a combination of factors, including insolation-controlled changes in higher-latitude precipitation leading to dilution/redox cycles, and in lower-latitude evaporation, leading to changes in surface water conditions and productivity cycles in the calcareous plankton. The data interpreted to reflect redox cycles appear to be more strongly influenced by obliquity, and show a weak precessional signal. In contrast, trends in the carbonate record show the opposite response. The complex bedding pattern observed in the Bridge Creek Limestone is interpreted to result from the competing influences of different orbital cycles expressed through different pathways of the depositional system, and was also affected by changes in sedimentation rates related to relative sea level fluctuations, aperiodic dilution by volcanic ash, and changes in organic-matter production and redox conditions related to a global "oceanic anoxic event". These factors complicate cycle analysis in the lower part of the member but leave a relatively undisturbed record in the upper Bridge Creek Limestone. Copyright ?? 1997, SEPM (Society for Sedimentary Geology).

  7. Surface modification of coronary artery stent by Ti-O/Ti-N complex film coating prepared with plasma immersion ion implantation and deposition

    International Nuclear Information System (INIS)

    Huang, N.; Leng, Y.X.; Yang, P.

    2006-01-01

    This paper reported the work of surface coating of Ti-O/Ti-N complex films on coronary stents by means of the plasma immersion ion implantation/deposition process. The deformation behavior of the Ti-O/Ti-N coated stainless steel stents was investigated. In vivo investigation of the anticoagulation behavior of Ti-O coated coronary stents was also performed. The results of mechanical characterization of the Ti-O/Ti-N coated stents show that the film has strong binding strength, and to some extent the ability to withstand plastic deformation. The biological response behavior of the coated stent surface was significantly different from the uncoated. The results of implantation of stents into rabbit ventral aorta show no thrombus formation on the surfaces of the Ti-O coated stents, although serious coagulation had occurred on the surfaces of unmodified stents over a period of 4 weeks under conditions with no anticoagulant

  8. Geochemical Cycling of Iodine Species in Soils

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Q; Moran, J E; Blackwood, V

    2007-08-23

    Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine in soils is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the content and speciation of stable iodine in representative surface soils, and sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at numerous nuclear facilities in the United States, where anthropogenic {sup 129}I from prior nuclear fuel processing activities poses an environmental risk. The surface soil samples were chosen for their geographic locations (e.g., near the ocean or nuclear facilities) and for their differing physico-chemical characteristics (organic matter, texture, etc). Extracted solutions were analyzed by IC and ICP-MS methods to determine iodine concentrations and to examine iodine speciation (iodide, iodate, and organic iodine). In natural soils, iodine is mostly (nearly 90% of total iodine) present as organic species, while inorganic iodine becomes important (up to 50%) only in sediments with low organic matter. Results from laboratory column studies, aimed at examining transport of different iodine species, showed much greater retardation of 4-iodoaniline than iodide or iodate. Careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. In addition to speciation, input concentration and residence time effects will influence the biogeochemical cycling of anthropogenic 129I deposited on surface soils.

  9. [Optimization on preparation of hawthorn fruit total flavonoids-phospholipid complex using Plackett-Burman design, central composite design and response surface methodology].

    Science.gov (United States)

    Shi, Ya-Jun; Wu, Pin-Jiang; Wei, Ping

    2010-03-01

    To choose the optimal conditions for the formation of the complex with total flavonoids in hawthorn fruit and phospholipid. Solvent evaporation process was used to prepare hawthorn total flavonoids phospholipid complex. The evaluation criterion was the complex ratio. The experiment inspected the significance of influential factor of preparation technology by Plackett-Burman design and optimized significance of factor and level with the central composite design. The binomial and linear equations were fitted to the data of overall desirabilities, and the resulting equation was used to produce 3-D response surface graphs, through which the optimal formulation was predicted. The ratio of total flavonoids to phospholipid, flavonoids concentration and reaction temperature had significant influence on the craft. It was showed that the correlation coefficient of second-order quadratic model was high. The correlation coefficient reached 0.9886. The optimum conditions for the preparation of the complex were as follows: phospholipids/total flavonoids was 3 : 1, the temperature was 40 degrees C and the concentration of principal agent was 10 mg/mL The deviation between the result of the best craft verification test and the binomial fitting equation forecast value was less than 2.0%. Response surface methodology is successfully used to optimize the preparation of total flavonoids in hawthorn phospholipid complex. The optimized process is reliable, stable and available for the industrial production.

  10. Geochemical signature of radioactive waste: oil NORM

    International Nuclear Information System (INIS)

    Costa, Gilberto T. de Paula; Costa-de-Moura, Jorge; Gomes, Carlos de Almeida; Sampaio, Emidio A. Lopes

    2017-01-01

    The Brazilian Nuclear Agency (CNEN) rules all nuclear activity in Brazil as demanded by the Federal Constitution, articles 21, XXIII, and 177, V, and by the Federal Acts 4.118/62 and 10.308/2001. Therefore, the CNEN is responsible for any radioactive waste disposal in the country. Oil Naturally Occurring Radioactive Materials (Oil NORM) in this paper refers to waste coming from oil exploration. Oil NORM has called much attention during the last decades, mostly because it is not possible to determine its primary source due to the actual absence of regulatory control mechanism. There is no efficient regulatory tool which allows determining the origin of such NORM wastes even among those facilities under regulatory control. This fact may encourage non-authorized radioactive material transportation, smuggling and terrorism. The aim of this project is to provide a geochemical signature for each oil NORM waste using its naturally occurring isotopic composition to identify its origin. The here proposed method is a specific geochemical modeling of oil sludge NORM samples which are analyzed for radioisotopes normally present in oil pipes, such as 228 Ac, 214 Bi and 214 Pb. The activity ratios are plotted in scatter diagrams. This method was successfully tested with data of different sources obtained from analysis reports from the Campos Basin/Brazil and from literature. (author)

  11. Forensic Analysis using Geological and Geochemical Techniques

    Science.gov (United States)

    Hoogewerff, J.

    2009-04-01

    Due to the globalisation of legal (and illegal) trade there is an increasing demand for techniques which can verify the geographical origin and transfer routes of many legal and illegal commodities and products. Although geological techniques have been used in forensic investigations since the emergence of forensics as a science in the late eighteen hundreds, the last decade has seen a marked increase in geo-scientists initiating concept studies using the latest analytical techniques, including studying natural abundance isotope variations, micro analysis with laser ablation ICPMS and geochemical mapping. Most of the concept studies have shown a good potential but uptake by the law enforcement and legal community has been limited due to concerns about the admissibility of the new methods. As an introduction to the UGU2009 session "Forensic Provenancing using Geological and Geochemical Techniques" I will give an overview of the state of the art of forensic geology and the issues that concern the admissibility of geological forensic evidence. I will use examples from the NITECRIME and FIRMS networks, the EU TRACE project and other projects and literature to illustrate the important issues at hand.

  12. Geochemical signature of radioactive waste: oil NORM

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Gilberto T. de Paula; Costa-de-Moura, Jorge; Gomes, Carlos de Almeida; Sampaio, Emidio A. Lopes, E-mail: gilberto.costa@cnen.gov.br, E-mail: jcmoura@cnen.gov.br, E-mail: cgomes@cnen.gov.br [Comissao Nacional de Energia Nuclear (CNEN), Rio de Janeiro, RJ (Brazil). Div. de Controle de Rejeitos e Transporte de Materiais Radioativos

    2017-07-01

    The Brazilian Nuclear Agency (CNEN) rules all nuclear activity in Brazil as demanded by the Federal Constitution, articles 21, XXIII, and 177, V, and by the Federal Acts 4.118/62 and 10.308/2001. Therefore, the CNEN is responsible for any radioactive waste disposal in the country. Oil Naturally Occurring Radioactive Materials (Oil NORM) in this paper refers to waste coming from oil exploration. Oil NORM has called much attention during the last decades, mostly because it is not possible to determine its primary source due to the actual absence of regulatory control mechanism. There is no efficient regulatory tool which allows determining the origin of such NORM wastes even among those facilities under regulatory control. This fact may encourage non-authorized radioactive material transportation, smuggling and terrorism. The aim of this project is to provide a geochemical signature for each oil NORM waste using its naturally occurring isotopic composition to identify its origin. The here proposed method is a specific geochemical modeling of oil sludge NORM samples which are analyzed for radioisotopes normally present in oil pipes, such as {sup 228}Ac, {sup 214}Bi and {sup 214}Pb. The activity ratios are plotted in scatter diagrams. This method was successfully tested with data of different sources obtained from analysis reports from the Campos Basin/Brazil and from literature. (author)

  13. Covalent co-immobilization of heparin/laminin complex that with different concentration ratio on titanium surface for selectively direction of platelets and vascular cells behavior

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jian; Chen, Yuan; Liu, Tao; Wang, Xue; Liu, Yang; Wang, Yuan; Chen, Junying, E-mail: chenjy@263.net; Huang, Nan

    2014-10-30

    Highlights: • Extracellular matrix inspired surface modification with fibronectin, heparin and VEGF to construct a favorable microenvironment for selectively anticoagulant and promote endothelialization. • Take the advantage of specific intermolecular interaction, the bioactivity of above biomolecules was more efficiently maintained in compared with the common used covalent immobilization method. • Poly-l-lysine was used as a novel interlayer for surface amination, and in comparison, PLL coating was more feasible and the degradation product had no harm to human body. - Abstract: Surface biofunctional modification of coronary artery stent to improve the hemocompatibility and selectively accelerate endothelium regeneration but prevent restenosis have been become a new hotspot. For this, a novel method was developed in this work by co-immobilization of Ln and heparin complex on poly-L-lysine modified Ti surface. Take the advantage of the specific interaction between Ln and heparin, Ln and heparin complexes with different concentration ratios were set up for creating different exposure density of these two types of biomolecules. According to biocompatibility evaluation results, the Hep/Ln complexes modified surface displayed less platelet adhesion and activation. Especially, on L(150)H and L(200)H surface, the AT III binding quantity, APTT value and anti-coagulation property of modified surface were significantly promoted. Furthermore, the adherent density and proliferation activity of ECs and EPCs were positively correlated with Ln concentration. Notably, the proliferation of both ECs and EPCs on L(100)H, L(150)H and L(200)H surface were greatly promoted. Another hand, the proliferation activity of SMCs was significantly inhibited on Hep/Ln modified surfaces, which was considered mainly due to the inhibitory effect of heparin to SMCs. According to the existing results, this study demonstrated that in a certain range of heparin and laminin concentration ratio

  14. A geochemical atlas of North Carolina, USA

    Science.gov (United States)

    Reid, J.C.

    1993-01-01

    A geochemical atlas of North Carolina, U.S.A., was prepared using National Uranium Resource Evaluation (NURE) stream-sediment data. Before termination of the NURE program, sampling of nearly the entire state (48,666 square miles of land area) was completed and geochemical analyses were obtained. The NURE data are applicable to mineral exploration, agriculture, waste disposal siting issues, health, and environmental studies. Applications in state government include resource surveys to assist mineral exploration by identifying geochemical anomalies and areas of mineralization. Agriculture seeks to identify areas with favorable (or unfavorable) conditions for plant growth, disease, and crop productivity. Trace elements such as cobalt, copper, chromium, iron, manganese, zinc, and molybdenum must be present within narrow ranges in soils for optimum growth and productivity. Trace elements as a contributing factor to disease are of concern to health professionals. Industry can use pH and conductivity data for water samples to site facilities which require specific water quality. The North Carolina NURE database consists of stream-sediment samples, groundwater samples, and stream-water analyses. The statewide database consists of 6,744 stream-sediment sites, 5,778 groundwater sample sites, and 295 stream-water sites. Neutron activation analyses were provided for U, Br, Cl, F, Mn, Na, Al, V, Dy in groundwater and stream water, and for U, Th, Hf, Ce, Fe, Mn, Na, Sc, Ti, V, Al, Dy, Eu, La, Sm, Yb, and Lu in stream sediments. Supplemental analyses by other techniques were reported on U (extractable), Ag, As, Ba, Be, Ca, Co, Cr, Cu, K, Li, Mg, Mo, Nb, Ni, P, Pb, Se, Sn, Sr, W, Y, and Zn for 4,619 stream-sediment samples. A small subset of 334 stream samples was analyzed for gold. The goal of the atlas was to make available the statewide NURE data with minimal interpretation to enable prospective users to modify and manipulate the data for their end use. The atlas provides only

  15. Assessment of Land Surface Complexity In Relation To Information Capacity and the Fractal Dimension in Different Landform Regions Using Landsat Data

    Science.gov (United States)

    Hong, Wang Xu; Huijie, Qin; Zhe, Zhang; Fei, Li

    2014-03-01

    Remote sensing images are highly structured, and contiguous pixels of space domain have strong correlations that contain abundant information on land surface structure features and land surface electromagnetic radiation features. The information capacity model, which is a quality evaluation model based on a multi-dimensional histogram, includes local correlations within different pixels. Thus, the information capacity can illustrate land surface structural information more objectively and effectively than other single-pixel calculation models. Our results reveal that the information capacity value correlates well with the meaningful grey level of remote sensing imagery. This high correlation is related to the complexity of terrestrial surface landscapes. Therefore, information capacity, as applied to geoscience, is introduced in this study to demonstrate the spatial differentiation of information capacity of different landform regions. Generally, the information capacity of a mountain is large and is followed in decreasing order by those of the hills and the plains. Moreover, the correlation between information capacity and the fractal dimension is analysed. Based on the results of this study, it can be concluded that the level of correlation for information capacity and the fractal dimension is high, and the correlation coefficient for the basic landform areas and the loess landform areas is 0.874 and 0.825, respectively. Finally, this paper proposes that information capacity be used as a new reference index for geoscientific analysis in quantitative research on the characteristics of land surface complexity.

  16. Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids

    Science.gov (United States)

    Frasconi, Marco; Mazzei, Franco

    2009-07-01

    This paper describes the characterization of a self-assembled β-cyclodextrin (β-CD)-derivative monolayer (β-CD-SAM) on a gold surface and the study of their inclusion complexes with glucocorticoids. To this aim the arrangement of a self-assembled β-cyclodextrin-derivative monolayer on a gold surface was monitored in situ by means of surface plasmon resonance (SPR) spectroscopy and double-layer capacitance measurements. Film thickness and dielectric constant were evaluated for a monolayer of β-CD using one-color-approach SPR. The selectivity of the β-CD host surface was verified by using electroactive species permeable and impermeable in the β-CD cavity. The redox probe was selected according to its capacity to permeate the β-CD monolayer and its electrochemical behavior. In order to evaluate the feasibility of an inclusion complex between β-CD-SAM with some steroids such as cortisol and cortisone, voltammetric experiments in the presence of the redox probes as molecules competitive with the steroids have been performed. The formation constant of the surface host-guest by β-CD-SAM and the steroids under study was calculated.

  17. Colloid transport in a geochemically heterogeneous porous medium: aquifer tank experiment and modeling.

    Science.gov (United States)

    Loveland, Jonathan P; Bhattacharjee, Subir; Ryan, Joseph N; Elimelech, Menachem

    2003-09-01

    To examine colloid transport in geochemically heterogeneous porous media at a scale comparable to field experiments, we monitored the migration of silica-coated zirconia colloids in a two-dimensional layered porous media containing sand coated to three different extents by ferric oxyhydroxides. Transport of the colloids was measured over 1.65 m and 95 days. Colloid transport was modeled by an advection-dispersion-deposition equation incorporating geochemical heterogeneity and colloid deposition dynamics (blocking). Geochemical heterogeneity was represented as favorable (ferric oxyhydroxide-coated) and unfavorable (uncoated sand) deposition surface areas. Blocking was modeled as random sequential adsorption (RSA). Release of deposited colloids was negligible. The time to colloid breakthrough after the onset of blocking increased with increasing ferric oxyhydroxide-coated surface area. As the ferric oxyhydroxide surface area increased, the concentration of colloids in the breakthrough decreased. Model-fits to the experimental data were made by inverse solutions to determine the fraction of surface area favorable for deposition and the deposition rate coefficients for the favorable (ferric oxyhydroxide-coated) and unfavorable sites. The favorable deposition rate coefficient was also calculated by colloid filtration theory. The model described the time to colloid breakthrough and the blocking effect reasonably well and estimated the favorable surface area fraction very well for the two layers with more than 1% ferric oxyhydroxide coating. If mica edges in the uncoated sand were considered as favorable surface area in addition to the ferric oxyhydroxide coatings, the model predicted the favorable surface area fraction accurately for the layer with less than 1% ferric oxyhydroxide coating.

  18. Multifunctional ultra-high vacuum apparatus for studies of the interactions of chemical warfare agents on complex surfaces.

    Science.gov (United States)

    Wilmsmeyer, Amanda R; Gordon, Wesley O; Davis, Erin Durke; Mantooth, Brent A; Lalain, Teri A; Morris, John R

    2014-01-01

    A fundamental understanding of the surface chemistry of chemical warfare agents is needed to fully predict the interaction of these toxic molecules with militarily relevant materials, catalysts, and environmental surfaces. For example, rules for predicting the surface chemistry of agents can be applied to the creation of next generation decontaminants, reactive coatings, and protective materials for the warfighter. Here, we describe a multifunctional ultra-high vacuum instrument for conducting comprehensive studies of the adsorption, desorption, and surface chemistry of chemical warfare agents on model and militarily relevant surfaces. The system applies reflection-absorption infrared spectroscopy, x-ray photoelectron spectroscopy, and mass spectrometry to study adsorption and surface reactions of chemical warfare agents. Several novel components have been developed to address the unique safety and sample exposure challenges that accompany the research of these toxic, often very low vapor pressure, compounds. While results of vacuum-based surface science techniques may not necessarily translate directly to environmental processes, learning about the fundamental chemistry will begin to inform scientists about the critical aspects that impact real-world applications.

  19. 12-Crown-4-based amphipathic lipid and corresponding metal cation complexes for gene therapy applications: FT-IR characterization and surface charge determination

    Science.gov (United States)

    Bruni, P.; Fino, V.; Pisani, M.; Tosi, G.; Stipa, P.; Ferraris, P.; Francescangeli, O.

    2009-02-01

    The new lipid 1,2- O-dioleyl-3- O-{2-[(12-crown-4)-methoxy]-ethyl}- sn-glycerol, 12C4L, has been synthesized. This molecule can coordinate different cations that should make the corresponding liposome a good candidate as vector of genetic material for possible applications in gene therapy. An important feature of the molecule is the possibility to modulate the net surface charge of their complexes with metal cations, which is important to provide efficient DNA transfections. The molecule and its complexes with some metal cations (Mg 2+, Ca 2+, Mn 2+) have been characterized by FT-IR spectroscopy and band attributions confirmed by Density Functional Theory calculations. The net surface charge has been determined by Z potential determinations.

  20. mineralogical and geochemical trends in lateritic weathering profiles ...

    African Journals Online (AJOL)

    Three soil profiles on the basement rocks in Awa-Oru-Ijebu Igbo area of southwestern Nigeria were investigated for the ... Geochemical data further revealed significant enrichment of Al2O3 and Fe2O3 in the laterite profile compared with the parent rock, ...... Mineralogical, Geochemical and Economic. Appraisal of some clay ...

  1. Behaviour of nature and technogenic radioisotopes in buried geochemical barriers

    International Nuclear Information System (INIS)

    Kuznetsov, V.A.; Onoshko, M.P.; Generalova, V.A.

    1998-01-01

    Behaviour of potassium 40, radium 226, thorium 232, strontium 90 and cesium 137 on geochemical barriers connected with buried soils and cut-off meander sediments of the Holocene age of the Sozh river valley are examined. Some sides of the barrier geochemical structure caused by syngeneic and epigenetic processes have been taken into consideration

  2. A surface complexation model of YREE sorption on Ulva lactuca in 0.05-5.0 M NaCl solutions

    Science.gov (United States)

    Zoll, Alison M.; Schijf, Johan

    2012-11-01

    We present distribution coefficients, log iKS, for the sorption of yttrium and the rare earth elements (YREEs) on BCR-279, a dehydrated tissue homogenate of a marine macroalga, Ulva lactuca, resembling materials featured in chemical engineering studies aimed at designing renewable biosorbents. Sorption experiments were conducted in NaCl solutions of different ionic strength (0.05, 0.5, and 5.0 M) at T = 25 °C over the pH range 2.7-8.5. Distribution coefficients based on separation of the dissolved and particulate phase by conventional filtration (3 kDa) using an existing pH-dependent model. Colloid-corrected values were renormalized to free-cation concentrations by accounting for YREE hydrolysis and chloride complexation. At each ionic strength, the pH dependence of the renormalized values is accurately described with a non-electrostatic surface complexation model (SCM) that incorporates YREE binding to three monoprotic functional groups, previously characterized by alkalimetric titration, as well as binding of YREE-hydroxide complexes (MOH2+) to the least acidic one (pKa ∼ 9.5). In non-linear regressions of the distribution coefficients as a function of pH, each pKa was fixed at its reported value, while stability constants of the four YREE surface complexes were used as adjustable parameters. Data for a single fresh U. lactuca specimen in 0.5 M NaCl show generally the same pH-dependent behavior but a lower degree of sorption and were excluded from the regressions. Good linear free-energy relations (LFERs) between stability constants of the YREE-acetate and YREE-hydroxide solution complex and surface complexes with the first and third functional group, respectively, support their prior tentative identifications as carboxyl and phenol. A similar confirmation for the second group is precluded by insufficient knowledge of the stability of YREE-phosphate complexes and a perceived lack of YREE binding in 0.05 M NaCl; this issue awaits further study. The results

  3. The control volume radial basis function method CV-RBF with Richardson extrapolation in geochemical problems

    Science.gov (United States)

    Florez, W. F.; Portapila, M.; Hill, A. F.; Power, H.; Orsini, P.; Bustamante, C. A.

    2015-03-01

    The aim of this paper is to present how to implement a control volume approach improved by Hermite radial basis functions (CV-RBF) for geochemical problems. A multi-step strategy based on Richardson extrapolation is proposed as an alternative to the conventional dual step sequential non-iterative approach (SNIA) for coupling the transport equations with the chemical model. Additionally, this paper illustrates how to use PHREEQC to add geochemical reaction capabilities to CV-RBF transport methods. Several problems with different degrees of complexity were solved including cases of cation exchange, dissolution, dissociation, equilibrium and kinetics at different rates for mineral species. The results show that the solution and strategies presented here are effective and in good agreement with other methods presented in the literature for the same cases.

  4. Slope of the Slope Derivative Surface used to characterize the complexity of the seafloor around St. John, USVI

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Slope of slope was calculated from the bathymetry surface for each raster cell by applying the ArcGIS Spatial Analyst 'Slope' Tool to a previously created slope...

  5. Methodological approaches in estimating anomalous geochemical field structure

    International Nuclear Information System (INIS)

    Gavrilov, R; Rudmin, M

    2015-01-01

    Mathematical statistic methods were applied to analyze the core samples from vertical expendable wells in Chertovo Koryto gold ore field. The following methods were used to analyse gold in samples: assay tests and atomic absorption method (AAS), while emission spectrum semiquantative method was applied to identify traces. The analysis of geochemical association distribution in one central profile demonstrated that bulk metasomatic aureoles are characteristic of concentric zonal structure. The distribution of geochemical associations is correlated to the hydrothermal stages of mineral formation identified in this deposit. It was proved that the processed geochemical data by factor and cluster analyses provided additional information on the anomalous geochemical field structure in gold- bearing black-shale strata. Such methods are effective tools in interpretating specific features of geochemical field structures in analogous potential ore-bearing areas

  6. Emergence of complex behavior in pili-based motility in early stages of P. aeruginosa surface adaptation

    Science.gov (United States)

    Brill-Karniely, Yifat; Jin, Fan; Wong, Gerard C. L.; Frenkel, Daan; Dobnikar, Jure

    2017-04-01

    Pseudomonas aeruginosa move across surfaces by using multiple Type IV Pili (TFP), motorized appendages capable of force generation via linear extension/retraction cycles, to generate surface motions collectively known as twitching motility. Pseudomonas cells arrive at a surface with low levels of piliation and TFP activity, which both progressively increase as the cells sense the presence of a surface. At present, it is not clear how twitching motility emerges from these initial minimal conditions. Here, we build a simple model for TFP-driven surface motility without complications from viscous and solid friction on surfaces. We discover the unanticipated structural requirement that TFP motors need to have a minimal amount of effective angular rigidity in order for cells to perform the various classes of experimentally-observed motions. Moreover, a surprisingly small number of TFP are needed to recapitulate movement signatures associated with twitching: Two TFP can already produce movements reminiscent of recently observed slingshot type motion. Interestingly, jerky slingshot motions characteristic of twitching motility comprise the transition region between different types of observed crawling behavior in the dynamical phase diagram, such as self-trapped localized motion, 2-D diffusive exploration, and super-diffusive persistent motion.

  7. An evaluation of geochemical models of bentonite pore water evolution

    International Nuclear Information System (INIS)

    Savage, D.; Watson, C.E.; Wilson, J.C.; Arthur, R.C.; Stroemberg, B.

    2010-01-01

    Document available in extended abstract form only. The understanding of the evolution of bentonite pore water composition with time underpins many EBS issues, such as: buffer erosion; canister corrosion; radionuclide solubility, sorption, diffusion; and plays a vital, if indirect, role in safety assessment. Models of bentonite-water interactions usually consider cation exchange, clay edge surface reactions, and the hydrolysis of calcite, gypsum, and quartz. Clay hydrolysis is usually ignored, which means that clay is assumed to be preserved indefinitely, even over million-year timescales. Unfortunately, this is contrary to evidence from natural systems, which indicates that smectites may be destroyed over safety-relevant timescales. Here, we present an alternative model that incorporates clay hydrolysis reactions, and which has been tested against laboratory data where Eh and pH have been measured directly in compacted bentonite. Simulations of 'end-point' pH measurements in batch bentonite-water slurry experiments showed different pH values according to the complexity of the system studied. The most complete system investigated (clay hydrolysis + cation exchange + trace mineral solubility + clay edge reactions) revealed pH values were a strong function of CO 2 (g) partial pressure, with pH increasing with decreasing pCO 2 (log pCO 2 values from -3.5 to -7.5 bars produced pH values from 7.9 to 9.6). A slightly less complex system excluding clay mineral hydrolysis produced essentially identical pH values ranging across the same values of pCO 2 . Therefore these 'end-point' calculations showed that the inclusion of clay mineral hydrolysis has an insignificant impact upon calculated pore fluid pH. Other simulations investigating disequilibrium between clay and pore fluid in lab squeezing cell tests with water (pH = 9.0) or a 1 M NaOH solution (pH = 12.1) ignored the presence of trace minerals, clay cation exchange, and clay edge reactions in the

  8. Geochemical fractionation of 210Pb in oxic estuarine sediments of Coatzacoalcos River, Gulf of Mexico

    International Nuclear Information System (INIS)

    Ontiveros-Cuadras, J.F.; Ruiz-Fernandez, A.C.; Perez-Bernal, L.H.; Sanchez-Cabeza, J.A.; Universitat Autonoma de Barcelona; Wee-Kwong, L.L.

    2012-01-01

    210 Pb activities were analyzed in surface sediments from the Coatzacoalcos River (Gulf of Mexico) to evaluate its distribution according to sediment grain size and in different geochemical compartments by using sequential extraction techniques. The geochemical fractionation experiments provided compatible results: by using the Tessier's method more than 90% of the 210 Pb activity in the samples was found the residual fraction (primary and secondary minerals) and the remaining ( 210 Pb content was found in comparative amounts in the reactive, the silicate, and the pyrite fractions (accounting together for >80%), and the rest was found in the residual fraction. The grain size fractionation analyses showed that the 210 Pb activities were mostly retained in the clay fraction, accounting up to 60-70% of the 210 Pb total activity in the sediment sample and therefore, it is concluded that the separation of the clay fraction can be useful to improve the analysis of low 210 Pb content sediments for dating purposes. (author)

  9. Expected Geochemical and Mineralogical Properties of Meteorites from Mercury: Inferences from Messenger Data

    Science.gov (United States)

    McCubbin, F. M.; McCoy, T. J.

    2016-01-01

    Meteorites from the Moon, Mars, and many types of asteroid bodies have been identified among our global inventory of meteorites, however samples of Mercury and Venus have not been identified. The absence of mercurian and venusian meteorites could be attributed to an inability to recognize them in our collections due to a paucity of