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Sample records for surfaces geochemical complexities

  1. Mineral Surfaces, Geochemical Complexities, and the Origins of Life

    PubMed Central

    Hazen, Robert M.; Sverjensky, Dimitri A.

    2010-01-01

    Crystalline surfaces of common rock-forming minerals are likely to have played several important roles in life’s geochemical origins. Transition metal sulfides and oxides promote a variety of organic reactions, including nitrogen reduction, hydroformylation, amination, and Fischer-Tropsch-type synthesis. Fine-grained clay minerals and hydroxides facilitate lipid self-organization and condensation polymerization reactions, notably of RNA monomers. Surfaces of common rock-forming oxides, silicates, and carbonates select and concentrate specific amino acids, sugars, and other molecular species, while potentially enhancing their thermal stabilities. Chiral surfaces of these minerals also have been shown to separate left- and right-handed molecules. Thus, mineral surfaces may have contributed centrally to the linked prebiotic problems of containment and organization by promoting the transition from a dilute prebiotic “soup” to highly ordered local domains of key biomolecules. PMID:20452963

  2. Surface complexation modeling

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Adsorption-desorption reactions are important processes that affect the transport of contaminants in the environment. Surface complexation models are chemical models that can account for the effects of variable chemical conditions, such as pH, on adsorption reactions. These models define specific ...

  3. Research-derived insights into surface geochemical hydrocarbon exploration

    USGS Publications Warehouse

    Price, L.C.

    1996-01-01

    Research studies based on foreland basins (mainly in eastern Colorado) examined three surface geochemical exploration (SGE) methods as possible hydrocarbon (HC) exploration techniques. The first method, microbial soil surveying, has high potential as an exploration tool, especially hi development and enhanced recovery operations. Integrative adsorption, the second technique, is not effective as a quantitative SGE method because water, carbon dioxide, nitrous oxide, unsaturated hydrocarbons, and organic compounds are collected by the adsorbent (activated charcoal) much more strongly than covalently bonded microseeping Q-Cs thermogenic HCs. Qualitative comparisons (pattern recognition) of C8+ mass spectra cannot gauge HC gas microseepage that involves only the Q-Cs HCs. The third method, soil cakite surveying, also has no potential as an exploration tool. Soil calcite concentrations had patterns with pronounced areal contrasts, but these patterns had no geometric relationship to surface traces of established or potential production, that is, the patterns were random. Microscopic examination of thousands of soils revealed that soil calcite was an uncrystallized caliche coating soil particles. During its precipitation, caliche captures or occludes any gases, elements, or compounds in its immediate vicinity. Thus, increased signal intensity of some SGE methods should depend on increasing soil calcite concentrations. Analyses substantiate this hypothesis. Because soil calcite has no utility as a surface exploration tool, any surface method that depends on soil calcite has a diminished utility as an SGE tool. Isotopic analyses of soil calcites revealed carbonate carbon ??13C values of -4.0 to +2.07co (indicating a strong influence of atmospheric CO2) as opposed to expected values of-45 to -30%c if the carbonate carbon had originated from microbial oxidation of microseeping HC gases. These analyses confirm a surface origin for this soil calcite (caliche), which is not

  4. Surface complexation of antimony on kaolinite.

    PubMed

    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 pH<6, but somewhat under predicted the experimental data above pH 6. At the higher initial antimony concentration (41.1 μM), the sorption envelope was of different shape than the lower load. The additive model, which considered binuclear surface complexes for quartz and gibbsite, resulted in over prediction of the adsorption data at pH>3.5. 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.

  5. Surface complexation of antimony on kaolinite.

    PubMed

    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 pH<6, but somewhat under predicted the experimental data above pH 6. At the higher initial antimony concentration (41.1 μM), the sorption envelope was of different shape than the lower load. The additive model, which considered binuclear surface complexes for quartz and gibbsite, resulted in over prediction of the adsorption data at pH>3.5. 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. PMID:25046527

  6. Zonation of the Newry Igneous Complex, Northern Ireland, based on geochemical and geophysical data

    NASA Astrophysics Data System (ADS)

    Anderson, P. E.; Cooper, M. R.; Stevenson, C. T.; Hastie, A. R.; Hoggett, M.; Inman, J.; Meighan, I. G.; Hurley, C.; Reavy, R. J.; Ellam, R. M.

    2016-09-01

    The Late Caledonian Newry Igneous Complex (NIC), Northern Ireland, comprises three largely granodioritic plutons, together with an intermediate-ultramafic body at its northeastern end. New whole-rock geochemical data, petrological classifications, and published data, including recent Tellus aeromagnetic and radiometric results, have been used to establish 15 distinct zones across the four bodies of the NIC. These become broadly younger to the southwest of the complex and toward the centres of individual plutons. In places, zones are defined by both current compositional data (geochemistry and petrology) and Tellus results. This is particularly clear at the eastern edge of the NIC, where a thorium-elevated airborne radiometric signature occurs alongside distinct concentrations of various elements from geochemistry. However, in the northeastern-most pluton of the NIC, a prominent ring-shaped aeromagnetic anomaly occurs independent of any observed surface compositional variation, and thus the zones in this area are defined by aeromagnetic data only. The origins of this and other aeromagnetic anomalies are as yet undetermined, although in places, these closely correspond to facies at the surface. The derived zonation for the NIC supports incremental emplacement of the complex as separate, distinct magma pulses. Each pulse is thought to have originated from the same fractionally crystallising source that periodically underwent mixing with more basic magma.

  7. Measurement of complex surfaces

    SciTech Connect

    Brown, G.M.

    1993-05-01

    Several of the components used in coil fabrication involve complex surfaces and dimensions that are not well suited to measurements using conventional dimensional measuring equipment. Some relatively simple techniques that are in use in the SSCL Magnet Systems Division (MSD) for incoming inspection will be described, with discussion of their suitability for specific applications. Components that are submitted for MSD Quality Assurance (QA) dimensional inspection may be divided into two distinct categories; the first category involves components for which there is an approved drawing and for which all nominal dimensions are known; the second category involves parts for which `reverse engineering` is required, the part is available but there are no available drawings or dimensions. This second category typically occurs during development of coil end parts and coil turn filler parts where it is necessary to manually shape the part and then measure it to develop the information required to prepare a drawing for the part.

  8. Geochemical Analysis of Surface Water in Rice County, Minnesota

    NASA Astrophysics Data System (ADS)

    Christenson, C.; Prullage, R.; Harvey, M.; Haileab, B.; Harrison, B. K.

    2012-12-01

    Monitoring the quality of surface water is essential to protecting freshwater systems from pollution. For the past four years, Rice County, located in southeastern Minnesota, has been subject to continuous research with the objective of determining the long-term effects of farmland runoff in the water systems. During the summer of 2012, 105 samples were collected from lakes, rivers, and streams. The samples were analyzed for conductivity, nitrate, chloride, calcium, and phosphate. Results show nitrate levels exceeding EPA restrictions (ranging 10-25 ppm) at some locations in the streams along farmlands in the southeast corner of the county. These findings are consistent with past results correlating nitrate levels with farmland runoff, with potential impact on contamination of surficial aquifers as well as significant lake eutrophication observed in the state. ICP-MS results on 67 samples exhibit complex geographical trends across the county not readily attributed to anthropogenic sources. Our findings should inform residents and policy makers taking measures to improve water quality in the county. In addition, annual studies should be continued to monitor water quality in Rice County.

  9. Geochemical and spectral characterization of naturally altered rock surfaces

    NASA Technical Reports Server (NTRS)

    Chang, L. L. Y.; Sommer, S. E.; Buckingham, W. F.

    1981-01-01

    The possibility of using the visible-near infrared region for compositional analysis of remotely sensed rock surfaces is studied. This would allow mapping rock type both on the Earth's surface and on other planetary surfaces. Reflectance spectroscopy, economic geology, optical depth determination, and X-ray diffraction mineralogy are discussed.

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

    SciTech Connect

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

    2011-03-15

    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{sup 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.

  11. Geochemical evolution of the metaluminous and peraluminous granites of Ganawuri Younger Granite Complex, northern Nigeria

    NASA Astrophysics Data System (ADS)

    Imeokparia, Ebo. Gab.

    The Ganawuri Complex is one of the numerous high level composite granitoid bodies occurring in the central plateau sector of the Nigerian Younger Granite province. Lithologically the Complex is composed of a hastingsite-fayalite granite, hastingsite-biotite granite and biotite granite. Although the major element chemistry of the constituent rock types shows only subtle variation typical of granites with minimum melt composition, the trace elements data and variation indicate that the granites in the Complex formed essentially by fractional crystallization. Geochemically the late-stage rock types are characterized by anomalously high contents of F, Li, Y, Th, Ga, Rb, Sn and Nb and by unusually low contents of Ba, Sr and Zr. These geochemical peculiarities are interpreted to be due to extreme fractionation. The ultimate product of fractional crystallization was a water-saturated melt, enriched in incompatible elements whose crystallization resulted in tin mineralization. The chemistry of the rocks can be compared with A-type granites which are considered typical of anorogenic extensional environments and/or Continental rifts.

  12. Geochemical heterogeneity in a small, stratigraphically complex moraine aquifer system (Ontario, Canada): Interpretation of flow and recharge using multiple geochemical parameters

    USGS Publications Warehouse

    Stotler, R.L.; Frape, S.K.; El Mugammar, H.T.; Johnston, C.; Judd-Henrey, I.; Harvey, F.E.; Drimmie, R.; Jones, J.P.

    2011-01-01

    The Waterloo Moraine is a stratigraphically complex system and is the major water supply to the cities of Kitchener and Waterloo in Ontario, Canada. Despite over 30 years of investigation, no attempt has been made to unify existing geochemical data into a single database. A composite view of the moraine geochemistry has been created using the available geochemical information, and a framework created for geochemical data synthesis of other similar flow systems. Regionally, fluid chemistry is highly heterogeneous, with large variations in both water type and total dissolved solids content. Locally, upper aquifer units are affected by nitrate and chloride from fertilizer and road salt. Typical upper-aquifer fluid chemistry is dominated by calcium, magnesium, and bicarbonate, a result of calcite and dolomite dissolution. Evidence also suggests that ion exchange and diffusion from tills and bedrock units accounts for some elevated sodium concentrations. Locally, hydraulic "windows" cross connect upper and lower aquifer units, which are typically separated by a clay till. Lower aquifer units are also affected by dedolomitization, mixing with bedrock water, and locally, upward diffusion of solutes from the bedrock aquifers. A map of areas where aquifer units are geochemically similar was constructed to highlight areas with potential hydraulic windows. ?? 2010 Springer-Verlag.

  13. Geochemical baseline distribution of harmful elements in the surface soils of Campania region.

    NASA Astrophysics Data System (ADS)

    Albanese, Stefano; Lima, Annamaria; Qu, Chengkai; Cicchella, Domenico; Buccianti, Antonella; De Vivo, Benedetto

    2015-04-01

    Environmental geochemical mapping has assumed an increasing relevance and the separation of values to discriminate between anthropogenic pollution and natural (geogenic) sources has become crucial to address environmental problems affecting the quality of life of human beings. In the last decade, a number of geochemical prospecting projects, mostly focused on surface soils (topsoils), were carried out at different scales (from regional to local) across the whole Campania region (Italy) to characterize the distribution of both harmful elements and persistent organic pollutants (POP) in the environment and to generating a valuable database to serve as reference in developing geomedical studies. During the 2014, a database reporting the distribution of 53 chemical elements in 3536 topsoil samples, collected across the whole region, was completed. The geochemical data, after necessary quality controls, were georeferenced and processed in a geochemistry dedicated GIS software named GEODAS. For each considered element a complete set of maps was generated to depict both the discrete and the spatially continuous (interpolated) distribution of elemental concentrations across the region. The interpolated maps were generated using the Multifractal Inverse Distance eighted (MIDW) algorithm. Subsequently, the S-A method, also implemented in GEODAS, was applied to MIDW maps to eliminate spatially limited anomalies from the original grid and to generate the distribution patterns of geochemical baselines for each element. For a selected group of elements geochemical data were also treated by means of a Compositional Data Analysis (CoDA) aiming at investigating the regionalised structure of the data by considering the joint behaviour of several elements constituting for each sample its whole composition. A regional environmental risk assessment was run on the basis of the regional distribution of heavy metals in soil, land use types and population. The risk assessment produced a

  14. Surface water geochemical and isotopic variations in an area of accelerating Marcellus Shale gas development.

    PubMed

    Pelak, Adam J; Sharma, Shikha

    2014-12-01

    Water samples were collected from 50 streams in an area of accelerating shale gas development in the eastern U.S.A. The geochemical/isotopic characteristics show no correlation with the five categories of Marcellus Shale production. The sub-watersheds with the greatest density of Marcellus Shale development have also undergone extensive coal mining. Hence, geochemical/isotopic compositions were used to understand sources of salinity and effects of coal mining and shale gas development in the area. The data indicates that while some streams appear to be impacted by mine drainage; none appear to have received sustained contribution from deep brines or produced waters associated with shale gas production. However, it is important to note that our interpretations are based on one time synoptic base flow sampling of a few sampling stations and hence do account potential intermittent changes in chemistry that may result from major/minor spills or specific mine discharges on the surface water chemistry. PMID:25201226

  15. Selected Geochemical Data for Modeling Near-Surface Processes in Mineral Systems

    USGS Publications Warehouse

    Giles, Stuart A.; Granitto, Matthew; Eppinger, Robert G.

    2009-01-01

    The database herein was initiated, designed, and populated to collect and integrate geochemical, geologic, and mineral deposit data in an organized manner to facilitate geoenvironmental mineral deposit modeling. The Microsoft Access database contains data on a variety of mineral deposit types that have variable environmental effects when exposed at the ground surface by mining or natural processes. The data tables describe quantitative and qualitative geochemical analyses determined by 134 analytical laboratory and field methods for over 11,000 heavy-mineral concentrate, rock, sediment, soil, vegetation, and water samples. The database also provides geographic information on geology, climate, ecoregion, and site contamination levels for over 3,000 field sites in North America.

  16. Surface water geochemical and isotopic variations in an area of accelerating Marcellus Shale gas development.

    PubMed

    Pelak, Adam J; Sharma, Shikha

    2014-12-01

    Water samples were collected from 50 streams in an area of accelerating shale gas development in the eastern U.S.A. The geochemical/isotopic characteristics show no correlation with the five categories of Marcellus Shale production. The sub-watersheds with the greatest density of Marcellus Shale development have also undergone extensive coal mining. Hence, geochemical/isotopic compositions were used to understand sources of salinity and effects of coal mining and shale gas development in the area. The data indicates that while some streams appear to be impacted by mine drainage; none appear to have received sustained contribution from deep brines or produced waters associated with shale gas production. However, it is important to note that our interpretations are based on one time synoptic base flow sampling of a few sampling stations and hence do account potential intermittent changes in chemistry that may result from major/minor spills or specific mine discharges on the surface water chemistry.

  17. Geochemical and geochronological constrains from the Heilongjiang Complex, NE China and its tectonic implication

    NASA Astrophysics Data System (ADS)

    Zhu, Yanlin; Zhao, Guochun

    2016-04-01

    The Heilongjiang complex, a sequence of high-pressure metamorphic rocks belt, is located along the suture zone that separates the Jiamusi and Songliao-Zhangguangcai Range blocks in NE China. The complex consists of mafic-ultramafic rocks, mainly has been metamorphosed to blueschists and greenschists and mica schists. Controversy has long surrounded the Helongjiang complex relating to when and how this complex has formed. The lithological association and geochemical features of the mafic rocks indicate that they were mostly generated in a rifting and oceanic islands settings with OIB and E-MORB affitnities. Magmatic zircons from several mafic samples indicate that they yielded protolithic ages ranging from 275 Ma to 140 Ma. The micaschists outcrop extensively in the Heilongjiang complex interlayered with blueschists, greenschists and amphibolites, but few study were focused on them. Our results about the U-Pb and Hf isotope compositions of the detrital zircons derived from these meta-sedimentary rocks reveal that the youngest concordant 206Pb/238U age is ~170Ma, suggesting that the latest depositional age of the mice-schists happened later than ~170Ma. These data suggest that the rifting between the Jiamusi and Songliao-Zhuangguangcai Range Blocks happened during Permian to Triassic time and this rift further developed into an ocean. The closure time of the ocean between the two blocks is not earlier than 140 Ma. Key words: Heilongjiang Complex, mafic rocks, micaschists Acknowledgements: NSFC (41190070, 41190075) and Hong Kong RGC GRF (HKU7063/13P).

  18. Geochemical Characteristics And Zones Of Surface Snow On East Antarctic Ice sheet

    NASA Astrophysics Data System (ADS)

    Kang, J.

    2004-12-01

    Geochemical characteristics and zones of surface snow on east Antarctic Ice Sheet Jiancheng KANG1,4, Leibao LIU1, Dahe QIN2, Dali WANG1, Jiahong WEN1, Dejun TAN1, Zhongqin LI2, Jun LI3 & Xiaowei ZHANG1,4 1 Polar Research Institute of China, Shanghai 200129, China; 2 Cold and Arid Regions Environmental and Engineering Research Institute, Chinese Academy of Sciences, Lanzhou 730000, China; 3 Australian Antarctic Division and Antarctic Climate and Ecosystems CRC, Private Bag 80 Hobart, Tasmania, 7001, Australia; 4 Geography Department of Lanzhou University, Lanzhou 730000, China Correspondence should be addressed to Jiancheng KANG (email: kangjc@sh163.net, kangjc@126.com ) Abstract The surface-snow geochemical characteristics are discussed on the East Antarctic Ice Sheet, depending on the stable isotopes ratios of oxygen and hydrogen, concentration of impurities (soluble-ions and insoluble micro-particle) in surface snow collected on the ice sheet. The purpose is to study geochemical zones on the East Antarctic Ice Sheet and to research sources and transportation route of the water vapor and the impurities in surface snow. It has been found that the ratio coefficients, as S1, d1 in the equation ƒOD = S1ƒO18O + d1, are changed near the elevation 2000m on the ice sheet. The weight ratio of Cl-/Na+ at the area below the elevation of 2000m is close to the ratio in the sea salt; but it is about 2 times that of the sea salt, at the inland area up to the elevation of 2000m. The concentrations of non-sea-salt Ca2+ ion (nssCa2+) and fine-particle increase at the interior up to the elevation 2000m. At the region below the elevation of 2000m, the impurity concentration is decreasing with the elevation increasing. Near coastal region, the surface snow has a high concentration of impurity, where the elevation is below 800m. Combining the translating processes of water-vapor and impurities, it suggests that the region up to the elevation 2000m is affected by large

  19. Structurally Complex Surface of Europa

    NASA Technical Reports Server (NTRS)

    1997-01-01

    This is a composite of two images of Jupiter's icy moon Europa obtained from a range of 2119 miles (3410 kilometers) by the Galileo spacecraft during its fourth orbit around Jupiter and its first close pass of Europa. The mosaic spans 11 miles by 30 miles (17 km by 49 km) and shows features as small as 230 feet (70 meters) across. This mosaic is the first very high resolution image data obtained of Europa, and has a resolution more than 50 times better than the best Voyager coverage and 500 times better than Voyager coverage in this area. The mosaic shows the surface of Europa to be structurally complex. The sun illuminates the scene from the right, revealing complex overlapping ridges and fractures in the upper and lower portions of the mosaic, and rugged, more chaotic terrain in the center. Lateral faulting is revealed where ridges show offsets along their lengths (upper left of the picture). Missing ridge segments indicate obliteration of pre-existing materials and emplacement of new terrain (center of the mosaic). Only a small number of impact craters can be seen, indicating the surface is not geologically ancient.

    The Jet Propulsion Laboratory, Pasadena, CA manages the mission for NASA's Office of Space Science, Washington, DC.

    This image and other images and data received from Galileo are posted on the Galileo mission home page on the World Wide Web at http://galileo.jpl.nasa.gov. Background information and educational context for the images can be found at URL http://www.jpl.nasa.gov/galileo/sepo

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

    PubMed

    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. PMID:24963803

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

    PubMed

    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.

  2. Emplacement and geochemical evolution of highly evolved syenites investigated by a combined structural and geochemical field study: The lujavrites of the Ilímaussaq complex, SW Greenland

    NASA Astrophysics Data System (ADS)

    Ratschbacher, Barbara C.; Marks, Michael A. W.; Bons, Paul D.; Wenzel, Thomas; Markl, Gregor

    2015-08-01

    Structural mapping and the combined study of magmatic to solid-state deformation textures and mineral compositions in highly evolved nepheline syenites (lujavrites) of the alkaline to peralkaline Ilímaussaq complex (South Greenland) reveal detailed insight into the emplacement and geochemical evolution of the melts they crystallized from. Based on magmatic to solid-state flow textures such as foliations and lineations, we propose that the investigated rock sequence forms a sill-like structure with a steep feeder zone that flattens out over a short distance and intrudes into less evolved overlying units as sub-horizontal sheets by roof uplift. Systematic compositional variation of early-magmatic eudialyte-group minerals (EGM) in the investigated rock sequence monitors the geochemical evolution of the lujavrite-forming melt(s). The chlorine contents of EGM decrease successively upwards within the rock sequence, which probably indicates a successive increase of water activity during differentiation, consistent with a change from sodic pyroxene (aegirine) to sodic amphibole (arfvedsonite) in the mineral assemblage. Both REE contents and Fe/Mn ratios of EGM are promising differentiation indicators, which increase and decrease, respectively, upwards within the sequence due to fractional crystallization. This closed-system evolution is interrupted by a shift towards less evolved melt compositions in one lujavrite unit, for which we assume magma recharge. Our study demonstrates the strength of a combined structural and petrological approach to understand the petrogenesis of an igneous body in more detail and highlights their close connection.

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

    SciTech Connect

    Puls, R.W.

    1991-07-01

    Identification and understanding of the chemical, physical, and biological processes controlling subsurface contaminant migration is essential for making accurate predictions on the fate and transport of these constituents. Remediation assessment requires these predictions where pollution from municipal and industrial activities has occurred, and for the responsible siting of waste isolation and storage facilities. Geochemical processes include ion-exchange, precipitation, organic partitioning, chemisorption, aqueous complexation, and colloidal stability and transport. Current approaches to quantify the effect of these processes on transport in a ground water system primarily involve laboratory techniques. These include the use of closed static systems (batch experiments) 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. The latter approach may be more representative of in situ conditions than the former, however, when compared to large-scale field experiments both are still 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, scaling factors for laboratory versus field data, corroboration or confirmation of batch and column results, and for validation of sampling techniques.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Geochemical fingerprint of desert surface sediments and aeolian dust exported from southern South America

    NASA Astrophysics Data System (ADS)

    Gili, S.; Gaiero, D. M.; Jweda, J.; Koestner, E.; Chemale, F.; Kaplan, M. R.; Goldstein, S. L.

    2012-12-01

    Wind-transported dust is a tracer of atmospheric circulation and also provides important information about the climatic conditions prevailing in dust source areas. Understanding the origin of mineral dust deposited in different environments (e.g., continent, ocean, polar ice sheet) and the variability of its concentration and composition, can be used as a proxy for the interpretation of the wind systems characteristics and probable changes in the atmospheric circulation patterns. In order to improve the atmospheric circulation models developed for the Southern Hemisphere, it is necessary to increase the understanding of the characteristics of the South American dust sources. Prospero et al., (2002), showed the existence of three present-day persist dust sources in South America: Patagonia (39°-52°S), central-western Argentina (26°-33°S), and the Puna-Altiplano plateau (19°-26°S). An important question to be addressed is whether these dust sources were also important during the last glacial-interglacial cycles. In most cases, researchers working in the reconstruction of paleo-environments in the Southern Hemisphere have employed sparse geochemical and isotopic data from southern South American samples. As a consequence, there are no regional or systematic studies that define their geochemical "fingerprints" of likely sources. The main goal of this work is to identify the "fingerprints" of materials exported from these areas by means of rare earth elements (REEs) and Sr-Nd-Pb-isotopes measured in surface sediments (topsoils) and mineral dust samples. Samples (n=86) were taken across the "arid diagonal" of southern South America in a N-S transect from Uyuni (20°39'S, 68°11'W, Bolivia) to Bahia Blanca (38°43'S, 62°15'W, Argentina) representing different geomorphologic environments: e.g., ephemeral lakes, lowland areas, edges of salt flats, alluvial fans, dunes, etc. Preliminary data indicate the existence of a heterogeneous chemical/isotopic signature along

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

    NASA Technical Reports Server (NTRS)

    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.

  7. Petrogenesis of the Sabongari alkaline complex, cameroon line (central Africa): Preliminary petrological and geochemical constraints

    NASA Astrophysics Data System (ADS)

    Njonfang, Emmanuel; Tchoneng, Gilbert Tchuenté; Cozzupoli, Domenico; Lucci, Federico

    2013-07-01

    The petrography, mineral chemistry and geochemical features of the Sabongari alkaline complex are presented and discussed in this paper with the aim of constraining its petrogenesis and comparing it with other alkaline complexes of the Cameroon Line. The complex is mainly made up of felsic rocks: (i) granites predominate and include pyroxene-amphibole (the most abundant), amphibole-biotite, biotite and pyroxene types; (ii) syenites are subordinate and comprise amphibole-pyroxene and amphibole-biotite quartz syenites; (iii) pyroxene-amphibole-biotite trachyte and (iv) relatively abundant rhyolite. The minor basic and intermediate terms associated with felsic rocks consist of basanites, microdiorite and monzodioites. Two groups of pyroxene bearing rocks are distinguished: a basanite-trachyte-granite (Group 1) bimodal series (SiO2 gap: 44 and 63 wt.%) and a basanite-microdiorite-monzodiorite-syenite-granite (Group 2) less pronounced bimodal series (reduced SiO2 gap: 56-67 wt.%). Both are metaluminous to peralkaline whereas felsic rocks bare of pyroxene (Group 3) are metaluminous to peraluminous. The Group 1 basanite is SiO2-undersaturated (modal analcite in the groundmass and 11.04 wt.% normative nepheline); its Ni (240 ppm) and Cr (450 ppm) contents, near mantle values, indicate its most primitive character. The Group 2 basanite is rather slightly SiO2-saturated (1.56 wt.% normative hypersthene), a marker of its high crustal contamination (low Nb/Y-high Rb/Y). The La/Yb and Gd/Yb values of both basanites (1: 19.47 and 2.92; 2: 9.09 and 2.23) suggest their common parental magma composition, and their crystallization through two episodes of partial melting (2% and 3% respectively) of a lherzolite mantle source with <4% residual garnet. The effects of crustal contamination were selectively felt in the values of HFSE/LREE, LREE/LILE and LREE/HFSE ratios, known as indicators. Similar features have been recently obtained in the felsic lavas of the Cameroon Volcanic Line.

  8. The geochemical nature of the Archean Ancient Gneiss Complex and Granodiorite Suite, Swaziland: a preliminary study

    USGS Publications Warehouse

    Hunter, D.R.; Barker, F.; Millard, H.T., Jr.

    1978-01-01

    The Ancient Gneiss Complex (AGC) of Swaziland, an Archean gray gneiss complex, lies southeast and south of the Barberton greenstone belt and includes the most structurally complex and highly metamorphosed portions of the eastern Kaapvaal craton. The AGC is not precisely dated but apparently is older than 3.4 Ga. The AGC consists of three major units: (a) a bimodal suite of closely interlayered siliceous, low-K gneisses and metabasalt; (b) homogeneous tonalite gneiss; and (c) interlayered siliceous microcline gneiss, metabasalt, and minor metasedimentary rocks - termed the metamorphite suite. A geologically younger gabbro-diorite-tonalite-trondhjemite suite, the Granodiorite Suite, is spatially associated with the AGC and intrusive into it. The bimodal suite consists largely of two types of low-K siliceous gneiss: one has SiO2 14%, low Rb/Sr ratios, and depleted heavy rare earth elements (REE's); the other has SiO2 > 75%, Al2O3 < 13%, high Rb/Sr ratios, and relatively abundant REE's except for negative Eu anomalies. The interlayered metabasalt ranges from komatiitic to tholeiitic compositions. Lenses of quartz monzonitic gneiss of K2O/Na2O close to 1 form a minor part of the bimodal suite. Tonalitic to trondhjemitic migmatite locally is abundant and has major-element abundances similar to those of non-migmatitic varieties. The siliceous gneisses of the metamorphic suite show low Al2O, K2O/Na2O ratios of about 1, high Rb/Sr ratios, moderate REE abundances and negative Eu anomalies. K/Rb ratios of siliceous gneisses of the bimodal suite are very low (???130); of the tonalitic gneiss, low (???225); of the siliceous gneiss of the metamorphite suite, moderate (???300); and of the Granodiorite Suite, high (???400). Rocks of the AGC differ geochemically in several ways from the siliceous volcanic and hypabyssal rocks of the Upper Onverwacht Group and from the diapirs of tonalite and trondhjemite that intrude the Swaziland Group. ?? 1978.

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

    USGS Publications Warehouse

    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

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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.

  11. An index of floodplain surface complexity

    USGS Publications Warehouse

    Scown, Murray W.; Thoms, Martin C.; DeJager, Nathan R.

    2016-01-01

    Floodplain surface topography is an important component of floodplain ecosystems. It is the primary physical template upon which ecosystem processes are acted out, and complexity in this template can contribute to the high biodiversity and productivity of floodplain ecosystems. There has been a limited appreciation of floodplain surface complexity because of the traditional focus on temporal variability in floodplains as well as limitations to quantifying spatial complexity. An index of floodplain surface complexity (FSC) is developed in this paper and applied to eight floodplains from different geographic settings. The index is based on two key indicators of complexity, variability in surface geometry (VSG) and the spatial organisation of surface conditions (SPO), and was determined at three sampling scales. FSC, VSG, and SPO varied between the eight floodplains and these differences depended upon sampling scale. Relationships between these measures of spatial complexity and seven geomorphological and hydrological drivers were investigated. There was a significant decline in all complexity measures with increasing floodplain width, which was explained by either a power, logarithmic, or exponential function. There was an initial rapid decline in surface complexity as floodplain width increased from 1.5 to 5 km, followed by little change in floodplains wider than 10 km. VSG also increased significantly with increasing sediment yield. No significant relationships were determined between any of the four hydrological variables and floodplain surface complexity.

  12. Geochemical and magnetic characteristics of aeolian transported materials under different near-surface wind fields: An experimental study

    NASA Astrophysics Data System (ADS)

    Wang, Xunming; Lang, Lili; Hua, Ting; Zhang, Caixia; Xia, Dunsheng

    2015-06-01

    By combining field investigations, field sampling, wind-tunnel experiments, and laboratory measurements, the relationships between near-surface winds and the geochemical and magnetic characteristics of wind-transported materials were statistically analyzed. Our study was conducted using bulk surface samples from a major potential dust source area in Central Asia (the Ala Shan Plateau). Under near-surface wind velocities ranging from 8 to 22 m/s, the coefficients of variation ranged between 1.6% and 14.9% for χlf, 1.4% and 11.0% for χARM, and 0.7% and 12.3% for SIRM of the transported materials. For the 26 elements and oxides investigated, the coefficients of variation of Ti, Cr, As, Zr, Ce, Pb, and Cu in the samples were greater than 10%. No consistent patterns were found between magnetic characteristics and elemental and iron oxide concentrations as a function of variations in near-surface wind velocities. In potential dust source areas under near-surface wind velocities, there are variations in the relationships between magnetic and geochemical characteristics in the fine fractions of transported materials with different particle sizes. Given the wide variation in magnetic and geochemical characteristics of aeolian-transported materials under different near-surface winds, their use as proxies for past climate reconstruction must be carefully appraised.

  13. Simultaneous application of dissolution/precipitation and surface complexation/surface precipitation modeling to contaminant leaching.

    PubMed

    Apul, Defne S; Gardner, Kevin H; Eighmy, T Taylor; Fällman, Ann-Marie; Comans, Rob N J

    2005-08-01

    This paper discusses the modeling of anion and cation leaching from complex matrixes such as weathered steel slag. The novelty of the method is its simultaneous application of the theoretical models for solubility, competitive sorption, and surface precipitation phenomena to a complex system. Selective chemical extractions, pH dependent leaching experiments, and geochemical modeling were used to investigate the thermodynamic equilibrium of 12 ions (As, Ca, Cr, Ba, SO4, Mg, Cd, Cu, Mo, Pb, V, and Zn) with aqueous complexes, soluble solids, and sorptive surfaces in the presence of 12 background analytes (Al, Cl, Co, Fe, K, Mn, Na, Ni, Hg, NO3, CO3, and Ba). Modeling results show that surface complexation and surface precipitation reactions limit the aqueous concentrations of Cd, Zn, and Pb in an environment where Ca, Mg, Si, and CO3 dissolve from soluble solids and compete for sorption sites. The leaching of SO4, Cr, As, Si, Ca, and Mg appears to be controlled by corresponding soluble solids.

  14. Surface geochemical survey for geothermal exploration in the south-east zone of Tenerife Island, Canary Islands

    NASA Astrophysics Data System (ADS)

    Diaz Requejo, M.; Marrero, R.; Padron, E.; Melian, G.; Guerrero, V.; Hernandez Perez, P. A.; Perez, N.; Hidalgo, R.

    2009-12-01

    Water and gas sampling of natural discharges are the most common type of geochemical surveys for geothermal exploration. However, these natural discharges are generally scarces at geothermal exploration areas where the extent of the field is not known. Therefore, soil-volatile (Hg, As, Sb, NH3 and B) and soil-gas surveys (222Rn, CO2, He, H2, CH4, O2, Ar) are becoming a useful geochemical tool to identify permeable areas and potential upflow or boiling zones. These surveys can also help to delineate the margins of a geothermal system, and therefore often complement geophysical surveys particularly where the interpretation of geophysical data shows some difficulties. During July and August, 2008, a surface geochemical survey was undertaken in a ~120 km2 area at the south-east slope of Tenerife Island, Spain. In order to obtain a representative distribution of the whole study area, during the field work a total of 577 sampling points were performed. In-situ measurement of radon (222Rn) and thoron (220Rn) activities together with Hg0 and H2S gas concentration and CO2 and H2S soil effluxes were performed at each sampling point. At the same time, gas samples were taken from the soil atmosphere at 40 cm depth for subsequent chemical analysis by means of micro-gas chromatography and quadrupole mass spectrometry (He, H2, Ne, N2, CO2, CH4, Ar and CO2). At least two geochemical anomalous zones have been identified in the present work: (A) one close to Siete Fuentes-Fasnia historical vents (1704-1705 AD) and (B) located on the southwestern limit of the study area. Relatively high concentrations of H2 and ΔHe as well as high H2/Ar and He/CO2 ratios were observed at both zones, indicating a clear evidence of the existence of an upflow zone with an important contribution of endogenous gases. The existence of a volcanic-hydrothermal system coupled with a vertical permeability structures in both zones could explain these geochemical anomalies observed in the surface environment

  15. Hydro-geochemical processes in the Complexe Terminal aquifer of southern Tunisia: An integrated investigation based on geochemical and multivariate statistical methods

    NASA Astrophysics Data System (ADS)

    Hadj Ammar, Friha; Chkir, Najiba; Zouari, Kamel; Hamelin, Bruno; Deschamps, Pierre; Aigoun, Aissa

    2014-12-01

    Hydrochemical data from a total of 104 groundwater samples were used to investigate the main factors and mechanisms that control the chemistry of groundwaters in the Complexe Terminal (CT) aquifer of Chott region in southern Tunisia. Multivariate statistical techniques combining Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) were applied to the dataset of 12 physicochemical parameters (i.e. pH, T°, depth, Na+, K+, Ca2+, Mg2+, HCO3-, NO3-, Cl-, SO42-, and TDS). The HCA using Ward's method and squared Euclidean distance classified the parameters into four clusters based on their dissimilarities. The application of PCA resulted in two factors explaining 64.25% variance. Geochemical methods combined with HCA and PCA confirm that groundwater chemistry is not controlled by the different lithological facies of the aquifer, but by the presence of evaporates randomly distributed in the basin. Although stable isotope data (2H and 18O) of some groundwater are consistent with a slight modern recharge, CT groundwaters are mostly depleted bearing witness to the recharge of the aquifer system occurred under different climatic conditions than present. The stable isotopic composition of these paleowaters which all lie to the right of the local meteoric water line also indicates more pronounced evaporation of rainfall during the recharge process than during present-day conditions.

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

    USGS Publications Warehouse

    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

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

    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

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

    SciTech Connect

    Dixon, David Adams

    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

  19. Generalized complex structures on Kodaira surfaces

    NASA Astrophysics Data System (ADS)

    Brinzanescu, Vasile; Turcu, Oana Adela

    2010-01-01

    We compute the deformations in the sense of generalized complex structures of the standard classical complex structure on a primary Kodaira surface and we prove that the obtained family of deformations is a smooth locally complete family depending on four complex parameters. This family is the same as the extended deformations (in the sense of Kontsevich and Barannikov) in degree two, obtained by Poon using differential Gerstenhaber algebras.

  20. Surface complexes of acrolein on oxide catalysts

    SciTech Connect

    Popova, G.Ya.; Davydov, A.A.; Andrushkevich, T.V.; Zakharov, I.I.

    1995-01-01

    It is shown that acrolein can be adsorbed by different mechanisms on the surface of oxide catalysts with the formation of {sigma}- and {pi}-complexes, H-complexes with surface OH groups; a species bound via the carbonyl group (the dissociative form of adsorption); and oxidized fragments, such as surface acrylates, carboxylates, formylacetates, and malonates. On the basis of the quantum-chemical analysis of the acrolein interaction with the surface of oxide catalysts in combination with IR-spectroscopic, thermodesorption, and catalytic studies, a conclusion has been drawn that the formation of a certain surface species and its reactivity are determined by the nature of an adsorption site and by the reactivity of surface oxygen.

  1. Geochemical characteristics of hydrous basaltic magmas due to assimilation and fractional crystallization: the Ikoma gabbroic complex, southwest Japan

    NASA Astrophysics Data System (ADS)

    Koizumi, N.; Okudaira, T.; Ogawa, D.; Yamashita, K.; Suda, Y.

    2016-02-01

    To clarify the processes that occur in hydrous basaltic magma chambers, we have undertaken detailed petrological and geochemical analyses of mafic and intermediate rocks from the Ikoma gabbroic complex, southwest Japan. The complex consists mainly of hornblende gabbros, hornblende gabbronorites, and hornblende leucogabbros. The hornblende leucogabbros are characterized by low TiO2 and high CaO contents, whereas the hornblende gabbronorites have high TiO2 and low CaO contents. The initial 87Sr/86Sr ratios (SrI) of the hornblende gabbronorites and hornblende gabbros are higher than those of the hornblende leucogabbros and plagioclase, and they may have resulted from a higher degree of assimilation of metasediments. The geochemical features of the hornblende leucogabbros and hornblende gabbronorites can be explained by accumulation of plagioclase and ilmenite, respectively, in a hybrid magma that formed by chemical interaction between mafic magma and metasediment, whereas the hornblende gabbros were produced by a high degree of crustal assimilation and fractional crystallization of this hybrid magma. As a result of the density differences between crystals and melt, the Ikoma gabbroic rocks formed by the accumulation of plagioclase in the middle of the magma chamber and by the accumulation of ilmenite in the bottom of the chamber. Taking into account the subsequent assimilation and fractional crystallization, our observations suggest an enriched mantle (SrI = ~0.7071) as the source material for the Ikoma gabbros.

  2. Translation and docking of an arc terrane: geological and geochemical evidence from the southern Zambales Ophiolite Complex, Philippines

    NASA Astrophysics Data System (ADS)

    Yumul, G. P.; Dimalanta, C. B.; Faustino, D. V.; De Jesus, J. V.

    1998-08-01

    The Zambales Ophiolite Complex is made up of three massifs: the Masinloc, Cabangan and San Antonio Massifs. Field, petrographic and geochemical analyses show that the Cabangan and San Antonio Massifs are genetically related to the Coto (transitional mid-ocean ridge-island arc) and Acoje (island arc) blocks of the Masinloc Massif, respectively. The Subic Bay Fault Zone, a left-lateral fault zone, separates the San Antonio Massif island arc terrane from the transitional mid-ocean ridge-island arc-like sheeted diabase dikes-pillow basalts of the Cabangan Massif. The San Antonio Massif is a rifted terrane from the Acoje block which was translated southward to its present position through the West Luzon Shear-Subic Bay Fault Zone. Tectonized clinopyroxenite and gabbronorite hills, which mimic the physical and geochemical characteristics of the Acoje block and the San Antonio Massif ultramafic-mafic cumulate rocks, were left behind along the western side of the Cabangan Massif during the translation of the arc massif southward. This scenario can account for the present-day configuration of the Zambales Ophiolite Complex.

  3. Geochemical characteristics of hydrous basaltic magmas due to assimilation and fractional crystallization: the Ikoma gabbroic complex, southwest Japan

    NASA Astrophysics Data System (ADS)

    Koizumi, N.; Okudaira, T.; Ogawa, D.; Yamashita, K.; Suda, Y.

    2016-10-01

    To clarify the processes that occur in hydrous basaltic magma chambers, we have undertaken detailed petrological and geochemical analyses of mafic and intermediate rocks from the Ikoma gabbroic complex, southwest Japan. The complex consists mainly of hornblende gabbros, hornblende gabbronorites, and hornblende leucogabbros. The hornblende leucogabbros are characterized by low TiO2 and high CaO contents, whereas the hornblende gabbronorites have high TiO2 and low CaO contents. The initial 87Sr/86Sr ratios (SrI) of the hornblende gabbronorites and hornblende gabbros are higher than those of the hornblende leucogabbros and plagioclase, and they may have resulted from a higher degree of assimilation of metasediments. The geochemical features of the hornblende leucogabbros and hornblende gabbronorites can be explained by accumulation of plagioclase and ilmenite, respectively, in a hybrid magma that formed by chemical interaction between mafic magma and metasediment, whereas the hornblende gabbros were produced by a high degree of crustal assimilation and fractional crystallization of this hybrid magma. As a result of the density differences between crystals and melt, the Ikoma gabbroic rocks formed by the accumulation of plagioclase in the middle of the magma chamber and by the accumulation of ilmenite in the bottom of the chamber. Taking into account the subsequent assimilation and fractional crystallization, our observations suggest an enriched mantle (SrI = ~0.7071) as the source material for the Ikoma gabbros.

  4. Geochemical forms and seasonal variations of phosphorus in surface sediments of the East China Sea shelf

    NASA Astrophysics Data System (ADS)

    Zhou, Fengxia; Gao, Xuelu; Yuan, Huamao; Song, Jinming; Chen, Chen-Tung Arthur; Lui, Hon-Kit; Zhang, Yong

    2016-07-01

    Geochemical characteristics of phosphorus (P) in the surface sediments of the East China Sea shelf (ECSS) were studied in spring and autumn, 2014. Distributions, seasonal variations, transformations and their influencing factors were discussed. Besides, burial fluxes of P in different seasons were also calculated. Five operationally defined forms of P, namely exchangeable or loosely sorbed P (Ads-P), iron-bound P (Fe-P), authigenic P (Au-P), detrital apatite plus other inorganic P (De-P) and organic P (OP), were obtained using a sequential extraction procedure. Generally, the concentrations of Ads-P, Fe-P, Au-P and OP decreased seaward and the concentrations of De-P increased seaward in both seasons. In spring, the average concentrations of Ads-P, Fe-P, Au-P, De-P and OP were 13.8 ± 5.0, 21.9 ± 7.6, 148.5 ± 44.5, 153.1 ± 55.8 and 91.7 ± 21.5 μg g- 1, respectively. The corresponding concentrations in autumn were 11.4 ± 4.3, 20.0 ± 10.9, 170.4 ± 53.6, 225.6 ± 101.7 and 77.1 ± 33.9 μg g- 1, respectively. The average percentages of P fractions in total P (TP) in spring and autumn were both in the order: De-P > Au-P > OP > Fe-P > Ads-P. The average concentrations of Bio-available P (Bio-P) were 127.4 ± 31.4 μg g- 1 in spring and 108.5 ± 47.2 μg g- 1 in autumn, accounting for 29.8% ± 7.3% and 21.5% ± 8.2% of corresponding TP, respectively. Seasonal variations of the primary production, hydrodynamic conditions, hypoxia and other environmental conditions were responsible for the seasonal variations of different phosphorus forms. The calculation of burial fluxes reflected that, in most parts of the studied area, TP had relative high burial fluxes in autumn, while Bio-P had relatively high burial fluxes in spring. The burial fluxes of other phosphorus forms also showed different seasonal variations in different parts of the studied area.

  5. Geochemical recognition of a captured back-arc basin metabasaltic complex, southwestern Oregon

    USGS Publications Warehouse

    Donato, M.M.

    1991-01-01

    An extensive fault-bounded amphibolite terrane of Late Jurassic (145 ?? 2 Ma) metamorphic age occurring in the northeastern Klamath Mountains of southern Oregon has been recognized as the remnants of an ancient back-arc basin. In spite of thorough metamorphic recrystallization under amphibolite-facies conditions, the amphibolite locally displays relict igneous textures which suggest that the protoliths included basaltic dikes or sills, shallow diabase intrusions, and gabbros. The geochemical data, together with the present-day geologic context, indicate that the tectonic setting of eruption/intrusion was probably within a back-arc basin that existed inboard (east) of a pre-Nevadan volcanic arc. The basalt (now amphibolite) and the overlying sediments (now the May Creek Schist) were metamorphosed and deformed during accretion to North America during the Late Jurassic Nevadan orogeny. -from Author

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

    SciTech Connect

    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.

  7. Exciton coupling of surface complexes on a nanocrystal surface.

    PubMed

    Xu, Xiangxing; Ji, Jianwei; Wang, Guan; You, Xiaozeng

    2014-08-25

    Exciton coupling may arise when chromophores are brought into close spatial proximity. Herein the intra-nanocrystal exciton coupling of the surface complexes formed by coordination of 8-hydroxyquinoline to ZnS nanocrystals (NCs) is reported. It is studied by absorption, photoluminescence (PL), PL excitation (PLE), and PL lifetime measurements. The exciton coupling of the surface complexes tunes the PL color and broadens the absorption and PLE windows of the NCs, and thus is a potential strategy for improving the light-harvesting efficiency of NC solar cells and photocatalysts.

  8. Geochemical speciation and ecological risk assessment of selected metals in the surface sediments of the northern Persian Gulf.

    PubMed

    Neyestani, Mahmoud Reza; Bastami, Kazem Darvish; Esmaeilzadeh, Marjan; Shemirani, Farzaneh; Khazaali, Aida; Molamohyeddin, Neda; Afkhami, Majid; Nourbakhsh, Shahram; Dehghani, Mohsen; Aghaei, Sina; Firouzbakht, Mohammad

    2016-08-15

    The present study aimed to geochemical speciation of metals in the surface sediments of the northern Persian Gulf. Metal contents in the sediment were observed in the order: Al>Fe>Cr>Ni>V>Zn>Cu>Co>As>Pb>Cd. The results of sequential extraction procedure revealed that all metals were predominantly associated with the residual fraction. Among the metals, Cu and As exhibited higher bioavailability. The risk assessment code (RAC) indicated that Cu, As and Cd had medium environmental risk at some sampling sites. Based on enrichment factor (EF), Cd and As had moderate to significant enrichment. PMID:27210564

  9. Global Geochemical Variation on the Lunar Surface: A Three-Element Approach

    NASA Technical Reports Server (NTRS)

    Thomsen, D. R.; Lawrence, D. J.; Vaniman, D.; Feldman, W. C.; Elphic, R. C.; Barraclough, B. L.; Maurice, S.; Lucey, P. G.; Binder, A. B.

    1999-01-01

    We present a method for displaying the relative abundances of three important elements (Th, Fe, and Ti) on the same map projection of the lunar surface. Using Th-, Fe-, and Ti-elemental abundances from orbital geochemical data and assigning each element a primary color, a false-color map of the lunar surface was created. This approach is similar to the ternary diagram approach presented by Davis and Spudis with some important differences, discussed later. For the present maps, Th abundances were measured by the Lunar Prospector (LP) Gamma-Ray Spectrometer(GRS).The new LPGRS low-altitude dataset was used in this analysis. Iron and Ti weight percentages were based on Clementine spectral reflectance data smoothed to the LP low altitude footprint. This method of presentation was designed to aid in the location and recognition of three principal lunar compositions: ferroan anorthosite (FAN), mare basalts (MB), and the Mg suite/ KREEP-rich rocks on the lunar surface, with special emphasis on the highlands and specific impact basins. In addition to the recognition of these endmember rock compositions, this method is an attempt to examine the relationship between elemental compositions that do not conform readily to previously accepted or observed endmember rocks in various specific regions of interest, including eastern highlands regions centered on 150 deg longitude, and a northern highlands Th-rich region observed. The LP low-altitude data has full width at half-maximum spatial resolution of about 40 km. The Clementine spectral reflectance datasets were adapted using an equal-area, gaussian smoothing routine to this footprint. In addition, these datasets, reported in weight percent of FeO and of Ti02, were adjusted to Fe and Ti weight percentages. Each dataset was then assigned one of the three primary colors: blue for Th, red for Fe, and green for Ti. For each element, the data range was normalized to represent the ratio of each point to the maximum in the dataset. (To

  10. Geochemical behaviour of palladium in soils and Pd/PdO model substances in the presence of the organic complexing agents L-methionine and citric acid.

    PubMed

    Zereini, Fathi; Wiseman, Clare L S; Vang, My; Albers, Peter; Schneider, Wolfgang; Schindl, Roland; Leopold, Kerstin

    2016-01-01

    Risk assessments of platinum group metal (PGE) emissions, notably those of platinum (Pt), palladium (Pd) and rhodium (Rh), have been mostly based on data regarding the metallic forms used in vehicular exhaust converters, known to be virtually biologically inert and immobile. To adequately assess the potential impacts of PGE, however, data on the chemical behaviour of these metals under ambient conditions post-emission is needed. Complexing agents with a high affinity for metals in the environment are hypothesized to contribute to an increased bioaccessibility of PGE. The purpose of this study is to examine the modulating effects of the organic complexing agents, L-methionine and citric acid, on the geochemical behavior of Pd in soils and model substances (Pd black and PdO). Batch experimental tests were conducted with soils and model substances to examine the impacts of the concentration of complexing agents, pH and length of extraction period on Pd solubility and its chemical transformation. Particle surface chemistry was examined using X-ray photoelectron spectroscopy (XPS) on samples treated with solutions under various conditions, including low and high O2 levels. Pd was observed to be more soluble in the presence of organic complexing agents, compared to Pt and Rh. Pd in soils was more readily solubilized with organic complexing agents compared to the model substances. After 7 days of extraction, L-methionine (0.1 M) treated soil and Pd black samples, for instance, had mean soluble Pd fractions of 12.4 ± 5.9% and 0.554 ± 0.024%, respectively. Surface chemistry analyses (XPS) confirmed the oxidation of metallic Pd surfaces when treated with organic complexing agents. The type of organic complexing agent used for experimental purposes was observed to be the most important factor influencing solubility, followed by solution pH and time of extraction. The results demonstrate that metallic Pd can be transformed into more bioaccessible species in the presence of

  11. Geochemical recognition of a captured back-arc basin metabasaltic complex, southwestern Oregon

    SciTech Connect

    Donato, M.M. )

    1991-09-01

    An extensive fault-bounded amphibolite terrane of Late Jurassic (145 {plus minus} 2 Ma) metamorphic age occurring in the northeastern Klamath Mountains of southern Oregon has been recognized as the remnants of an ancient back-arc basin. In spite of through metamorphic recrystallization under amphibolite-facies conditions, the amphibolite locally displays relict igneous textures which suggest that the protoliths included basaltic dikes or sills, shallow diabase intrusions, and gabbros. The major- and minor-element chemistry of the amphibolite indicates that some alteration of original compositions has occurred. Nevertheless, certain elements (e.g. Zr, Ti, Y, Hf, P, Th, Ta, and the REE) were probably immobile and retain their original igneous abundances, Chondrite-normalized REE patterns are similar to those of mid-ocean ridge basalt (MORB): concave-downward and flat or slightly LREE-depleted, with abundances about six to 30 times chondritic values. Patterns are slightly LREE-enriched and HREE-depleted relative to average MORB. Most samples plot in or near MORB fields in tectonomagmatic discrimination diagrams, but relative enrichment in Th, and the LREE suggest the involvement of subduction-related fluids in magma genesis. In this regard, the amphibolite is very similar to some back-arc basin basalts. The geochemical data, together with the present-day geologic context, indicate that the tectonic setting of eruption/intrusion was probably within a back-arc basin that existed inboard (east) of a pre-Nevadan volcanic arc. The basalt (now amphibolite) and the overlying sediments (now the May Creek Schist) were metamorphosed and deformed during accretion to North America during the Late Jurassic Nevadan orogeny.

  12. Geochemical investigation of Archaean Bimodal and Dwalile metamorphic suites, Ancient Gneiss Complex, Swaziland

    USGS Publications Warehouse

    Hunter, D.R.; Barker, F.; Millard, H.T.

    1984-01-01

    The bimodal suite (BMS) comprises leucotonalitic and trondhjemitic gneisses interlayered with amphibolites. Based on geochemical parameters three main groups of siliceous gneiss are recognized: (i) SiO2 14%, and fractionated light rare-earth element (REE) and flat heavy REE patterns; (ii) SiO2 and Al2O3 contents similar to (i) but with strongly fractionated REE patterns with steep heavy REE slopes; (iii) SiO2 > 73%, Al2O3 < 14%, Zr ??? 500 ppm and high contents of total REE having fractionated light REE and flat heavy REE patterns with large negative Eu anomalies. The interlayered amphibolites have major element abundances similar to those of basaltic komatiites, Mg-tholeiites and Fe-rich tholeiites. The former have gently sloping REE patterns, whereas the Mg-tholeiites have non-uniform REE patterns ranging from flat (??? 10 times chondrite) to strongly light REE-enriched. The Fe-rich amphibolites have flat REE patterns at 20-30 times chondrite. The Dwalile metamorphic suite, which is preserved in the keels of synforms within the BMS, includes peridotitic komatiites that have depleted light REE patterns similar to those of compositionally similar volcanics in the Onverwacht Group, Barberton, basaltic komatiites and tholeiites. The basaltic komatiites have REE patterns parallel to those of the BMS basaltic komatiites but with lower total REE contents. The Dwalile tholeiites have flat REE patterns. The basic and ultrabasic liquids were derived by partial melting of a mantle source which may have been heterogeneous or the heterogeneity may have resulted from sequential melting of the mantle source. The Fe-rich amphibolites were derived either from liquids generated at shallow levels or from liquids generated at depth which subsequently underwent extensive fractionation. ?? 1984.

  13. Geochemical and mineralogical characteristics of the Yonghwa phoscorite-carbonatite complex, South Korea, and genetic implications

    NASA Astrophysics Data System (ADS)

    Seo, Jieun; Choi, Seon-Gyu; Park, Jung-Woo; Whattam, Scott; Kim, Dong Woo; Ryu, In-Chang; Oh, Chang Whan

    2016-10-01

    The Yonghwa phoscorite-carbonatite complex occurs as an isolated individual body with an inclined pipe shape within the Precambrian Gyeonggi Massif, South Korea. The phoscorite consists mainly of olivine, apatite, magnetite, carbonates, amphibole, and phlogopite, and can be subdivided into two types, olivine-rich and apatite-rich. The carbonatite is composed of calcite, Mg-rich dolomite, Fe-rich dolomite, magnetite, apatite, and/or siderite. Intensive fenitization occurred along the boundary between the complex and the wall rocks of leucocratic banded gneiss and garnet-bearing metabasite. The paragenetic sequences of the phoscorite-carbonatite complex demonstrate that the early crystallization of silicate minerals was followed by the crystallization of carbonates as the carbonatitic melt cooled. Magnetite occurs within the complex, and the carbonatites have Fe contents that are higher than typical ferrocarbonatites, due to the high magnetite contents. The rare earth elements (REEs) in the phoscorites and carbonatites are weakly fractionated and show enrichments of LREEs and Nb relative to HREEs. Furthermore, the apatites reflect the fractionated trends of LREEs relative to HREEs. Phoscorite apatites are enriched in Sr and show substitutions between Ca and Sr. Mica chemistry reflects the evolutionary trend of Fe2 + and Mg2 + in the phoscorite-carbonatite melt without Al substitution. Micas exhibit high values of Mg# in the phoscorite-carbonatite complex, but lower values in fenites. Via thermodynamic analysis, the early stability fields of magnetite-pyrrhotite-graphite-carbonate assemblages indicate that the Yonghwa phoscorite and carbonatite crystallized under conditions of 600 °C, 2 kbar, and XCO2 = 0.2. Afterward, melts underwent an evolution to the late stability fields of magnetite-pyrite-pyrrhotite-ilmenite assemblages. The δ13C and δ18O isotopic compositions of carbonates in the Yonghwa phoscorite-carbonatite complex are - 8.2‰ to - 3.4‰ and 6.6 to 11

  14. Origin of late Archean granite: geochemical evidence from the Vermilion Granitic Complex of northern Minnesota

    NASA Astrophysics Data System (ADS)

    Day, Warren C.; Weiblen, P. W.

    1986-07-01

    The 2,700-Ma Vermilion Granitic Complex of northern Minnesota is a granite-migmatite terrane composed of supracrustal metasedimentary rocks, mafic rocks, tonalitic and granodioritic plutonic rocks, and granite. The metasedimentary rocks are predominantly graywacke, which has been regionally metamorphosed to garnet-sillimanite-muscovite-bearing biotite schist, and has locally undergone anatexis. The mafic rocks form early phases within the complex and are of two types: (1) basaltic amphibolite, and (2) monzodiorite and essexite rich in large ion lithophile elements (LILE). The members of the early plutonic suite form small bodies that intrude the metasedimentary rocks and mafic rocks, producing an early migmatite. The granite is of two distinct varieties: (1) white garnet-muscovite-biotite leucogranite ( S-type; Chappell and White 1974) and (2) grayish-pink biotite-magnetite Lac La Croix Granite ( I-type). The leucogranite occurs in the early migmatite and in paragneissic portions of the complex, whereas the Lac La Croix Granite is a late-stage intrusive phase that invades the early migmatite and metasediment (producing a late migmatite) and forms a batholith. This study focuses specifically on the origin of granite in the Vermilion Granitic Complex. Chemical mass-balance calculations suggest that the S-type two-mica leucogranite had a metagraywacke source, and that the I-type Lac La Croix Granite formed via partial fusion of calc-alkaline tonalitic material, which may have been similar to rocks of the early plutonic suite. This model is satisfactory for petrogenesis of similar Late Archean post-kinematic granites throughout the Canadian Shield.

  15. Origin of late Archean granite: geochemical evidence from the Vermilion Granitic Complex of northern Minnesota

    USGS Publications Warehouse

    Day, W.C.; Weiblen, P.W.

    1986-01-01

    The 2,700-Ma Vermilion Granitic Complex of northern Minnesota is a granite-migmatite terrane composed of supracrustal metasedimentary rocks, mafic rocks, tonalitic and granodioritic plutonic rocks, and granite. The metasedimentary rocks are predominantly graywacke, which has been regionally metamorphosed to garnet-sillimanite-muscovite-bearing biotite schist, and has locally undergone anatexis. The mafic rocks form early phases within the complex and are of two types: (1) basaltic amphibolite, and (2) monzodiorite and essexite rich in large ion lithophile elements (LILE). The members of the early plutonic suite form small bodies that intrude the metasedimentary rocks and mafic rocks, producing an early migmatite. The granite is of two distinct varieties: (1) white garnet-muscovite-biotite leucogranite (S-type; Chappell and White 1974) and (2) grayish-pink biotite-magnetite Lac La Croix Granite (I-type). The leucogranite occurs in the early migmatite and in paragneissic portions of the complex, whereas the Lac La Croix Granite is a late-stage intrusive phase that invades the early migmatite and metasediment (producing a late migmatite) and forms a batholith. This study focuses specifically on the origin of granite in the Vermilion Granitic Complex. Chemical mass-balance calculations suggest that the S-type two-mica leucogranite had a metagraywacke source, and that the I-type Lac La Croix Granite formed via partial fusion of calc-alkaline tonalitic material, which may have been similar to rocks of the early plutonic suite. This model is satisfactory for petrogenesis of similar Late Archean post-kinematic granites throughout the Canadian Shield. ?? 1986 Springer-Verlag.

  16. A petrological and geochemical study of the Surna Nappe (Seve Nappe Complex?) in the Central Scandinavian Caledonides, Norway

    NASA Astrophysics Data System (ADS)

    Weigand, Silvia; Hauzenberger, Christoph; Gasser, Deta

    2016-04-01

    The Seve Nappe Complex, mainly outcropping and investigated in Sweden, comprises relics of Ordovician HP and UHP metamorphic rocks, which were overprinted by upper amphibolite facies metamorphism and anataxis during the Silurian. In Norway, in the hinterland of the Caledonian orogen, rocks of the Surna and Blåhø nappes are generally correlated with the Seve Nappe Complex. However, no detailed metamorphic studies are available from these units to compare it with the Seve Nappe Complex. The Surna and Blåhø nappes are located between the oceanic-derived Støren nappe and the continentally-derived Sætra nappe. Due to a strong post-Caledonian extensional and transtensional overprint and a close proximity to the MTFC (Møre-Trøndelag Fault Complex, a prominent post-Caledonian strike-slip fault complex) investigations of the early metamorphic history of the Surna and Blåhø nappes are challenging. In this contribution we present the results of a petrological and geochemical study of the Surna Nappe, from a ca. 10 km wide transect across this nappe west of Trondheim in Norway. The nappe is lithologically very heterogenous, consisting of quartz-rich mica-schists, amphibole-garnet-mica-schists, amphibolites, calcsilicates as well as pegmatites. Geochemically, the whole rock compositions vary from ultrabasic to acidic, but a distinction between metavolcanic and metasedimentary origin of the lithologies is not always straightforward. Although there are metabasic rocks present they do not show a mineral assemblage with a relic eclogite facies. Garnet occurs in several lithologies and is used together with plagioclase and biotite for conventional geothermobarometry using the TWQ and PET software tools. Additionally, Zr-in-rutile and garnet-biotite thermometers were applied. PT calculations from 18 different samples reveal PT conditions of 600 to 700°C and pressures of 10 to 16 kbar. The elevated phengite content in muscovite (Si up to 3.28) in a few samples may indicate

  17. Application of the surface complexation concept to complex mineral assemblages

    USGS Publications Warehouse

    Davis, J.A.; Coston, J.A.; Kent, D.B.; Fuller, C.C.

    1998-01-01

    Two types of modeling approaches are illustrated for describing inorganic contaminant adsorption in aqueous environments: (a) the component additivity approach and (b) the generalized composite approach. Each approach is applied to simulate Zn2+ adsorption by a well-characterized sediment collected from an aquifer at Cape Cod, MA. Zn2+ adsorption by the sediment was studied in laboratory batch experiments with a range of pH and Zn(II) concentrations selected to encompass conditions observed in the aquifer. In the generalized composite approach, one, and two-site surface complexation model parameters were calibrated with the experimental data using FITEQL. The pH dependence of Zn2+ adsorption was simulated without explicit representation of electrostatic energy terms. Surface acidity constants and ion pair formation by major electrolyte ions were also not required in the model thereby minimizing the number of fitted parameters. Predictions of Zn2+ adsorption with the component additivity modeling approach did not simulate the experimental data adequately without manipulation of surface area or site density parameter values. To apply the component additivity approach to environmental sorbents, further research is needed to better characterize the composition of sediment surface coatings. The generalized composite modeling approach requires less information and can be viewed as more practical for application within solute transport models. With only three adjustable parameters, this approach could simulate Zn2+ adsorption over a range of chemical conditions that would cause several orders of magnitude variation in the distribution coefficient (K(d)) for Zn2+ within the aquifer.Two types of modeling approaches are illustrated for describing inorganic contaminant adsorption in aqueous environments: (a) the component additivity approach and (b) the generalized composite approach. Each approach is applied to simulate Zn2+ adsorption by a well-characterized sediment

  18. Soft Landing of Complex Molecules on Surfaces *

    NASA Astrophysics Data System (ADS)

    Johnson, Grant E.; Hu, Qichi; Laskin, Julia

    2011-07-01

    Soft and reactive landing of mass-selected ions onto surfaces has become a topic of substantial interest due to its promising potential for the highly controlled preparation of materials. For example, there are possible applications in the production of peptide and protein microarrays for use in high-throughput screening, protein separation and conformational enrichment of peptides, redox protein characterization, thin-film production, and the preparation of catalysts through deposition of clusters and organometallic complexes. Soft landing overcomes many of the limitations associated with conventional thin-film production techniques and offers unprecedented selectivity and specificity of preparation of deposited species. This review discusses the fundamental aspects of soft and reactive landing of mass-selected ions on surfaces that pertain to applications of these techniques in biomaterials, molecular electronics, catalysis, and interfacial chemistry.

  19. Geochemical characterization of loess-soil complexes on the Terek-Kuma Plain and the Azov-Kuban' Lowland

    NASA Astrophysics Data System (ADS)

    Kalinin, P. I.; Alekseev, A. O.

    2011-12-01

    The changes in the material composition of the buried soils and loesses in relation to the dynamics of the climate and sediment accumulation were studied for revealing the pedogenetic features and assessing the natural conditions in the steppe zone of the southern Russian Plain. A comparative analysis of the chemical compositions of the different-aged Pleistocene loess-soil complexes (the Otkaznoe, Port-Katon, and Shabel'skoe profiles) on the Terek-Kuma Plain and the Azov-Kuban' Lowland was performed. An increase in the concentrations of Fe and Mn, which are intensively involved in the biological cycle, and Rb, which is accumulated due to the activation of weathering processes, was observed in the paleosols that developed in interglacial periods of activation of pedogenesis. Increased coefficients of weathering (chemical index of alteration (CIA)) = [Al/(Al + Ca + Na + K)] 100, Al/(Al + Ca + Na + Mg), Rb/Sr, and Mn/Sr), leaching (Ba/Sr), and biological activity and bioproductivity (Mn/Fe, Mn/Al) were also noted for the paleosol horizons as compared with the loess horizons. It is argued that geochemical coefficients can be used as an efficient tool in the soil and paleogeographic studies aimed at the reconstruction and refinement of the schemes of changes in the bioclimatic conditions during the Pleistocene.

  20. Structure, stability and geochemical role of palladium chloride complexes in hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Bazarkina, Elena F.; Pokrovski, Gleb S.; Hazemann, Jean-Louis

    2014-12-01

    In situ X-ray absorption spectroscopy (XANES and EXAFS) was applied to study palladium speciation in model (Na,Li)Cl-HCl-HNO3-HClO4-H2O solutions and to measure the solubility of PdO(s) and PdS(s) in NaCl-HCl-H2O solutions up to 450 °C and 600 bar. In HNO3 and HClO4 solutions, the square planar Pd(H2O)42+ cation with an average Pd-O distance of 2.00 ± 0.01 Å is the dominant form at 30-100 °C. At T > 100 °C, this cation undergoes hydrolysis resulting in Pd precipitation. In (Na,Li)Cl-HCl solutions Pd forms square planar PdCln(H2O)4-n2-n complexes with Pd-O and Pd-Cl distances of 2.00-2.10 and 2.26-2.31 Å, respectively. At 30-250 °C our data are consistent with a mixture of PdCl(H2O)3+, PdCl2(H2O)20(aq), PdCl3(H2O)-, and PdCl42-, but at T > 250 °C PdCl3(H2O)- and PdCl42- become dominant over a wide range of chloride concentration, from ∼0.03 to at least 9 mol/kg H2O. XANES and EXAFS analyses of these species distribution allowed derivation of the stability constant of the reaction PdCl3- + Cl- = PdCl42- from 300 to 450 °C and 600 bar. These results, coupled with in situ PdO(s) and PdS(s) solubility measurements of this study and a revision of thermodynamic data for these solid phases, allowed generation of a self-consistent thermodynamic data set of the system PdS(s)-PdO(s)-PdCl3--PdCl42-. Our data indicate that Pd can be significantly mobilized as chloride complexes only in sulfide-free oxidizing geological settings (e.g., Chudnoe deposits in Russia, Waterberg deposits in South Africa, Jacutinga-type deposits in Brazil). By contrast, at typical pH (4-8), chlorinity (<10-15 wt% NaCl) and H2S contents (0.001-0.1 wt%) of most hydrothermal fluids, the absolute concentration of Pd-Cl complexes is too low to explain Pd enrichment in volcanogenic massive sulfide, modern seafloor sulfide, and porphyry Cu-Au-Mo deposits. Complexes with S-bearing ligands, very likely other than H2S/HS-, such as S3- and other polysulfide anions, are required to account for Pd

  1. Surface complexation clues to dolomite growth

    SciTech Connect

    Brady, P.V.; Krumhansl, J.L.; Papenguth, H.W.

    1996-02-01

    Calcium and magnesium adsorb in near-stoichiometric proportions to dolomite over wide ranges in [Ca{sup 2+}]/[Mg{sup 2+}], ionic strength, and solution composition pointing to minimal mixing of metal cations between the CaCO{sub 3} and MgCO{sub 3} layer edges exposed at the dolomite surface. Near-neutral pH Mg and Ca adsorb as hydrated ions, or, in sulfate-rich solutions, as metal sulfate complexes. Near-stoichiometric adsorption of Ca and Mg points to dehydration and subsequent carbonation of adsorbed Mg as the likely rate-limiting step for dolomite growth at near-Earth surface conditions. We propose that one path for dolomite growth from low-temperature natural waters is through the initial adsorption of Mg-sulfate complexes onto either (1) growing dolomite crystals or (2) rate-limiting dolomite nucleii. Field relations, as well as homogeneous synthesis at low temperatures (25{degrees}C < T < 100{degrees}C) support this hypothesis and provide a mechanistic explanation for dolomite growth from sulfate-rich natural waters. 36 refs.

  2. Pyrochlores from the Lueshe carbonatite complex (Democratic Republic of Congo): a geochemical record of different alteration stages

    NASA Astrophysics Data System (ADS)

    Nasraoui, M.; Bilal, E.

    2000-04-01

    Magmatic pyrochlores from the Lueshe syenite-carbonatite complex from the northeastern part of Democratic Republic of Congo (ex-Zaı̈re) are characterized by Ta/Nb ratios in an increasing order from pyroxenite, calcite-carbonatite (sövite), silicate xenoliths (nodules) to syenite. Substitutions involving Nb, Ta, Ti and REE have been precisely described. Hydrothermal alteration of Lueshe pyrochlore involves the substitution of Na ++F -=VA+VY and Ca+O=VA+VY (VA=A-site vacancy and VY=Y-site vacancy). In calcite carbonatite, hydrothermal alteration of pyrochlore took place during and after the precipitation of ancylite-(Ce), strontianite, celestite, baryte and fayalite according to a fluid composition of relatively low pH, aNa +, aCa 2+ and aHF, and high aSr 2+ and aLREE 3+. The supergene alteration is characterized by complete leaching of Na, Ca and F and partial incorporation of K, Ba, Sr and Ce resulting in the formation of kali-, bario-, strontio- and ceriopyrochlore respectively. The Na-poor pyrochlore may be an intermediate variety corresponding to an alteration stage between the hydrothermal and weathered pyrochlores. The IR spectroscopic study has indicated that the weathered pyrochlore is a hydrated variety containing two bands of OH vibration modes at 3413 and 1630 cm -1. During hydrothermal and supergene alterations, the cations at B-site remain relatively constant. The variable chemical compositions of the pyrochlores from the Lueshe complex represent geochemical memories of the different alteration conditions including the variation in the oxidation-reduction environment.

  3. The geochemical characteristics of Haiyang A-type granite complex in Shandong, eastern China

    NASA Astrophysics Data System (ADS)

    Li, He; Ling, Ming-xing; Ding, Xing; Zhang, Hong; Li, Cong-ying; Liu, Dun-yi; Sun, Wei-dong

    2014-07-01

    Haiyang granite complex consists of K-feldspar granite and syenite, with a total exposure area of ~ 600 km2. The K-feldspar granite is metaluminous (A/CNK = 0.70 to 0.99) and the syenite is slightly peraluminous (A/CNK = 1.01 to 1.10), both of which have typical characteristics of A-type granite with high total alkali contents and FeOT/(FeOT + MgO) ratios. Zircon U-Pb age are 116.8 ± 1.7 Ma and 115.8 ± 2.2 Ma, for the K-feldspar granite and the syenite, respectively. This is consistent with field observation that the syenite intruded into the K-feldspar granite. Varied zircon O isotope (5.65-7.78‰ for K-feldspar granite and 4.68-7.08‰ for syenite) with peak values that are marginally higher than those of mantle zircon reflects important mantle contributions. These together with large variation of zircon εHf(t) values of K-feldspar granite (- 22.4 to - 15.6) and syenite (- 24.6 to - 13.5), can best be explained by the involvement of at least two components, e.g., enriched lithospheric mantle +/- subducted materials, and upwelling asthenosphere. Apatite has right decline REE pattern. The apatite from K-feldspar granite has higher Cl contents than those of syenite, implying more influence from a subduction released fluid in K-feldspar granite source. This distinction is supported by the systematically higher oxygen fugacity of K-feldspar granite as indicated by zircon Ce4 +/Ce3 + ratios. In the Yb/Ta-Y/Nb, Ce/Nb-Y/Nb diagrams, both K-feldspar granite and syenite plot in A1-type, with K-feldspar granite plotting closer to A2. In the Nb-Y-3Ga and Nb-Y-Ce charts, syenite plots near the boundary between A1 and A2, whereas some K-feldspar granite samples plot in A2 field, indicating a tendency of transition originally from A2 to A1. In general A1 granites form in intraplate settings, whereas A2 granite forms in post-collision. It is likely that mantle components metasomatized by subduction released fluids are easier to be partially melted, forming K-feldspar granite

  4. Petrological and geochemical constraints on granitoid formation: The Waldoboro Pluton Complex, Maine

    SciTech Connect

    Barton, M. . Dept. of Geological Science); Sidle, W.S. )

    1992-01-01

    The Waldoboro Pluton Complex (WPC) comprises seven units ranging from qtz-diorite to aplite. The country rocks are biotite-rich metagraywackes with minor shales mostly belonging to the Proterozoic Z-Ordovician Bucksport Formation. Field evidence strongly suggests that the WPC formed in-situ: contacts with the country rock are cryptic, transitional and concordant; restitic minerals in the granitoids are identical to those in the country rocks; prolific metasedimentary enclaves in the WPC are locally derived. Major and trace element data for country rock and the most voluminous units of the WPC define consistent linear trends suggesting limited melt segregation and retention of a high proportion of restite. Mixing models and partial melting models require 54--76% melting for generation of the gneissic granites and two-mica granites. Garnet-biotite geothermometry and garnet-Al[sub 2]SiO[sub 5]-SiO[sub 2]-plagioclase geobarometry indicate that the WPC formed at T = 740--780 C and P = 0.4--0.7 GPa. Published experimental data show that < 50% melting is likely under these conditions if melting is controlled by dehydration reactions. Bucksport lithologies contain < 20% biotite, suggesting that the maximum amount of melt that could have formed by dehydration melting is < 20%, even if all biotite was consumed during melting. It seems probable that a free fluid phase was required to generate the WPC. Migmatization is apparent in all lithologies (including amphibolites) in the vicinity of the WPC, consistent with fluid-present melting. Fluid may have ingressed along the St. George thrust, but the source of the fluid is unknown.

  5. The Mount Manengouba, a complex volcano of the Cameroon Line: Volcanic history, petrological and geochemical features

    NASA Astrophysics Data System (ADS)

    Pouclet, André; Kagou Dongmo, Armand; Bardintzeff, Jacques-Marie; Wandji, Pierre; Chakam Tagheu, Pulchérie; Nkouathio, David; Bellon, Hervé; Ruffet, Gilles

    2014-09-01

    The volcanic story of Mount Manengouba is related to four chronological stages: (1) forming of the early Manengouba shield volcano between 1.55 and 0.94 Ma, (2) building of the Eboga strato-cone between 0.94 and 0.89 Ma, (3) caldera collapse and silicic extrusions of the Elengoum Complex between 0.89 and 0.70 Ma, and (4) intra-caldera and flank activity between 0.45 and 0.11 Ma. The volume of the volcano is calculated at 320 km3 ± 5%. The volcanic rocks are attributed to two magmatic outputs. The first and main magma generation produced the shield volcano, the strato-cone, and the syn- to post-caldera extrusions, displaying a complete series from basanites to trachytes (magmatic Group 1). The second magma generation is limited to the late and flank activity evolving from basanites to trachy-phonolite (magmatic Group 2). Both magmatic groups belong to the under-saturated alkaline sodic series. Petrological calculations locate the magmatic reservoir between 37 and 39 km in the upper mantle for the Group 1 lavas, and between 42 and 44 km for the Group 2 lavas. Trachytes were generated in a secondary crustal reservoir. Magmatic series evolve with medium to low pressure fractional crystallization of olivine, pyroxene, oxides, feldspar, and apatite. Significant crustal assimilation is evidenced in trachytes. The magma of Group 1 was generated with 3-6% of partial melting of a moderately enriched source containing 3-7% of garnet. Melting took place in the spinel to garnet transition zone located at 70-90 km and around 25 kb. The magma of Group 2 resulted from a slightly higher partial melting from a less garnet-rich source that indicates uprising of the melting column in the upper part of transition zone. Sr, Nd, and Pb isotope data of the Manengouba rocks and neighboring lavas are analyzed and compared with those of the mafic lavas of the CVL. Three source components are distinguished: a depleted component originated from the asthenospheric swell, a radiogenic component

  6. Molecular Basis for Microbial Adhesion to Geochemical Surfaces: Computer Simulation of Pseudomonas aeruginosa Adhesion to Goethite

    PubMed Central

    Shroll, Robert M.; Straatsma, T. P.

    2003-01-01

    The adhesion of Pseudomonas aeruginosa to the goethite mineral is investigated using classical molecular simulation. A fragment model for goethite has been integrated into a fully atomistic membrane model. Properties for the resulting system are evaluated for a 1.5-ns simulation in the isothermal-isobaric ensemble. The response of the membrane to the presence of the mineral is investigated. Radial distribution functions are used to present an average picture of the hydrogen bonding. Orientational vectors, assigned to the saccharide groups, reveal the extent of the mineral's perturbations on the membrane. Significant structural changes were observed for the outermost saccharide groups, several of which rotate to form hydrogen bonds with the mineral surface. The structure of the inner core, and the corresponding integrity of the membrane, is maintained. The mineral surface dehydrates slightly in the presence of the membrane as saccharide hydroxyl groups compete with water molecules for hydrogen-bonding sites on its surface. PMID:12609878

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

    NASA Astrophysics Data System (ADS)

    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

  8. Geochemical Relations between Surface Water and Groundwater In Fractured Rock In Nevada County, CA

    NASA Astrophysics Data System (ADS)

    Soltero, E.

    2013-12-01

    The Sierra Nevada foothills in the South Yuba River basin Nevada County, CA is underlain by plutonic, metabasic rocks of pre-Tertiary age. Fifty-six water samples from five sites were analyzed for spatial and temporal variations using stable isotopes of water and major element chemistry. Hydrogeochemical data from surface water and groundwater indicate site specific, depth related spatial variations. Temporal variations are evident in most surface water data and absent in most groundwater data. Data for 18O and deuterium (D) plot close to the global meteoric water line confirming a meteoric source and minimal subsequent evaporative fractionation or effects of gas-water-rock interactions. An altitude effect presented in surface and groundwater data as a 0.1 per mil decrease in δ 18O and a 0.5- 0.7 per mil decrease in δ D per 30.5 meter (100ft) increase between 305 and 884 meters (1,000 and 2,900 feet) in elevation. Major element chemistry was dominated by sodium, magnesium, and calcium bicarbonate in dilute concentrations. Most groundwater data had higher Ca/Na (1.8:1), Ca/Mg (4:3), and HCO3- /Cl- (3:1) ratios than surface water data from the same site, indicative of local gas-water-rock interactions or mixing of infiltrating water with other groundwater sources. Most deep groundwater data (>91 meters or 300ft) had similar Ca/Na (0.9:1), and higher Ca/Mg (1.6:1) and HCO3- /Cl- (1.6:1) ratios than shallow groundwater data. Most groundwater samples were under saturated or close to saturation with respect to calcite. Aqueous speciation modeling, EQ3NR version 7.2c, adjusted for lab conditions, indicated acceptable charge balance relations. Most water data are consistent with fracture flow in the granitic and metamorphic rocks of the region. Data suggest a precipitation dominated hydrologic regime where local surface waters are related to local groundwaters. Most data indicate that infiltration by way of secondary porosity contributes to groundwater production in

  9. Surface water types in the Western Canadian Arctic: geochemical evolution and aquatic carbon transport

    NASA Astrophysics Data System (ADS)

    Dean, Joshua F.; Billett, Mike F.; Dinsmore, Kerry J.; Lessels, Jason S.; Street, Lorna; Washbourne, Ian; Subke, Jens-Arne; Tetzlaff, Doerthe; Baxter, Robert; Wookey, Philip A.

    2015-04-01

    Arctic surface waters are a substantial conduit for terrestrial C flow as well as a potential source of GHGs to the atmosphere - a significant positive feedback to global climate warming and a key component of the net ecosystem carbon balance in permafrost regions. As temperatures rise in the Arctic, permafrost thaw deepens releasing C from the landscape into the aquatic system making streams and lakes increasingly important conduits and reactors of both allochthonous and autochthonous C. The HYDRA project ('Permafrost catchments in transition: hydrological controls on carbon cycling and greenhouse gas budgets'), aims to quantify the assimilation of C and the controls of C movement between the plant-soil-water-atmosphere continuum. The specific aspect of the project presented here considers the different aquatic pathways in warming Arctic permafrost catchments, and the potential role that they play in GHG emissions and aquatic C cycling. This study presents the surface water geochemistry of Siksik Creek, a small (

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

    NASA Astrophysics Data System (ADS)

    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

  11. Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

    SciTech Connect

    Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.; Zachara, John M.; Zhu, Weihuang

    2013-03-15

    Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on the temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.

  12. Diatom and Geochemical Constraints on Pliocene Sea Surface Conditions on the Wilkes Land Margin, East Antarctica

    NASA Astrophysics Data System (ADS)

    Riesselman, C. R.; Taylor-Silva, B.

    2015-12-01

    The mid-Pliocene is the most recent interval in Earth's history to sustain global temperatures within the range of warming predicted for the 21st century, providing an appealing analog with which to examine the changes we might encounter in the coming century. Diatom-based Southern Ocean sea surface and sea ice reconstructions by the USGS Pliocene Research Interpretations and Synoptic Mapping (PRISM) Group suggest an average +2° summer SST anomaly during the 3.3-3.0 Ma interval relative to modern. Here, we present a reconstruction of Pliocene sea surface conditions from a marine sediment core collected at IODP Site U1361, on the continental rise of the Wilkes Land margin. U1361 biogenic silica concentrations document the alternation of diatom-rich and diatom-poor lithologies; we interpret 8 diatom-rich mudstones within this sequence to record interglacial conditions between 3.8 and 2.8 Ma, across the transition from obliquity control to precession control on East Antarctic ice volumes. This progression also preserves 3 packages of interglacial sediments within the 3.3-3.0 PRISM interval, providing an opportunity for direct comparison to proximal PRISM site Eltanin 50-28. Diatom assemblages in both cores are characterized by Fragilariopsis barronii and Rouxia antarctica, extinct species with an inferred ecological preference for waters south of the polar front. However F. weaveri, an extinct diatom with inferred preference for more northerly waters and moderate abundance in E50-28, has not been identified at U1361. This may indicate that the polar frontal zone migrated across E50-28 (62° 54'S) but remained north of U1361 (64° 25'S) during the mid-Pliocene. This interpretation is bolstered by the low abundance of extant polar front species (e.g., Thalassiosira oliverana, T. lentiginosa) at U1361; these diatoms dominate the E50-28 assemblage. In contrast, the U1361 assemblage includes a number of extant sea ice indicators (F. sublinearis, F. curta, Chaetoceros

  13. Geochemical diversity of shergottite basalts: Mixing and fractionation, and their relation to Mars surface basalts

    NASA Astrophysics Data System (ADS)

    Treiman, Allan H.; Filiberto, Justin

    2015-04-01

    The chemical compositions of shergottite meteorites, basaltic rocks from Mars, provide a broad view of the origins and differentiation of these Martian magmas. The shergottite basalts are subdivided based on their Al contents: high-Al basalts (Al > 5% wt) are distinct from low-Al basalts and olivine-phyric basalts (both with Al < 4.5% wt). Abundance ratios of highly incompatible elements (e.g., Th, La) are comparable in all the shergottites. Abundances of less incompatible elements (e.g., Ti, Lu, Hf) in olivine-phyric and low-Al basalts correlate well with each other, but the element abundance ratios are not constant; this suggests mixing between components, both depleted and enriched. High-Al shergottites deviate from these trends consistent with silicate mineral fractionation. The "depleted" component is similar to the Yamato-980459 magma; approximately, 67% crystal fractionation of this magma would yield a melt with trace element abundances like QUE 94201. The "enriched" component is like the parent magma for NWA 1068; approximately, 30% crystal fractionation from it would yield a melt with trace element abundances like the Los Angeles shergottite. This component mixing is consistent with radiogenic isotope and oxygen fugacity data. These mixing relations are consistent with the compositions of many of the Gusev crater basalts analyzed on Mars by the Spirit rover (although with only a few elements to compare). Other Mars basalts fall off the mixing relations (e.g., Wishstone at Gusev, Gale crater rocks). Their compositions imply that basalt source areas in Mars include significant complexities that are not present in the source areas for the shergottite basalts.

  14. Geochemical Signature of Land-based Activities in Caribbean Coral Surface Samples

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

    Anthropogenic threats to the Mesoamerican Caribbean Reef Ecoregion, resulting from increased sedimentation, agrochemical run-off, coastal development, tourism and overfishing, are of great concern for future coral reef health and sustainability. Abundances of trace metal in corals can be used to monitor and identify the impact of land-based activities on the reef itself. In this study we demonstrate that surface coral samples from four sites in the Mesoamerican Caribbean Reef Ecoregion, Turneffe Atoll, Sapodilla Cayes and Honduras Bay Islands (Utila and Cayos Cochinos), yield statistically different chemical signatures due to their water quality and relative distance from pollution sources. Specifically, samples from the Sapodilla Cayes and the Bay Islands of Honduras yield elevated Ba/Ca and Mn/Ca levels, indicative of greater exposure to sediment-laden runoff form the south. In a similar manner, elevated coral Pb/Ca and Zn/Ca, and Sb/Ca and Cu/Ca values can be linked to mining activities and the use of antifouling paints, respectively. In addition, site heterogeneity was investigated by analyzing replicate cores at a single site from different colonies. We show that regional variability within the Sapodilla Cayes Marine Reserve can be explained by relative location and orientation within the reef and distance from the continental shelf. Our results indicate good reproducibility for the majority of trace metals investigated (not including Sr/Ca or Mg/Ca), suggesting that local environmental changes such as seawater chemistry, and not climate, is the dominant influence on the metal/Ca ratios.

  15. GEOQUÌMICO : an interactive tool for comparing sorption conceptual models (surface complexation modeling verus K[D]).

    SciTech Connect

    Hammond, Glenn E.; Cygan, Randall Timothy

    2007-11-01

    Within reactive geochemical transport, several conceptual models exist for simulating sorption processes in the subsurface. Historically, the K{sub 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{sub 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.

  16. Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

    USGS Publications Warehouse

    Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

    2006-01-01

    Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

  17. Characterization of surface-water quality in the S-Line Canal and potential geochemical reactions from storage of surface water in the Basalt aquifer near Fallon, Nevada

    USGS Publications Warehouse

    Welch, Alan H.; Maurer, Douglas K.; Lico, Michael S.; McCormack, John K.

    2005-01-01

    The Fallon basalt aquifer serves as the sole source of municipal water supply for the Lahontan Valley in west-central Nevada. Principal users include the City of Fallon, Naval Air Station Fallon, and the Fallon Paiute-Shoshone Tribe. Pumpage from the aquifer increased from about 1,700 acre-feet per year in the early 1970's to more than 3,000 acre-feet per year in the late 1990's, and has been accompanied by declines in water levels and changes in water quality. Storage of surface water in the basalt may mitigate the effects of pumpage, but may cause undesirable changes in water chemistry. In May 2001, the U.S. Geological Survey began a study, in cooperation with the Fallon Paiute-Shoshone Tribe, to characterize the surface-water quality of the S-Line Canal, a likely source of water for augmenting recharge. Because arsenic concentrations in ground water of the basalt aquifer exceed drinking water standards, the potential for arsenic release to artificial recharge was explored by using geochemical modeling. Model results suggest that arsenic release may increase concentrations to levels that could limit the use of artificial recharge. Field-based experiments are needed to evaluate the underlying model assumptions.

  18. Utilizing hydrologic, statistical, and geochemical tools to assess uranium mobility in surface and near-surface environments

    NASA Astrophysics Data System (ADS)

    Naftz, D. L.; Walton-Day, K. E.; Fuller, C.; Dam, W. L.; Briggs, M. A.; Snyder, T.

    2015-12-01

    Legacy uranium (U) mining and processing activities have resulted in soil and water contamination on Federal, state, and tribal lands in the western United States. Sites include legacy mill sites associated with U extraction now managed by the Department of Energy and thousands of waste dumps associated with U exploration, mining, and processing. Recently (2012), over 400,000 hectares of federally managed land in northern Arizona was withdrawn from consideration of mining for a 20-year period to protect the Grand Canyon watershed from potentially adverse effects of U mineral exploration and development. Ore from active and recently active U mines in the Colorado Plateau, the Henry Mountains Complex, and the Arizona Strip is transported to the only currently (2015) active conventional mill site in the western United States, located in Utah. Previous and ongoing U.S. Geological Survey assessments to examine U mobility at a variety of legacy and active sites associated with ore exploration, extraction, and processing will be presented as field-scale examples. Topics associated with site investigations will include: (1) offsite migration of radionuclides associated with the operation of the White Mesa U mill; (2) long-term contaminant transport from legacy U waste dumps on Bureau of Land Management regulated land in Utah; (3) application of incremental soil sampling techniques to determine pre- and post-mining radionuclide levels associated with planned and operating U mines in northern Arizona; (4) application of fiber optic digital temperature sensing equipment to identify areas where shallow groundwater containing elevated U levels may be discharging to a river adjacent to a reclaimed mill site in central Wyoming; and (5) field-scale manipulation of groundwater chemistry to limit U migration from a legacy upgrader site in southeastern Utah.

  19. Combined Use of GIS, Hydrostratigraphic, Geochemical, and Multi-Isotope Analysis for Groundwater Preservation and Development in a Complex Karst Setting

    NASA Astrophysics Data System (ADS)

    Murgulet, D.; Cook, M. R.

    2011-12-01

    The complex stratigraphy and geologic structure characteristic to fractured karst aquifers underlying an urban part of the north-central Alabama Valley and Ridge Setting make the development and protection of groundwater sources difficult. In this area, population growth accompanied by increased impervious surfaces, storm water runoff, contaminants, subsidence, and pumping rates have rendered the groundwater resource. The potential for aquifer recharge and flow conditions were evaluated in order to determine the current and future alternative water sources available in this area. Geochemical and multi-isotope techniques were coupled with hydrostratigraphic and geomorphic spatial (GIS) analyses to determine the primary mechanisms controlling recharge and flow and evaluate seasonal impacts on groundwater resources and recharge environments. Groundwater samples, collected in summer and fall (2010) from wells developed in the Bangor Limestone and Tuscumbia Fort Payne aquifers (north-central Alabama), were analyzed for major ions, stable isotopes of oxygen (δ^18O), hydrogen (δD), and carbon (δ^13C), and anthropogenic isotopes such as chlorofluorocarbon (CFCs) and sulphur hexafluoride (SF_6). Stable isotope investigations suggest that recharge occurs under relatively closed conditions, with fast percolation rates in short periods (characteristic to karst aquifers) and low evaporation rates during the colder seasons. The average δ^13C value (-11.4±2% PDB, n=9) lies near the combined average δ^13C values of soil CO_2 and the carbonate. Therefore, groundwater δ^13C signature is mainly controlled by two factors: soil CO_2 and carbonate dissolution. Static water levels decrease over the summer causing drawdowns (2 to 5.2 meters) in all the production wells and a slight shift of the δ^18O and δD values towards a more positive member (summer range--δ^18O: -5.1±0.1 to -5.7±0.1% VSMOW, n=11; δD: -25.0±1 to -30.6±1% VSMOW, n=11 and fall range--δ^18O: -4.8±0.1 to

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

    NASA Astrophysics Data System (ADS)

    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 < 5, where the values predicted by the model were lower than the experimental results. The Cd complexes of X2Cd, SOCd+, R-COOCd+, and R-POCd+ were the predominant species on the composite surface over the pH range of 3 to 8. The distribution ratio of the adsorbed Cd between montmorillonite and bacterial fractions in the composite as predicted by CA-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.

  1. Complex Optical Surfaces Formed by Replica Molding Against Elastomeric Masters

    PubMed

    Xia; Kim; Zhao; Rogers; Prentiss; Whitesides

    1996-07-19

    Complex, optically functional surfaces in organic polymers can be fabricated by replicating relief structures present on the surface of an elastomeric master with an ultraviolet or thermally curable organic polymer, while the master is deformed by compression, bending, or stretching. The versatility of this procedure for fabricating surfaces with complex, micrometer- and submicrometer-scale patterns was demonstrated by the production of (i) diffraction gratings with periods smaller than the original grating; (ii) chirped, blazed diffraction gratings (where the period of a chirped grating changes continuously with position) on planar and curved surfaces; (iii) patterned microfeatures on the surfaces of approximately hemispherical objects (for example, an optical surface similar to a fly's eye); and (iv) arrays of rhombic microlenses. These topologically complex, micropatterned surfaces are difficult to fabricate with other techniques.

  2. Petrogenesis of coeval silica-saturated and silica-undersaturated alkaline rocks: Mineralogical and geochemical evidence from the Saima alkaline complex, NE China

    NASA Astrophysics Data System (ADS)

    Zhu, Yu-Sheng; Yang, Jin-Hui; Sun, Jin-Feng; Zhang, Ji-Heng; Wu, Fu-Yuan

    2016-03-01

    A combined study of zircon U-Pb ages, mineral chemistry, whole-rock elements and Sr-Nd-Hf isotopes was carried out for the Saima alkaline complex in the northeastern China, in order to investigate the source and petrogenesis of coeval silica-saturated and silica-undersaturated alkaline rocks. The Saima alkaline complex consists of nepheline syenites, quartz-bearing syenites and alkaline volcanic rocks (i.e., phonolite and trachyte), with minor mafic dikes and carbonatitic veins. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) and secondary ion mass spectrometry (SIMS) zircon U-Pb dating gives consistent ages of 230-224 Ma for these rocks, suggesting that they are coeval. All alkaline rocks in the Saima complex are enriched in large ion lithophile elements (LILEs) and light rare earth elements (LREEs), and depleted in high field strength elements (HFSEs) with significant negative Nb, Ta and Ti anomalies. Geochemical data and Sr-Nd-Hf isotopic compositions indicate that the various alkaline rocks were all derived from partial melting of an ancient, re-enriched lithospheric mantle in the garnet stability field, but experienced variable siliceous- or carbonate-rich crustal contamination. Based on petrographic evidence, mineral compositions, and whole-rock geochemical data, two distinct magmatic evolutionary trends are proposed to explain the coeval emplacement of the various rock types within the Saima alkaline complex. The silica-undersaturated rocks (nepheline syenites and phonolites) result from alkali feldspar + apatite + titanite crystal fractionation of an alkaline mafic parental melt combined with assimilation of marine carbonate host rocks. In contrast, the generation of silica-saturated rocks (quartz-bearing syenites and trachytes) may be attributed to subsequent and continued clinopyroxene + apatite + biotite crystal fractionation coupled with assimilation of siliceous sediments.

  3. Surface complexation of Pb(II) by hexagonal birnessite nanoparticles

    SciTech Connect

    Kwon, K.; Refson, K.; Sposito, G.

    2010-10-15

    Natural hexagonal birnessite is a poorly-crystalline layer type Mn(IV) oxide precipitated by bacteria and fungi which has a particularly high adsorption affinity for Pb(II). X-ray spectroscopic studies have shown that Pb(II) forms strong inner-sphere surface complexes mainly at two sites on hexagonal birnessite nanoparticles: triple corner-sharing (TCS) complexes on Mn(IV) vacancies in the interlayers and double edge-sharing (DES) complexes on lateral edge surfaces. Although the TCS surface complex has been well characterized by spectroscopy, some important questions remain about the structure and stability of the complexes occurring on the edge surfaces. First-principles simulation techniques such as density functional theory (DFT) offer a useful way to address these questions by providing complementary information that is difficult to obtain by spectroscopy. Following this computational approach, we used spin-polarized DFT to perform total-energy-minimization geometry optimizations of several possible Pb(II) surface complexes on model birnessite nanoparticles similar to those that have been studied experimentally. We first validated our DFT calculations by geometry optimizations of (1) the Pb-Mn oxyhydroxide mineral, quenselite (PbMnO{sub 2}OH), and (2) the TCS surface complex, finding good agreement with experimental structural data while uncovering new information about bonding and stability. Our geometry optimizations of several protonated variants of the DES surface complex led us to conclude that the observed edge-surface species is very likely to be this complex if the singly-coordinated terminal O that binds to Pb(II) is protonated. Our geometry optimizations also revealed that an unhydrated double corner-sharing (DCS) species that has been proposed as an alternative to the DES complex is intrinsically unstable on nanoparticle edge surfaces, but could become stabilized if the local coordination environment is well-hydrated. A significant similarity exists

  4. Surface energy fluxes in complex terrain

    NASA Technical Reports Server (NTRS)

    Reiter, E. R.; Sheaffer, J. D.; Bossert, J. E.

    1986-01-01

    The emphasis of the 1985 NASA project activity was on field measurements of wind data and heat balance data. Initiatives included a 19 station mountaintop monitoring program, testing and refining the surface flux monitoring systems and packing and shipping equipment to the People's Republic of China in preparation for the 1986 Tibet Experiment. Other work included more extensive analyses of the 1984 Gobi Desert and Rocky Mountain observations plus some preliminary analyses of the 1985 mountaintop network data. Details of our field efforts are summarized and results of our data analyses are presented.

  5. Mineralogical and geochemical evidence for hydrothermal activity at the west wall of 12°50′N core complex (Mid-Atlantic ridge): a new ultramafic-hosted seafloor hydrothermal deposit?

    USGS Publications Warehouse

    Dekov, Vesselin; Boycheva, Tanya; Halenius, Ulf; Billstrom, Kjell; Kamenov, George D.; Shanks, Wayne C.; Stummeyer, Jens

    2011-01-01

    Dredging along the west wall of the core complex at 12°50′N Mid-Atlantic Ridge sampled a number of black oxyhydroxide crusts and breccias cemented by black and dark brown oxyhydroxide matrix. Black crusts found on top of basalt clasts (rubble) are mainly composed of Mn-oxides (birnessite, 10-Å manganates) with thin films of nontronite and X-ray amorphous FeOOH on their surfaces. Their chemical composition (low trace- and rare earth-element contents, high Li and Ag concentrations, rare earth element distribution patterns with negative both Ce and Eu anomalies), Sr–Nd–Pb-isotope systematic and O-isotope data suggest low-temperature (~ 20 °C) hydrothermal deposition from a diffuse vent area on the seafloor. Mineralogical, petrographic and geochemical investigations of the breccias showed the rock clasts were hydrothermally altered fragments of MORBs. Despite the substantial mineralogical changes caused by the alteration the Sr–Nd–Pb-isotope ratios have not been significantly affected by this process. The basalt clasts are cemented by dark brown and black matrix. Dark brown cement exhibits geochemical features (very low trace- and rare earth- element contents, high U concentration, rare earth element distribution pattern with high positive Eu anomaly) and Nd–Pb-isotope systematics (similar to that of MORB) suggesting that the precursor was a primary, high-temperature Fe-sulfide, which was eventually altered to goethite at ambient seawater conditions. The data presented in this work points towards the possible existence of high- and low-temperature hydrothermal activity at the west wall of the core complex at 12°50′N Mid-Atlantic Ridge. Tectonic setting at the site implies that the proposed hydrothermal field is possibly ultramafic-hosted.

  6. Molecularly imprinted Ru complex catalysts integrated on oxide surfaces.

    PubMed

    Muratsugu, Satoshi; Tada, Mizuki

    2013-02-19

    Selective catalysis is critical for the development of green chemical processes, and natural enzymes that possess specialized three-dimensional reaction pockets with catalytically active sites represent the most sophisticated systems for selective catalysis. A reaction space in an enzyme consists of an active metal center, functional groups for molecular recognition (such as amino acids), and a surrounding protein matrix to prepare the reaction pocket. The artificial design of such an integrated catalytic unit in a non-enzymatic system remains challenging. Molecular imprinting of a supported metal complex provides a promising approach for shape-selective catalysis. In this process, an imprinted cavity with a shape matched to a template molecule is created in a polymer matrix with a catalytically active metal site. In this Account, we review our studies on molecularly imprinted metal complex catalysts, focusing on Ru complexes, on oxide surfaces for shape-selective catalysis. Oxide surface-attached transition metal complex catalysts not only improve thermal stability and catalyst dispersion but also provide unique catalytic performance not observed in homogeneous precursors. We designed molecularly imprinted Ru complexes by using surface-attached Ru complexes with template ligands and inorganic/organic surface matrix overlayers to control the chemical environment around the active metal complex catalysts on oxide surfaces. We prepared the designed, molecularly imprinted Ru complexes on SiO(2) surfaces in a step-by-step manner and characterized them with solid-state (SS) NMR, diffuse-reflectance (DR) UV-vis, X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller isotherm (BET), X-ray fluorescence (XRF), and Ru K-edge extended X-ray absorption fine structure (EXAFS). The catalytic performances of these Ru complexes suggest that this process of molecular imprinting facilitates the artificial integration of catalytic functions at surfaces. Further advances such

  7. Geochemical characterization of surface water and spring water in SE Kashmir Valley, western Himalaya: Implications to water-rock interaction

    NASA Astrophysics Data System (ADS)

    Jeelani, Gh; Bhat, Nadeem A.; Shivanna, K.; Bhat, M. Y.

    2011-10-01

    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 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 decrease in altitude. However, high TDS of some streams at higher altitudes and low TDS of some springs at lower altitudes indicated contribution of high TDS waters from glacial lakes and low TDS waters from streams, respectively. The results show that some karst springs are recharged by surface water; Achabalnag by the Bringi stream and Andernag and Martandnag by the Liddar stream. Calcite dissolution, dedolomitization and silicate weathering were found to be the main processes controlling the chemistry of the spring waters and calcite dissolution as the dominant process in controlling the chemistry of the surface waters. The spring waters were undersaturated with respect to calcite and dolomite in most of the seasons except in November, which is attributed to the replenishment of the CO2 by recharging waters during most of the seasons.

  8. Time-series Measurements of Geochemical Tracers and Electrical Resistivity to Evaluate Groundwater-Surface Water Interactions on Anvers Island, Antarctica

    NASA Astrophysics Data System (ADS)

    Corbett, D. R.; Peterson, L.; Crenshaw, J.; Hawkins, D.; Null, K.; Peterson, R. N.; Viso, R. F.

    2013-12-01

    Submarine groundwater discharge (SGD) has been measured along coasts throughout most of the globe. SGD has been defined as the total discharge into a water body across the sediment water interface, including subsurface freshwater and recirculated seawater regardless of the driving force. Recent studies have demonstrated that the transport of groundwater to the coast is a significant contributor to the nutrient, carbon, and geochemical budgets of many marine nearshore waters. Until recently, SGD had not been considered as an important physical process delivering water or associated dissolved constituents to coastal waters near the Antarctic continent. As part of a new NSF-funded project, our group is quantifying the rate of SGD, the flux of nutrients and iron to the coastal waters near Anvers Island, and the mixing of these constituents across the continental shelf of the Western Antarctic Peninsula. As part of this project, we conducted a time-series experiment on Point 8, Anvers Island near Palmer Station during the 2012-2013 austral summer. The rapidly retreating glacier recently exposed this area of Anvers Island and offered us an opportunity to directly measure groundwater/surface water interactions through measurements of electrical resistivity and geochemical tracers. Time-series resistivity profiles using a 56 electrode (110-m long) marine cable produced detailed profiles of the fresh water/salt water interface over the course of two tidal cycles. Geochemical tracers (Ra-223, 224, 226, Rn-222) measured in groundwater and nearshore surface waters during the same time series complement the geophysical measurements and indicate tidally dependent discharge. Our results suggest that the underlying hydrogeologic framework along Anvers Island is favorable for substantial SGD and could serve as an important, yet unquantified, source of iron and other biogeochemically important nutrients to nearshore waters and potentially the Southern Ocean.

  9. Conformal Nanopatterning of Extracellular Matrix Proteins onto Topographically Complex Surfaces

    PubMed Central

    Sun, Yan; Jallerat, Quentin; Szymanski, John M.

    2015-01-01

    We report a method for conformal nanopatterning of extracellular matrix proteins onto engineered surfaces independent of underlying microtopography. This enables fibronectin, laminin, and other proteins to be applied to biomaterial surfaces in complex geometries inaccessible using traditional soft lithography techniques. Engineering combinatorial surfaces that integrate topographical and biochemical micropatterns enhances control of the biotic-abiotic interface, used here to understand cardiomyocyte response to competing physical and chemical cues in the microenvironment. PMID:25506720

  10. Effect on Groundwater Quality from Proximal Surface Water Bodies and Effect on Arsenic Distribution in Bangladesh: Geochemical Controls

    NASA Astrophysics Data System (ADS)

    Barua, S.; Kulkarni, H.; Mladenov, N.; Khan, M. A.; Mahfuz, M.; Ahmed, K. M.; Datta, S.

    2014-12-01

    Matlab is one of the areas in SE Bangladesh highly affected with elevated concentrations of dissolved As in drinking waters. Matlab is stratigraphically composed of thick floodplain deposits of Holocene age overlying Plio-Pleistocene grey fine to coarse sands with considerable clay (Dupi Tila). The dissolved As concentrations in the studied area ranged from <1 to 3644 μg/l and more than 70% of functioning tubewells exceeded the WHO guideline of 10 μg/l. To test the hypothesis that young labile organic carbon (LOC) accelerates As release in reducing aquifer systems as long as As-bearing iron oxides/hydroxides are available, we collected 19 groundwater (depths from 14 to 240 m) and 9 surface water (8 pond and 1 canal in proximity to the piezeometer nests) samples from 4 nests in north and south Matlab, respectively, during monsoon months (Jun-Jul, 2014). Dissolved organic carbon (DOC), fluorescent properties of dissolved organic matter (DOM) and fecal indicator bacteria (FIB) (e.g., E. coli) counts using field ColilertTM test kits were undertaken to understand the chemical character and potential sources of dissolved organic matter (DOM) in groundwater and surface waters. DOC concentrations were high (1.5-12.2 mg/l) in shallow aquifers (14-33 m) where dissolved As ranged from 100-500 µg/l. DOC concentrations were lower (0.7-4.2 mg/l) in intermediate to deeper depths (52-240 m) with lower As concentrations of 0-50 µg/l. In surface water bodies, the range of DOC was 2.9-8.1 mg/l. MPN based analyses for both ground and surface waters indicate the frequency of E. coli detection in shallow well waters (MPN= 3.6-74.1) was high as well as in ponds and canals (MPN= 8.5-433.4). Microbial activity in groundwater was lower than in unprotected surface waters. Freshness index (β:α), humification index (HIX), fluorescence source index (FI) values showed that DOM in shallow and surface water bodies was distinct from deep groundwater. Concurrent with the lower DOC in deeper

  11. Surface enhanced raman spectroscopy of pyridine on Ag electrodes. Surface complex formation

    NASA Astrophysics Data System (ADS)

    Pettinger, B.; Wtzel, H.

    1981-03-01

    Experimental evidence is given for surface complexes consisting of metal-adatom, pyridine and halide ions with which the surface enhanced Raman process can occur. A large part of the enhanced continuum turns out to result from a super-position of numerous extremely weak SER lines attributed to these complexes.

  12. Floodplain complexity and surface metrics: influences of scale and geomorphology

    USGS Publications Warehouse

    Scown, Murray W.; Thoms, Martin C.; DeJager, Nathan R.

    2015-01-01

    Many studies of fluvial geomorphology and landscape ecology examine a single river or landscape, thus lack generality, making it difficult to develop a general understanding of the linkages between landscape patterns and larger-scale driving variables. We examined the spatial complexity of eight floodplain surfaces in widely different geographic settings and determined how patterns measured at different scales relate to different environmental drivers. Floodplain surface complexity is defined as having highly variable surface conditions that are also highly organised in space. These two components of floodplain surface complexity were measured across multiple sampling scales from LiDAR-derived DEMs. The surface character and variability of each floodplain were measured using four surface metrics; namely, standard deviation, skewness, coefficient of variation, and standard deviation of curvature from a series of moving window analyses ranging from 50 to 1000 m in radius. The spatial organisation of each floodplain surface was measured using spatial correlograms of the four surface metrics. Surface character, variability, and spatial organisation differed among the eight floodplains; and random, fragmented, highly patchy, and simple gradient spatial patterns were exhibited, depending upon the metric and window size. Differences in surface character and variability among the floodplains became statistically stronger with increasing sampling scale (window size), as did their associations with environmental variables. Sediment yield was consistently associated with differences in surface character and variability, as were flow discharge and variability at smaller sampling scales. Floodplain width was associated with differences in the spatial organization of surface conditions at smaller sampling scales, while valley slope was weakly associated with differences in spatial organisation at larger scales. A comparison of floodplain landscape patterns measured at different

  13. Geochronological and geochemical constraints on the Lüliang Group in the Lüliang Complex: Implications for the tectonic evolution of the Trans-North China Orogen

    NASA Astrophysics Data System (ADS)

    Liu, Chaohui; Zhao, Guochun; Liu, Fulai; Shi, Jianrong

    2014-06-01

    The Lüliang Complex is located at the western margin of the middle segment of the Trans-North China Orogen, along which the Western and Eastern Blocks amalgamated to form the basement of the North China Craton. The complex consists of the late Neoarchean to Paleoproterozoic granitic plutons and meta-supracrustal rocks, of which the latter are subdivided into the Jiehekou, Lüliang, Yejishan, and Heichashan/Lanhe Groups. The Lüliang Group is composed mainly of siliciclastic rocks in the lower part and volcanic rocks in the upper part, all of which have been metamorphosed from greenschist- to amphibolite-facies. U-Pb ages of detrital zircons from meta-sedimentary rocks in the Lüliang Group yield four populations of 3061-2920 Ma, 2790-2600 Ma, 2599-2280 Ma and 2211-2202 Ma, suggesting that their provenances were derived mainly from the Lüliang and Taihua Complexes in the Trans-North China Orogen. The meta-volcanic rocks give igneous zircon U-Pb ages of 2209-2178 Ma and εHf(t) values of - 0.8 to + 3.6. Geochemically, they are subalkaline basalts and andesites that can be classified into two groups, of which one group has flat LREEs, weak enrichment in LREEs relative to HREEs and flat HREEs and displays E-MORB-like spider diagrams with the exception of insignificantly negative Nb-Ta, Zr-Hf and Ti anomalies. In contrast, the other group displays stronger LREE fractionation, stronger enrichment in LREEs relative to HREEs and mildly fractionated HREEs and is characterized by “spiky” spider diagrams similar to arc volcanic rocks. The first group is interpreted to have originated from a Neoarchean E-MORB source, whereas the second group shows inputs of newly subduction-derived fluids in the mantle source. These geochronological and geochemical signatures indicate the existence of an 2.2-2.1 Ga continental back-arc system in the Lüliang Complex of the Trans-North China Orogen, which is consistent with the model that the collision between the Eastern and Western

  14. Complexity and diffusion of magnetic flux surfaces in anisotropic turbulence

    SciTech Connect

    Servidio, S.; Matthaeus, W. H.; Wan, M.; Rappazzo, A. F.; Ruffolo, D.; Oughton, S.

    2014-04-10

    The complexity of magnetic flux surfaces is investigated analytically and numerically in static homogeneous magnetic turbulence. Magnetic surfaces are computed to large distances in magnetic fields derived from a reduced magnetohydrodynamic model. The question addressed is whether one can define magnetic surfaces over large distances when turbulence is present. Using a flux surface spectral analysis, we show that magnetic surfaces become complex at small scales, experiencing an exponential thinning that is quantified here. The computation of a flux surface is of either exponential or nondeterministic polynomial complexity, which has the conceptual implication that global identification of magnetic flux surfaces and flux exchange, e.g., in magnetic reconnection, can be intractable in three dimensions. The coarse-grained large-scale magnetic flux experiences diffusive behavior. The link between the diffusion of the coarse-grained flux and field-line random walk is established explicitly through multiple scale analysis. The Kubo number controls both large and small scale limits. These results have consequences for interpreting processes such as magnetic reconnection and field-line diffusion in astrophysical plasmas.

  15. Local cortical surface complexity maps from spherical harmonic reconstructions.

    PubMed

    Yotter, Rachel A; Nenadic, Igor; Ziegler, Gabriel; Thompson, Paul M; Gaser, Christian

    2011-06-01

    Altered cortical surface complexity and gyrification differences may be a potentially sensitive marker for several neurodevelopmental disorders. We propose to use spherical harmonic (SPH) constructions to measure cortical surface folding complexity. First, we demonstrate that the complexity measure is accurate, by applying our SPH approach and the more traditional box-counting method to von Koch fractal surfaces with known fractal dimension (FD) values. The SPH approach is then applied to study complexity differences between 87 patients with DSM-IV schizophrenia (with stable psychopathology and treated with antipsychotic medication; 48 male/39 female; mean age=35.5 years, SD=11.0) and 108 matched healthy controls (68 male/40 female; mean age=32.1 years, SD=10.0). The global FD for the right hemisphere in the schizophrenia group was significantly reduced. Regionally, reduced complexity was also found in temporal, frontal, and cingulate regions in the right hemisphere, and temporal and prefrontal regions in the left hemisphere. These results are discussed in terms of previously published findings. Finally, the anatomical implications of a reduced FD are highlighted through comparison of two subjects with vastly different complexity maps.

  16. Conformal nanopatterning of extracellular matrix proteins onto topographically complex surfaces.

    PubMed

    Sun, Yan; Jallerat, Quentin; Szymanski, John M; Feinberg, Adam W

    2015-02-01

    Our Patterning on Topography (PoT) printing technique enables fibronectin, laminin and other proteins to be applied to biomaterial surfaces in complex geometries that are inaccessible using traditional soft lithography techniques. Engineering combinatorial surfaces that integrate topographical and biochemical micropatterns enhances control of the biotic-abiotic interface. Here, we used this method to understand cardiomyocyte response to competing physical and chemical cues in the microenvironment.

  17. Surface grid generation for complex three-dimensional geometries

    NASA Technical Reports Server (NTRS)

    Luh, Raymond Ching-Chung

    1988-01-01

    An outline is presented for the creation of surface grids from primitive geometry data such as obtained from CAD/CAM systems. The general procedure is applicable to any geometry including full aircraft with wing, nacelle, and empennage. When developed in an interactive graphics environment, a code base on this procedure is expected to substantially improve the turn around time for generating surface grids on complex geometries. Results are shown for a general hypersonic airplane geometry.

  18. Surface grid generation for complex three-dimensional geometries

    NASA Technical Reports Server (NTRS)

    Luh, Raymond Ching-Chung

    1988-01-01

    An outline is presented for the creation of surface grids from primitive geometry data such as obtained from CAD/CAM systems. The general procedure is applicable to any geometry including full aircraft with wing, nacelle, and empennage. When developed in an interactive graphics environment, a code based on this procedure is expected to substantially improve the turn around time for generating surface grids on complex geometries. Results are shown for a general hypersonic airplane geometry.

  19. Surfaces of complex intermetallic compounds: insights from density functional calculations.

    PubMed

    Hafner, Jürgen; Krajčí, Marian

    2014-11-18

    CONSPECTUS: Complex intermetallic compounds are a class of ordered alloys consisting of quasicrystals and other ordered compounds with large unit cells; many of them are approximant phases to quasicrystals. Quasicrystals are the limiting case where the unit cell becomes infinitely large; approximants are series of periodic structures converging to the quasicrystal. While the unique properties of quasicrystals have inspired many investigations of their surfaces, relatively little attention has been devoted to the surface properties of the approximants. In general, complex intermetallic compounds display rather irregular, often strongly corrugated surfaces, making the determination of their atomic structure a very complex and challenging task. During recent years, scanning tunneling microscopy (STM) has been used to study the surfaces of several complex intermetallic compounds. If atomic resolution can be achieved, STM permits visualization of the local atomistic surface structure. However, the interpretation of the STM images is often ambiguous and sometimes even impossible without a realistic model of the structure of the surface and the distribution of the electronic density above the surface. Here we demonstrate that ab initio density functional theory (DFT) can be used to determine the energetics and the geometric and electronic structures of the stable surfaces of complex intermetallic compounds. Calculations for surfaces with different chemical compositions can be performed in the grand canonical ensemble. Simulated cleavage experiments permit us to determine the formation of the cleavage planes requiring the lowest energy. The investigation of the adsorption of molecular species permits a comparison with temperature-programmed thermal desorption experiments. Calculated surface electronic densities of state can be compared with the results of photoelectron spectroscopy. Simulations of detailed STM images can be directly confronted with the experimental results

  20. The mafic-ultramafic complex of Aniyapuram, Cauvery Suture Zone, southern India: Petrological and geochemical constraints for Neoarchean suprasubduction zone tectonics

    NASA Astrophysics Data System (ADS)

    Yellappa, T.; Venkatasivappa, V.; Koizumi, T.; Chetty, T. R. K.; Santosh, M.; Tsunogae, T.

    2014-12-01

    Several Precambrian mafic-ultramafic complexes occur along the Cauvery Suture Zone (CSZ) in Southern Granulite Terrain, India. Their origin, magmatic evolution and relationship with the associated high-grade rocks have not been resolved. The Aniyapuram Mafic-Ultramafic Complex (AMUC), the focus of the present study in southern part of the CSZ, is dominantly composed of peridotites, pyroxenites, gabbros, metagabbros/mafic granulites, hornblendites, amphibolites, plagiogranites, felsic granulites and ferruginous cherts. The rock types in the AMUC are structurally emplaced within hornblende gneiss (TTG) basement rocks and are highly deformed. The geochemical signature of the amphibolites indicates tholeiitic affinity for the protolith with magma generation in island arc-setting. N-MORB normalized pattern of the amphibolites show depletion in HFS-elements (P, Zr, Sm, Ti, and Y) and enrichment of LIL-elements (Rb, Ba, Th, Sr) with negative Nb anomalies suggesting involvement of subduction component in the depleted mantle source and formation in a supra-subduction zone tectonic setting. Our new results when correlated with the available age data suggest that the lithological association of AMUC represent the remnants of the Neoarchean oceanic lithosphere.

  1. Surface-Guided Formation of an Organocobalt Complex.

    PubMed

    Weber, Peter B; Hellwig, Raphael; Paintner, Tobias; Lattelais, Marie; Paszkiewicz, Mateusz; Casado Aguilar, Pablo; Deimel, Peter S; Guo, Yuanyuan; Zhang, Yi-Qi; Allegretti, Francesco; Papageorgiou, Anthoula C; Reichert, Joachim; Klyatskaya, Svetlana; Ruben, Mario; Barth, Johannes V; Bocquet, Marie-Laure; Klappenberger, Florian

    2016-05-01

    Organocobalt complexes represent a versatile tool in organic synthesis as they are important intermediates in Pauson-Khand, Friedel-Crafts, and Nicholas reactions. Herein, a single-molecule-level investigation addressing the formation of an organocobalt complex at a solid-vacuum interface is reported. Deposition of 4,4'-(ethyne-1,2-diyl)dibenzonitrile and Co atoms on the Ag(111) surface followed by annealing resulted in genuine complexes in which single Co atoms laterally coordinated to two carbonitrile groups undergo organometallic bonding with the internal alkyne moiety of adjacent molecules. Alternative complexation scenarios involving fragmentation of the precursor were ruled out by complementary X-ray photoelectron spectroscopy. According to density functional theory analysis, the complexation with the alkyne moiety follows the Dewar-Chatt-Duncanson model for a two-electron-donor ligand where an alkyne-to-Co donation occurs together with a strong metal-to-alkyne back-donation. PMID:27059261

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Stable isotopic and geochemical variability within shallow groundwater beneath a hardwood hammock and surface water in an adjoining slough (Everglades National Park, Florida, USA).

    PubMed

    Florea, Lee J; McGee, Dorien K

    2010-06-01

    Data from a 10-month monitoring study during 2007 in the Everglades ecosystem provide insight into the variation of delta(18)O, deltaD, and ion chemistry in surface water and shallow groundwater. Surface waters are sensitive to dilution from rainfall and input from external sources. Shallow groundwater, on the other hand, remains geochemically stable during the year. Surface water input from canals derived from draining agricultural areas to the north and east of the Everglades is evident in the ion data. delta(18)O and deltaD values in shallow groundwater remain near the mean of-2.4 and-12 per thousand, respectively. (18)O and D values are enriched in surface water compared with shallow groundwater and fluctuate in sync with those measured in rainfall. The local meteoric water line (LMWL) for precipitation is in close agreement with the global meteoric water line; however, the local evaporation line (LEL) for surface water and shallow groundwater is delta D=5.6 delta(18)O+1.5, a sign that these waters have experienced evaporation. The intercept of the LMWL and LEL indicates that the primary recharge to the Everglades is tropical cyclones or fronts. delta deuterium to delta(18)O excess (D(ex) values) generally reveal two moisture sources for precipitation, a maritime source during the fall and winter (D (ex)>10 per thousand) and a continental-influenced source (D (ex)<10 per thousand) in the spring and summer.

  4. CMM probe compensation methods for measuring complex screw surface

    NASA Astrophysics Data System (ADS)

    Zhao, Qiancheng; Yang, Tianlong; Yin, Xiyun

    2013-01-01

    At present, probe compensation is the key problem in measuring geometric parameters of complex screw surface with CMM due to its complicated 3D shape, aiming at this problem, some new measurement methods are proposed based on geometric feature models, expressing the screw surface and its offset surface separately. Supposing the parameter lead of a screw surface is known, it's realized by scanning one single profile to complete probe compensation and calculate out all parameters, and the probe compensation is done by two improved methods, named as modified cross product and offset surface virtual measurement respectively, the theory and detailed process of which are discussed in this paper. After performing systematic experiments of profile scan, probe compensation and error evaluation, results show that the new measurement methods provide higher precision, stability and realizability.

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

    NASA Technical Reports Server (NTRS)

    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).

  6. Geochronological and geochemical constraints on the origin of clastic meta-sedimentary rocks associated with the Yuanjiacun BIF from the Lüliang Complex, North China

    NASA Astrophysics Data System (ADS)

    Wang, Changle; Zhang, Lianchang; Dai, Yanpei; Lan, Caiyun

    2015-01-01

    The Lüliang Complex is situated in the central part of the western margin of the Trans-North China Orogen (TNCO) in the North China Craton (NCC), and consists of metamorphic volcanic and sedimentary rocks and granitoid intrusions. The Yuanjiacun Formation metasediments occupy roughly the lowest part of the Lüliang Group and are mainly represented by well-bedded meta-pelites (chlorite schists and sericite-chlorite phyllites), banded iron formations (BIFs) and meta-arenites (sericite schists), which have undergone greenschist-facies metamorphism. The youngest group of detrital zircons from the meta-arenite samples constrains their maximum depositional age at ~ 2350 Ma. In combination with previous geochronological studies on meta-volcanic rocks in the overlying Jinzhouyu Formation, the depositional age of the Yuanjiacun Formation can be constrained between 2350 and 2215 Ma. The metasediments have suffered varying degrees of source weathering, measured using widely employed weathering indices (e.g., CIA, CIW, PIA and Th/U ratios). Source rocks of the low-Al meta-pelites have undergone severe chemical weathering, whereas those of the meta-arenites and high-Al meta-pelites have suffered relatively moderate chemical weathering. Significant secondary K addition is recognized in the A-CN-K diagram for most of the studied samples. Diagnostic geochemical features like the Al2O3/TiO2 values, trace element ratios (e.g., Th/Sc) and REE patterns, suggest that the meta-arenites and high-Al meta-pelites are predominantly derived from felsic igneous sources, whereas the low-Al meta-pelites are sourced mainly from mafic rocks. Coupled with Nd isotopic data, it is proposed that the meta-arenites and high-Al meta-pelites were sedimentary erosion products of the less differential felsic terrain (likely the old upper continental crust). The low-Al meta-pelites, however, have geochemical affinities with both pelite- and BIF-like components, suggesting that they were mixtures of these

  7. Adsorption of L-aspartate to rutile (α-TiO 2): Experimental and theoretical surface complexation studies

    NASA Astrophysics Data System (ADS)

    Jonsson, Caroline M.; Jonsson, Christopher L.; Estrada, Charlene; Sverjensky, Dimitri A.; Cleaves, H. James, II; Hazen, Robert M.

    2010-04-01

    Interactions between aqueous amino acids and mineral surfaces influence many geochemical processes from biomineralization to the origin of life. However, the specific reactions involved and the attachment mechanisms are mostly unknown. We have studied the adsorption of L-aspartate on the surface of rutile (α-TiO 2, pH PPZC = 5.4) in NaCl(aq) over a wide range of pH, ligand-to-solid ratio and ionic strength, using potentiometric titrations and batch adsorption experiments. The adsorption is favored below pH 6 with a maximum of 1.2 μmol of adsorbed aspartate per m 2 of rutile at pH 4 in our experiments. The adsorption decreases at higher pH because the negatively charged aspartate molecule is repelled by the negatively charged rutile surface above pH PPZC. At pH values of 3-5, aspartate adsorption increases with decreasing ionic strength. The adsorption of aspartate on rutile is very similar to that previously published for glutamate ( Jonsson et al., 2009). An extended triple-layer model was used to provide a quantitative thermodynamic characterization of the aspartate adsorption data. Two reaction stoichiometries identical in reaction stoichiometry to those for glutamate were needed. At low surface coverages, aspartate, like glutamate, may form a bridging-bidentate surface species binding through both carboxyl groups, i.e. "lying down" on the rutile surface. At high surface coverages, the reaction stoichiometry for aspartate was interpreted differently compared to glutamate: it likely involves an outer-sphere or hydrogen bonded aspartate surface species, as opposed to a partly inner-sphere complex for glutamate. Both the proposed aspartate species are qualitatively consistent with previously published ATR-FTIR spectroscopic results for aspartate on amorphous titanium dioxide. The surface complexation model for aspartate was tested against experimental data for the potentiometric titration of aspartate in the presence of rutile. In addition, the model correctly

  8. Unusual evolution of silica-under- and -oversaturated alkaline rocks in the Cenozoic Ambohimirahavavy Complex (Madagascar): Mineralogical and geochemical evidence

    NASA Astrophysics Data System (ADS)

    Estrade, Guillaume; Béziat, Didier; Salvi, Stefano; Tiepolo, Massimo; Paquette, Jean-Louis; Rakotovao, Soatsitohaina

    2014-10-01

    The almost unknown Ambohimirahavavy ring complex in the Cenozoic alkaline province of northwestern Madagascar has recently attracted considerable interest because of the discovery of important rare-metal mineralization. The complex consists of arc-shaped bodies made up of silica-under- and -oversaturated syenites and extremely evolved peralkaline granitic dykes, as well as several mafic to felsic volcanic units, including basalt, phonolite and trachyte, all of which have an alkaline affinity. Uranium-lead zircon ages of 24.2 ± 0.6 Ma and 23.5 ± 6.8 Ma have been obtained for nepheline syenites and peralkaline granitic dykes, respectively, which, together with field data and ages of neighboring complexes, support emplacement controlled by regional lithospheric structures, rather than an evolving hot spot. Whole-rock major and trace-element and Sr-Nd isotopic data for the mafic suite suggest that the parental melt of this complex was generated by low degrees of melting of a metasomatized mantle source with residual amphibole. Fractional crystallization of this alkali basaltic melt likely produced the silica-undersaturated suite. We propose that the silica-oversaturated suite evolved from the undersaturated melt after contamination of the latter by crustal material. Further evolution to peralkaline compositions in both suites is attributed mainly to plagioclase and alkali feldspar segregation. Nepheline and feldspar compositions, as well as considerations of mineral equilibria among mafic silicates and Fe-Ti oxide minerals indicate crystallization temperatures of 1000 to 700 °C and an oxygen fugacity of 0.4 to 0.8 log units below the fayalite-magnetite-quartz (FMQ) buffer at 1 kbar for the silica-undersaturated melt, and temperatures of 860 to 570 °C and an oxygen fugacity of 1.5 to 3.8 log units below FMQ for the oversaturated syenitic melt. The undersaturated melt evolved towards a more peralkaline composition. Crystallization of arfvedsonite plus aegirine

  9. Efficient stochastic simulations of complex reaction networks on surfaces.

    PubMed

    Barzel, Baruch; Biham, Ofer

    2007-10-14

    Surfaces serve as highly efficient catalysts for a vast variety of chemical reactions. Typically, such surface reactions involve billions of molecules which diffuse and react over macroscopic areas. Therefore, stochastic fluctuations are negligible and the reaction rates can be evaluated using rate equations, which are based on the mean-field approximation. However, in case that the surface is partitioned into a large number of disconnected microscopic domains, the number of reactants in each domain becomes small and it strongly fluctuates. This is, in fact, the situation in the interstellar medium, where some crucial reactions take place on the surfaces of microscopic dust grains. In this case rate equations fail and the simulation of surface reactions requires stochastic methods such as the master equation. However, in the case of complex reaction networks, the master equation becomes infeasible because the number of equations proliferates exponentially. To solve this problem, we introduce a stochastic method based on moment equations. In this method the number of equations is dramatically reduced to just one equation for each reactive species and one equation for each reaction. Moreover, the equations can be easily constructed using a diagrammatic approach. We demonstrate the method for a set of astrophysically relevant networks of increasing complexity. It is expected to be applicable in many other contexts in which problems that exhibit analogous structure appear, such as surface catalysis in nanoscale systems, aerosol chemistry in stratospheric clouds, and genetic networks in cells.

  10. The Development and Study of Surface Bound Ruthenium Organometallic Complexes

    NASA Astrophysics Data System (ADS)

    Abbott, Geoffrey Reuben

    The focus of this project has been on the use of mono-diimine ruthenium organometallic complexes, of the general structure [H(Ru)(CO)(L)2(L') 2][PF6] (L=PPh3, DPPENE and L'=Bpy, DcBpy, MBpyC, Phen, AminoPhen) bound to surfaces as luminescent probes. Both biological and inorganic/organic hybrid surfaces have been studied. The complexes were characterized both bound and unbound using standard analytical techniques such as NMR, IR and X-ray crystallography, as well as through several photophysical methods as well. Initially the study focused on how the photophyscial properties of the complexes were affected by incorporation into biological membranes. It was found that by conjugating the probes to a more rigid cholesterol moiety that luminescence was conserved, compared to conjugation with a far more flexible lipid moiety, where luminescence was either lost or reduced. Both the cholesterol and lipid conjugates were able to insert into a lipid membrane, and in the more rigid environment some of the lipid conjugates regained some of their luminescence, but often blue shifted and reduced, depending on the conjugation site. Silica Polyamine Composites (SPCs) were a hybrid material developed in the Rosenberg Lab as useful metal separation materials, that could be easily modified, and had several benefits over current commercially available polymers, or inorganic materials. These SPCs also provided an opportunity for the development of a heterogeneous platform for luminescent complexes as either catalysts or sensors. Upon binding of the luminescent Ru complexes to the surface no loss, or major change in luminescence was seen, however, when bound to the rigid surface a significant increase in excited state lifetime was measured. It is likely that through binding and interacting with the surface that the complexes lost non-radiative decay pathways, resulting in the increase in lifetime, however, these interactions do not seem to affect the energy level of the MLCT band in a

  11. Sensitivity of geological, geochemical and hydrologic parameters in complex reactive transport systems for in-situ uranium bioremediation

    NASA Astrophysics Data System (ADS)

    Yang, G.; Maher, K.; Caers, J.

    2015-12-01

    Groundwater contamination associated with remediated uranium mill tailings is a challenging environmental problem, particularly within the Colorado River Basin. To examine the effectiveness of in-situ bioremediation of U(VI), acetate injection has been proposed and tested at the Rifle pilot site. There have been several geologic modeling and simulated contaminant transport investigations, to evaluate the potential outcomes of the process and identify crucial factors for successful uranium reduction. Ultimately, findings from these studies would contribute to accurate predictions of the efficacy of uranium reduction. However, all these previous studies have considered limited model complexities, either because of the concern that data is too sparse to resolve such complex systems or because some parameters are assumed to be less important. Such simplified initial modeling, however, limits the predictive power of the model. Moreover, previous studies have not yet focused on spatial heterogeneity of various modeling components and its impact on the spatial distribution of the immobilized uranium (U(IV)). In this study, we study the impact of uncertainty on 21 parameters on model responses by means of recently developed distance-based global sensitivity analysis (DGSA), to study the main effects and interactions of parameters of various types. The 21 parameters include, for example, spatial variability of initial uranium concentration, mean hydraulic conductivity, and variogram structures of hydraulic conductivity. DGSA allows for studying multi-variate model responses based on spatial and non-spatial model parameters. When calculating the distances between model responses, in addition to the overall uranium reduction efficacy, we also considered the spatial profiles of the immobilized uranium concentration as target response. Results show that the mean hydraulic conductivity and the mineral reaction rate are the two most sensitive parameters with regard to the overall

  12. Mars - A planet with a complex surface evolution

    NASA Technical Reports Server (NTRS)

    Arvidson, R. E.; Coradini, M.

    1975-01-01

    The surface of Mars has evolved to its present form through a complex sequence of tectonism and associated volcanism, impact processes, water erosion, mass movements, and wind action. The diversity of geological processes active in past Martian history far exceeded most predictions. By the same token, predictions of processes modifying the satellites of the outer planets may fall far short of the true range of phenomena. A summary of present though with regard to Martian surface evolution is presented to serve as a case in point of the value of imagery and topography data in making interpretations of geological histories.

  13. Speciation of aqueous mononuclear Al(III)-hydroxo and other Al(III) complexes at concentrations of geochemical relevance by aluminum-27 nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Faust, Bruce C.; Labiosa, William B.; Dai, K'o. H.; MacFall, Janet S.; Browne, Bryant A.; Ribeiro, Anthony A.; Richter, Daniel D.

    1995-07-01

    Aluminum-27 (27Al) nuclear magnetic resonance (NMR) spectroscopy was used to characterize Al(III)-hydroxo complexes, in aqueous solutions with total Al(III) concentrations of 1.0-10 μM, using a custom-built NMR probe, coil, and sample bottle with low background aluminum impurities. Published 27Al NMR spectroscopy studies have traditionally used total Al(III) concentrations that are generally outside the range of geochemical interest (total [ Al(III) l ≥ 1000 μM). In this study, lower Al(III) concentrations (≤ 10 μM) were used to more closely approximate natural conditions, while allowing the measurement of mononuclear Al(III) species by 27Al NMR spectroscopy. The sensitivity of the 27Al NMR spectroscopy system, as measured by the signal-to-noise ratio (S/N), is S/N= 5 for 1.0 μM Al(III) at pH 2.00 and S/N= 3 for 10 μM Al(III) at pH 5.20. This level of sensitivity is within the range of geochemically relevant Al(III) concentrations found in slightly acidic natural waters. Quantitative models are developed which link observations of NMR chemical shifts and linewidth ratios to the calculated equilibrium speciation of mononuclear Al(III) for 10 μM Al(III) solutions at pH values 2.00 to 5.20 (prepared by titrating acidic AI(III) solutions with pyridine). Linear-regression best fits of the models to the NMR data are used to determine the intrinsic chemical shifts and linewidths of individual mononuclear Al(III) species. The intrinsic chemical shift of each Al(III) species "i", δi (ppm), is (1) δAl3+ ≡ 0 for Al3+ (defined by convention), (2) δAl(OH)2+ = 3.5 (SE= 1.3, N = 10) for Al(OH)2+, (3) δAl(OH)2+ ≅ 3.7 (SE= 1.4, N = 10) for Al(OH)2+ , and (4) δAl(OH)4- = 79.9 (SE= 0.03, N = 4) for Al(OH)4-; where positive chemical shifts are "downfield," SE = standard error, and N =number of samples. A convention is delineated in which the linewidth of the Al(III) species/peak of interest is normalized with respect to that of a reference species (Al3+) under the

  14. Metamorphic and geochemical signatures within calc-silicate gneisses of the Sawtooth Metamorphic Complex, ID: Implications for western North America crustal evolution

    NASA Astrophysics Data System (ADS)

    Fukai, I.; Dutrow, B. L.; Henry, D.; Mueller, P. A.; Foster, D. A.

    2012-12-01

    High resolution sampling and petrologic/geochemical analyses of calc-silicate metamorphic rocks from the Sawtooth Metamorphic Complex (SMC), ID, constrain the evolution of a key area in North America. The SMC lies within the proposed Paleoproterozoic Selway basement terrane on the southwestern margin of Laurentia. Multi-equilibria thermobarometry calculations on SMC aluminous gneisses yield lower-granulite facies peak metamorphic conditions of 765-795 °C and 7 kbar, suggesting the SMC represents a segment of lower-middle crust. Twenty-five calc-silicate samples were collected 1 km east of the aluminous gneisses along a 132 m transect across the regional N-S strike of the SMC. Samples have a mineral assemblage of clinopyroxene + quartz + tremolite + plagioclase + titanite + apatite ± K-feldspar ± clinozoisite ± biotite ± epidote ± graphite ± calcite, and display a range in whole-rock compositions (wt.%) of SiO2 (53.9-80.9), Al2O3 (3.4-12.4), FeO (1.0-5.9), CaO (5.2-21.5), MgO (3.3-9.5), and K2O (0.04-3.8). Samples exhibit decreasing modal amounts of qz, pl, kf, and bt from west to east, along with an increase in cpx, ttn, czo, ep, gr and cal. Major element geochemical trends are consistent with the observed mineralogical variations, revealing higher weight percentages of SiO2 (62-81) and K2O (0.8-3.8) in western samples, and higher TiO2, Al2O3, FeO, MgO CaO, and LOI in the easternmost samples. Eastern samples have lower compositions of Rb and Ba, and higher Sr and Cr relative to western samples that correspond respectively to decreased modal amounts of fsp and bt, and an increase in cal and cpx. Trace elements Ni, Sc, V, Y, Nb, Ce, Nd, Cu, Pb, Th, and La do not show systematic variations. SMC calc-silicates have an average Th/Sc ratio of 0.89, consistent with Post-Archean values (>0.7), and display high concentrations of Zr relative to Th, and Sc, more characteristic of an evolved, recycled, continental sediment source. Application of the hornblende

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

    USGS Publications Warehouse

    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.

  16. Element distribution over the surface of fish scales and its connection to the geochemical environment of habitats: a potential biogeochemical tag.

    PubMed

    Wang, TsingHai; Lai, Yan-Chen; Chiang, Chia-Che; Cheng, Yu-Rong; Hsieh, Yi-Kong; Wang, Chu-Fang

    2016-03-01

    The elemental content of fish scales is known to be a reliable biogeochemical tag for tracing the origin of fishes. In this study, this correlation is further confirmed to exist on the surface of fish scales using a novel environmental analytical method, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), which bypasses several complicated sample preparation procedures such as acid digestion and pre-concentration. The results suggest that the elemental ratios of Sr/Ca, Ba/Ca, and Mn/Ca on the surface of fish scales are strongly correlated with the geochemical environment of their original habitat. This correlation is further demonstrated to be sensitive to variation of water in the habitat due to the adsorbed inorganic ions. In this sense, the limitation of fish scales as a biogeochemical tag is the sensitivity of LA-ICP-MS toward the studied elements. Graphical abstract Illustration of the connection between element distribution pattern over the surface of fish scales and biogeochemical environment of its habitat.

  17. A Comparative Analysis of the Influence of Surface Mining on Hydrological and Geochemical Response of Selected Headwater Streams in the Elk Valley, British Columbia, Canada.

    NASA Astrophysics Data System (ADS)

    Carey, S. K.; Shatilla, N. J.; Szmudrowska, B.; Rastelli, J.; Wellen, C.

    2014-12-01

    Surface mining is a common method of accessing coal. Blasting of overburden rock allows access to mineable ore. In high-elevation environments, the removed overburden rock is deposited in adjacent valleys as waste rock spoils. As part of a multi-year R&D program examining the influence of surface mining on watershed hydrological and water quality responses in the Elk Valley, British Columbia, this study reports on how surface mining affects streamflow hydrological and geochemical response at four reference and four mine-influenced catchments. The hydrology of this environment is dominated by snowmelt and steep topographic gradients. Flows were attenuated in mine-influenced catchments, with spring freshet delayed and more muted responses to precipitation events observed. Dissolved ions were an order of magnitude greater in mine-influenced streams, with more dilution-based responses to flows compared with chemostatic behavior observed in reference streams. Stable isotope signatures in stream water suggested that in both mine-influenced and reference watersheds, stream water was derived from well mixed groundwater as annual variability of stream isotope signatures was dampened compared with precipitation signatures. However, deflection of stream isotopes in response to precipitation were more apparent in reference watersheds. As a group, mine influenced catchments had a heavier isotope signature than reference watersheds, suggesting an enhanced influence of rainfall on recharge. Transit time distributions indicate existing waste rock spoils increase the average time water takes to move through the catchment.

  18. Geochemical distribution and removal of As, Fe, Mn and Al in a surface water system affected by acid mine drainage at a coalfield in Southwestern China

    NASA Astrophysics Data System (ADS)

    Wu, Pan; Tang, Changyuan; Liu, Congqiang; Zhu, Lijun; Pei, Tingquan; Feng, Lijuan

    2009-06-01

    The chemical characteristics, formation and natural attenuation of pollutants in the coal acid mine drainage (AMD) at Xingren coalfield, Southwest China, are discussed in this paper based on the results of a geochemical investigation as well as geological and hydrogeological background information. The chemical composition of the AMD is controlled by the dissolution of sulfide minerals in the coal seam, the initial composition of the groundwater and the water-rock interaction. The AMD is characterized by high sulfate concentrations, high levels of dissolved metals (Fe, Al, Mn, etc.) and low pH values. Ca2+ and SO4 2- are the dominant cation and anion in the AMD, respectively, while Ca2+ and HCO3 - are present at significant levels in background water and surface water after the drainage leaves the mine site. The pH and alkalinity increase asymptotically with the distance along the flow path, while concentrations of sulfate, ferrous iron, aluminum and manganese are typically controlled by the deposition of secondary minerals. Low concentrations of As and other pollutants in the surface waters of the Xingren coalfield could be due to relatively low quantities being released from coal seams, to adsorption and coprecipitation on secondary minerals in stream sediments, and to dilution by unpolluted surface recharge. Although As is not the most serious water quality problem in the Xingren region at present, it is still a potential environmental problem.

  19. Geochemical evidence for multiple magma injections in the formation of the Spruce Road Cu-Ni deposit, Duluth Complex, Minnesota

    SciTech Connect

    Lee, I.; Ripley, E.M. . Dept. of Geological Sciences)

    1993-03-01

    The Spruce Road Cu-Ni deposit is located in the northeast portion of the Duluth Complex, and consists of disseminated sulfide mineralization within gabbroic to troctolitic rock types. Mineralization occurs along basal contacts with footwall rocks of the Giants Range Massif, and is in general similar to that found in other basal zone deposits located to the southwest. Sulfide mineral assemblages are composed principally of chalcopyrite, pyrrhotite, cubanite, and pentlandite. Several distinct zones are recognized in drill core 34870-A (740 m in length) based on mineral modes and textures, plus major and trace element variations. Unit 6 exhibits well-defined trends related to in situ fractional crystallization. Sulfide is thought to have accumulated at the base of this pulse due to gravitational segregation of an immiscible sulfide liquid. Unit 5 represents emplacement of a more evolved, but sulfide-free magmatic pulse. Unit 4 is composed of two well-differentiated pulses, whereas Unit 3 appears to have fractionated very little, but may have been saturated in sulfide at the time of emplacement. Unit 1 is a more evolved and sulfide-rich pulse (or series of pulses) that may have mixed with more primitive magma of Unit 2. Sulfur in Units 1, 3, and 6 is characterized by [delta][sup 34]S values of 4.1 to 10.2 per mil CDT, and is thought to have been derived from crustal sources. The sequence in the Spruce Road area represents periodic emplacement of magmas that had undergone various degrees of fractionation and crustal contamination in sub-volcanic staging chambers.

  20. Atmospheric and Science Complexity Effects on Surface Bidirectional Reflectance

    NASA Technical Reports Server (NTRS)

    Diner, D. J. (Principal Investigator); Martonchik, J. V.; Sythe, W. D.; Hessom, C.

    1985-01-01

    Among the tools used in passive remote sensing of Earth resources in the visible and near-infrared spectral regions are measurements of spectral signature and bidirectional reflectance functions (BDRFs). Determination of surface properties using these observables is complicated by a number of factors, including: (1) mixing of surface components, such as soil and vegetation, (2) multiple reflections of radiation due to complex geometry, such as in crop canopies, and (3) atmospheric effects. In order to bridge the diversity in these different approaches, there is a need for a fundamental physical understanding of the influence of the various effects and a quantiative measure of their relative importance. In particular, we consider scene complexity effects using the example of reflection by vegetative surfaces. The interaction of sunlight with a crop canopy and interpretation of the spectral and angular dependence of the emergent radiation is basically a multidimensional radiative transfer problem. The complex canopy geometry, underlying soil cover, and presence of diffuse as well as collimated illumination will modify the reflectance characteristics of the canopy relative to those of the individual elements.

  1. Synthesizing Earth's geochemical data for hydrogeochemical analysis

    NASA Astrophysics Data System (ADS)

    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

  2. Petrological and Geochemical Characteristics of the Charnockitic and Associated A-Type Granitoid Rocks from the Basement Complex of Bangladesh

    NASA Astrophysics Data System (ADS)

    Hossain, M. S.; Ameen, S. M. M.; Bari, Z.; Zaman, M. N.

    2015-12-01

    We present the first discovery of charnockite and A-type Granitoid rocks from the basement rocks in Bangladesh. These lie within the Dinajpur block, located between the Indian Craton to the southwest and the Shillong Massif to the east. There are no surface outcrops and the rocks were intersected by drill holes. They consist of a suite of monzogranite and granitic rocks. The core samples encountered between the depths of 2897 ft to 3510 ft of drillhole GDH-31, Dariapur, Gaibandha district. They consist of a suite of charnockite, monzogranite and granitic rocks. Megascopic study of structure and fabric of rocks suggest that the basement rocks are largely felsic massive igneous with a minor gneiss. The microscopic study reveals that the monzogranite and granite contain plagioclase feldspar, quartz and K-feldspar as predominant mineral constituents and zircon, garnet, rutile, apatite, and opaque minerals as common accessories. In most of the felsic rocks, antiperthite, perthite, myrmekite, graphic, granophyric and micrographic intergrowth textures are seen. The basement rocks in Gaibandha therefore, are considered to have formed as a part of a granitoid, that belongs to a pluton overall displays metaluminous to peraluminous, high K calc-alkaline, ferroan, A2 subtype for the rocks of A-type suite. The rocks are enriched in large Ion Lithophile elements, such as Ba, Sr and moderate to low averaging Ni, Cr, Co, V contents as well as the Zr, Y, Ce, Ga/Al, SiO2, Na2O+K2O and REE content is relatively high. Primitive Mantle-normalized incompatible trace element patterns are also broadly similar for all the rocks with moderate negative Th, Nb and Ti anomalies. The major and trace elements illustrate a post/late-collisional tectonic setting for the granitoid samples. In the first stage, partial melting in a collisional setting with mantle wedge influence and by assimilation of country rocks, the calc-alkaline felsic rocks were formed. Crustal thickening and delamination

  3. Assessment of geochemical mobility of metals in surface sediments of the Santa Rosalia mining region, Western Gulf of California.

    PubMed

    Shumilin, Evgueni; Gordeev, Vyacheslav; Figueroa, Griselda Rodríguez; Demina, Liudmila; Choumiline, Konstantin

    2011-01-01

    To asses the geomobility of cadmium, copper, iron, manganese, nickel, lead, and zinc in marine sediments near the Santa Rosalía copper smelter, which is located on the eastern coast of the Baja California Peninsula, sequential leaching was applied to sediment samples containing different levels of Cu: (1) uncontaminated or slightly contaminated (<55 mg kg⁻¹ Cu); (2) moderately contaminated (55-500 mg kg⁻¹ Cu); and (3) heavily contaminated (>500 mg kg⁻¹ Cu). Concentrations of Cd, Cu, Fe, Mn, Ni, Pb, and Zn in four fractions of the leachate (mobile fraction F1, relatively mobile fraction F2, associated with organic matter/sulphides fraction F3, and residual fraction F4) were measured by atomic absorption spectrophotometry (AAS). The sediments with Cu concentration <500 mg kg⁻¹ displayed prevalence of mobile acid-leachable fraction F1 and reducible fraction F2 for Cd, Cu, Mn, and Pb, whereas the relative contribution of fraction F3 was relatively low for all of the examined metals. Residual fraction F4 was highest (>65%) for Fe and Ni because both metals are associated with the crystalline matrix of natural sediments. The sediments heavily contaminated with Cu (>500 mg kg⁻¹) had dramatically increased percentages of Cu, Mn, Pb, and Zn, ranging on average from 63 to 81%, in the residual fraction. In the case of Cu, for example, the relative abundances of this element in the different fractions of such sediments followed this sequence: residual fraction F4 (76 ± 5%) >absorbed form and carbonates fraction F1 (15 ± 5%) >Fe and Mn oxyhydroxides fraction F2 (5 ± 2%) >fraction associated with organic matter and sulphides F3 (4.5 ± 3.9%). Copper, Pb, and Zn contents in each geochemical fraction of all samples were compared with sediment-quality guideline values ("effects range low" [ERL] and "effects range medium" [ERM]) to assess their possible negative effects on biota. Copper contents in mobile fractions F1 and F2, which were moderately contaminated

  4. Assessment of geochemical mobility of metals in surface sediments of the Santa Rosalia mining region, Western Gulf of California.

    PubMed

    Shumilin, Evgueni; Gordeev, Vyacheslav; Figueroa, Griselda Rodríguez; Demina, Liudmila; Choumiline, Konstantin

    2011-01-01

    To asses the geomobility of cadmium, copper, iron, manganese, nickel, lead, and zinc in marine sediments near the Santa Rosalía copper smelter, which is located on the eastern coast of the Baja California Peninsula, sequential leaching was applied to sediment samples containing different levels of Cu: (1) uncontaminated or slightly contaminated (<55 mg kg⁻¹ Cu); (2) moderately contaminated (55-500 mg kg⁻¹ Cu); and (3) heavily contaminated (>500 mg kg⁻¹ Cu). Concentrations of Cd, Cu, Fe, Mn, Ni, Pb, and Zn in four fractions of the leachate (mobile fraction F1, relatively mobile fraction F2, associated with organic matter/sulphides fraction F3, and residual fraction F4) were measured by atomic absorption spectrophotometry (AAS). The sediments with Cu concentration <500 mg kg⁻¹ displayed prevalence of mobile acid-leachable fraction F1 and reducible fraction F2 for Cd, Cu, Mn, and Pb, whereas the relative contribution of fraction F3 was relatively low for all of the examined metals. Residual fraction F4 was highest (>65%) for Fe and Ni because both metals are associated with the crystalline matrix of natural sediments. The sediments heavily contaminated with Cu (>500 mg kg⁻¹) had dramatically increased percentages of Cu, Mn, Pb, and Zn, ranging on average from 63 to 81%, in the residual fraction. In the case of Cu, for example, the relative abundances of this element in the different fractions of such sediments followed this sequence: residual fraction F4 (76 ± 5%) >absorbed form and carbonates fraction F1 (15 ± 5%) >Fe and Mn oxyhydroxides fraction F2 (5 ± 2%) >fraction associated with organic matter and sulphides F3 (4.5 ± 3.9%). Copper, Pb, and Zn contents in each geochemical fraction of all samples were compared with sediment-quality guideline values ("effects range low" [ERL] and "effects range medium" [ERM]) to assess their possible negative effects on biota. Copper contents in mobile fractions F1 and F2, which were moderately contaminated

  5. Four year geochemical analysis of surface waters surrounding Horseshoe Lake and McLeod Lake at Mammoth Lakes, CA

    NASA Astrophysics Data System (ADS)

    Luu, N. C.; Ellis, A. S.

    2013-12-01

    four year span will provide further insight into the primary mechanisms present that govern the geochemical signatures of the streams and lakes of interest.

  6. Renewable Interfaces: Surface Topography Actuation for Complex Biological Adhesion Control

    NASA Astrophysics Data System (ADS)

    Pocivavsek, Luka; Ye, Sangho; Cao, Kathleen; Lee, Ka Yee C.; Velankar, Sachin; Wagner, William

    2015-03-01

    Controlling adhesion at biological interfaces is a complex problem with great biomedical importance. We use dynamic wrinkling, generated with PDMS/UVO chemistry under different macroscopic strains (ɛij ~ 0 . 3), to create a mechanical interfacial term that frustrates particle adhesion. This device actuates surface topography between flat (zero surface confinement χij) and wrinkled surfaces (χij ~(A / λ) 2 , where A and λ are wrinkle amplitude and wavelength, respectively), with a maximum rate of 0.6 Hz. Un-actuated PDMS placed in contact with whole sheep blood shows near total surface coverage with adhered platelets over 90 min. Actuation showed a nearly 100-fold decrease in platelet adhesion. Interestingly, topographic actuation is four times as effective compared to flat surface actuation in controlling platelet adhesion. Our model explores the competition between surface tension terms (Uγ = γɛij) and interfacial elastic terms (Uχ =Eij (t .ɛij2 +t3 . (χij /λ2)) generated because of actuation and wrinkling, where Eij is platelet modulus and t is characteristic platelet length scale. The condition for de-adhesion is Uχ >Uγ .

  7. Exploring complex networks via topological embedding on surfaces.

    PubMed

    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.

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

    PubMed

    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.

  9. Geochemical background and ecological risk of heavy metals in surface sediments from the west Zhoushan Fishing Ground of East China Sea.

    PubMed

    Xu, Gang; Liu, Jian; Pei, Shaofeng; Hu, Gang; Kong, Xianghuai

    2015-12-01

    Surface sediment grain size as well as the spatial distribution, pollution status, and source identification of heavy metals in the west Zhoushan Fishing Ground (ZFG) of the East China Sea were analyzed to study the geochemical background concentrations of heavy metals and to assess their potential ecological risk. Our results show that surface sediments in the eastern part of study area were mainly composed of sand-sized components. Spatial distributions of heavy metals were mainly controlled by grain size and terrigenous materials, and their concentrations in the coarsest grain sediments formed primarily during the Holocene transgressive period could represent the element background values of our study area. Contamination factor suggests that there was no pollution of Pb, Zn, and Cr generally in our study area and slight pollution of Cu, Cd, and As (especially Cu) at some stations. In addition, ecological harm coefficient indicates that the ecological risk of each heavy metal, except for Cd, at two stations was low as well. These results are consistent with the pollution load index and ecological risk index, which suggest both the overall level of pollution and the overall ecological risk of six studied metals in sediment were relatively low in our study area. Enrichment factor indicates that the heavy metals came mostly from the natural source. Summarily, the quality level of sediment in our study area was relatively good, and heavy metals in sediments could not exert threat to aquatic lives in the ZFG until now.

  10. Complex Behavior of Caffeine Crystallites on Muscovite Mica Surfaces

    PubMed Central

    2015-01-01

    Defined fabrication of organic thin films is highly desired in technological, as well as pharmaceutical, applications since morphology and crystal structure are directly linked to physical, electrical, and optical properties. Within this work, the directed growth of caffeine deposited by hot wall epitaxy (HWE) on muscovite mica is studied. Optical and atomic force microscopy measurements reveal the presence of caffeine needles exhibiting a preferable alignment in the azimuthal directions with respect to the orientation of the defined mica surface. Specular X-ray diffraction and X-ray diffraction pole figure measurements give evidence that the β-polymorphic form of caffeine forms on the mica surface. All results consent that caffeine molecules have an edge-on conformation i.e. minimizing their interaction area with the surface. Furthermore, the azimuthal alignment of the long caffeine needle axis takes place along the [11̅0], [100], and [110] real space directions of mica; needles are observed every 60° azimuthally. While mica has a complex surface structure with mirror planes and lowered oxygen rows, the slightly disturbed 3-fold symmetry dictates the crystal alignment. This is different to previous findings for solution cast caffeine growth on mica. For HWE the needles align solely along the mica main directions whereby solution cast needles show an additional needle splitting due to a different alignment of caffeine with respect to the surface. PMID:26366127

  11. Surface complexation of aluminum on isolated fish gill cells

    SciTech Connect

    Wilkinson, K.J. Campbell, G.C.; Bertsch, P.M.; Jagoe, C.H.

    1993-06-01

    Cells from the gills of largemouth bass (Micropterus salmoides) were isolated and exposed to dilute solutions of Al, Al in the presence of fluoride, or Al plus dissolved organic matter (DOM) to determine the cells` metal binding potential in an acidic medium. Microelectrophoresis was employed to monitor the extent of aluminum sorption to cells in the presence of added ligand. In the absence of Al, the gill cells exhibit an appreciable negative charge; Al binding to the cell surface increases the electric potential at the shear plane and leads to a reduction in the cell`s (negative) electrophoretic mobility. In the presence of both Al and F, aluminum complexation at the gill surface is only marginally reduced; the formation of a mixed ligand complex, [F-Al-L-cell], is proposed to account for the observed results. The presence of such ternary complexes was subsequently verified by {sup 19}F nuclear magnetic resonance spectroscopy and by potentiometry. Addition of DOM increased the negative electrophoretic mobility of the isolated gill cells both in the presence and absence of aluminum (7.4 {mu}M). 45 refs., 7 figs., 1 tab.

  12. Neptunium (V) Adsorption to a Halophilic Bacterium Under High Ionic Strength Conditions: A Surface Complexation Modeling Approach

    SciTech Connect

    Ams, David A

    2012-06-11

    Rationale for experimental design: Np(V) -- important as analog for Pu(V) and for HLW scenarios; High ionic strength -- relevant to salt-based repositories such as the WIPP; Halophilic microorganisms -- representative of high ionic strength environments. For the first time showed: Significant adsorbant to halophilic microorganisms over entire pH range under high ionic strength conditions; Strong influence of ionic strength with increasing adsorption with increasing ionic strength (in contrast to trends of previous low ionic strength studies); Effect of aqueous Np(V) and bacterial surface site speciation on adsorption; and Developed thermodynamic models that can be incorporated into geochemical speciation models to aid in the prediction of the fate and transport of Np(V) in more complex systems.

  13. Complex inductance, excess noise, and surface magnetism in dc SQUIDs.

    PubMed

    Sendelbach, S; Hover, D; Mück, M; McDermott, R

    2009-09-11

    We have characterized the complex inductance of dc SQUIDs cooled to millikelvin temperatures. The SQUID inductance displays a rich, history-dependent structure as a function of temperature, with fluctuations of order 1 fH. At a fixed temperature, the SQUID inductance fluctuates with a 1/f power spectrum; the inductance noise is highly correlated with the conventional 1/f flux noise. The data are interpreted in terms of the reconfiguration of clusters of surface spins, with correlated fluctuations of effective magnetic moments and relaxation times.

  14. SEDIMENT GEOCHEMICAL MODEL

    EPA Science Inventory

    Until recently, sediment geochemical models (diagenetic models) have been only able to explain sedimentary flux and concentration profiles for a few simplified geochemical cycles (e.g., nitrogen, carbon and sulfur). However with advances in numerical methods, increased accuracy ...

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

    SciTech Connect

    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.

  16. Global geochemical problems

    NASA Technical Reports Server (NTRS)

    Harriss, R. C.

    1980-01-01

    Application of remote sensing techniques to the solution of geochemical problems is considered with emphasis on the 'carbon-cycle'. The problem of carbon dioxide sinks and the areal extent of coral reefs are treated. In order to assess the problems cited it is suggested that remote sensing techniques be utilized to: (1)monitor globally the carbonate and bicarbonate concentrations in surface waters of the world ocean; (2)monitor the freshwater and oceanic biomass and associated dissolved organic carbon; (3) inventory the coral reef areas and types and the associated oceanographic climatic conditions; and (4)measure the heavy metal fluxes from forested and vegetated areas, from volcanos, from different types of crustal rocks, from soils, and from sea surfaces.

  17. Molecular assembly and organic film growth on complex intermetallic surfaces

    NASA Astrophysics Data System (ADS)

    Al-Mahboob, Abdullah; Sharma, Hem Raj; Sadowski, Jerzy T.; Ledieu, Julian; Fournée, Vincent; McGrath, Ronan

    We extensively studied the role of molecular symmetry and symmetry/structures of wide ranges of substrate-surfaces from non-periodic to periodic to quasi-crystalline in nucleation, growth and phase transition in films made of organic molecular materials. Recently, most interest in quasicrystals is due to the generalization of aperiodic ordering to several classes of systems. Compared to periodic materials, these provide a closer approximation to an isotropic first Brillouin zone, which is of great importance to the design of new functional materials. Here, we present results obtained from our ongoing study of interface mediated molecular assembly extended on complex intermetallic surfaces with specific examples of C60 and Zn-phthalocyanine on quasicrystalline and approximant surfaces. We employed in-situ real-time low-energy electron microscopy (LEEM) for investigation of the processes in assembly and film growth and post-growth STM study and DFT calculations to understand structural details and growth mechanism. Research were carried out in part at the Center for Functional Nanomaterials, Brookhaven National Lab, USA; partly at Institut Jean Lamour, Université de Lorraine, France; and partly at the Surface Science Research Centre, University of Liverpool, UK.

  18. Solvation of complex surfaces via molecular density functional theory.

    PubMed

    Levesque, Maximilien; Marry, Virginie; Rotenberg, Benjamin; Jeanmairet, Guillaume; Vuilleumier, Rodolphe; Borgis, Daniel

    2012-12-14

    We show that classical molecular density functional theory, here in the homogeneous reference fluid approximation in which the functional is inferred from the properties of the bulk solvent, is a powerful new tool to study, at a fully molecular level, the solvation of complex surfaces and interfaces by polar solvents. This implicit solvent method allows for the determination of structural, orientational, and energetic solvation properties that are on a par with all-atom molecular simulations performed for the same system, while reducing the computer time by two orders of magnitude. This is illustrated by the study of an atomistically-resolved clay surface composed of over a thousand atoms wetted by a molecular dipolar solvent. The high numerical efficiency of the method is exploited to carry a systematic analysis of the electrostatic and non-electrostatic components of the surface-solvent interaction within the popular Clay Force Field (CLAYFF). Solvent energetics and structure are found to depend weakly upon the atomic charges distribution of the clay surface, even for a rather polar solvent. We conclude on the consequences of such findings for force-field development.

  19. Geochemical processes controlling mobilization of arsenic and trace elements in shallow aquifers and surface waters in the Antequera and Poopó mining regions, Bolivian Altiplano

    NASA Astrophysics Data System (ADS)

    Ramos Ramos, Oswaldo Eduardo; Rötting, Tobias S.; French, Megan; Sracek, Ondra; Bundschuh, Jochen; Quintanilla, Jorge; Bhattacharya, Prosun

    2014-10-01

    A geochemical approach was applied to understand the factors controlling the mobilization of As and trace elements (TEs) in mining areas of the Poopó and Antequera River sub-basins on the Bolivian Altiplano. A total of 52 samples (surface, groundwater and geothermal water) were collected during the rainy season (2009). Arsenic, Cd and Mn concentrations exceed World Health Organization (WHO) drinking water guidelines and Bolivian regulations for drinking water in 28 groundwater samples, but Cu, Ni, Pb and Zn do not. Arsenic, Cd, Mn, Pb and Zn concentrations exceed World Health Organization guidelines for drinking water and Bolivian regulations Class A standard for discharge to water bodies in 20 surface water samples, whereas levels of Cu do not, and Ni and Fe rarely exceed regulation and guideline values. Factor analysis was applied to 18 hydrochemical parameters of 52 samples. Five factors for groundwater (plagioclase weathering, dissolution of gypsum and halite, TEs mobilization at acidic pH, sulfide oxidation, and release of As) account for 86.5% of the total variance for Antequera and 83.9% for Poopó sub-basins. Four factors for surface water data (weathering and mobilization of TEs influenced by pH, dissolution of evaporate salts, neutralization of acid mine drainage, and As release due to dissolution of Mn and Fe oxides) account for 91% of the total variance in Antequera and 96% in Poopó sub-basins. The As and TEs mobilized in these regions could affect the local water sources, which is a prevalent concern with respect to water resource management in this semi-arid Altiplano region. Presence of both natural and anthropogenic sources of contamination requires careful monitoring of water quality.

  20. Surface Complexation of Actinides with Iron Oxides: Implications for Radionuclide Transport in Near-Surface Aquifers

    NASA Astrophysics Data System (ADS)

    Jerden, J. L.; Kropf, A. J.; Tsai, Y.

    2005-12-01

    The surface complexation of actinides with iron oxides plays a key role in actinide transport and retardation in geosphere-biosphere systems. The development of accurate actinide transport models therefore requires a mechanistic understanding of surface complexation reactions (i.e. knowledge of chemical speciation at mineral/fluid interfaces). Iron oxides are particularly important actinide sorbents due to their pH dependent surface charges, relatively high surface areas and ubiquity in oxic and suboxic near-surface systems. In this paper we present results from field and laboratory investigations that elucidate the mechanisms involved in binding uranium and neptunium to iron oxide mineral substrates in near neutral groundwaters. The field study involved sampling and characterizing uranium-bearing groundwaters and solids from a saprolite aquifer overlying an unmined uranium deposit in the Virginia Piedmont. The groundwaters were analyzed by inductively coupled mass spectrometry and ion chromatography and the aquifer solids were analyzed by electron microprobe. The laboratory study involved a series of batch sorption tests in which U(VI) and Np(V) were reacted with goethite, hematite and magnetite in simulated groundwaters. The pH, ionic strength, aging time, and sorbent/sorbate ratios were varied in these experiments. The oxidation state and coordination environment of neptunium in solutions and sorbents from the batch tests were characterized by X-ray absorption spectroscopy (XAS) at the Advanced Photon Source, Argonne National Laboratory. Results from this work indicate that, in oxidizing near-surface aquifers, the dissolved concentration of uranium may be limited to less than 30 parts per billion due to uptake by iron oxide mineral coatings and the precipitation of sparingly soluble U(VI) phosphate minerals. Results from the batch adsorption tests showed that, in near neutral groundwaters, a significant fraction of the uranium and neptunium adsorbed as strongly

  1. SURFACE COMPLEXATION OF ACTINIDES WITH IRON OXIDES: IMPLICATIONS FOR RADIONUCLIDE TRANSPORT IN NEAR-SURFACE AQUIFERS

    SciTech Connect

    J.L. Jerden Jr.; A.J. Kropf; Y. Tsai

    2005-08-25

    The surface complexation of actinides with iron oxides plays a key role in actinide transport and retardation in geosphere-biosphere systems. The development of accurate actinide transport models therefore requires a mechanistic understanding of surface complexation reactions (i.e. knowledge of chemical speciation at mineral/fluid interfaces). Iron oxides are particularly important actinide sorbents due to their pH dependent surface charges, relatively high surface areas and ubiquity in oxic and suboxic near-surface systems. In this paper we present results from field and laboratory investigations that elucidate the mechanisms involved in binding uranium and neptunium to iron oxide mineral substrates in near neutral groundwaters. The field study involved sampling and characterizing uranium-bearing groundwaters and solids from a saprolite aquifer overlying an unmined uranium deposit in the Virginia Piedmont. The groundwaters were analyzed by inductively coupled mass spectrometry and ion chromatography and the aquifer solids were analyzed by electron microprobe. The laboratory study involved a series of batch sorption tests in which U(VI) and Np(V) were reacted with goethite, hematite and magnetite in simulated groundwaters. The pH, ionic strength, aging time, and sorbent/sorbate ratios were varied in these experiments. The oxidation state and coordination environment of neptunium in solutions and sorbents from the batch tests were characterized by X-ray absorption spectroscopy (XAS) at the Advanced Photon Source, Argonne National Laboratory. Results from this work indicate that, in oxidizing near-surface aquifers, the dissolved concentration of uranium may be limited to less than 30 parts per billion due to uptake by iron oxide mineral coatings and the precipitation of sparingly soluble U(VI) phosphate minerals. Results from the batch adsorption tests showed that, in near neutral groundwaters, a significant fraction of the uranium and neptunium adsorbed as strongly

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

    SciTech Connect

    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

  3. Benzenecarboxylate surface complexation at the goethite (α-FeOOH)/water interface: II. Linking IR spectroscopic observations to mechanistic surface complexation models for phthalate, trimellitate, and pyromellitate

    NASA Astrophysics Data System (ADS)

    Boily, Jean-François; Persson, Per; Sjöberg, Staffan

    2000-10-01

    A study combining information from infrared spectroscopy and adsorption experiments was carried out to investigate phthalate, trimellitate, and pyromellitate complexes at the goethite (α-FeOOH)/water interface. Infrared spectra showed evidence for inner-sphere complexes below pH 6 and outer-sphere complexes in the pH range 3 to 9. Normalized infrared peak areas were used as a semi-quantitative tool to devise diagrams showing the molecular level surface speciation as a function of pH. Surface complexation models that simultaneously predict these diagrams, the proton balance data and the ligand adsorption data were developed with surface complexation theory. Surface complexation modeling was carried out with a Charge Distribution Multisite Complexation Model (CD-MUSIC), assuming goethite particles with surfaces represented by the {110} plane (90% of total particle surface area) and by the {001} plane (10% of total particle surface area). Inner-sphere complexes were described as mononuclear chelates at the {001} plane, whereas outer-sphere complexes were described as binuclear complexes with singly coordinated sites on the {110} plane. The Three-Plane Model (TPM) was used to described surface electrostatics and to distribute the charges of the inner- and the outer-sphere complexes on different planes of adsorption.

  4. Sclerochronology and geochemical variation in limpet shells (Patella vulgata): A new archive to reconstruct coastal sea surface temperature

    NASA Astrophysics Data System (ADS)

    Fenger, Tracy; Surge, Donna; SchöNe, Bernd; Milner, Nicky

    2007-07-01

    Climate archives contained in shells of the European limpet, Patella vulgata, accumulated in archaeological deposits can potentially provide much needed information about Holocene environmental change in midlatitude coastal areas. Before reconstructing climate information preserved in these zooarchaeological records, we studied the controls on oxygen and carbon isotope ratios (δ18O and δ13C, respectively) in modern specimens. We tested the hypothesis that P. vulgata precipitates its shell in isotopic equilibrium with the ambient water by comparing δ18OSHELL with predicted values. Predicted δ18OSHELL was constructed using observed sea surface temperature (SST) records and the equilibrium fractionation equation for calcite and water. We assumed a constant δ18OWATER value of +0.10‰ (VSMOW) based on published regional measurements. Comparison of δ18OSHELL with predicted values revealed that δ18OSHELL values were higher than expected by +1.01 ± 0.21‰. Consequently, estimated SST calculated from δ18OSHELL was 4.2 ± 2.3°C lower than observed SST. However, because of the relatively uniform offset between observed and expected δ18O, an adjustment can be made to account for this predictable vital effect. Thus past climate can be reliably reconstructed using this temperature proxy once the offset is taken into account. δ13C values have a similar cyclicity to the δ18O variation and therefore vary seasonally. However, δ13C is slightly out of phase relative to δ18O. An overall negative shift in δ13CSHELL over the lifetime of the individual indicates a vital effect associated with ontogeny. Further study of environmental and ecological factors that influence shell δ13C is required to evaluate fully the potential of carbon isotope ratios as a useful environmental proxy.

  5. Geochemical and isotopic constraints on the age and origin of the Nidar Ophiolitic Complex, Ladakh, India: Implications for the Neo-Tethyan subduction along the Indus suture zone

    NASA Astrophysics Data System (ADS)

    Ahmad, T.; Tanaka, T.; Sachan, H. K.; Asahara, Y.; Islam, R.; Khanna, P. P.

    2008-04-01

    The Nidar ophiolite complex is exposed within the Indus suture zone in eastern Ladakh, India. The suture zone is considered to represent remnant Neo-Tethyan Ocean that closed via subduction as the Indian plate moved northward with respect to the Asian plate. The two plates ultimately collided during the Middle Eocene. The Nidar ophiolite complex comprises a sequence of ultra-mafic rocks at the base, gabbroic rocks in the middle and volcano-sedimentary assemblage on the top. Earlier studies considered the Nidar ophiolite complex to represent an oceanic floor sequence based on lithological assemblage. However, present study, based on new mineral and whole rock geochemical and isotopic data (on bulk rocks and mineral separates) indicate their generation and emplacement in an intra-oceanic subduction environment. The plutonic and volcanic rocks have nearly flat to slightly depleted rare earth element (REE) patterns. The gabbroic rocks, in particular, show strong positive Sr and Eu anomalies in their REE and spidergram patterns, probably indicating plagioclase accumulation. Depletion in high field strength elements (HFSE) in the spidergram patterns may be related to stabilization of phases retaining the HFSE in the subducting slab and / or fractional crystallization of titano-magnetite phases. The high radiogenic Nd- and low radiogenic Sr-isotopic ratios for these rocks exclude any influence of continental material in their genesis, implying an intra-oceanic environment. Nine point mineral-whole rock Sm-Nd isochron corresponds to an age of 140 ± 32 Ma with an initial 143Nd/ 144Nd of 0.513835 ± 0.000053 ( ENdt = + 7.4). This age is consistent with the precise Early Cretaceous age of Hauterivian (132 ± 2 to 127 ± 1.6 Ma) to Aptian (121 ± 1.4 to 112 ±1.1 Ma) for the overlying volcano-sedimentary (radiolarian bearing chert) sequences based on well-preserved radiolarian fossils (Kojima, S., Ahmad, T., Tanaka, T., Bagati, T.N., Mishra, M., Kumar, R. Islam, R., Khanna, P

  6. Sialomucin complex at the rat ocular surface: a new model for ocular surface protection.

    PubMed Central

    Price-Schiavi, S A; Meller, D; Jing, X; Merritt, J; Carvajal, M E; Tseng, S C; Carraway, K L

    1998-01-01

    The ocular surface, which is among the most accessible and vulnerable tissues in mammals, is protected by a complex tear film composed of lipid, aqueous and mucin layers. In spite of its importance, the molecular nature of the mucin contribution remains uncertain. Since membrane mucins have been implicated in the protection of other epithelia, we have analysed rat corneal and conjunctival tissues for sialomucin complex (SMC), a membrane mucin found at the apical epithelial cell surfaces in the airway and uterus. Using Northern and Western blot analyses, SMC expression was found in both ocular tissues, being particularly abundant in the cornea. In contrast with the other known membrane mucin, MUC1, SMC was localized more heavily towards the apical surface of the epithelial cells. SMC in ocular surface epithelia was produced in both soluble and membrane forms, the latter being found predominantly in the most superficial cells and at apical surfaces. The soluble form was found loosely adsorbed to apical cell surfaces, particularly of the cornea, as indicated by a mild rinsing protocol. Finally, the tear fluid contained substantial amounts of SMC. From these results, we propose a new model for tear mucin components in which SMC is expressed at the apical ocular surface in both membrane-bound and adsorbed soluble forms to provide a direct protective barrier. SMC secreted into the tear fluid may also participate in maintaining the stability of the preocular tear film by acting with other secreted mucins to determine the physical properties and protective behaviour of the tear film. PMID:9761747

  7. Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination

    SciTech Connect

    Samuel Traina; Shankar Sharma

    2005-07-12

    The Department of Energy has a goal of decontaminating an estimated 180,000 metric tons of metal wastes in various surplus facilities. Uranium (U) and other radioactive actinides and lanthanides are embedded within the mixed oxide structures of the passivity layers of corroded iron and steel. These toxic metals can be dissolved out of the surface layers by a naturally occurring bacterial siderophore called Desferrioxamine B (DFB). DFB is a trihydroxamate ligand with one amine and three hydroxamate groups, which chelates with metals through hydroxamate coordination. Complexation of DFB with U can be utilized in decontamination strategy of the passivity layers. Therefore, we have been studying reactions of uranyl U(VI) with zerovalent iron (Fe0) followed by dissolution by DFB. The objectives were to determine the structure and speciation of solution and solid phases of U and to assess the effectiveness of DVB in U dissolution.

  8. Efficient parametrization of complex molecule-surface force fields.

    PubMed

    Gao, David Z; Federici Canova, Filippo; Watkins, Matthew B; Shluger, Alexander L

    2015-06-15

    We present an efficient scheme for parametrizing complex molecule-surface force fields from ab initio data. The cost of producing a sufficient fitting library is mitigated using a 2D periodic embedded slab model made possible by the quantum mechanics/molecular mechanics scheme in CP2K. These results were then used in conjunction with genetic algorithm (GA) methods to optimize the large parameter sets needed to describe such systems. The derived potentials are able to well reproduce adsorption geometries and adsorption energies calculated using density functional theory. Finally, we discuss the challenges in creating a sufficient fitting library, determining whether or not the GA optimization has completed, and the transferability of such force fields to similar molecules.

  9. Efficient parametrization of complex molecule-surface force fields.

    PubMed

    Gao, David Z; Federici Canova, Filippo; Watkins, Matthew B; Shluger, Alexander L

    2015-06-15

    We present an efficient scheme for parametrizing complex molecule-surface force fields from ab initio data. The cost of producing a sufficient fitting library is mitigated using a 2D periodic embedded slab model made possible by the quantum mechanics/molecular mechanics scheme in CP2K. These results were then used in conjunction with genetic algorithm (GA) methods to optimize the large parameter sets needed to describe such systems. The derived potentials are able to well reproduce adsorption geometries and adsorption energies calculated using density functional theory. Finally, we discuss the challenges in creating a sufficient fitting library, determining whether or not the GA optimization has completed, and the transferability of such force fields to similar molecules. PMID:25891018

  10. Geochemical Evidence of a Near Surface History for the Source Rocks of the Central Coast Mountains Batholith, British Columbia

    NASA Astrophysics Data System (ADS)

    Stremtan, C. C.; Wetmore, P. H.; Ducea, M. N.

    2009-04-01

    Major and trace elemental concentrations as well as Sr, Pb and O isotopic data, completed on 41 plutonic samples from the Coast Mountains Batholith (CMB) ranging in age from ~108 Ma to ~50 Ma indicate that the source regions for these rocks were relatively uniform and typical for island arcs around the Pacific. The studied rocks are mineralogically and chemically metaluminous to weakly peraluminous and are mainly calc-alkaline with a few samples (mostly from the eastern part of the Coastal Shear Zone (CSZ) and three samples from the western part) showing a high-K calc-alkaline feature. Trace elements, especially REE, suggest a mafic source, probably oceanic plateau or island arc in origin, buried to different depths in the crust and that underwent various degrees of partial melting. Initial whole-rock 87Sr/86Sr range from 0.7035 up to 0.7053, whereas lead isotopic data range from 18.586 to 19.078 for 206Pb/204Pb, 15.545 to 15.634 for 207Pb/204Pb, and 37.115 to 38.661 for 208Pb/204Pb. In contrast to these fairly primitive isotopic data, δ18O values for quartz separates determined for 19 of the samples range from 6.8 up to 10.0 . Such δ18O values exclude the possibility that these melts were solely generated from the Mesozoic mantle wedge of this continental arc, just as the Sr and Pb data preclude significant involvement of an old (Precambrian) crustal/mantle lithospheric source. We interpret the high δ18O component to represent materials that had a multi-stage crustal evolution. They were originally mafic rocks derived from a circum-Pacific juvenile mantle wedge that experienced a period of near surface residence after initial crystallization. During this interval these primitive rocks interacted with meteoric waters at low temperatures, as indicated by the high δ18O values. Subsequently, these materials were buried to lower crustal depths where they re-melted to form the high δ18O component of the CMB. We estimate that, based on REE ratios and the presence of

  11. Surface Complexation of Neptunium(V) with Goethite

    SciTech Connect

    Jerden, James L.; Kropf, A. Jeremy

    2007-07-01

    Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH less than 5.0 to greater than 10,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg){sub sorbed} / (moles/kg){sub solution} were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np

  12. Surface complexation model of uranyl sorption on Georgia kaolinite

    USGS Publications Warehouse

    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.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    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

  16. Surface x-ray diffraction of complex metal oxide surfaces and interfaces--a new era

    SciTech Connect

    Schlepuetz, C. M.; Willmott, P. R.; Pauli, S. A.; Herger, R.; Martoccia, D.; Bjoerck, M.; Kumah, D.; Clarke, R.; Yacoby, Y.

    2009-01-29

    The availability of high-brilliance hard x-ray synchrotron radiation and the advent of novel photon counting area detectors have brought surface x-ray diffraction (SXRD) into a new era. It is now possible to record large numbers of structure factors with much improved reliability within reasonable beamtime durations. As a result, structural determination of the surfaces and interfaces of complex crystallographic systems and heterostructures has now become feasible, especially in conjunction with phase-retrieval methods. It is thereby hoped that detailed structural information will shed light on the unusual physical properties of these systems. Complex metal oxide systems investigated at the Materials Science beamline of the Swiss Light Source, including the surface of SrTiO{sub 3}, the interface between LaAlO{sub 3} and SrTiO{sub 3}, and the structure of YBa{sub 2}Cu{sub 3}O{sub 7} grown on NdGaO{sub 3}, SrTiO{sub 3}, and (LaSr)(AlTa)O{sub 3} will be presented as examples of what is now possible using SXRD.

  17. Studies of the surface charge of amorphous aluminosilicates using surface complexation models.

    PubMed

    Jara, Alejandra A; Goldberg, Sabine; Mora, M L

    2005-12-01

    Synthetic noncrystalline aluminosilicates with variable charge, similar to allophanes present naturally in volcanic soils, were studied. The surface charge behavior was determined by zero point charge (ZPC) measured by electrophoretic mobility (isoelectric points, IEP) and determined by potentiometric titration (point of zero salt effect, PZSE). The ZPC calculated by Parks model (ZPC(c)), compared with IEP values, showed that the aluminosilicate (AlSi) surface was slightly enriched by AlOH (34% Al(2)O(3) and 66% SiO(2)) compared with the bulk composition (29% Al(2)O(3) and 71% SiO(2)). For aluminosilicate coated with iron oxide (AlSiFe) the ZPC(c) (4.4) was lower than the IEP (8.46), showing that the surface composition is formed mainly from iron oxide. The PZSE values for AlSi and AlSiFe were 6.2 and 4.8, respectively. The differences between the IEP and PZSE are attributed to the formation of Si-O-Fe or Si-O-Al bonds; therefore, the reactivity of Fe and Al atoms was modified on the surface. Two mechanistic models, the constant capacitance model (CCM) and the triple layer model (TLM), using the program FITEQL 3.2 were able to describe the surface behavior of both synthetic aluminosilicates. The acidity constants determined using both models for the aluminosilicates showed differences with respect to pure oxide, mainly attributed to the presence of SiOH sites on the internal surfaces. The ionic strength showed a good relation with the parameters obtained using the CCM (pK(int)(a1), pK(int)(a2) and capacitance values) and the TLM (pK(int)(a1), pK(int)(a2), pK(int)(Cl-), pK(int)(K+), and inner capacitance) for both aluminosilicates. However, the TLM was able to describe the acidity and complexation constants better since it considered the formation of the outer sphere complex between the background electrolyte and the surface. Then, the TLM makes it possible to describe real systems.

  18. Complexity in surfaces of densest packings for families of polyhedra

    NASA Astrophysics Data System (ADS)

    Klotsa, Daphne; Chen, Elizabeth R.; Engel, Michael; Damasceno, Pablo F.; Glotzer, Sharon C.

    2014-03-01

    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, colloidal matter, and biology. In all these fields, particle shape is important for structure and properties, especially upon crowding. In this talk, we explore packing as a function of shape. By combining simulations and analytic calculations, we study three 2-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 (20-hedral, 8-hedral, 4-hedral) and interpolate between various symmetric solids (Platonic, Archimedean, Catalan). We find that maximum packing density surfaces reveal unexpected richness and complexity, containing as many as 130 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 propose a method to distinguish regions of packings and classify types of transitions between them.

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

    NASA Astrophysics Data System (ADS)

    Chen, Elizabeth R.; Klotsa, Daphne; Engel, Michael; Damasceno, Pablo F.; Glotzer, Sharon C.

    2014-01-01

    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.

  20. Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: Arsenate on hematite (0001) and (10-12)

    USGS Publications Warehouse

    Waychunas, G.; Trainor, T.; Eng, P.; Catalano, J.; Brown, G.; Davis, J.; Rogers, J.; Bargar, J.

    2005-01-01

    X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c(0001) and r(10-12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of "edge-sharing" bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. ?? Springer-Verlag 2005.

  1. Eocene Granitoids of the Okhotsk Complex in Sakhalin Island, Russian Far East: Petrogenesis and tectonic implications from zircon U-Pb ages, geochemical and Sr-Nd isotopic characteristics

    NASA Astrophysics Data System (ADS)

    Liao, Jia Ping; Alexandrov, Igor; Jahn, Bor-ming

    2016-04-01

    Sakhalin Island represents an important part of the Western Pacific Orogenic Belt (or "Nipponides"). The island comprises several accreted terrains that have recorded strike-slip displacements and block rotations from Cretaceous to Tertiary. These terrains include fore-arc basins, accretionary complexes and island arc assemblages. The stratigraphic features of most terrains can be correlated to those of Hokkaido Island of Japan. However, little research has been undertaken on the magmatic activities on Sakhalin, so a direct comparison of crustal development and tectonic activities with Hokkaido has not been fulfilled. We intend to study the petrogenesis of granitic complexes of Sakhalin to resolve this problem. In this work, we present new results of age determination and geochemical analyses of the Okhotsk Complex and discuss the tectonic implications. The Okhotsk complex is one of the three main granitoid complexes in Sakhalin Island. It intruded into the Ozersk accretionary terrain that is composed of island arc assemblages and marine sediments and has traveled northward and accreted to Sakhalin Island in Eocene. Eleven samples from the Okhotsk Complex, including 7 granitoids, 1 enclave, 2 rhyolites, and 1 dacite, were subject to zircon U-Pb dating, whole-rock geochemical and Sr-Nd isotopic analyses. The results show that the entire complex was emplaced within 42 to 44 Ma. The 7 granitoids are slightly peraluminous, ferroan, and alkali-calcic. The REE abundances of granitoids show consistent patterns with weak LREE enrichment and negative Eu anomaly. The spidergrams show negative Ta-Nb-Ti anomaly as expected in most granitoids. They possess transitional characteristics between I- and A-type granites. For isotopic signatures, the granitoids have ɛNd(t) values of +2.8 to +3.7, initial 87Sr/86Sr ratios of 0.7047 to 0.7050, and Sm-Nd model ages (TDM-1) of 700-1100 Ma. The middle Eocene magmatic episode (42-44 Ma) of the Okhotsk Complex can find its counterpart in

  2. Unravelling the complex interaction between mantle and crustal magmas encoded in the lavas of San Vincenzo (Tuscany, Italy). Part II: Geochemical overview and modelling

    NASA Astrophysics Data System (ADS)

    Ridolfi, Filippo; Renzulli, Alberto; Perugini, Diego; Cesare, Bernardo; Braga, Roberto; Del Moro, Stefano

    2016-02-01

    This work reports a geochemical overview and modelling of the lavas erupted ~ 4.4 Ma ago at San Vincenzo (Tuscan Magmatic Province, TMP). Although these lavas cover a relatively small area (~ 10 km2), they show very large geochemical variations caused by the interaction of mantle-derived and crustal-anatectic magmas. The lavas consist of peraluminous rhyolites (87Sr/86Sr(i) up to 0.726) hosting primarily variably sized magmatic enclaves with shoshonite/latite compositions (87Sr/86Sr(i) down to 0.708). New whole-rock data for a large shoshonite enclave show high concentrations of LREE, LILE, and tetravalent HFSE, coupled with pentavalent HFSE depletions and enrichments in compatible elements such as Cr and Co. The chondrite-normalised REE pattern is strongly fractionated and characterised by a negative Eu anomaly (Eu/Eu* = 0.79). Hybridisation and AFC models suggest that the shoshonite enclave is the result of 12% rhyolite contamination of a mantle-derived magma akin to the potassic trachybasalt/shoshonite lavas of Capraia Island (~ 4.6 Ma; TMP), following an 18.5% assimilation of Late Triassic metasediments (13% evaporite and 5.5% carbonate) and 56% fractionation of clinopyroxene (39%), plagioclase (10%), and biotite (7%). Each rhyolite sample is characterised by mineral-scale isotopic disequilibria (e.g., 87Sr/86Sr(i) = 0.711-0.726), glass inclusions with large K2O/Na2O variations (1.1-3.4) and a poli-thermobarometric history of crustal melt production at eutectic conditions. A multi-parametric approach accounting for K2O/Na2O (1.3-2.2), 87Sr/86Sr(i) (0.713-0.725), Sr (104-311 ppm) and Rb (294-403 ppm) whole-rock variations, allowed us to divide the anatectic (A) rhyolites into five groups (A1, A2.1, A2.2, A2.3, A3). Group A1 shows the highest 87Sr/86Sr(i) ratios and the lowest values of Sr, K2O/Na2O and Rb. It is related to A2.1 and A3 rhyolites by positive K2O/Na2O-Rb and K2O/Na2O-FeO correlations. These three rhyolite groups crop out in the south of San

  3. Spectra over complex terrain in the surface layer

    SciTech Connect

    Panofsky, H.A.; Dutton, J.A.; Larko, D.; Lipschutz, R.; Stone, G.

    1982-09-01

    For design and control of Wind Energy Conversion Systems (WECS), the spectral distribution of wind speeds over frequencies needs to be known as well as velocity variances. Velocity spectra and other velocity statistics are estimated over three types of complex terrain: on tops of hills or escarpments; on land a short distance downwind from a water body; and over rolling farm land. The most important characteristics of turbulence models over uniform terrain are summarized briefly. Theoretical aspects of spectral characteristics over complex terrain are discussed, followed by detailed observations over complex terrain and procedures for their estimation. A theory is presented for calculation of response of engineering systems to wind fluctuations. (LEW)

  4. Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

    USGS Publications Warehouse

    Waite, T.D.; Davis, J.A.; Payne, T.E.; Waychunas, G.A.; Xu, N.

    1994-01-01

    A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, FesOH and FewOH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO2)UO2. The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO2CO30 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation. ?? 1994.

  5. Shape index distribution based local surface complexity applied to the human cortex

    PubMed Central

    Kim, Sun Hyung; Fonov, Vladimir; Collins, D. Louis; Gerig, Guido; Styner, Martin A.

    2015-01-01

    The quantification of local surface complexity in the human cortex has shown to be of interest in investigating population differences as well as developmental changes in neurodegenerative or neurodevelopment diseases. We propose a novel assessment method that represents local complexity as the difference between the observed distributions of local surface topology to its best-fit basic topology model within a given local neighborhood. This distribution difference is estimated via Earth Move Distance (EMD) over the histogram within the local neighborhood of the surface topology quantified via the Shape Index (SI) measure. The EMD scores have a range from simple complexity (0.0), which indicates a consistent local surface topology, up to high complexity (1.0), which indicates a highly variable local surface topology. The basic topology models are categorized as 9 geometric situation modeling situations such as crowns, ridges and fundi of cortical gyro and sulci. We apply a geodesic kernel to calculate the local SI histrogram distribution within a given region. In our experiments, we obtained the results of local complexity that shows generally higher complexity in the gyral/sulcal wall regions and lower complexity in some gyral ridges and lowest complexity in sulcal fundus areas. In addition, we show expected, preliminary results of increased surface complexity across most of the cortical surface within the first years of postnatal life, hypothesized to be due to the changes such as development of sulcal pits. PMID:26028803

  6. Shape index distribution based local surface complexity applied to the human cortex

    NASA Astrophysics Data System (ADS)

    Kim, Sun Hyung; Fonov, Vladimir; Collins, D. Louis; Gerig, Guido; Styner, Martin A.

    2015-03-01

    The quantification of local surface complexity in the human cortex has shown to be of interest in investigating population differences as well as developmental changes in neurodegenerative or neurodevelopment diseases. We propose a novel assessment method that represents local complexity as the difference between the observed distributions of local surface topology to its best-fit basic topology model within a given local neighborhood. This distribution difference is estimated via Earth Move Distance (EMD) over the histogram within the local neighborhood of the surface topology quantified via the Shape Index (SI) measure. The EMD scores have a range from simple complexity (0.0), which indicates a consistent local surface topology, up to high complexity (1.0), which indicates a highly variable local surface topology. The basic topology models are categorized as 9 geometric situation modeling situations such as crowns, ridges and fundi of cortical gyro and sulci. We apply a geodesic kernel to calculate the local SI histogram distribution within a given region. In our experiments, we obtained the results of local complexity that shows generally higher complexity in the gyral/sulcal wall regions and lower complexity in some gyral ridges and lowest complexity in sulcal fundus areas. In addition, we show expected, preliminary results of increased surface complexity across most of the cortical surface within the first years of postnatal life, hypothesized to be due to the changes such as development of sulcal pits.

  7. Extracting mineral system event histories from geophysical and geochemical data in geologically complex terrain - an example from the southeastern Fennoscandian Shield.

    NASA Astrophysics Data System (ADS)

    Sorjonen-Ward, Peter; Kontinen, Asko; Lerssi, Jouni; Mertanen, Satu; Molnar, Ferenc; O'Brien, Hugh; Pohjolainen, Esa; Halla, Jaana; Korhonen, Fawna; Mattila, Jussi

    2015-04-01

    The mineral systems concept is intended to extend and inform exploration capability, through understanding processes of metal extraction, transport and precipitation within a well-defined architectural framework, as opposed to simple - or even sophisticated - targeting of geophysical or geochemical anomalies. Given that geophysical and geochemical data represent a summation of all events and processes that have affected a body of rock, the use of advanced inversion techniques could be impeded unless we can extract an accurate event history and derive a comprehensive understanding of the history of hydrothermal events and their structural framework, even in a qualitative sense. In ideal cases, we may be able to place age constraints using isotopes or paleomagnetism, if hydrothermal mineral reactions enhance (or disperse) geochemical and geophysical signals. Given a the tendency for deformation in the brittle regime to occur preferentially by reactivation of existing zones of weakness, we might also expect a progressive linear enhancement or dilution of anomalies, where fluid-flow is focused within permeable fault zones. We illustrate these issues through an analysis of event histories and their relationship to diverse mineralization styles and episodes in the southeastern part of the Fennoscandian Shield, where the oldest mineral systems are represented by orogenic gold deposits in Neoarchean greenstone belts and the youngest events are recorded locally by Paleozoic crystallization of uraninite in repeatedly reactivated fault zones. The Neoarchean Karelian craton was subjected to thermal reworking as the foreland terrain to the 1.9-1.8 Ga Svecofennian Orogeny, as demonstrated by resetting of K-Ar, Ar-Ar, Rb-Sr and locally Pb-Pb isotopic systems in feldspars and pyrite, both within gold deposits, and regionally. However, retention of Archean strain patterns and observations of the strain state of Proterozoifc dyke swarms indicate an essentially brittle response, with

  8. Evidence for surface Ag + complexes as the SERS-active sites on Ag electrodes

    NASA Astrophysics Data System (ADS)

    Watanabe, T.; Kawanami, O.; Honda, K.; Pettinger, B.

    1983-12-01

    Evidence is given that SERS-active sites at Ag electrodes are associated with Ag + ions, forming sparingly soluble surface complexes with ligands such as pyridine molecules and halide ions. Such surface Ag + complexes contribute a factor of >800 to the overall (10 7-fold) enhancement, possibly via a resonance Raman effect.

  9. A universal surface complexation framework for modeling proton binding onto bacterial surfaces in geologic settings

    USGS Publications Warehouse

    Borrok, D.; Turner, B.F.; Fein, J.B.

    2005-01-01

    Adsorption onto bacterial cell walls can significantly affect the speciation and mobility of aqueous metal cations in many geologic settings. However, a unified thermodynamic framework for describing bacterial adsorption reactions does not exist. This problem originates from the numerous approaches that have been chosen for modeling bacterial surface protonation reactions. In this study, we compile all currently available potentiometric titration datasets for individual bacterial species, bacterial consortia, and bacterial cell wall components. Using a consistent, four discrete site, non-electrostatic surface complexation model, we determine total functional group site densities for all suitable datasets, and present an averaged set of 'universal' thermodynamic proton binding and site density parameters for modeling bacterial adsorption reactions in geologic systems. Modeling results demonstrate that the total concentrations of proton-active functional group sites for the 36 bacterial species and consortia tested are remarkably similar, averaging 3.2 ?? 1.0 (1??) ?? 10-4 moles/wet gram. Examination of the uncertainties involved in the development of proton-binding modeling parameters suggests that ignoring factors such as bacterial species, ionic strength, temperature, and growth conditions introduces relatively small error compared to the unavoidable uncertainty associated with the determination of cell abundances in realistic geologic systems. Hence, we propose that reasonable estimates of the extent of bacterial cell wall deprotonation can be made using averaged thermodynamic modeling parameters from all of the experiments that are considered in this study, regardless of bacterial species used, ionic strength, temperature, or growth condition of the experiment. The average site densities for the four discrete sites are 1.1 ?? 0.7 ?? 10-4, 9.1 ?? 3.8 ?? 10-5, 5.3 ?? 2.1 ?? 10-5, and 6.6 ?? 3.0 ?? 10-5 moles/wet gram bacteria for the sites with pKa values of 3

  10. Antimicrobial ruthenium complex coating on the surface of titanium alloy. High efficiency anticorrosion protection of ruthenium complex.

    PubMed

    El-Gamel, Nadia E A; Fekry, Amany M

    2015-08-01

    A ruthenium complex was prepared and structurally characterized using various techniques. Antibacterial and antifungal activities of ruthenium complex were evaluated. High significant antimicrobial activity against Escherichia coli, Staphylococcus aureus and Candida albicans was recorded. Minor cytotoxicity records were reported at the highest concentration level using MTT assay. The influence of Cu(II), Cr(III), Fe(III) and Ru(III) metal ions of salen Schiff base on the corrosion resistance of Ti-alloy in 0.5M HCl was studied. In vitro corrosion resistance was investigated using electrochemical impedance spectroscopy (EIS) measurements and confirmed by surface examination via scanning electron microscope (SEM) technique. Both impedance and phase angle maximum (θ(max)) values were at maximum in the case of the ruthenium complex with promising antibacterial and antifungal activities. The surface film created by the ruthenium complex was highly resistant against attack or deterioration by bacteria. The EIS study showed high impedance values for the ruthenium complex with increasing exposure time up to 8 days. SEM images showed uniform distribution and adsorption of Ru(III) ions on Ti-alloy surface. The ruthenium complex, as a model of organic-inorganic hybrid complex, offered new prospects with desired properties in industrial and medical applications.

  11. Pb-Sr-Nd isotope study of the 100- to 2700-Ma old alkalic rock-carbonatite complexes in the Canadian shield: inferences on the geochemical and structural evolution of the mantle

    SciTech Connect

    Kwon, S.T.

    1986-01-01

    The isotopic signatures of young continental alkalic complexes (CAC) display a remarkable similarity to those of oceanic island basalts (OIB). A study of Sr isotopic evolution showed that the mantle, presumably similar to the source of OIB, beneath the shield appears to have been depleted in large ion lithophile elements (LILE) and to have remained as a closed system since ca. 3000 Ma ago. The present investigations apply Pb and Nd as well as Sr isotopic systems for those complexes to study the secular geochemical evolution of the mantle over the past 2700 million years, and address the question of the processes responsible for the geochemical heterogeneity of the mantle. The data suggest: (1) Like Sr, Pb and Nd isotopic data indicate LILE depleted sources for the southern Canadian shield CAC over at least the past 1900 Ma. (2) Sr, Nd and Pb are compatible with an age of ca. 3000 Ma for the depleted source. (3) In contrast to Sr, and probably Nd, the Pb isotopic data cannot be explained by a closed system model for the depleted mantle source. (4) Coherent fractionation patterns are observed in the mantle sources of CAC since at least 1900 Ma ago: higher U/Pb and Sm/Nd, and lower Th/U and Rb/Sr ratios versus lower U/Pb and Sm/Nd, and higher Th/U and Rb/Sr ratios, indicating OlB-like sources for CAC. (5) The inverse correlation between /sup 206/Pb//sup 204/Pb and /sup 87/Sr//sup 86/Sr initial ratios permit calculation of apparent mean earth Pb isotope ratios with time, which yield 8.35 for the present day /sup 238/U//sup 204/Pb ratio, and 17.82 for /sup 206/Pb//sup 204/Pb. (6) A model for the geochemical and structural evolution of the mantle is based on the diverging isotopic evolution of the midocean ridge basalts (MORB) and OlB sources.

  12. Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

    USGS Publications Warehouse

    Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

    2009-01-01

    A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

  13. Double bi-material cantilever structures for complex surface plasmon modulation.

    PubMed

    Song, Eui-Young; Cho, Jaebum; Kim, Hwi; Choi, Woo Young; Lee, Byoungho

    2015-03-01

    A complex modulation structure of surface plasmon polaritons using double bi-material cantilevers is proposed. It is shown with numerical analysis that the thermally controlled mechanical actuation of double bi-material cantilevers can modulate the amplitude and phase of surface plasmon polaritons across a full complex modulation range independently and simultaneously. The complex modulation structures designed for visible wavelengths are presented and their multi-wavelength integration is discussed.

  14. Surface Complexation at the TiO(2) (anatase)/Aqueous Solution Interface: Chemisorption of Catechol.

    PubMed

    Rodríguez; Blesa; Regazzoni

    1996-01-15

    Catechol adsorbs at the TiO(2) (anatase)/aqueous solution interface forming inner-sphere surface complexes. The UV-visible differential reflectance spectrum of surface titanium-catecholate complexes presents a band centered at 420 nm which corresponds to the ligand to metal charge transfer transition within the surface complexes. At pH values below pK(a1), the surface excess of catechol is almost insensitive toward pH and presents a Langmuirian dependence with the concentration of uncomplexed catechol. The ratio Gamma(max):N(S) (N(S) being the measured density of available OH surface groups) indicates a prevailing 1 to 2 ligand exchange adsorption stoichiometry. In the range pH >/= pK(a1), the catechol surface excess decreases markedly with increasing pH. Formation of 1 to 1 surface complexes produces an excess of negative surface charge that is revealed by the shift of the iep to lower pH values. The reported data, which are supplemented with information on the charging behavior of TiO(2) suspended in indifferent electrolyte solutions, are interpreted in terms of the multi-site surface complexation model. In this model, two types of surface OH groups are considered: identical withTiOH(1/3-) and identical withOH(1/3+). Although both surface groups undergo protonation-deprotonation reactions, only identical withTiOH(1/3-) are prone to chemisorption.

  15. A carbonate-silicate aqueous geochemical cycle model for Mars

    NASA Technical Reports Server (NTRS)

    Schaefer, M. W.; Leidecker, H.

    1992-01-01

    A model for the carbonate-silicate geochemical cycle of an early, wet Mars is under development. The results of this study will be used to constrain models of the geochemical history of Mars and the likely mineralogy of its present surface. Although Mars today is a cold, dry planet, it may once have been much warmer and wetter. Values of total outgassed CO2 from several to about 10 bars are consistent with present knowledge (Pollack et al. 1987), and this amount of CO2 implies an amount of water outgassed at least equal to an equivalent depth of 500-1000 meters (Carr 1986). Pollack et al. (1987), in addition, estimate that a thick CO2 atmosphere may have existed for an extended period of time, perhaps as long as a billion years. The greenhouse effect of such an atmosphere would permit the presence of liquid water on the surface, most likely in the form of a shallow sea in the lowest regions of the planet, such as the northern plains (Schaefer 1990). The treatment of geochemical cycles as complex kinetic chemical reactions has been undertaken for terrestrial systems in recent years with much success (Lasaga 1980, 1981; Berner et al. 1983; Lasaga et al. 1985). Although the Martian system is vastly less well understood, and hence less well-constrained, it is also a much simpler system, due to the lack of biogenic reactions that make the terrestrial system so complex. It should be possible, therefore, to use the same techniques to model the Martian system as have been used for terrestrial systems, and to produce useful results. A diagram of the carbonate-silicate cycle for Mars (simplified from the terrestrial system) is given.

  16. Efficient modelling of droplet dynamics on complex surfaces.

    PubMed

    Karapetsas, George; Chamakos, Nikolaos T; Papathanasiou, Athanasios G

    2016-03-01

    This work investigates the dynamics of droplet interaction with smooth or structured solid surfaces using a novel sharp-interface scheme which allows the efficient modelling of multiple dynamic contact lines. The liquid-gas and liquid-solid interfaces are treated in a unified context and the dynamic contact angle emerges simply due to the combined action of the disjoining and capillary pressure, and viscous stresses without the need of an explicit boundary condition or any requirement for the predefinition of the number and position of the contact lines. The latter, as it is shown, renders the model able to handle interfacial flows with topological changes, e.g. in the case of an impinging droplet on a structured surface. Then it is possible to predict, depending on the impact velocity, whether the droplet will fully or partially impregnate the structures of the solid, or will result in a 'fakir', i.e. suspended, state. In the case of a droplet sliding on an inclined substrate, we also demonstrate the built-in capability of our model to provide a prediction for either static or dynamic contact angle hysteresis. We focus our study on hydrophobic surfaces and examine the effect of the geometrical characteristics of the solid surface. It is shown that the presence of air inclusions trapped in the micro-structure of a hydrophobic substrate (Cassie-Baxter state) result in the decrease of contact angle hysteresis and in the increase of the droplet migration velocity in agreement with experimental observations for super-hydrophobic surfaces. Moreover, we perform 3D simulations which are in line with the 2D ones regarding the droplet mobility and also indicate that the contact angle hysteresis may be significantly affected by the directionality of the structures with respect to the droplet motion. PMID:26828706

  17. Probing Potential Energy Surface Exploration Strategies for Complex Systems.

    PubMed

    N'Tsouaglo, Gawonou Kokou; Béland, Laurent Karim; Joly, Jean-François; Brommer, Peter; Mousseau, Normand; Pochet, Pascal

    2015-04-14

    The efficiency of minimum-energy configuration searching algorithms is closely linked to the energy landscape structure of complex systems, yet these algorithms often include a number of steps of which the effect is not always clear. Decoupling these steps and their impacts can allow us to better understand both their role and the nature of complex energy landscape. Here, we consider a family of minimum-energy algorithms based, directly or indirectly, on the well-known Bell-Evans-Polanyi (BEP) principle. Comparing trajectories generated with BEP-based algorithms to kinetically correct off-lattice kinetic Monte Carlo schemes allow us to confirm that the BEP principle does not hold for complex systems since forward and reverse energy barriers are completely uncorrelated. As would be expected, following the lowest available energy barrier leads to rapid trapping. This is why BEP-based methods require also a direct handling of visited basins or barriers. Comparing the efficiency of these methods with a thermodynamical handling of low-energy barriers, we show that most of the efficiency of the BEP-like methods lie first and foremost in the basin management rather than in the BEP-like step. PMID:26574398

  18. Probing Potential Energy Surface Exploration Strategies for Complex Systems.

    PubMed

    N'Tsouaglo, Gawonou Kokou; Béland, Laurent Karim; Joly, Jean-François; Brommer, Peter; Mousseau, Normand; Pochet, Pascal

    2015-04-14

    The efficiency of minimum-energy configuration searching algorithms is closely linked to the energy landscape structure of complex systems, yet these algorithms often include a number of steps of which the effect is not always clear. Decoupling these steps and their impacts can allow us to better understand both their role and the nature of complex energy landscape. Here, we consider a family of minimum-energy algorithms based, directly or indirectly, on the well-known Bell-Evans-Polanyi (BEP) principle. Comparing trajectories generated with BEP-based algorithms to kinetically correct off-lattice kinetic Monte Carlo schemes allow us to confirm that the BEP principle does not hold for complex systems since forward and reverse energy barriers are completely uncorrelated. As would be expected, following the lowest available energy barrier leads to rapid trapping. This is why BEP-based methods require also a direct handling of visited basins or barriers. Comparing the efficiency of these methods with a thermodynamical handling of low-energy barriers, we show that most of the efficiency of the BEP-like methods lie first and foremost in the basin management rather than in the BEP-like step.

  19. Principles of landscape-geochemical studies in the zones contaminated by technogenical radionuclides for ecological and geochemical mapping

    NASA Astrophysics Data System (ADS)

    Korobova, Elena; Romanov, Sergey

    2013-04-01

    Efficiency of landscape-geochemical approach was proved to be helpful in spatial and temporal evaluation of the Chernobyl radionuclide distribution in the environment. The peculiarity of such approach is in hierarchical consideration of factors responsible for radionuclide redistribution and behavior in a system of inter-incorporated landscape-geochemical structures of the local and regional scales with due regard to the density of the initial fallout and patterns of radionuclide migration in soil-water-plant systems. The approach has been applied in the studies of distribution of Cs-137, Sr-90 and some other radionuclides in soils and vegetation cover and in evaluation of contribution of the stable iodine supply in soils to spatial variation of risk of thyroid cancer in areas subjected to radioiodine contamination after the Chernobyl accident. The main feature of the proposed approach is simultaneous consideration of two types of spatial heterogeneities: firstly, the inhomogeneity of external radiation exposure due to a complex structure of the contamination field, and, secondly, the landscape geochemical heterogeneity of the affected area, so that the resultant effect of radionuclide impact could significantly vary in space. The main idea of risk assessment in this respect was to reproduce as accurately as possible the result of interference of two surfaces in the form of risk map. The approach, although it demands to overcome a number of methodological difficulties, allows to solve the problems associated with spatially adequate protection of the affected population and optimization of the use of contaminated areas. In general it can serve the basis for development of the idea of the two-level structure of modern radiobiogeochemical provinces formed by superposition of the natural geochemical structures and the fields of technogenic contamination accompanied by the corresponding peculiar and integral biological reactions.

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

    NASA Astrophysics Data System (ADS)

    Pastuszko, Robert

    2012-04-01

    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. Conducting molecular nanostructures assembled from charge-transfer complexes grafted onto silicon surfaces

    NASA Astrophysics Data System (ADS)

    Stires, John C., IV; Kasibhatla, Bala S. T.; Siegel, Dustin S.; Kwong, Jinny C.; Caballero, Jonathan B.; Labonte, Andre P.; Reifenberger, Ronald G.; Datta, Supriyo; Kubiak, Clifford P.

    2003-12-01

    Heterodimeric electon-donor/electron-acceptor charge-transfer complexes chemisorbed onto Au(111) by attachment of the electron-donor to the surface have been characterized by scanning tunneling microscopy and Kelvin probe experiments. Conductance measurements exhibit nearly Ohmic I(V) responses at low bias. The electrical properties of the charge-transfer complex are vastly different than those of the electron-donor alone which exhibits insulating behavior at low bias. In an extension of this work, strategies are being developed for attachment of charge-transfer complexes to semiconducting or insulating surfaces. Fabrication of nanoscale molecular electronic devices is being investigated by attaching one component of a charge-transfer complex to a silicon surface by chemically directed self-assembly. The single component-functionalized surface is then used as a substrate on which the second component of the charge-transfer complex is deposited by the atomic force microscopy method, dip-pen nanolithography (DPN). Derivatives of hexamethylbenze (electron-donor) with terminal olefins attached to crystalline silicon surfaces via hydrosilylation form monolayer-functionalized silicon surfaces that are expected to have insulating properties. Well-defined features can be "drawn" onto the donor-functionalized surfaces by DPN using tetracyanoethylene (electron-acceptor) as the "ink." The resulting charge-transfer complex nanostructures have conducting properties suitable for device function and are flanked by an insulating monolayer, thus creating "wires" made from charge-transfer complexes.

  2. Surface complexes of acetate on edge surfaces of 2:1 type phyllosilicate: Insights from density functional theory calculation

    NASA Astrophysics Data System (ADS)

    Liu, Xiandong; Lu, Xiancai; Wang, Rucheng; Zhou, Huiqun; Xu, Shijin

    2008-12-01

    To explore the complexation mechanisms of carboxylate on phyllosilicate edge surfaces, we simulate acetate complexes on the (0 1 0) type edge of pyrophyllite by using density functional theory method. We take into account the intrinsic long-range order and all the possible complex sets under common environments. This study discloses that H-bonding interactions occur widely and play important roles in both inner-sphere and outer-sphere fashions. In inner-sphere complexes, one acetate C-O bond elongates to form a covalent bond with surface Al atom; the other C-O either forms a covalent bond with Al or interacts with surface hydroxyls via H-bonds. In outer-sphere complexes, the acetate can capture a proton from the surface groups to form an acid molecule. For the groups of both substrate and ligand, the variations in geometrical parameters caused by H-bonding interactions depend on the role it plays (i.e., proton donor or acceptor). By comparing the edge structures before and after interaction, we found that the carboxylate binding can modify the surface structures. In the inner-sphere complexes, the exposed Al atom can be stabilized by a single acetate ion through either monodentate or bidentate schemes, whereas the Al atoms complexing both an acetate and a hydroxyl may significantly deviate outwards from the bulk equilibrium positions. In the outer-sphere complexes, some H-bondings are strong enough to polarize the metal-oxygen bonds and therefore distort the local coordination structure of metal in the substrate, which may make the metal susceptible to release.

  3. Complex surface concentration gradients by stenciled "electro click chemistry".

    PubMed

    Hansen, Thomas S; Lind, Johan U; Daugaard, Anders E; Hvilsted, Søren; Andresen, Thomas L; Larsen, Niels B

    2010-10-19

    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 active ligands including cell binding peptides are patterned in gradients by this method without losing their biological function or the conductivity of the polymer. PMID:20860406

  4. Complex surface concentration gradients by stenciled "electro click chemistry".

    PubMed

    Hansen, Thomas S; Lind, Johan U; Daugaard, Anders E; Hvilsted, Søren; Andresen, Thomas L; Larsen, Niels B

    2010-10-19

    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 active ligands including cell binding peptides are patterned in gradients by this method without losing their biological function or the conductivity of the polymer.

  5. Theory of polyelectrolyte adsorption on heterogeneously charged surfaces applied to soluble protein-polyelectrolyte complexes

    NASA Astrophysics Data System (ADS)

    de Vries, R.; Weinbreck, F.; de Kruif, C. G.

    2003-03-01

    Existing theoretical approaches to polymer adsorption on heterogeneous surfaces are applied to the problems of polyelectrolyte and polyampholyte adsorption on randomly charged surfaces. Also, analytical estimates are developed for the critical pH at which weakly charged polyelectrolytes and globular proteins start forming soluble complexes. Below a critical salt concentration, soluble complexes form "on the wrong side" of the protein isoelectric point due to the heterogeneity of the protein surface charge distribution. The analytical estimates are consistent with experimental data on soluble complexes in mixtures of gum arabic and whey protein isolate.

  6. New method to predict the surface tension of complex synthetic and biological polyelectrolyte/surfactant mixtures.

    PubMed

    Ábraham, Ágnes; Campbell, Richard A; Varga, Imre

    2013-09-17

    Although the surface tension of complex mixtures determines the fate of many important natural processes, the property is notoriously difficult to interpret. Here we announce a new method that successfully predicts the surface tension of two synthetic and one biological polyelectrolyte/surfactant mixtures in the phase-separation region after dynamic changes in the bulk phase behavior have reached completion. The approach is based on the nonequilibrium framework of a lack of colloidal stability of bulk complexes in compositions around the charge match point of the oppositely charged components and requires as input parameters only the surface tension isotherm of the pure surfactant and some bulk measurements of the mixtures; no surface measurements of the mixtures are required. The complexity of the problem is reduced to a single empirical equation. This simplification in our understanding of the surface properties of strongly interacting mixtures involving macromolecules can lead to the optimization of applications involving synthetic polymers and biomacromolecules such as DNA at surfaces.

  7. The origin of the 1.73-1.70 Ga anorogenic Ulkan volcano-plutonic complex, Siberian platform, Russia: inferences from geochronological, geochemical and Nd-Sr-Pb isotopic data

    USGS Publications Warehouse

    Larin, A.M.; Amelin, Yu. V.; Neymark, L.A.; Krymsky, R. Sh

    1997-01-01

    The Ulkan volcano-plutonic complex, a part of a 750 km Bilyakchian-Ulkan anorogenic belt, is located in the eastern part of the Archean-Paleoproterozoic Aldan shield. The tectonic position and geochemistry indicate that the Ulkan Complex is a typical A-type or intraplate magmatic association. The felsic volcanics of the Uian Group and granitoids of the North Uchur Massif, the major igneous components of the Ulkan Complex, have U-Pb zircon and monazite ages between 1721±1 Ma and 1703±18 Ma. Together with the spatially associated 1736±6 Ma Dzhugdzhur anorthosite massif, the Ulkan Complex forms a typical Proterozoic anorthosite-granite-volcanic association with the minimum duration of formation of 12 m.y. Initial εNd values between 0 and 1.1, similar for the Uian felsic volcanics, early granitoid phases of the North Uchur Massif and high-grade metamorphic basement rocks, indicate, along with geochemical data, that the crustal source of the Ulkan parental magmas may be similar to the basement rocks. The higher εNd(T) values of -0.3 to +1.9 in the later North Uchur granitoids and associated ore-bearing metasomatites, and relatively low time-integrated Rb/Sr, U/Pb, and Th/U estimated for their sources, may demonstrate involvement of variable amounts of a depleted mantle-derived component in the generation of later phases of the North Uchur Massif. The preferred model of formation of magmas parental to the Ulkan Complex involves thermal interaction of an uprising mantle diapir with Paleoproterozoic lower crust, which was accompanied by chemical interaction between a fluid derived from the diapir, with the lower crustal rocks.

  8. Uranium plume persistence impacted by hydrologic and geochemical heterogeneity in the groundwater and river water interaction zone of Hanford site

    NASA Astrophysics Data System (ADS)

    Chen, X.; Zachara, J. M.; Vermeul, V. R.; Freshley, M.; Hammond, G. E.

    2015-12-01

    The behavior of a persistent uranium plume in an extended groundwater- river water (GW-SW) interaction zone at the DOE Hanford site is dominantly controlled by river stage fluctuations in the adjacent Columbia River. The plume behavior is further complicated by substantial heterogeneity in physical and geochemical properties of the host aquifer sediments. Multi-scale field and laboratory experiments and reactive transport modeling were integrated to understand the complex plume behavior influenced by highly variable hydrologic and geochemical conditions in time and space. In this presentation we (1) describe multiple data sets from field-scale uranium adsorption and desorption experiments performed at our experimental well-field, (2) develop a reactive transport model that incorporates hydrologic and geochemical heterogeneities characterized from multi-scale and multi-type datasets and a surface complexation reaction network based on laboratory studies, and (3) compare the modeling and observation results to provide insights on how to refine the conceptual model and reduce prediction uncertainties. The experimental results revealed significant spatial variability in uranium adsorption/desorption behavior, while modeling demonstrated that ambient hydrologic and geochemical conditions and heterogeneities in sediment physical and chemical properties both contributed to complex plume behavior and its persistence. Our analysis provides important insights into the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by surface water and groundwater interactions.

  9. New geologic mapping combined with geochemical, paleomagnetic, and high-precision 40Ar/39Ar analyses reveal multiple overlapping calderas formed 16.4-15.7 Ma at High Rock caldera complex, northwestern Nevada

    NASA Astrophysics Data System (ADS)

    Coble, M. A.; Mahood, G. A.

    2012-12-01

    We present new evidence from 1:100,000- and 1:24,000-scale geologic mapping for the presence of at least four overlapping calderas, 24 to 40 km in diameter, that formed in an interval of only 0.7 m.y. during the mid-Miocene at High Rock caldera complex in northwest Nevada and southern Oregon. In total, an estimated minimum volume of ~725 km3 of rhyolitic magma erupted from the complex between 16.5 and 15.5 Ma, covering an area of ~9,000 km2. Rapid eruption of numerous units at volumetric rates as high as 3,000-4,000 km3/m.y., strong welding of lithic-poor ignimbrites, extensive vapor-phase alteration of lavas and ignimbrites alike, a limited range of phenocryst content and assemblage, silicification along faults, and a lack of well-exposed stratigraphic sections has hindered previous reconnaissance-scale mapping and identification of caldera centers. Calderas are located based on truncation of precaldera rhyolitic lavas by caldera topographic walls, by arcuate patterns of rhyolite lavas that erupted along buried caldera ring faults, and by the presence of pumiceous caldera lake sediments. We attribute formation of the Virgin Valley, Badger Mountain, Hanging Rock, and Cottonwood Creek Calderas to collapse on eruption, respectively, of the ca. 16.37 Ma Idaho Canyon Tuff, the 16.34 Ma Summit Lake Tuff, the 16.0 Ma Soldier Meadows Tuff, and the 15.7 Ma Tuff of Yellow Rock Canyon. Additional smaller-volume pyroclastic units erupted during emplacement of geochemically similar rhyolitic lavas. More than 60 new 40Ar/39Ar ages were obtained on ignimbrites, fall deposits, and rhyolitic, trachytic and basaltic lavas. Many of the eruptive units in the HRCC differ in age by less than 100 k.y., which, at ca. 16 Ma, requires precision at the 1-2‰ (2σ standard error) level to distinguish units using 40Ar/39Ar geochronology. The high-precision of the analyses of sanidine in the rhyolites, coupled with geochemical and paleomagnetic measurements, allowed us to correlate far

  10. Assembly, characterization, and electrochemical properties of immobilized metal bipyridyl complexes on silicon(111) surfaces.

    PubMed

    Lattimer, Judith R C; Blakemore, James D; Sattler, Wesley; Gul, Sheraz; Chatterjee, Ruchira; Yachandra, Vittal K; Yano, Junko; Brunschwig, Bruce S; Lewis, Nathan S; Gray, Harry B

    2014-10-28

    Silicon(111) surfaces have been functionalized with mixed monolayers consisting of submonolayer coverages of immobilized 4-vinyl-2,2'-bipyridyl (1, vbpy) moieties, with the remaining atop sites of the silicon surface passivated by methyl groups. As the immobilized bipyridyl ligands bind transition metal ions, metal complexes can be assembled on the silicon surface. X-ray photoelectron spectroscopy (XPS) demonstrates that bipyridyl complexes of [Cp*Rh], [Cp*Ir], and [Ru(acac)2] were formed on the surface (Cp* is pentamethylcyclopentadienyl, acac is acetylacetonate). For the surface prepared with Ir, X-ray absorption spectroscopy at the Ir LIII edge showed an edge energy as well as post-edge features that were essentially identical with those observed on a powder sample of [Cp*Ir(bpy)Cl]Cl (bpy is 2,2'-bipyridyl). Charge-carrier lifetime measurements confirmed that the silicon surfaces retain their highly favorable photoelectronic properties upon assembly of the metal complexes. Electrochemical data for surfaces prepared on highly doped, n-type Si(111) electrodes showed that the assembled molecular complexes were redox active. However the stability of the molecular complexes on the surfaces was limited to several cycles of voltammetry.

  11. 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

    USGS Publications Warehouse

    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.

  12. Inhibiting Smooth Muscle Cell Proliferation via Immobilization of Heparin/Fibronectin Complexes on Titanium Surfaces.

    PubMed

    Li, Gui Cai; Xu, Qi Fei; Yang, Ping

    2015-05-01

    The aim of this study was to investigate the inhibitory effect of heparin/fibronectin (Hep/Fn) complexes on neointimal hyperplasia following endovascular intervention. Hep/Fn complexes were immobilized onto titanium (Ti) surfaces, with subsequent X-ray photoelectron spectroscopy (XPS), Toluidine Blue O (TBO) and immunohistochemistry methods were used to characterize surface properties. Smooth muscle cell (SMC) cultures were used to evaluate the effect of Hep/Fn complexes on SMC proliferation. Results showed that Hep/Fn complexes successfully immobilized onto Ti surfaces and resulted in an inhibition of SMC proliferation. This study suggests that Hep/Fn surface-immobilized biomaterials develop as a new generation of biomaterials to prevent neointimal hyperplasia, particularly for use in cardiovascular implants. PMID:26055566

  13. EXAFS Study of Uranyl Complexation at Pseudomonas fluorescens Cell Surfaces

    NASA Astrophysics Data System (ADS)

    Bencheikh, R.; Bargar, J. R.; Tebo, B. M.

    2002-12-01

    Little is known about the roles of microbial biomass as a sink and source for uranium in contaminated aquifers, nor of the impact of bacterial biochemistry on uranium speciation in the subsurface. A significant role is implied by the high affinities of both Gram positive and Gram negative cells for binding uranyl (UO2{ 2+}). In the present study, Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy was used to identify membrane functional groups involved in uranyl binding to the Gram negative bacterium Pseudomonas fluorescens from pH 3 to pH 8. Throughout this pH-range, EXAFS spectra can be described primarily in terms of coordination of carboxylic groups to uranyl. U-C distances characteristic of 4-, 5- and 8- membered rings were observed, as well as the possibility of phosphato groups. Both shell-by-shell fits and principle component analyses indicate that the functional groups involved in binding of uranyl to the cell surface do not vary systematically across the pH range investigated. This result contrasts with EXAFS results of uranyl sorbed to Gram positive bacteria, and suggests an important role for long-chain carboxylate-terminated membrane functional groups in binding uranyl.

  14. Geochronology and isotopic-geochemical characteristics of magmatic complexes of gold-silver ore-magmatic structures in the Chukotka sector of the Russian Arctic coast

    NASA Astrophysics Data System (ADS)

    Sakhno, V. G.; Grigoriev, N. V.; Kurashko, V. V.

    2016-05-01

    The first results of SHRIMP dating of magmatic complexes and associated gold-silver deposits and ore occurrences (Kupol, Dvoinoe, Moroshka, and others) in the Chukotka sector of the Russian Arctic coast are discussed. The petrological and isotopic-geochronological data are used for reconstructing their formation conditions.

  15. Open geochemical database

    NASA Astrophysics Data System (ADS)

    Zhilin, Denis; Ilyin, Vladimir; Bashev, Anton

    2010-05-01

    We regard "geochemical data" as data on chemical parameters of the environment, linked with the geographical position of the corresponding point. Boosting development of global positioning system (GPS) and measuring instruments allows fast collecting of huge amounts of geochemical data. Presently they are published in scientific journals in text format, that hampers searching for information about particular places and meta-analysis of the data, collected by different researchers. Part of the information is never published. To make the data available and easy to find, it seems reasonable to elaborate an open database of geochemical information, accessible via Internet. It also seems reasonable to link the data with maps or space images, for example, from GoogleEarth service. For this purpose an open geochemical database is being elaborating (http://maps.sch192.ru). Any user after registration can upload geochemical data (position, type of parameter and value of the parameter) and edit them. Every user (including unregistered) can (a) extract the values of parameters, fulfilling desired conditions and (b) see the points, linked to GoogleEarth space image, colored according to a value of selected parameter. Then he can treat extracted values any way he likes. There are the following data types in the database: authors, points, seasons and parameters. Author is a person, who publishes the data. Every author can declare his own profile. A point is characterized by its geographical position and type of the object (i.e. river, lake etc). Value of parameters are linked to a point, an author and a season, when they were obtained. A user can choose a parameter to place on GoogleEarth space image and a scale to color the points on the image according to the value of a parameter. Currently (December, 2009) the database is under construction, but several functions (uploading data on pH and electrical conductivity and placing colored points onto GoogleEarth space image) are

  16. Geochemical Interpretation of Collision Volcanism

    NASA Astrophysics Data System (ADS)

    Pearce, Julian

    2014-05-01

    collision type with extreme LILE and significant HFSE enrichment relative to MORB and with large negative Nb-Ta and Ti anomalies. Post-collision volcanism is usually ascribed to combinations of slab detachment, delamination, and slab roll back (orogenic) and extension (post-orogenic). The magma source is typically conductively-heated, sub-continental mantle lithosphere with composition and depth of melting depending on the nature and evolution of the collision zone in question. Geochemical patterns may be similar to those of syn-collision basalts or of intraplate, continental basalts - or transitional between these. This variability in space and time, though problematic for geochemical fingerprinting, can give clues to the polarity and development of the collision zone, for example by highlighting the distribution of subduction-modified mantle lithosphere and hence of pre-collision subduction zones. One characteristic common to this setting is a high crustal input resulting from the presence of a hot, thick 'crustal chemical filter' which is evident on geochemical projections that highlight AFC-type processes. Using this, and other, geochemical features it is possible to develop methodologies to at least partly see through the complexity of collision terranes.

  17. Hydrological and geochemical investigations of selenium behavior at Kesterson Reservoir

    SciTech Connect

    Benson, S.M.; Tokunaga, T.K.; Zawislanski, P.; Yee, A.W.; Daggett, J.S.; Oldfather, J.M.; Tsao, L.; Johannis, P.W.

    1990-10-01

    From 1985 to the present we have studied the behavior of selenium in various habitats and environments at Kesterson reservoir, shifting emphasis as remedial actions altered the physical setting. Investigations have evaluated the efficacy of several remedial alternatives, from innovative techniques relying on the complex geochemical behavior of selenium alternatives, from innovative techniques relying on the complex geochemical behavior of selenium in aquatic environments to conventional excavation schemes. Results of these studies supported two cost-effective remedial measures; drain water deliveries were terminated in 1986 and, in 1988, 1 million cubic yards of soil were imported and used to fill the low lying areas of the former Kesterson Reservoir. To date, these two actions appear to have eliminated the aquatic habitat that caused waterfowl death and deformity at Kesterson from the early 1980's to 1987. Biological, surface water and groundwater monitoring data collected by the USBR indicate that Kesterson is now a much safer environment than in past years when drainage water containing 300{mu}g/l of selenium was delivered to the Reservoir. The continued presence of a large inventory of selenium within the upper portions of unfilled areas of Kesterson Reservoir and immediately below the fill material requires that a continued awareness of the status of this inventory be maintained and improved upon. 83 refs., 130 figs., 19 tabs.

  18. VARIABLE BOUND-SITE CHARGING CONTRIBUTIONS TO SURFACE COMPLEXATION MASS ACTION EXPRESSIONS

    EPA Science Inventory

    One and two pK models of surface complexation reactions between reactive surface sites (>SOH) and the proton (H+) use mass action expressions of the form: Ka={[>SOHn-1z-1]g>SOH(0-1)aH+EXP(-xeY/kT)}/{[>SOHnz]g>SOH(n)} where Ka=the acidity constant, [ ]=reactive species concentrati...

  19. Surface-water-quality assessment of the upper Illinois River basin in Illinois, Indiana, and Wisconsin; spatial distribution of geochemicals in the fine fraction of streambed sediment, 1987

    USGS Publications Warehouse

    Fitzpatrick, Faith A.; Arnold, Terri L.; Colman, John A.

    1998-01-01

    Geochemical data for the upper Illinois River Basin are presented for concentrations of 39 elements in streambed sediment collected by the U.S. Geological Survey in the fall of 1987. These data were collected as part of the pilot phase of the National Water-Quality Assessment Program. A total of 372 sites were sampled, with 238 sites located on first- and second-order streams, and 134 sites located on main stems. Spatial distribution maps and exceedance probability plots are presented for aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, calcium, carbon (total, inorganic, and organic), cerium, chromium, cobalt, copper, gallium, iron, lanthanum, lead, lithium, magnesium, manganese, mercury, molybdenum, neodymium, nickel, niobium, phosphorus, potassium, scandium, selenium, silver, sodium, strontium, sulfur, thorium, titanium, uranium, vanadium, yttrium, and zinc. For spatial distribution maps, concentrations of the elements are grouped into four ranges bounded by the minimum concentration, the 10th, 50th, and 90th percentiles, and the maximum concentrations. These ranges were selected to highlight streambed sediment with very low or very high element concentrations relative to the rest of the streambed sediment in the upper Illinois River Basin. Exceedance probability plots for each element display the differences, if any, in distributions between high- and low-order streams and may be helpful in determining differences between background and elevated concentrations.

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

    PubMed Central

    Carroll, Susan A; Roberts, Sarah K; Criscenti, Louise J; O'Day, Peggy A

    2008-01-01

    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 a robust surface

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

    PubMed

    Carroll, Susan A; Roberts, Sarah K; Criscenti, Louise J; O'Day, Peggy A

    2008-01-01

    Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25 degrees 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 beta-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 beta-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 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 concentrations for the development of a robust

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

    SciTech Connect

    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

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

    PubMed

    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

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

    PubMed

    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

  5. Coeval potassic and sodic calc-alkaline series in the post-collisional Hercynian Tanncherfi intrusive complex, northeastern Morocco: geochemical, isotopic and geochronological evidence

    NASA Astrophysics Data System (ADS)

    Ajaji, Tamimount; Weis, Dominique; Giret, André; Bouabdellah, Mohamed

    1998-12-01

    The post-collisional late Hercynian Tanncherfi intrusive complex (TIC) is part of a widespread intrusive episode in the Moroccan Meseta. The complex contains a wide range of rock types, from monzogabbros to monzogranites. Two distinct magmatic series are recognized: (1) a potassic (shoshonitic) series consisting of monzogabbros, quartz monzonites and monzogranites; and (2) a sodic (granodioritic) series represented by quartz monzodiorites and granodiorites. All the Tanncherfi plutonic rocks display similar spider-diagram profiles, with LILE and LREE enrichment and Nb, Ta, Ti depletion, which are typical of subduction-related magmas. Combined major, trace element compositions and Sr, Nd isotopic results indicate that the two series have been derived from a LILE- and LREE-enriched continental lithospheric mantle source, under different partial melting and/or depth conditions. Intrusion of the Tanncherfi rocks was not temporally related to subduction and the enrichment of their source is likely to be linked to preceding subduction events. The two series evolved by fractional crystallization, of clinopyroxene, plagioclase, hornblende, biotite, K-feldspar and accessories (Fe-Ti oxide minerals, titanite, apatite and zircon) for the potassic series while the sodic series combined fractional crystallization with assimilation of felsic magmas with lower Sr isotopic ratio than the more mafic term of the series, the quartz monzodiorite. The intrusion of the potassic magmas (344±6 Ma) marks a major change in the tectonic regime of eastern Meseta. These magmas intruded during post-thickening uplift and extension, both probably favored by convective thinning of the lithosphere. This model provides a reasonable mechanism for the genesis of other Hercynian intrusive complexes in Morocco.

  6. Early Jurassic subduction of the Paleo-Pacific Ocean in NE China: Petrologic and geochemical evidence from the Tumen mafic intrusive complex

    NASA Astrophysics Data System (ADS)

    Guo, Feng; Li, Hongxia; Fan, Weiming; Li, Jingyan; Zhao, Liang; Huang, Miwei; Xu, Wenliang

    2015-05-01

    Subduction of the Paleo-Pacific Oceanic Plate is widely considered to have caused extensive Mesozoic magmatism, lithospheric deformation and mineralization in East Asia. However, it is still unclear when this subduction began. Here we report an Early Jurassic (~ 187 Ma) mafic intrusive complex (including olivine norite, gabbro, and diorite) from the Tumen area in NE China. The olivine norite contains a mineral assemblage of olivine, pyroxene, Ca-plagioclase, and hornblende that crystallized in a water-saturated parental magma. The rocks in the complex show variable degrees of plagioclase and ferromagnesian mineral accumulation as reflected by positive Sr and Eu anomalies in primitive mantle-normalized incompatible element patterns. Mass-balance calculations indicate that the parental magma was calc-alkaline with arc-type trace element features (i.e., large ion incompatible and light rare earth element enrichment and Nb-Ta depletion). It also had Sr-Nd-Hf isotopic compositions (87Sr/86Sr(i) = 0.7042 to 0.7044, εNd(t) = + 2.5 to + 3.5 and εHf(t) = + 8.4 to + 10.5) similar to those of modern arc basalts. The parental magma was likely derived from 5 to 20% melting of a mantle wedge metasomatized by an addition of 3-4% hydrous sediment melt from the subducting Paleo-Pacific Oceanic slab. The Tumen mafic intrusive complex, together with other contemporaneous mafic intrusions, I-type granitoids, and felsic lavas, constitutes an Early Jurassic N-S-trending arc magmatic belt that was formed by westward subduction of the Paleo-Pacific Ocean.

  7. Cork-resin ablative insulation for complex surfaces and method for applying the same

    NASA Technical Reports Server (NTRS)

    Walker, H. M.; Sharpe, M. H.; Simpson, W. G. (Inventor)

    1980-01-01

    A method of applying cork-resin ablative insulation material to complex curved surfaces is disclosed. The material is prepared by mixing finely divided cork with a B-stage curable thermosetting resin, forming the resulting mixture into a block, B-stage curing the resin-containing block, and slicing the block into sheets. The B-stage cured sheet is shaped to conform to the surface being insulated, and further curing is then performed. Curing of the resins only to B-stage before shaping enables application of sheet material to complex curved surfaces and avoids limitations and disadvantages presented in handling of fully cured sheet material.

  8. Oxidation of formic acid on platinum surfaces decorated with cobalt(III) macrocyclic complexes

    NASA Astrophysics Data System (ADS)

    Stevanović, S.; Babić-Samardžija, K.; Sovilj, S. P.; Tripković, A.; Jovanović, V. M.

    2009-09-01

    Platinum electrode decorated with three different mixed-ligand cobalt(III) complexes of the general formula [Co(Rdtc)cyclam](ClO4)2 [cyclam = 1,4,8,11-tetraazacyclotetradecane, Rdtc- = morpholine-(Morphdtc), piperidine-(Pipdtc), and 4-methylpiperidine-(4-Mepipdtc) dithiocarbamates, respectively] was used to study oxidation of formic acid in acidic solution. The complexes were adsorbed on differently prepared Pt surfaces, at open circuit potential. The preliminary results show increased catalytic activity of Pt for formic acid oxidation with complex ion adsorbed on the polycrystalline surfaces. The increase in catalytic activity depends on the structure of the complex applied and follows the order of metal-coordinated bidentate ligand as Morphdtc > Pipdtc > 4-Mepipdtc. Based on IR and NMR data, the main characteristics of the Rdtc ligands do not vary dramatically, but high symmetry of the corresponding complexes decreases in the same order. Accordingly, the complexes are distinctively more mobile, causing chemical interactions to occur on the surface with appreciable speed and enhanced selectivity. The effect of the complexes on catalytic activity presumably depends on structural changes on Pt surfaces caused by their adsorption.

  9. Multiple Plasmodium falciparum Merozoite Surface Protein 1 Complexes Mediate Merozoite Binding to Human Erythrocytes.

    PubMed

    Lin, Clara S; Uboldi, Alessandro D; Epp, Christian; Bujard, Hermann; Tsuboi, Takafumi; Czabotar, Peter E; Cowman, Alan F

    2016-04-01

    Successful invasion of human erythrocytes byPlasmodium falciparummerozoites is required for infection of the host and parasite survival. The early stages of invasion are mediated via merozoite surface proteins that interact with human erythrocytes. The nature of these interactions are currently not well understood, but it is known that merozoite surface protein 1 (MSP1) is critical for successful erythrocyte invasion. Here we show that the peripheral merozoite surface proteins MSP3, MSP6, MSPDBL1, MSPDBL2, and MSP7 bind directly to MSP1, but independently of each other, to form multiple forms of the MSP1 complex on the parasite surface. These complexes have overlapping functions that interact directly with human erythrocytes. We also show that targeting the p83 fragment of MSP1 using inhibitory antibodies inhibits all forms of MSP1 complexes and disrupts parasite growthin vitro.

  10. Structural, geochemical and geochronological analysis of metasedimentary and metavolcanic rocks of the Coatlaco area, Acatlán Complex, southern Mexico

    NASA Astrophysics Data System (ADS)

    Grodzicki, K. R.; Nance, R. D.; Keppie, J. D.; Dostal, J.; Murphy, J. B.

    2008-12-01

    Low-grade, siliciclastic metasedimentary and mafic metavolcanic rocks near Coatlaco, southern Mexico, form part of the Acatlán Complex, which has been interpreted as a vestige of either the Iapetus or Rheic Oceans. They form two tectonically interleaved units, the Canoas unit consisting of interbedded psammites and pelites, and the Coatlaco unit made up of interbedded quartzite and tholeiitic, within-plate, pillow basalts. Detrital zircons in these two units yielded different age population peaks: Ordovician (459 ± 14 Ma) and ca. 900-1250 Ma detrital zircons in the Canoas unit, and 357 ± 35 Ma, 563 ± 22 Ma, 837 ± 28 Ma, and 1156 ± 74 Ma in the Coatlaco unit. Whereas a source for the Paleozoic zircons may be found in the Acatlán Complex, and provenance for the ca. 900-1250 Ma zircons is likely the adjacent Oaxacan Complex, the Neoproterozoic zircons probably have a more exotic source in Amazonia. The contrasting age populations in the Canoas and Coatlaco units may be due to either (a) different ages of deposition, post-453 ± 6 Ma and post-Devonian, respectively; or (b) contemporaneous deposition in distinct environments; continental margin vs. oceanic with currents perpendicular and parallel to the margin, respectively. The Canoas unit was deformed by four phases of deformation: D 1 and D 2 produced NE-SW, steeply dipping, composite, axial planar solution cleavages (S CN1 and S CN2) with variably plunging, tight-isoclinal folds (F CN1 and F CN2) under lower greenschist facies metamorphic conditions; D 3 produced a sub-vertical, NE-SW, crenulation cleavage parallel to the axial planes of open to close folds, whose plunges show a NE-SW great circle distribution. D 4 produced small, vertically plunging chevron and kink folds (F CN4) in the pelitic rocks. The Coatlaco basalts are massive, lack deformational fabrics, and were altered under greenschist facies metamorphic conditions. The Coatlaco quartzites, in contrast, record two phases of deformation; (i) an S

  11. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    SciTech Connect

    Stack, Andrew G.; Kent, Paul R. C.

    2014-11-10

    Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineral surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.

  12. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    DOE PAGES

    Stack, Andrew G.; Kent, Paul R. C.

    2014-11-10

    Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineralmore » surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.« less

  13. The IUGS/IAGC Task Group on Global Geochemical Baselines

    USGS Publications Warehouse

    Smith, David B.; Wang, Xueqiu; Reeder, Shaun; Demetriades, Alecos

    2012-01-01

    The Task Group on Global Geochemical Baselines, operating under the auspices of both the International Union of Geological Sciences (IUGS) and the International Association of Geochemistry (IAGC), has the long-term goal of establishing a global geochemical database to document the concentration and distribution of chemical elements in the Earth’s surface or near-surface environment. The database and accompanying element distribution maps represent a geochemical baseline against which future human-induced or natural changes to the chemistry of the land surface may be recognized and quantified. In order to accomplish this long-term goal, the activities of the Task Group include: (1) developing partnerships with countries conducting broad-scale geochemical mapping studies; (2) providing consultation and training in the form of workshops and short courses; (3) organizing periodic international symposia to foster communication among the geochemical mapping community; (4) developing criteria for certifying those projects whose data are acceptable in a global geochemical database; (5) acting as a repository for data collected by those projects meeting the criteria for standardization; (6) preparing complete metadata for the certified projects; and (7) preparing, ultimately, a global geochemical database. This paper summarizes the history and accomplishments of the Task Group since its first predecessor project was established in 1988.

  14. Integrating geochemical (surface waters, stream sediments) and biological (diatoms) approaches to assess AMD environmental impact in a pyritic mining area: Aljustrel (Alentejo, Portugal).

    PubMed

    Luís, Ana Teresa; Durães, Nuno; de Almeida, Salomé Fernandes Pinheiro; da Silva, Eduardo Ferreira

    2016-04-01

    Aljustrel mines were classified as having high environmental hazard due to their large tailings volume and high metal concentrations in waters and sediments. To assess acid mine drainage impacted systems whose environmental conditions change quickly, the use of biological indicators with short generation time such as diatoms is advantageous. This study combined geochemical and diatom data, whose results were highlighted in 3 groups: Group 1, with low pH (1.9-5.1) and high metal/metalloid (Al, As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn; 0.65-1032 mg/L) and SO4 (405-39124 mg/L) concentrations. An acidophilic species, Pinnularia aljustrelica, was perfectly adapted to the adverse conditions; in contrast, teratological forms of Eunotia exigua were found, showing that metal toxicity affected this species. The low availability of metals/metalloids in sediments of this group indicates that metals/metalloids of the exchangeable fractions had been solubilized, which in fact enables metal/metalloid diatom uptake and consequently the occurrence of teratologies; Group 2, with sites of near neutral pH (5.0-6.8) and intermediate metal/metalloid (0.002-6 mg/L) and SO4 (302-2179 mg/L) concentrations; this enabled the existence of typical species of uncontaminated streams (Brachysira neglectissima, Achnanthidium minutissimum); Group 3, with samples from unimpacted sites, showing low metal/metalloid (0-0.8 mg/L) and SO4 (10-315 mg/L) concentrations, high pH (7.0-8.4) and Cl contents (10-2119 mg/L) and the presence of brackish to marine species (Entomoneis paludosa). For similar conditions of acidity, differences in diversity, abundance and teratologies of diatoms can be explained by the levels of metals/metalloids. PMID:27090714

  15. Crystal mat-formation as an igneous layering-forming process: Textural and geochemical evidence from the 'lower layered' nepheline syenite sequence of the Ilímaussaq complex, South Greenland

    NASA Astrophysics Data System (ADS)

    Lindhuber, Matthias J.; Marks, Michael A. W.; Bons, Paul D.; Wenzel, Thomas; Markl, Gregor

    2015-05-01

    The lower layered nepheline syenite sequence (kakortokites) of the Mesoproterozoic alkaline to peralkaline Ilímaussaq complex, South Greenland shows spectacular rhythmic meter-scale igneous layering. The 29 exposed units have sharp contacts against each other and each of these units consists of three modally graded layers dominated by arfvedsonitic amphibole, eudialyte-group minerals, and alkali feldspar, respectively. This study uses field observations on changes in mineral orientation, recurrent mineral textures, compositional data from eudialyte-group minerals and amphibole, and settling rate calculations based on a modified Stokes' equation to explain the igneous layering of the kakortokites. We propose that the three major cumulus minerals (amphibole, eudialyte s.l., and alkali feldspar) were separated from each other by density contrasts, resulting in modally graded layers within each unit. The densest of these three minerals (amphibole) formed crystal mats within the cooling magma body. These crystal mats acted as barriers that inhibited large-scale vertical migration of melts and crystals with increasing effectiveness over time. The sub-volumes of magma captured in between the crystal mats evolved largely as geochemically independent sub-systems, as indicated by the observed trends in mineral composition.

  16. Geometric and kinematic analysis, and geochemical study of the Corbin Gneiss Complex and its associated sheared rocks in the Blue Ridge of NW Georgia

    SciTech Connect

    Gargi, S.P.

    1985-01-01

    The Corbin Gneiss Complex forms the core of the Salem Church anticlinorium in the Blue Ridge of NW Georgia, and is composed of quartz monzodiorite (Corbin gneiss) and pyroxene-biotite diorite. The observed foliation and the presence of thin zones of ultramylonites and phyllonites in the rocks of the gneiss complex are the result of the ductile shearing. Subsequent to the development of the mylonitic foliation these rocks were subjected for four episodes of flexural slip folding. The first generation folds were associated with the formation of the Salem Church anticlinorium. The northeasterly striking axial planes and the southeasterly plunging fold axes of the last three systems of folds suggest that these folds were formed on the southeasterly dipping foliation planes of the Salem Church anticlinorium. The trace element study of the pyroxene-biotite diorite, the Corbin gneiss (quartz monzodiorite) including its variably sheared equivalents shows that these rocks originated from independent sources by primary petrogenetic processes, and do not show any mixing relationship. The whole rock Rb-Sr isochron of the ultramylonitic Corbin gneiss yields an age of 296 +/- 4 Ma and an initial /sup 87/Sr//sup 86/Sr ratio of 0.7208 +/- 7. The much younger age of the ultramylonite in comparison to that of the unsheared Corbin gneiss (age approx. 1 Ga) is the result of resetting of the Rb-Sr systematics of the latter due to shearing, and denotes the minimum age limit of the shearing. A two point whole rock isochron of the diorite gives an apparent age of 1.22 Ga and an initial /sup 87/Sr//sup 86/Sr ratio of 0.7036. The total crustal age of the diorite is slightly greater than the Corbin gneiss.

  17. Geochemical modeling: a review

    SciTech Connect

    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.

  18. Complex technology of vacuum-arc processing of structural material surface

    NASA Astrophysics Data System (ADS)

    Arustamov, V. N.; Ashurov, Kh. B.; Kadyrov, Kh. Kh.; Khudoikulov, I. Kh.

    2015-08-01

    The development of environmentally friendly and energy-resource-saving technologies based on vacuum arc discharge is a topical problem in science and engineering. In view of their unique properties, cathode spots of a vacuum arc induce cleaning of the surface of an article (cathode) from various contaminations and pulsed thermal action on the surface layers. These processes occur in complex with vacuum-arc deposition of coatings in the same technological cycle, which makes it possible to considerably increase the efficiency of methods for changing physical, mechanical, and chemical properties of the surface of steel articles, which considerably increase their service life. Analysis of the formation of the temperature regime of the surface during vacuum arc action and of the parameters of the deposited coating will make it possible to optimize the regimes of complex treatment of the surfaces of articles and is of considerable theoretical and practical importance.

  19. Cd adsorption onto Anoxybacillus flavithermus: Surface complexation modeling and spectroscopic investigations

    SciTech Connect

    Burnett, Peta-Gaye; Daughney, Christopher J.; Peak, Derek

    2008-06-09

    Several recent studies have applied surface complexation theory to model metal adsorption behaviour onto mesophilic bacteria. However, no investigations have used this approach to characterise metal adsorption by thermophilic bacteria. In this study, we perform batch adsorption experiments to quantify cadmium adsorption onto the thermophile Anoxybacillus flavithermus. Surface complexation models (incorporating the Donnan electrostatic model) are developed to determine stability constants corresponding to specific adsorption reactions. Adsorption reactions and stoichiometries are constrained using spectroscopic techniques (XANES, EXAFS, and ATR-FTIR). The results indicate that the Cd adsorption behaviour of A. flavithermus is similar to that of other mesophilic bacteria. At high bacteria-to-Cd ratios, Cd adsorption occurs by formation of a 1:1 complex with deprotonated cell wall carboxyl functional groups. At lower bacteria-to-Cd ratios, a second adsorption mechanism occurs at pH > 7, which may correspond to the formation of a Cd-phosphoryl, CdOH-carboxyl, or CdOH-phosphoryl surface complex. X-ray absorption spectroscopic investigations confirm the formation of the 1:1 Cd-carboxyl surface complex, but due to the bacteria-to-Cd ratio used in these experiments, other complexation mechanism(s) could not be unequivocally resolved by the spectroscopic data.

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

    NASA Astrophysics Data System (ADS)

    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

  1. Reply to the comment by L.-O. Öhman on "speciation of aqueous mononuclear" Al(III)-hydroxo and other Al(III) complexes at concentrations of geochemical relevance by aluminum-27 nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Faust, Bruce C.; Labiosa, William B.; Dai, K'O. H.; MacFall, Janet S.; Browne, Bryant A.; Ribeiro, Anthony A.; Richter, Daniel D.

    1997-08-01

    To summarize, it is important to recognize that (1) the major objective of our GCA paper (Faust et al., 1995) was on the development of 27Al NMR spectroscopy for characterizing mononuclear Al (III) species at concentrations of geochemical relevance; (2) Öhman has only minor comments related to this major objective; and (3) these comments are rebutted above in section 1. We appreciate Öhman's suggestion to consider adsorption of Al(III) onto the Teflon NMR sample bottle. Indeed, a small but significant percentage of Al(III) was adsorbed to the surfaces of the Teflon NMR sample bottle under the conditions of our experiments, partially accounting for the decrease in total concentration of mononuclear Al(III) species that was detected by 27Al NMR spectroscopy. As noted above in section 1, since the 27Al NMR spectroscopic parameters are not affected by decreases in total concentration of mononuclear Al(III) species, this does not affect the interpretation of the 27Al NMR chemical shifts or linewidths.

  2. Managing complexity in simulations of land surface and near-surface processes

    DOE PAGES

    Coon, Ethan T.; Moulton, J. David; Painter, Scott L.

    2016-01-12

    Increasing computing power and the growing role of simulation in Earth systems science have led to an increase in the number and complexity of processes in modern simulators. We present a multiphysics framework that specifies interfaces for coupled processes and automates weak and strong coupling strategies to manage this complexity. Process management is enabled by viewing the system of equations as a tree, where individual equations are associated with leaf nodes and coupling strategies with internal nodes. A dynamically generated dependency graph connects a variable to its dependencies, streamlining and automating model evaluation, easing model development, and ensuring models aremore » modular and flexible. Additionally, the dependency graph is used to ensure that data requirements are consistent between all processes in a given simulation. Here we discuss the design and implementation of these concepts within the Arcos framework, and demonstrate their use for verification testing and hypothesis evaluation in numerical experiments.« less

  3. Application of surface complexation models to anion adsorption by natural materials.

    PubMed

    Goldberg, Sabine

    2014-10-01

    Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation-transport models is critical. PMID:24619924

  4. 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)

    NASA Astrophysics Data System (ADS)

    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 (<5 to >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

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

    PubMed

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

    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(-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 qCO2. Significant correlations were found between the dissolved metal content and the microbiological health parameters, a negative one for Cmic/Corg ratio, and a positive one for qCO2. 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.

  6. The measurement of optical reflector with complex surface using nano-CMM

    NASA Astrophysics Data System (ADS)

    Wu, Zhichao; Guo, Tong; Chen, Jinping; Fu, Xing; Hu, Xiaotang

    2012-11-01

    Among variety of methods to measure complex surfaces, coordinate measurement is widely used in reverse engineering and measuring complex topography. In this paper, a coordinate measuring system based on 3D tactile probe is introduced. This system can measure complex surface with resolution of 1nm, measuring range of 25mm×25mm×5mm. The component of the measuring system, the principle and advantages of the probe are also introduced as the major part. We used the nano-CMM to test an optical reflector with sine curve surface. The fluctuation of the topography is about 5 micrometers. The result is compared with the data of AFM and the source of deviation is analyzed in the conclusions.

  7. Polyampholyte/surfactant complexes at the water-air interface: a surface tension study.

    PubMed

    Fechner, Mabya; Koetz, Joachim

    2013-06-25

    The present paper is related to interactions between strongly alternating polyampholytes, i.e., copolymers of N,N'-diallyl-N,N'-dimethylammonium chloride and maleamic acid derivatives, varying in hydrophobicity and excess charges and the oppositely charged anionic surfactant sodium dodecyl sulfate (SDS). Surface tension measurements have revealed a complex behavior with the formation of polyampholyte-SDS complexes at water-air interfaces which depends on both the hydrophobic character of the polyampholyte and electrostatic attractive forces between the polyampholyte and the anionic surfactant in dependence on pH. Hereby, maleamic acid copolymers with additional carboxylic groups in the phenylic side chain show a significant lower surface tension at the critical association concentration (CAC) due to the formation of surface-active SDS complexes and multicomplexes. In the presence of only one carboxylic group in the p-position the CAC can be strongly shifted by varying the pH due to repulsive electrostatic interactions.

  8. Geobiochemistry: Placing Biochemistry in Its Geochemical Context

    NASA Astrophysics Data System (ADS)

    Shock, E.; Boyer, G. M.; Canovas, P. A., III; Prasad, A.; Dick, J. M.

    2014-12-01

    Goals of geobiochemistry include simultaneously evaluating the relative stabilities of microbial cells and minerals, and predicting how the composition of biomolecules can change in response to the progress of geochemical reactions. Recent developments in theoretical geochemistry make it possible to predict standard thermodynamic properties of proteins, nucleotides, lipids, and many metabolites including the constituents of the citric acid cycle, at all temperatures and pressures where life is known to occur, and beyond. Combining these predictions with constraints from geochemical data makes it possible to assess the relative stabilities of biomolecules. Resulting independent predictions of the environmental occurrence of homologous proteins and lipid side-chains can be compared with observations from metagenomic and metalipidomic data to quantify geochemical driving forces that shape the composition of biomolecules. In addition, the energetic costs of generating biomolecules from within a diverse range of habitable environments can be evaluated in terms of prevailing geochemical variables. Comparisons of geochemical bioenergetic calculations across habitats leads to the generalization that the availability of H2 determines the cost of autotrophic biosynthesis relative to the aquatic environment external to microbial cells, and that pH, temperature, pressure, and availability of C, N, P, and S are typically secondary. Increasingly reduced conditions, which are determined by reactions of water with mineral surfaces and mineral assemblages, allow many biosynthetic reactions to shift from costing energy to releasing energy. Protein and lipid synthesis, as well as the reverse citric acid cycle, become energy-releasing processes under these conditions. The resulting energy balances that determine habitability contrast dramatically with assumptions derived from oxic surface conditions, such as those where human biochemistry operates.

  9. Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

    PubMed

    Mocchiutti, Paulina; Schnell, Carla N; Rossi, Gerardo D; Peresin, María S; Zanuttini, Miguel A; Galván, María V

    2016-10-01

    Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper.

  10. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    NASA Astrophysics Data System (ADS)

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-Dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-12-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.

  11. A Field-Scale Reactive Transport Model for U(VI) Migration Influenced by Coupled Multirate Mass Transfer and Surface Complexation Reactions

    SciTech Connect

    Ma, Rui; Zheng, Chunmiao; Prommer, Henning; Greskowiak, Janek; Liu, Chongxuan; Zachara, John M.; Rockhold, Mark L.

    2010-05-06

    A field-scale reactive transport model was developed that incorporates laboratory-characterized U(VI) surface complexation reactions (SCR) and multi-rate mass transfer processes, and field-measured hydrogeochemical conditions at Department of Energy, Hanford 300A site, Washington, where an Integrated Field Research Challenge project is ongoing. The model was used to assess the importance of multi-rate mass transfer processes on sorption-retarded U(VI) reactive transport at the 300A site and to evaluate the effect of variable geochemical conditions on U(VI) plume migration caused by dynamic river stage fluctuations at the east side of the site. Model simulations revealed a complex spatio-temporal variations of groundwater geochemistry that affects U(VI) speciation, adsorption, and plume migration. In general, the river water intrusion enhances uranium adsorption and lowers groundwater aqueous uranium concentration as a result of river water dilution that decreases aqueous carbonate concentration, which subsequently weakens aqueous U(VI)-carbonate complexation and enhances U(VI)-surface complexation. The simulations also found that SCR-retarded U migration becomes more dynamic and more in sync with the groundwater flow field when multi-rate mass transfer processes are involved. Strong U(VI) adsorption was simulated at the 300A site based on the field-measured hydrogeochemical conditions, suggesting a slow dissipation of U(VI) plume, a phenomenon consistent with the observation at the site. Uranium breakthrough curves at selected observation points and the mass changes over time in the simulation indicate that uranium adsorption/desorption never attains steady state as a result of both the highly dynamic flow field and the chemistry variations caused by river water intrusion. Thus, the multi-rate SCM model appears to be a crucial feature for future reactive transport simulations of uranium at the 300A site.

  12. Surface plasmon resonance biosensor as a tool for the measurement of complex refractive indices.

    PubMed

    Filion-Cote, Sandrine; Tabrizian, Maryam; Kirk, Andrew G

    2015-01-01

    Optical characterisation of liquids through the measurement of their complex refractive index is critical in environmental monitoring, food industry and medicine. While surface plasmon resonance is widely used for measurement of the real part of the refractive index there have been few studies to date on measurement of complex refractive index with this method. We present a systematic study which highlights the challenges associated with this approach. Instrument design and data analysis techniques are presented together with preliminary experimental results. PMID:26737760

  13. Complex organic molecules at metal surfaces: bonding, organisation and chirality [review article

    NASA Astrophysics Data System (ADS)

    Barlow, S. M.; Raval, R.

    2003-08-01

    Surface science techniques have now reached a stage of maturity that has enabled their successful deployment in the study of complex adsorption systems. A particular example of this success has been the understanding that has been gained regarding the behaviour of multi-functional organic molecules at metal surfaces. These organic-metal systems show enormous diversity, starting from their local description which can vary in terms of chemical structure, orientation and bonding. Additionally, in many cases, these complex organic molecules self-organise into beautiful, ordered superstructures held together by networks of intermolecular bonds. Both these aspects enable a single organic molecule-metal system to exhibit a wide-ranging and flexible approach to its environment, leading to a variety of adsorption phases, according to the prevailing temperature and coverage conditions. In this review we have attempted to capture this complexity by constructing adsorption phase diagrams from the available literature for complex carboxylic acids, amino acids, anhydrides and ring systems, all deposited under controlled conditions onto defined metal surfaces. These provide an accessible, pictorial basis of the adsorption phases which are then discussed further in the text of the review. Finally, interest has recently focused on the property of chirality that can be bestowed at an achiral metal surface by the adsorption of these complex organic molecules. The creation of such architectures offers the opportunity for ultimate stereocontrol of reactions and responses at surfaces. We have, therefore, specifically examined the various ways in which chirality can be expressed at a surface and provide a framework for classifying chiral hierarchies that are manifested at surfaces, with particular attention being paid to the progression of chirality from a local to a global level.

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

    PubMed

    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.

  15. Testing Limits on Matte Surface Color Perception in Three-Dimensional Scenes with Complex Light Fields

    PubMed Central

    Doerschner, K.; Boyaci, H.; Maloney, L. T.

    2007-01-01

    We investigated limits on the human visual system’s ability to discount directional variation in complex lights field when estimating Lambertian surface color. Directional variation in the light field was represented in the frequency domain using spherical harmonics. The bidirectional reflectance distribution function of a Lambertian surface acts as a low-pass filter on directional variation in the light field. Consequently, the visual system needs to discount only the low-pass component of the incident light corresponding to the first nine terms of a spherical harmonics expansion (Basri & Jacobs, 2001; Ramamoorthi & Hanrahan, 2001) to accurately estimate surface color. We test experimentally whether the visual system discounts directional variation in the light field up to this physical limit. Our results are consistent with the claim that the visual system can compensate for all of the complexity in the light field that affects the appearance of Lambertian surfaces. PMID:18053846

  16. Toroidal surface complexes of bacteriophage {phi}12 are responsible for host-cell attachment

    SciTech Connect

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

    2011-06-05

    Cryo-electron tomography and subtomogram averaging are utilized to determine that the bacteriophage {phi}12, 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 {phi}12 demonstrates that the gene for the hexameric spike is located in {phi}12'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 {phi}12 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.

  17. Controlled fragrant molecule release from surface-tethered cyclodextrin host-guest inclusion complexes.

    PubMed

    Schofield, W C E; Badyal, J P S

    2011-06-01

    β-cyclodextrin barrels can be tethered to solid surfaces using the Williamson ether synthesis reaction via an intermediate pulsed plasma deposited poly(4-vinylbenzyl chloride) linker layer. The loading and release of perfume molecules through host-guest inclusion complex formation with surface tethered β-cyclodextrin has been followed by infrared spectroscopy and quartz crystal microbalance measurements. Fragrance release lasts for several months and can be easily recharged.

  18. Chilling out: a cool aqueous environment promotes the formation of gas-surface complexes.

    PubMed

    Ota, Stephanie T; Richmond, Geraldine L

    2011-05-18

    SO(2), an important atmospheric pollutant, has been implicated in environmental phenomena such as acid rain, climate change, and cloud formation. In addition, SO(2) is fundamentally interesting because it forms spectroscopically identifiable complexes with water at aqueous surfaces. Vibrational sum frequency spectroscopy (VSFS) is used here to further investigate the mechanism by which SO(2) adsorbs to water at tropospherically relevant temperatures (0-23 °C). The spectral results lead to two important conclusions. SO(2) surface affinity is enhanced at colder temperatures, with nearly all of the topmost water molecules showing evidence of binding to SO(2) at 0 °C as compared to a much lower fraction at room temperature. This surface adsorption results in significant changes in water orientation at the surface, but is reversible at the temperatures examined here. Second, the SO(2) complex formation at aqueous surfaces is independent of aqueous solution acidity. One challenge in previous uptake studies was the ability to distinguish between the effects of surface adsorption as compared to bulk accommodation. The surface and vibrational specificity of these studies make this distinction possible, allowing a selective study of how the aqueous properties temperature and pH influence SO(2) surface affinity.

  19. Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface

    SciTech Connect

    Russell, Selena M.; Kim, Yousoo; Liu, Da-Jiang; Evans, J. W.; Thiel, P. A.

    2013-02-15

    We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution.

  20. High bandwidth linear viscoelastic properties of complex fluids from the measurement of their free surface fluctuations

    NASA Astrophysics Data System (ADS)

    Pottier, Basile; Talini, Laurence; Frétigny, Christian

    2012-02-01

    We present a new optical method to measure the linear viscoelastic properties of materials, ranging from complex fluids to soft solids, within a large frequency range (about 0.1--10^4 Hz). The surface fluctuation specular reflection technique is based on the measurement of the thermal fluctuations of the free surfaces of materials at which a laser beam is specularly reflected. The propagation of the thermal surface waves depends on the surface tension, density, and complex viscoelastic modulus of the material. For known surface tension and density, we show that the frequency dependent elastic and loss moduli can be deduced from the fluctuation spectrum. Using a viscoelastic solid (a cross-linked PDMS), which linear viscoelastic properties are known in a large frequency range from rheometric measurements and the time--temperature superposition principle, we show that there is a good agreement between the rheological characterization provided by rheometric and fluctuation measurements. We also present measurements conducted with complex fluids that are supramolecular polymer solutions. The agreement with other low frequency and high frequency rheological measurements is again very good, and we discuss the sensitivity of the technique to surface viscoelasticity.

  1. Electromagnetic wave band structure due to surface plasmon resonances in a complex plasma.

    PubMed

    Vladimirov, S V; Ishihara, O

    2016-07-01

    The dielectric properties of complex plasma containing either metal or dielectric spherical inclusions (macroparticles, dust) are investigated. We focus on surface plasmon resonances on the macroparticle surfaces and their effect on electromagnetic wave propagation. It is demonstrated that the presence of surface plasmon oscillations can significantly modify plasma electromagnetic properties by resonances and cutoffs in the effective permittivity. This leads to related branches of electromagnetic waves and to the wave band gaps. The conditions necessary to observe the band-gap structure in laboratory dusty plasma and/or space (cosmic) dusty plasmas are discussed.

  2. Electromagnetic wave band structure due to surface plasmon resonances in a complex plasma.

    PubMed

    Vladimirov, S V; Ishihara, O

    2016-07-01

    The dielectric properties of complex plasma containing either metal or dielectric spherical inclusions (macroparticles, dust) are investigated. We focus on surface plasmon resonances on the macroparticle surfaces and their effect on electromagnetic wave propagation. It is demonstrated that the presence of surface plasmon oscillations can significantly modify plasma electromagnetic properties by resonances and cutoffs in the effective permittivity. This leads to related branches of electromagnetic waves and to the wave band gaps. The conditions necessary to observe the band-gap structure in laboratory dusty plasma and/or space (cosmic) dusty plasmas are discussed. PMID:27575225

  3. Analytical estimation of solid angle subtended by complex well-resolved surfaces for infrared detection studies.

    PubMed

    Mahulikar, Shripad P; Potnuru, Santosh K; Kolhe, Pankaj S

    2007-08-01

    The solid angle (Omega) subtended by the hot power-plant surfaces of a typical fighter aircraft, on the detector of an infrared (IR) guided missile, is analytically obtained. The use of the parallel rays projection method simplifies the incorporation of the effect of the optical blocking by engine surfaces, on Omega-subtended. This methodology enables the evaluation of the relative contribution of the IR signature from well-resolved distributed sources, and is important for imaging infrared detection studies. The complex 3D surface of a rear fuselage is projected onto an equivalent planar area normal to the viewing aspect, which would give the same Omega-subtended. PMID:17676106

  4. The synthesis of nanocomposite structures on the surface of geometrically complex products

    NASA Astrophysics Data System (ADS)

    Brzhozovsky, B.; Martynov, V.; Zinina, E.; Brovkova, M.; Bochkarev, P.

    2016-07-01

    The paper presents the technology of nanocomposite structure synthesis in the surface layer of geometrically complex products under the impact of low-temperature plasma and the results of experimental study of their properties. An example is given of practical application of the nanocomposite structure product to improve the efficiency of ultrasonic dimensional processing.

  5. Stable U(IV) complexes form at high-affinity mineral surface sites.

    PubMed

    Latta, Drew E; Mishra, Bhoopesh; Cook, Russell E; Kemner, Kenneth M; Boyanov, Maxim I

    2014-01-01

    Uranium (U) poses a significant contamination hazard to soils, sediments, and groundwater due to its extensive use for energy production. Despite advances in modeling the risks of this toxic and radioactive element, lack of information about the mechanisms controlling U transport hinders further improvements, particularly in reducing environments where U(IV) predominates. Here we establish that mineral surfaces can stabilize the majority of U as adsorbed U(IV) species following reduction of U(VI). Using X-ray absorption spectroscopy and electron imaging analysis, we find that at low surface loading, U(IV) forms inner-sphere complexes with two metal oxides, TiO2 (rutile) and Fe3O4 (magnetite) (at <1.3 U nm(-2) and <0.037 U nm(-2), respectively). The uraninite (UO2) form of U(IV) predominates only at higher surface loading. U(IV)-TiO2 complexes remain stable for at least 12 months, and U(IV)-Fe3O4 complexes remain stable for at least 4 months, under anoxic conditions. Adsorbed U(IV) results from U(VI) reduction by Fe(II) or by the reduced electron shuttle AH2QDS, suggesting that both abiotic and biotic reduction pathways can produce stable U(IV)-mineral complexes in the subsurface. The observed control of high-affinity mineral surface sites on U(IV) speciation helps explain the presence of nonuraninite U(IV) in sediments and has important implications for U transport modeling.

  6. Application of surface complexation models to anion adsorption by natural materials

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Various chemical models of ion adsorption will be presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model w...

  7. Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

    DOE PAGES

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P.; Maksymovych, Petro; Yates, Jr, John T.

    2016-01-12

    Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

  8. Formation, Migration, and Reactivity of Au-CO Complexes on Gold Surfaces.

    PubMed

    Wang, Jun; McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Baddorf, Arthur P; Maksymovych, Petro; Yates, John T

    2016-02-10

    We report experimental as well as theoretical evidence that suggests Au-CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au-CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10(-8) to 10(-4) Torr (dosage up to 10(6) langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au-CO complex formation and diffusion, and Au adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au-CO complex result from the reduced Au-Au bonding at elbows and step edges leading to stronger Au-CO bonding and to the formation of a more positively charged CO (CO(δ+)) on Au. Our studies indicate that the mobile Au-CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers. PMID:26754257

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

    SciTech Connect

    Reed, Donald Timothy; Deo, Randhir P; Rittmann, Bruce E; Songkasiri, Warinthorn

    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.

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

    NASA Astrophysics Data System (ADS)

    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).

  11. Origin of complex impact craters on native oxide coated silicon surfaces

    NASA Astrophysics Data System (ADS)

    Samela, Juha; Nordlund, Kai; Popok, Vladimir N.; Campbell, Eleanor E. B.

    2008-02-01

    Crater structures induced by impact of keV-energy Arn+ cluster ions on silicon surfaces are measured with atomic force microscopy. Complex crater structures consisting of a central hillock and outer rim are observed more often on targets covered with a native silicon oxide layer than on targets without the oxide layer. To explain the formation of these complex crater structures, classical molecular dynamics simulations of Ar cluster impacts on oxide coated silicon surfaces, as well as on bulk amorphous silica, amorphous Si, and crystalline Si substrates, are carried out. The diameter of the simulated hillock structures in the silicon oxide layer is in agreement with the experimental results, but the simulations cannot directly explain the height of hillocks and the outer rim structures when the oxide coated silicon substrate is free of defects. However, in simulations of 5keV /atom Ar12 cluster impacts, transient displacements of the amorphous silicon or silicon oxide substrate surfaces are induced in an approximately 50nm wide area surrounding the impact point. In silicon oxide, the transient displacements induce small topographical changes on the surface in the vicinity of the central hillock. The comparison of cluster stopping mechanisms in the various silicon oxide and silicon structures shows that the largest lateral momentum is induced in the silicon oxide layer during the impact; thus, the transient displacements on the surface are stronger than in the other substrates. This can be a reason for the higher frequency of occurrence of the complex craters on oxide coated silicon.

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

    USGS Publications Warehouse

    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.

  13. Cell-surface Attachment of Bacterial Multienzyme Complexes Involves Highly Dynamic Protein-Protein Anchors*

    PubMed Central

    Cameron, Kate; Najmudin, Shabir; Alves, Victor D.; Bayer, Edward A.; Smith, Steven P.; Bule, Pedro; Waller, Helen; Ferreira, Luís M. A.; Gilbert, Harry J.; Fontes, Carlos M. G. A.

    2015-01-01

    Protein-protein interactions play a pivotal role in the assembly of the cellulosome, one of nature's most intricate nanomachines dedicated to the depolymerization of complex carbohydrates. The integration of cellulosomal components usually occurs through the binding of type I dockerin modules located at the C terminus of the enzymes to cohesin modules located in the primary scaffoldin subunit. Cellulosomes are typically recruited to the cell surface via type II cohesin-dockerin interactions established between primary and cell-surface anchoring scaffoldin subunits. In contrast with type II interactions, type I dockerins usually display a dual binding mode that may allow increased conformational flexibility during cellulosome assembly. Acetivibrio cellulolyticus produces a highly complex cellulosome comprising an unusual adaptor scaffoldin, ScaB, which mediates the interaction between the primary scaffoldin, ScaA, through type II cohesin-dockerin interactions and the anchoring scaffoldin, ScaC, via type I cohesin-dockerin interactions. Here, we report the crystal structure of the type I ScaB dockerin in complex with a type I ScaC cohesin in two distinct orientations. The data show that the ScaB dockerin displays structural symmetry, reflected by the presence of two essentially identical binding surfaces. The complex interface is more extensive than those observed in other type I complexes, which results in an ultra-high affinity interaction (Ka ∼1012 m). A subset of ScaB dockerin residues was also identified as modulating the specificity of type I cohesin-dockerin interactions in A. cellulolyticus. This report reveals that recruitment of cellulosomes onto the cell surface may involve dockerins presenting a dual binding mode to incorporate additional flexibility into the quaternary structure of highly populated multienzyme complexes. PMID:25855788

  14. Analysis the complex interaction among flexible nanoparticles and materials surface in the mechanical polishing process

    NASA Astrophysics Data System (ADS)

    Han, Xuesong; Gan, Yong X.

    2011-02-01

    Mechanical polishing (MP), being the important technique of realizing the surface planarization, has already been widely applied in the area of microelectronic manufacturing and computer manufacturing technology. The surface planarization in the MP is mainly realized by mechanical process which depended on the microdynamic behavior of nanoparticle. The complex multibody interaction among nanoparticles and materials surface is different from interaction in the macroscopic multibody system which makes the traditional classical materials machining theory cannot accurately uncover the mystery of the surface generation in the MP. Large-scale classical molecular dynamic (MD) simulation of interaction among nanoparticles and solid surface has been carried out to investigate the physical essence of surface planarization. The particles with small impact angle can generate more uniform global planarization surface but the materials removal rate is lower. The shear interaction between particle and substrate may induce large friction torque and lead to the rotation of particle. The translation plus rotation makes the nanoparticle behaved like micro-milling tool. The results show that the nanoparticles may aggregrate together and form larger cluster thus deteriorate surface the quality. This MD simulation results illuminate that the final planarized surface can only be acquired by synergic behavior of all particles using various means such as cutting, impacting, scratching, indentation and so on.

  15. A physically-based hybrid framework to estimate daily-mean surface fluxes over complex terrain

    NASA Astrophysics Data System (ADS)

    Huang, Hsin-Yuan; Hall, Alex

    2016-06-01

    In this study we developed and examined a hybrid modeling approach integrating physically-based equations and statistical downscaling to estimate fine-scale daily-mean surface turbulent fluxes (i.e., sensible and latent heat fluxes) for a region of southern California that is extensively covered by varied vegetation types over a complex terrain. The selection of model predictors is guided by physical parameterizations of surface flux used in land surface models and analysis showing net shortwave radiation that is a major source of variability in the surface energy budget. Through a structure of multivariable regression processes with an application of near-surface wind estimates from a previous study, we successfully reproduce dynamically-downscaled 3 km resolution surface flux data. The overall error in our estimates is less than 20 % for both sensible and latent heat fluxes, while slightly larger errors are seen in high-altitude regions. The major sources of error in estimates include the limited information provided in coarse reanalysis data, the accuracy of near-surface wind estimates, and an ignorance of the nonlinear diurnal cycle of surface fluxes when using daily-mean data. However, with reasonable and acceptable errors, this hybrid modeling approach provides promising, fine-scale products of surface fluxes that are much more accurate than reanalysis data, without performing intensive dynamical simulations.

  16. Surface induced dissociation yields substructure of Methanosarcina thermophila 20S proteasome complexes

    PubMed Central

    Ma, Xin; Loo, Joseph A.; Wysocki, Vicki H.

    2015-01-01

    Native mass spectrometry (MS) and surface induced dissociation (SID) have been applied to study the stoichiometry and quaternary structure of non-covalent protein complexes. In this study, Methanosarcina thermophila 20S proteasome, which consists of four stacked heptameric rings (α7β7β7α7 symmetry), has been selected to explore the SID dissociation pattern of a complicated stacked ring protein complex. SID produces both α and β subunits while collision induced dissociation (CID) produces only highly charged α subunit. In addition, the charge reduced 20S proteasome produces the α7β7 fragment, reflecting the stacked ring topology of the complex. The combination of SID and charge reduction is shown to be a powerful tool for the study of protein complex structure. PMID:26005366

  17. Geochemical partitioning and pollution assessment of Ni and V as indicator of oil pollution in surface sediments from Shadegan wildlife refuge, Iran.

    PubMed

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

    2016-10-15

    The total concentrations and chemical partitioning of Ni, V and Fe have been assessed in surface sediments from 160 sites along the Shadegan wildlife refuge. The results showed that the average total level of Ni, V and Fe in surface sediments were 45.08±12.09, 25.25±20.8 and 25,979.01±6917.91μg/g dw, respectively. On the average, the chemical speciation of Ni, V and Fe in most stations were in the order of residual>oxidisable-organic>acid-reducible>exchangeable. In all fractions, the residual was accounted the highest proportion for the metals analyzed. Among the non-residual phases, the proportion of heavy metals in organic matter fraction was higher than other phases collected from all locations. The comparison between measured values in this study and some fresh water sediment quality guidelines indicated that the levels of nickel would be expected to sporadically cause harmful biological impacts on biota in the Shadegan wildlife refuge. PMID:27546735

  18. Geochemical partitioning and pollution assessment of Ni and V as indicator of oil pollution in surface sediments from Shadegan wildlife refuge, Iran.

    PubMed

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

    2016-10-15

    The total concentrations and chemical partitioning of Ni, V and Fe have been assessed in surface sediments from 160 sites along the Shadegan wildlife refuge. The results showed that the average total level of Ni, V and Fe in surface sediments were 45.08±12.09, 25.25±20.8 and 25,979.01±6917.91μg/g dw, respectively. On the average, the chemical speciation of Ni, V and Fe in most stations were in the order of residual>oxidisable-organic>acid-reducible>exchangeable. In all fractions, the residual was accounted the highest proportion for the metals analyzed. Among the non-residual phases, the proportion of heavy metals in organic matter fraction was higher than other phases collected from all locations. The comparison between measured values in this study and some fresh water sediment quality guidelines indicated that the levels of nickel would be expected to sporadically cause harmful biological impacts on biota in the Shadegan wildlife refuge.

  19. A closer look at the complex hydrophilic/hydrophobic interactions forces at the human hair surface

    NASA Astrophysics Data System (ADS)

    Baghdadli, N.; Luengo, G. S.; Recherche, L.

    2008-03-01

    The complex chemical structure of the hair surface is far from being completely understood. Current understanding is based on Rivett's model1 that was proposed to explain the macroscopic hydrophobic nature of the surface of natural hair. In this model covalently-linked fatty acids are chemically grafted to the amorphous protein (keratin) through a thio-ester linkage2,3. Nevertheless, experience like wetting and electrical properties of human hair surface4 shows that the complexity of the hair surface is not fully understand based on this model in literature. Recent studies in our laboratory show for the first time microscopic evidence of the heterogeneous physico-chemical character of the hair surface. By using Chemical Force Microscopy, the presence of hydrophobic and ionic species are detected and localized, before and after a cosmetic treatment (bleaching). Based on force curve analysis the mapping of the local distribution of hydrophilic and hydrophobic groups of hair surface is obtained. A discussion on a more plausible hair model and its implications will be presented based on these new results.

  20. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

    USGS Publications Warehouse

    Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

    1999-01-01

    A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron-oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

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

    PubMed

    Veselská, Veronika; Fajgar, Radek; Číhalová, Sylva; Bolanz, Ralph M; Göttlicher, Jörg; Steininger, Ralph; Siddique, Jamal A; Komárek, Michael

    2016-11-15

    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 (0.001-0.1M KNO3), sorbate concentrations (10(-4), 10(-5), and 10(-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.

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

    PubMed

    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.

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

    PubMed

    Veselská, Veronika; Fajgar, Radek; Číhalová, Sylva; Bolanz, Ralph M; Göttlicher, Jörg; Steininger, Ralph; Siddique, Jamal A; Komárek, Michael

    2016-11-15

    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 (0.001-0.1M KNO3), sorbate concentrations (10(-4), 10(-5), and 10(-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. PMID:27450335

  4. ATR-FTIR spectroscopic characterization of coexisting carbonate surface complexes on hematite

    USGS Publications Warehouse

    Bargar, J.R.; Kubicki, J.D.; Reitmeyer, R.; Davis, J.A.

    2005-01-01

    The speciation of carbonate adsorbed to hematite in air-equilibrated aqueous solutions has been studied using ATR-FTIR spectroscopy. Samples were measured over a range of pH conditions, at 0.1 M NaCl and at low ionic strength, and in H2O and D2O solutions to permit a multispecies analysis of the data. Second-derivative analyses and fits to the spectra indicate the presence of two major and two minor surface-bound carbonate species. The two major complexes coexist at near-neutral pH and low ionic strength. One of these two complexes is relatively sensitive to ionic strength, being displaced at 0.1 M NaCl, whereas the other is not. Comparison of experimental to DFT/MO-calculated frequencies suggest these two major species to be (a) a monodentate binuclear inner-sphere carbonate surface complex, and (b) a fully or partially solvated carbonate (CO32-) species that is symmetry broken and appears to reside in the structured vicinal water layers at the hematite-water interface, retained by hydrogen bonding and/or other forces. Minor carbonate complexes include diffuse layer CO32- and an unidentified inner-sphere species. Both of the dominant species observed here are likely to be significant controls of the surface charge and sorptive properties of Fe-oxides. Copyright ?? 2005 Elsevier Ltd.

  5. Surface complexation of carboxylate adheres Cryptosporidium parvum oocysts to the hematite-water interface

    USGS Publications Warehouse

    Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

    2009-01-01

    The interaction of viable Cryptosporidium parvum ??ocysts at the hematite (??-Fe2O3)-water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed ??ocysts showed distinctchangesin carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, ??ocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, ??ocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions. ?? 2009 American Chemical Society.

  6. Connections between surface complexation and geometric models of mineral dissolution investigated for rhodochrosite

    NASA Astrophysics Data System (ADS)

    Duckworth, Owen W.; Martin, Scot T.

    2003-05-01

    Mineral dissolution rates have been rationalized in the literature by surface complexation models (SCM) and morphological and geometric models (GM), and reconciliation of these conceptually different yet separately highly successful models is an important goal. In the current work, morphological alterations of the surface are observed in real time at the microscopic level by atomic force microscopy (AFM) while dissolution rates are simultaneously measured at the macroscopic level by utilizing the AFM fluid cell as a classic flow-through reactor. Rhodochrosite dissolution is studied from pH = 2 to 11 at 298 K, and quantitative agreement is found between the dissolution rates determined from microscopic and macroscopic observations. Application of a SCM model for the interpretation of the kinetic data indicates that the surface concentration of >CO 3H regulates dissolution for pH < 7 while the surface concentration of >MnOH 2+ regulates dissolution for pH > 7. A GM model explains well the microscopic observations, from which it is apparent that dissolution occurs at steps associated with anisotropic pit expansion. On the basis of the observations, we combine the SCM and GM models to propose a step-site surface complexation model (SSCM), in which the dissolution rates are quantitatively related to the surface chemical speciation of steps. The governing SSCM equation is as follows: R = χ 1/2( k co + k ca)[>CO 3H] + χ 1/2( k mo + k ma)[>MnOH 2+ ], where R is the dissolution rate (mol m -2 s -1), 2χ 1/2 is the fraction of surface sites located at steps, [>CO 3H] and [>MnOH 2+ ] are surface concentrations (mol m -2), and k co, k ca, k mo, and k ma are the respective dissolution rate coefficients (s -1) for the >CO 3H and the >MnOH 2+ surface species on obtuse and acute steps. We find k co = 2.7 s -1, k ca = 2.1 × 10 -1 s -1, k mo = 4.1 × 10 -2 s -1, k ma = 3.7 × 10 -2 s -1, and χ 1/2 = 0.015 ± 0.005. The rate coefficients quantify the net result of complex surface

  7. An empirical potential energy surface for the Ne-OH/D complexes

    SciTech Connect

    Lee, Hee-Seung; McCoy, Anne B.; Harding, Lawrence B.; Carter, Christopher C.; Miller, Terry A.

    1999-12-08

    An empirical potential energy surface has been developed for the Ne-OH/D complexes from the experimentally observed vibrational and rotational energy levels with the results of ab initio calculations being used to provide initial estimates of the values of the parameters in the empirical potential. To determine the final surface a reassignment of the A(tilde sign) {sup 2}{sigma}{sup +}-X(tilde sign) {sup 2}{pi} bend-stretch combination bands, to fundamentals of the bend, was made, and the experimental data for both the Ne-OH and Ne-OD complexes were fit simultaneously due to the small number of available values. The vibrational energies and rotational constants resulting from the fit surface are within 0.2 and 0.0013 cm-1, respectively, of the experimental values. The details of the potential energy surface are discussed in relationship to those of other inert gas complexes containing OH and SH, as well as HCl and HF. (c) 1999 American Institute of Physics.

  8. Interaction of monogalactosyldiacylglycerol with cytochrome b₆f complex in surface films.

    PubMed

    Georgiev, G As; Ivanova, Sl; Jordanova, A; Tsanova, A; Getov, V; Dimitrov, M; Lalchev, Z

    2012-03-23

    The interaction of monogalactosyldiacylglycerol (MGDG) with cytochrome b(6)f complex (cyt b(6)f), a major component of the photosynthetic apparatus, was studied in Langmuir monolayers during compression/expansion cycling and at constant surface pressure mode. The surface pressure/area isotherms of the mixed films were analyzed in terms of surface compressional modulus and two-dimensional virial equation of state. The morphology and the surface potential of the monolayers were monitored by Brewster angle microscopy and vibrating plate sensor respectively. Our results suggested that there is a specific interaction between MGDG and cyt b(6)f which resulted in depletion of lipid molecules from the interface. The current work sheds light on the still unclear question how b(6)f complex gets in touch with the major compound of the thylakoid membranes, the non-charged lipid MGDG. The interaction occured even at very low sub-nanomolar concentration of the complex. This effect most probably could be attributed to hydrogen bonding between the galactose headgroup of the lipid and the protein moiety of cyt b(6)f. PMID:22374069

  9. Geochemical Speciation Mass Transfer

    1985-12-01

    PHREEQC is designed to model geochemical reactions. Based on an ion association aqueous model, PHREEQC can calculate pH, redox potential, and mass transfer as a function of reaction progress. It can be used to describe geochemical processes for both far-field and near-field performance assessment and to evaluate data acquisition needs and test data. It can also calculate the composition of solutions in equilibrium with multiple phases. The data base, including elements, aqueous species, and mineralmore » phases, is independent of the program and is completely user-definable. PHREEQC requires thermodynamic data for each solid, gaseous, or dissolved chemical species being modeled. The two data bases, PREPHR and DEQPAK7, supplied with PHREEQC are for testing purposes only and should not be applied to real problems without first being carefully examined. The conceptual model embodied in PHREEQC is the ion-association model of Pearson and Noronha. In this model a set of mass action equations are established for each ion pair (and controlling solid phases when making mass transfer calculations) along with a set of mass balance equations for each element considered. These sets of equations are coupled using activity coefficient values for each aqueous species and solved using a continued fraction approach for the mass balances combined with a modified Newton-Raphson technique for all other equations. The activity coefficient expressions in PHREEQC include the extended Debye-Huckel, WATEQ Debye-Huckel, and Davies equations from the original United States Geological Survey version of the program. The auxiliary preprocessor program PHTL, which is derived from EQTL, converts EQ3/6 thermodynamic data to PHREEQC format so that the two programs can be compared. PHREEQC can be used to determine solubility limits on the radionuclides present in the waste form. These solubility constraints may be input to the WAPPA leach model.« less

  10. [Microbial geochemical calcium cycle].

    PubMed

    Zavarzin, G A

    2002-01-01

    The participation of microorganisms in the geochemical calcium cycle is the most important factor maintaining neutral conditions on the Earth. This cycle has profound influence on the fate of inorganic carbon, and, thereby, on the removal of CO2 from the atmosphere. The major part of calcium deposits was formed in the Precambrian, when prokaryotic biosphere predominated. After that, calcium recycling based on biogenic deposition by skeletal organisms became the main process. Among prokaryotes, only a few representatives, e.g., cyanobacteria, exhibit a special calcium function. The geochemical calcium cycle is made possible by the universal features of bacteria involved in biologically mediated reactions and is determined by the activities of microbial communities. In the prokaryotic system, the calcium cycle begins with the leaching of igneous rock predominantly through the action of the community of organotrophic organisms. The release of carbon dioxide to the soil air by organotrophic aerobes leads to leaching with carbonic acid and soda salinization. Under anoxic conditions, of major importance is the organic acid production by primary anaerobes (fermentative microorganisms). Calcium carbonate is precipitated by secondary anaerobes (sulfate reducers) and to a smaller degree by methanogens. The role of the cyanobacterial community in carbonate deposition is exposed by stromatolites, which are the most common organo-sedimentary Precambrian structures. Deposition of carbonates in cyanobacterial mats as a consequence of photoassimilation of CO2 does not appear to be a significant process. It is argued that carbonates were deposited at the boundary between the "soda continent", which emerged as a result of subaerial leaching with carbonic acid, and the ocean containing Ca2+. Such ecotones provided favorable conditions for the development of the benthic cyanobacterial community, which was a precursor of stromatolites.

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

    PubMed Central

    Lund, Tracy J; Koretsky, Carla M; Landry, Christopher J; Schaller, Melinda S; Das, Soumya

    2008-01-01

    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. PMID:18783619

  12. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

    SciTech Connect

    Loring, John S.; Chen, Jeffrey; Benezeth, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2015-06-16

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, the implication of these results is that mineral trapping in scCO2 dominated fluids will be insignificant and limited to surface complexation unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

  13. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide

    SciTech Connect

    Loring, John S.; Chen, Jeffrey; Benezeth Ep Gisquet, Pascale; Qafoku, Odeta; Ilton, Eugene S.; Washton, Nancy M.; Thompson, Christopher J.; Martin, Paul F.; McGrail, B. Peter; Rosso, Kevin M.; Felmy, Andrew R.; Schaef, Herbert T.

    2015-07-14

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and post-reaction samples were examined by ex situ techniques, including SEM, XPS, FIB-TEM, TGA-MS, and MAS-NMR. Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 µmol/m2. Above this concentration and up to 76 µmol/m2, monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 µmol/m2, crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O concentration give insights regarding forsterite dissolution processes and magnesite nucleation and growth.

  14. Macrophage recognition of immune complexes: development and application of novel cell surface labeling procedures.

    PubMed

    Petty, H R; Dereski, W

    1985-07-16

    A fluorescein- and lactoperoxidase-conjugated ferritin-anti-ferritin immune complex has been prepared for cell surface labeling experiments on immune recognition and effector function. Lactoperoxidase (LPO) has been covalently coupled to affinity-purified anti-ferritin antibodies with p-benzoquinone by a modified version of the method of Ternynck and Avrameas [Ternynck, T., & Avrameas, S. (1976) Ann. Immunol. (Paris) 127C, 197]. The conjugate is a heterodimer of Mr230 000 with linkages to either or both of the heavy and light chains of the antibody, as judged by two-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) in the absence and presence of 2-mercaptoethanol. The conjugate retains antibody-binding activity as measured by a quantitative precipitin assay. When incorporated into immune complexes, the modified antibody also retains Fc receptor recognition ability as determined by erythrocyte-antibody rosette inhibition assays. Electron microscopy demonstrated that the antigen, ferritin, was monodisperse with complete apoprotein sheaths surrounding the core. Ferritin-anti-ferritin-LPO complexes were formed in 4-fold antigen excess. Complexes were verified by fluorescence and electron microscopy. Immune complexes were masked with "cold" iodine by use of the endogenous LPO activity. The complexes bound to cells at 4 degrees C as shown by electron microscopy and fluorescence video/intensification microscopy. The LPO delivered to the cell surface in this fashion can be utilized to iodinate the surface with 125I. Under saturation conditions, the labeling with local LPO delivery followed by SDS-PAGE and autoradiography is identical with labeling with free LPO. Labeling has also been conducted under conditions of substrate deficit.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:4052386

  15. Native Liquid Extraction Surface Analysis Mass Spectrometry: Analysis of Noncovalent Protein Complexes Directly from Dried Substrates

    NASA Astrophysics Data System (ADS)

    Martin, Nicholas J.; Griffiths, Rian L.; Edwards, Rebecca L.; Cooper, Helen J.

    2015-08-01

    Liquid extraction surface analysis (LESA) mass spectrometry is a promising tool for the analysis of intact proteins from biological substrates. Here, we demonstrate native LESA mass spectrometry of noncovalent protein complexes of myoglobin and hemoglobin from a range of surfaces. Holomyoglobin, in which apomyoglobin is noncovalently bound to the prosthetic heme group, was observed following LESA mass spectrometry of myoglobin dried onto glass and polyvinylidene fluoride surfaces. Tetrameric hemoglobin [(αβ)2 4H] was observed following LESA mass spectrometry of hemoglobin dried onto glass and polyvinylidene fluoride (PVDF) surfaces, and from dried blood spots (DBS) on filter paper. Heme-bound dimers and monomers were also observed. The `contact' LESA approach was particularly suitable for the analysis of hemoglobin tetramers from DBS.

  16. Determination of surface complex nonlinear optical susceptibilities and molecular orientational distribution functions using resonant surface second-harmonic generation

    NASA Astrophysics Data System (ADS)

    Park, Byoungchoo; Yoo, Jeong-Geun; Sakai, Takahiro; Hoshi, Hajime; Ishikawa, Ken; Takezoe, Hideo

    1998-10-01

    Using the resonant optical surface second-harmonic generation (SHG), we have determined the relative values of the complex nonlinear optical (NLO) components (χzzz, χzxx, and χxxz) at isotropic interfaces (C∞v) of a polymer with SHG active side chains. The introduced configuration of the SHG experiment was a polarizer-rotating quarter wave plate-sample-analyzer. It was shown that this configuration gives information on complex NLO coefficients without using the Kleinmann symmetry. For the experiments, we measured resonant surface SHG from the air-polymer and the substrate-polymer interfaces of a thick polymer film. By theoretically fitting the SHG data, we unambiguously determined the nonlinear susceptibility components at the both interfaces of the polymer film. Moreover, unbiased molecular orientational distribution functions (ODFs) at both interfaces were also determined using the modified maximum entropy method. The obtained ODFs were found to be quite different from the previous ones obtained by assuming the Kleinmann symmetry, indicating the important role of the imaginary part of χ's played when determining ODFs.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Grafting of functionalized [Fe(III)(salten)] complexes to Au(111) surfaces via thiolate groups: surface spectroscopic characterization and comparison of different linker designs.

    PubMed

    Jacob, Hanne; Kathirvel, Ketheeswari; Petersen, Finn; Strunskus, Thomas; Bannwarth, Alexander; Meyer, Sven; Tuczek, Felix

    2013-07-01

    Functionalization of surfaces with spin crossover complexes is an intensively studied topic. Starting from dinuclear iron(III)-salten complexes [Fe(salten)(pyS)]2(BPh4)2 and [Fe(thiotolylsalten)(NCS)]2 with disulfide-containing bridging ligands, corresponding mononuclear complexes [Fe(salten)(pyS)](+) and [Fe(thiotolylsalten)(NCS)] are covalently attached to Au(111) surfaces (pySH, pyridinethiol; salten, bis(3-salicylidene-aminopropyl)amine). The adsorbed monolayers are investigated by infrared reflection absorption spectroscopy (IRRAS) in combination with X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). Comparison of the surface vibrational spectra with bulk data allows us to draw conclusions with respect to the geometry of the adsorbed complexes. An anomaly is observed in the spectra of the surface-adsorbed monolayer of [Fe(salten)(pyS)](+), which suggests that the salten ligand is partially decoordinated from the Fe(III) center and one of its phenolate arms binds to the Au(111) surface. For complex [Fe(thiotolylsalten)(NCS)] that is bound to the Au(111) surface via a thiolate-functionalized salten ligand, this anomaly is not observed, which indicates that the coordination sphere of the complex in the bulk is retained on the surface. The implications of these results with respect to the preparation of surface-adsorbed monolayers of functional transition-metal complexes are discussed.

  20. Spectroscopic identification of binary and ternary surface complexes of Np(V) on gibbsite.

    PubMed

    Gückel, Katharina; Rossberg, André; Müller, Katharina; Brendler, Vinzenz; Bernhard, Gert; Foerstendorf, Harald

    2013-12-17

    For the first time, detailed molecular information on the Np(V) sorption species on amorphous Al(OH)3 and crystalline gibbsite was obtained by in situ time-resolved Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The results consistently demonstrate the formation of mononuclear inner sphere complexes of the NpO2(+) ion irrespective of the prevailing atmospheric condition. The impact of the presence of atmospheric equivalent added carbonate on the speciation in solution and on the surfaces becomes evident from vibrational data. While the 1:1 aqueous carbonato species (NpO2CO3(-)) was found to become predominant in the circumneutral pH range, it is most likely that this species is sorbed onto the gibbsite surface as a ternary inner sphere surface complex where the NpO2(+) moiety is directly coordinated to the functional groups of the gibbsite's surface. These findings are corroborated by results obtained from EXAFS spectroscopy providing further evidence for a bidentate coordination of the Np(V) ion on amorphous Al(OH)3. The identification of the Np(V) surface species on gibbsite constitutes a basic finding for a comprehensive description of the dissemination of neptunium in groundwater systems.

  1. Modeling the surface tension of complex, reactive organic-inorganic mixtures

    NASA Astrophysics Data System (ADS)

    Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. Faye

    2013-11-01

    Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as heterogeneous reactivity, ice nucleation, and cloud droplet formation. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two semi-empirical surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling of aerosol systems because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling results and goodness-of-fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  2. Modeling the surface tension of complex, reactive organic-inorganic mixtures

    NASA Astrophysics Data System (ADS)

    Schwier, A. N.; Viglione, G. A.; Li, Z.; McNeill, V. F.

    2013-01-01

    Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as cloud condensation nuclei (CCN) ability. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2-6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well-described by a weighted Szyszkowski-Langmuir (S-L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling fits and goodness of fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

  3. DFT calculations of magnetic parameters for molybdenum complexes and hydroxymethyl intermediates trapped on silica surface

    NASA Astrophysics Data System (ADS)

    Sojka, Zbigniew; Pietrzyk, Piotr

    2006-03-01

    Density functional theory (DFT) calculations of EPR parameters and their structure sensitivity for selected surface paramagnetic species involved in oxidative dehydrogenation of methanol over silica grafted molybdenum catalyst were investigated. Two surface complexes, Mo 4 c/SiO 2 and {O -sbnd Mo 4 c}/SiO 2, as well as rad CH 2OH radical trapped on the SiO 2 matrix were taken as the examples. The spin-restricted zeroth order regular approximation (ZORA) implemented in the Amsterdam Density Functional suite was used to calculate the electronic g tensor for those species. The predicted values were in satisfactory agreement with experimental EPR results. Five different coordination modes of the rad CH 2OH radical on the silica surface were considered and the isotropic 13C, 17O, and 1H hyperfine coupling constants (HFCC) of the resultant surface complexes were calculated. Structure sensitivity of the HFCC values was discussed in terms of the angular deformations caused by hydrogen bonding with the silica surface.

  4. DFT calculations of magnetic parameters for molybdenum complexes and hydroxymethyl intermediates trapped on silica surface.

    PubMed

    Sojka, Zbigniew; Pietrzyk, Piotr

    2006-03-13

    Density functional theory (DFT) calculations of EPR parameters and their structure sensitivity for selected surface paramagnetic species involved in oxidative dehydrogenation of methanol over silica grafted molybdenum catalyst were investigated. Two surface complexes, Mo(4c)/SiO2 and {O(-)-Mo(4c)}/SiO2, as well as *CH2OH radical trapped on the SiO2 matrix were taken as the examples. The spin-restricted zeroth order regular approximation (ZORA) implemented in the Amsterdam Density Functional suite was used to calculate the electronic g tensor for those species. The predicted values were in satisfactory agreement with experimental EPR results. Five different coordination modes of the *CH2OH radical on the silica surface were considered and the isotropic 13C, 17O, and 1H hyperfine coupling constants (HFCC) of the resultant surface complexes were calculated. Structure sensitivity of the HFCC values was discussed in terms of the angular deformations caused by hydrogen bonding with the silica surface.

  5. Monte Carlo Simulation Of Contaminant Transport To And Deposition On Complex Spacecraft Surfaces

    NASA Astrophysics Data System (ADS)

    Phillips, Jon R.; Fong, Michael C.; Panczak, T. D.

    1990-01-01

    A test molecule Monte Carlo simulation algorithm was devised and tested to compute near equilibrium transitional flow and resulting mass flux on complex surface geometries. The results agreed, within the calculated statistical error of the simulation, with known analytical solutions at the free molecular limit, and gave satisfactory agreement near the continuum limit, when compared to a diffusion model with slip boundary conditions. The effects of the Knudsen number on dimensionless mass exchange factors are considered for slip flow in an aperture geometry. A variety of surface outgassing and surface adsorption-migration kinetics models can be mated with the test molecule simulation to compute surface deposition values. A multimolecular layer model with two-neighbor migration is considered as one such alternative for surface adsorption-migration kinetics. Calculations of surface deposition for heavy chain oil molecules, known as DC-704, are compared to experi-mental data, showing good agreement. This kinetic model can serve as a boundary condition when computing the exchange of mass among various surfaces.

  6. A new potential energy surface and microwave and infrared spectra of the He-OCS complex

    SciTech Connect

    Wang, Zhongquan Zhang, Chunzao; Sun, Chunyan; Feng, Eryin

    2014-11-07

    A new high quality potential energy surface for the He-OCS van der Waals complex was calculated using the CCSD(T) method and avqz+33221 basis set. It is found that the global minimum energy is −51.33 cm{sup −1} at R{sub e} = 6.30a{sub 0} and θ{sub e} = 110.0°, the shallower minimum is located at R = 8.50a{sub 0} and θ = 0° with well depth −32.26 cm{sup −1}. Using the fitted potential energy surface, we have calculated bound energy levels of the He-OCS, He-O{sup 13}CS, He-OC{sup 34}S, and {sup 3}He-OCS complexes. The theoretical results are all in better agreement compared to previous theoretical work.

  7. Retrieving the size of particles with rough and complex surfaces from two-dimensional scattering patterns

    NASA Astrophysics Data System (ADS)

    Ulanowski, Z.; Hirst, E.; Kaye, P. H.; Greenaway, R.

    2012-12-01

    Scattered intensity measurement is a commonly used method for determining the size of small particles. However, it requires calibration and is subject to errors due to changes in incident irradiance or detector sensitivity. Analysis of two-dimensional scattering patterns offers an alternative approach. We test morphological image processing operations on patterns from a diverse range of particles with rough surfaces and/or complex structure, including mineral dust, spores, pollen, ice analogs and sphere clusters from 4 to 88 μm in size. It is found that the median surface area of intensity peaks is the most robust measure, and it is inversely proportional to particle size. The trend holds well for most particle types, as long as substantial roughness or complexity is present. One important application of this technique is the sizing of atmospheric particles, such as ice crystals.

  8. Sub-monolayer film growth of a volatile lanthanide complex on metallic surfaces

    PubMed Central

    Chen, Jinjie; Edelmann, Kevin; Wulfhekel, Wulf

    2015-01-01

    Summary We deposited a volatile lanthanide complex, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)terbium(III), onto metal surfaces of Cu(111), Ag(111) and Au(111) in vacuum and observed well-ordered sub-monolayer films with low temperature (5 K) scanning tunneling microscopy. The films show a distorted three-fold symmetry with a commensurate structure. Scanning tunneling spectroscopy reveals molecular orbitals delocalized on the ligands of the molecule. Our results imply that this complex can be transferred onto the metal substrates without molecular decomposition or contamination of the surface. This new rare-earth-based class of molecules broadens the choice of molecular magnets to study with scanning tunneling microscopy. PMID:26733215

  9. Long-Lived, Sub-Surface Layers of Toxic Oil in the Deep-Sea: A Molecular Organic and Isotopic Geochemical Approach to Understanding their Nature, Molecular Distribution, Origin and Impact to the Northern Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Hollander, D. J.; Freeman, K. H.; Ellis, G.; Diefendorf, A. F.; Peebles, E. B.; Paul, J.

    2010-12-01

    Here we present the results from two research cruises to the Northern Gulf of Mexico (GoM) during May and August 2010, after the April 20th blowout of BP’s Deepwater Horizon (DWH) drilling rig. Not only was the DWH tragedy the largest oil spill to have ever occurred in the United States but it was also the first blowout of a deep-sea oil exploration well. The BP oil spill presents the scientific community with a critically important and unique opportunity: i) to characterize the occurrence, molecular distribution and abundance of the hydrocarbons in the sub-surface, ii) to identify the source of the oil in the environment and, iii) to study how the distribution and chemistry of the hydrocarbons change over time and space and whether the sub-surface hydrocarbons are toxic to marine plankton and bacteria. Using sonar, fluorometry and backscatter, we were able to trace the occurrence of layers of sub-surface oil. These oil layers were found suspended at depths of 400 m and 1000-1400 m in the form of small microdroplets that were not visible to the naked eye. Both the 400 and the 1000 m layers were traced for more than 20 miles in length and 4 miles in width. Molecular organic geochemical analyses determined that petroleum hydrocarbons were the dominant components of the 400 and 1000 m layers. Interesting, the distribution of compounds was extremely consistent among all the samples with n-alkanes ranging from C24 to C37 with a maximum at C28. The loss of the lower molecular weight components of the crude oil is attributed to biodegradation. This distribution of n-alkanes was the same regardless of whether the samples were from 400 or 1000 m, whether the sites were 25 or 45 miles from the DWH site or whether the samples were collected in May or August. These observations strongly suggest that the bacteria are not able to consume all of the oil, and that these higher molecular weight compounds may persist in the environment for extended lengths of time, at least months

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

    PubMed

    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.

  11. Archean crust-mantle geochemical differentiation

    NASA Technical Reports Server (NTRS)

    Tilton, G. R.

    1983-01-01

    Isotope measurements on carbonatite complexes and komatiites can provide information on the geochemical character and geochemical evolution of the mantle, including the sub-continental mantle. Measurements on young samples establish the validity of the method. These are based on Sr, Nd and Pb data from the Tertiary-Mesozoic Gorgona komatiite and Sr and Pb data from the Cretaceous Oka carbonatite complex. In both cases the data describe a LIL element-depleted source similar to that observed presently in MORB. Carbonatite data have been used to study the mantle beneath the Superior Province of the Canadian Shield one billion years (1 AE) ago. The framework for this investigation was established by Bell et al., who showed that large areas of the province appear to be underlain by LIL element-depleted mantle (Sr-85/Sr-86=0.7028) at 1 AE ago. Additionally Bell et al. found four complexes to have higher initial Sr ratios (Sr-87/Sr-86=0.7038), which they correlated with less depleted (bulk earth?) mantle sources, or possibly crustal contamination. Pb isotope relationships in four of the complexes have been studied by Bell et al.

  12. Modeling Low-temperature Geochemical Processes

    NASA Astrophysics Data System (ADS)

    Nordstrom, D. K.

    2003-12-01

    Geochemical modeling has become a popular and useful tool for a wide number of applications from research on the fundamental processes of water-rock interactions to regulatory requirements and decisions regarding permits for industrial and hazardous wastes. In low-temperature environments, generally thought of as those in the temperature range of 0-100 °C and close to atmospheric pressure (1 atm=1.01325 bar=101,325 Pa), complex hydrobiogeochemical reactions participate in an array of interconnected processes that affect us, and that, in turn, we affect. Understanding these complex processes often requires tools that are sufficiently sophisticated to portray multicomponent, multiphase chemical reactions yet transparent enough to reveal the main driving forces. Geochemical models are such tools. The major processes that they are required to model include mineral dissolution and precipitation; aqueous inorganic speciation and complexation; solute adsorption and desorption; ion exchange; oxidation-reduction; or redox; transformations; gas uptake or production; organic matter speciation and complexation; evaporation; dilution; water mixing; reaction during fluid flow; reaction involving biotic interactions; and photoreaction. These processes occur in rain, snow, fog, dry atmosphere, soils, bedrock weathering, streams, rivers, lakes, groundwaters, estuaries, brines, and diagenetic environments. Geochemical modeling attempts to understand the redistribution of elements and compounds, through anthropogenic and natural means, for a large range of scale from nanometer to global. "Aqueous geochemistry" and "environmental geochemistry" are often used interchangeably with "low-temperature geochemistry" to emphasize hydrologic or environmental objectives.Recognition of the strategy or philosophy behind the use of geochemical modeling is not often discussed or explicitly described. Plummer (1984, 1992) and Parkhurst and Plummer (1993) compare and contrast two approaches for

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

    SciTech Connect

    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.

  14. Origin of complex impact craters on native oxide coated silicon surfaces

    SciTech Connect

    Samela, Juha; Nordlund, Kai; Popok, Vladimir N.; Campbell, Eleanor E. B.

    2008-02-15

    Crater structures induced by impact of keV-energy Ar{sub n}{sup +} cluster ions on silicon surfaces are measured with atomic force microscopy. Complex crater structures consisting of a central hillock and outer rim are observed more often on targets covered with a native silicon oxide layer than on targets without the oxide layer. To explain the formation of these complex crater structures, classical molecular dynamics simulations of Ar cluster impacts on oxide coated silicon surfaces, as well as on bulk amorphous silica, amorphous Si, and crystalline Si substrates, are carried out. The diameter of the simulated hillock structures in the silicon oxide layer is in agreement with the experimental results, but the simulations cannot directly explain the height of hillocks and the outer rim structures when the oxide coated silicon substrate is free of defects. However, in simulations of 5 keV/atom Ar{sub 12} cluster impacts, transient displacements of the amorphous silicon or silicon oxide substrate surfaces are induced in an approximately 50 nm wide area surrounding the impact point. In silicon oxide, the transient displacements induce small topographical changes on the surface in the vicinity of the central hillock. The comparison of cluster stopping mechanisms in the various silicon oxide and silicon structures shows that the largest lateral momentum is induced in the silicon oxide layer during the impact; thus, the transient displacements on the surface are stronger than in the other substrates. This can be a reason for the higher frequency of occurrence of the complex craters on oxide coated silicon.

  15. Voltammetric measurements at the surface of cotton: absorption and catalase reactivity of a dinuclear manganese complex.

    PubMed

    Marken, Frank; Taylor, James E; Bonné, Michael J; Helton, Matthew E; Parry, Matthew L; McKee, Vickie

    2007-02-13

    Voltammetric measurements at the surface of cotton fabric were conducted after impregnating the surface of the textile with graphite flakes. The resulting conducting surface contact was connected to a conventional basal plane pyrolytic graphite substrate electrode and employed both in stagnant solution and in rotating disc voltammetry mode. Diffusion through the immobilized cotton sample (inter-fiber) is probed with the aqueous Fe(CN)6(4-/3-) redox system. With a small amount of platinum immobilized at the cotton surface, catalase reactivity toward hydrogen peroxide was observed and used to further quantify the diffusion (intra- and inter-fiber) into the reactive zone at the graphite-cotton interface. A well-known catalase model system, the dinuclear manganese metal complex [Mn(IV)2(micro-O)3L2](PF6)2 (with L=1,4,7-trimethyl-1,4,7-triazacyclononane), is investigated in aqueous 0.1 M carbonate buffer at pH 9.8 in contact with cotton fabric. Absorption of the metal complex is monitored and quantified by voltammetric methods. A Langmurian binding constant of approximately K=2x103 M-1 was determined. Voltammetric measurements of the adsorbed metal complex reveal strong absorption and chemically irreversible reduction characteristics similar to those observed in solution. In the presence of hydrogen peroxide, catalyst coverage dependent anodic catalase activity was observed approximately following the rate law rate=k[catalyst]surface[H2O2]solution and with k=3x104 dm3 s-1 mol-1. The catalyst reactivity was modified by the presence of cotton.

  16. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

    PubMed Central

    Prado, Yoann; Daffé, Niéli; Michel, Aude; Georgelin, Thomas; Yaacoub, Nader; Grenèche, Jean-Marc; Choueikani, Fadi; Otero, Edwige; Ohresser, Philippe; Arrio, Marie-Anne; Cartier-dit-Moulin, Christophe; Sainctavit, Philippe; Fleury, Benoit; Dupuis, Vincent; Lisnard, Laurent; Fresnais, Jérôme

    2015-01-01

    Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude. PMID:26634987

  17. Cationic and anionic polyelectrolyte complexes of xylan and chitosan. Interaction with lignocellulosic surfaces.

    PubMed

    Mocchiutti, Paulina; Schnell, Carla N; Rossi, Gerardo D; Peresin, María S; Zanuttini, Miguel A; Galván, María V

    2016-10-01

    Cationic (CatPECs) and anionic (AnPECs) polyelectrolyte complexes from xylan and chitosan were formed, characterized and adsorbed onto unbleached fibers for improving the papermaking properties. They were prepared at a level of 30% of neutralization charge ratio by modifying the order of addition of polyelectrolytes and the ionic strength (0.01N and 0.1N NaCl). The charge density, colloidal stability and particle size of polyelectrolyte complexes (PECs) was measured using polyelectrolyte titration method, Turbiscan and Zetasizer Nano equipments, respectively. All the complexes were stable even after seven days from PEC formation. DRIFT spectra of complexes were also analyzed. The adsorption behavior of them onto cellulose nanofibrils model surfaces was studied using quartz crystal microbalance with dissipation monitoring, and surface plasmon resonance. It was found that the PEC layers were viscoelastic and highly hydrated. Finally, it is shown that the adsorbed PECs onto cellulosic fibers markedly improved the tensile and crushing strengths of paper. PMID:27312617

  18. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone–Ag complex

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

    2016-06-01

    The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN–Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN–Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN–Ag complex is presented. The results reveal that only the intermolecular charge transfer with π–π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN–Ag complex.

  19. Unravelling nonspecific adsorption of complex protein mixture on surfaces with SPR and MS.

    PubMed

    Breault-Turcot, Julien; Chaurand, Pierre; Masson, Jean-Francois

    2014-10-01

    Characterization of protein adsorption to surfaces has implications from biosensing to protective biocoatings. While research studies have principally focused on determining the magnitude of protein adsorption to surfaces, the proteins involved in the process remains only broadly identified and has not been investigated on several surfaces. To further elucidate the nonspecific adsorption process of serum to surfaces, surface plasmon resonance (SPR) and matrix assisted laser desorption ionization mass spectrometry (MALDI-MS) were used in combination to obtain quantitative and qualitative information about the process of protein adsorption to surfaces. To validate the technique, crude serum was nonspecifically adsorbed on four self-assembled monolayer (SAM) on gold: 16-mercaptohexadecanoic acid (16-MHA), 11-mercaptoundecane(ethylene glycol)3-COOH (PEG), 3-MPA-LHDLHD-OH, and 3-MPA-HHHDD-OH. Direct MS analysis of the nonspecifically adsorbed proteins suggested the presence of a variety of protein (BSA, IgG, and apolipoprotein A-1). Performing a trypsin digestion of the nonspecifically adsorbed proteins confirmed the presence of BSA and apolipoprotein A-1 and further revealed the complexity of the process by detecting the presence of complement C3, SHC-transforming protein 1, and kininogen 2. The level of nonspecific adsorption on different surfaces measured by SPR sensing directly correlated with the intensity of the serum protein and indirectly with the tryptic peptides measured by MS. Detailed analysis of the BSA peptides digested on 16-MHA and for BSA digested in solution was used to investigate the orientation of BSA on this surface. The combination of SPR and MS allows the quantitative and qualitative understanding of protein adsorption processes to surfaces. PMID:25287274

  20. Pulsed supersonic molecular beam for characterization of chemically active metal-organic complexes at surfaces

    NASA Astrophysics Data System (ADS)

    Lear, Amanda M.

    Metal-organic coordination networks (MOCNs) at surfaces consist of a complex of organic ligands bound to an atomic metal center. The MOCNs, when chosen appropriately, can form highly-ordered arrays at surfaces. Ultra-high vacuum surface studies allow control of surface composition and provide 2D growth restrictions, which lead to under-coordinated metal centers. These systems provide an opportunity to tailor the chemical function of the metal centers due to the steric restrictions imposed by the surface. Tuning the adsorption/desorption energy at a metal center and developing a cooperative environment for catalysis are the key scientific questions that motivate the construction of a molecular beam surface analysis system. Characterization of the created systems can be performed utilizing a pulsed supersonic molecular beam (PSMB) in unison with a quadrupole mass spectrometer. A PSMB allows for the highly controlled delivery of reactants with well-defined energy to a given platform making it possible to elucidate detailed chemical tuning information. In this thesis, a summary of prior theoretical molecular beam derivations is provided. Design considerations and an overview of the construction procedure for the current molecular beam apparatus, including initial characterization experiments, are presented. By impinging an Ar beam on a Ag(111) surface, the location of the specular angle (˜65°) and rough sample perimeter coordinates were determined. Additionally, surface analysis experiments, mainly Auger Electron Spectroscopy (AES), were performed to investigate the oxidation of epitaxial graphene on the SiC(0001) surface utilizing an oxygen cracking method. The AES experiments are described in detail and highlight the challenges that were faced when several different graphene samples were used for the oxygen adsorption/desorption experiments.

  1. Interpreting Ground Temperature Measurements for Thermophysical Properties on Complex Surfaces of the Moon and Mars

    NASA Astrophysics Data System (ADS)

    Vasavada, A. R.; Hamilton, V. E.; Team, M.

    2013-12-01

    With the successful deployments of the Diviner radiometer on the Lunar Reconnaissance Orbiter and the REMS ground temperature sensor on the Curiosity Mars rover, records of ground temperature with high accuracy and finely sampled diurnal and seasonal cycles have become available. The detailed shapes of these temperature profiles allow inferences beyond just bulk thermophysical properties. Subtle (or sometime significant) effects of surface roughness, slope, and lateral and vertical heterogeneity may be identified in the surface brightness temperature data. For example, changes in thermal or physical properties with depth in the shallow subsurface affect the conduction and storage of thermal energy. These affect the surface energy balance and therefore surface temperatures, especially the rate of cooling at night. Making unique determinations of subsurface soil properties requires minimizing the uncertainties introduced by other effects. On Mars, atmospheric aerosol opacity and wind-driven sensible heat fluxes also affect the diurnal and annual temperature profiles. On both bodies, variations in thermal inertia, slopes, roughness, albedo, and emissivity within the radiometer footprint will cause the composite brightness temperature to differ from a kinetic temperature. Nevertheless, we have detected potential effects of complex surfaces in the temperature data from both Diviner and Curiosity. On the Moon, the results reveal a nearly ubiquitous surface structure, created mechanically by impact gardening, that controls the thermal response of the surface. On Mars, the thermal response is controlled primarily by grain size, cementation, lithification, and composition. However, the secondary effects of near-surface layering aid in the interpretation of stratigraphy and in the identification of geologic processes that have altered the surface.

  2. Quantum chemical study on surface complex structures of phosphate on gibbsite

    NASA Astrophysics Data System (ADS)

    Luengo, Carina V.; Castellani, Norberto J.; Ferullo, Ricardo M.

    2015-08-01

    Quantum mechanics calculations based on the density functional theory (DFT) were used to identify phosphate surface complexes on gibbsite at low and high pH. The different phosphate species were represented using the Al6(OH)18(H2O)6 cluster model considering four different geometries: monodentate mononuclear (Pmm), monodentate binuclear (Pmb), bidentate mononuclear (Pbm) and bidentate binuclear (Pbb). The corresponding adsorption reactions were modelled via ligand exchange between phosphate species and surface functional groups (hydroxyls and protonated hydroxyls at high and low pH, respectively). The theoretical results indicate that phosphate surface complexes are thermodynamically more favored at acid pH, in agreement with experimental evidences. The first step in these reactions, i.e., the generation of required aluminum vacant sites, was predicted to be particularly favorable when singly coordinated aquo groups are released. Stretching and bending vibrational frequencies associated with the different surface structures were calculated at both pH conditions. The corresponding values at low pH were found to be shifted to higher frequencies with respect to those ones at high pH. ATR-FTIR studies were also carried out. The resulting spectra are dominated by a strong band within the 800-840 cm-1 interval due to P-OH stretching modes. The corresponding peak appearing around 820 cm-1 at high pH is shifted to lower frequencies with respect to the position at low pH, a tendency well predicted by DFT calculations.

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

    NASA Astrophysics Data System (ADS)

    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. Double-Ended Surface Walking Method for Pathway Building and Transition State Location of Complex Reactions.

    PubMed

    Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

    2013-12-10

    Toward the activity prediction with large-scale computations, here a double-ended surface walking (DESW) method is developed for connecting two minima on a potential energy surface (PES) and locating the associated transition state (TS) using only the first derivatives. The method operates two images starting from the initial and the final states, respectively, to walk in a stepwise manner toward each other. The surface walking involves repeated bias potential addition and local relaxation with the constrained Broyden dimer method to correct the walking direction. We apply the method to a model PES, a large set of gas phase Baker reactions, and complex surface catalytic reactions, which demonstrates that the DESW method can establish a low energy pathway linking two minima even without iterative optimization of the pathway, from which the TS can be located readily. By comparing the efficiency of the new method with the existing methods, we show that the DESW method is much less computationally demanding and is applicable for reactions with complex PESs. We hope that the DESW method may be integrated with the PES sampling methods for automated reaction prediction.

  5. Downscaling surface wind predictions from numerical weather prediction models in complex terrain with WindNinja

    NASA Astrophysics Data System (ADS)

    Wagenbrenner, Natalie S.; Forthofer, Jason M.; Lamb, Brian K.; Shannon, Kyle S.; Butler, Bret W.

    2016-04-01

    Wind predictions in complex terrain are important for a number of applications. Dynamic downscaling of numerical weather prediction (NWP) model winds with a high-resolution wind model is one way to obtain a wind forecast that accounts for local terrain effects, such as wind speed-up over ridges, flow channeling in valleys, flow separation around terrain obstacles, and flows induced by local surface heating and cooling. In this paper we investigate the ability of a mass-consistent wind model for downscaling near-surface wind predictions from four NWP models in complex terrain. Model predictions are compared with surface observations from a tall, isolated mountain. Downscaling improved near-surface wind forecasts under high-wind (near-neutral atmospheric stability) conditions. Results were mixed during upslope and downslope (non-neutral atmospheric stability) flow periods, although wind direction predictions generally improved with downscaling. This work constitutes evaluation of a diagnostic wind model at unprecedented high spatial resolution in terrain with topographical ruggedness approaching that of typical landscapes in the western US susceptible to wildland fire.

  6. Preparation and surface photoelectric properties of Fe(II/III) complexes

    NASA Astrophysics Data System (ADS)

    Jin, Jing; Xu, Xiao-Ting; Li, Dan; Han, Xiao; Li, Lei; Chi, Yu-Xian; Niu, Shu-Yun; Zhang, Guang-Ning

    2013-05-01

    Four Fe(II/III) supramolecules, {[Fe(Hpdc)2(H2O)2]·2H2O} (1), [Fe(HImbc)2(H2O)2] (2), [Fe(phen)2(CN)2]·CH3CH2OH·2H2O (3), K[Fe(tp)2]·SO4 (4) (H2pdc = 2,5-Pyridinedicarboxylic acid, H2Imbc = 4,5-Imidazoledicarboxylic acid, phen = 1,10-phenanthroline, tp- = poly(pyrazolyl)borate), were synthesized by hydrothermal and room temperature stirring methods. They were characterized by single crystal X-ray diffraction, surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), electron paramagnetic resonance (EPR), UV-Vis absorption spectra (UV-Vis), infrared spectra (IR) and element analysis. The structural analyses indicate that complex (1) is a supramolecule with 2D structure connected by hydrogen bonds. Complex (2) is a supramolecule with hydrogen-bonded 3D structure. Complexes (3) and (4) are both 1D supramolecules connected by hydrogen bonds. The electronic state of central metal Fe(II) ions in complexes (1) and (2) is d6 with FeN2O4 coordination mode, lying in weaker distorted octahedral field. The electronic state of Fe(II) ion in complex (3) is d6 with Fe(CN)2N4 mode in the strong distorted octahedral field. The electronic state of Fe(III) ion in complex (4) is d5 with FeN6 mode, lying in the strong octahedral field. The micro-environment of Fe(II/III) ions in the four complexes is further investigated by EPR. The SPS of four complexes all exhibit photovoltage responses in the range of 300-700 nm. This indicates that they all possess certain photoelectric conversion capability. The effects of component, structure, type of ligands of the complexes, valence state and coordination micro-environment of the central metal ions on the SPS were discussed. Furthermore, the SPS and UV-Vis absorption spectra were interrelated.

  7. Geochemical indications for underground disposal site selection: The Mayak enterprise area, Southern Urals, Russia

    SciTech Connect

    Asadulin, A.A.; Poluektov, V.V.; Petrov, V.A.

    1995-12-31

    Geoscience study of the ``Mayak`` area with the aim of site selecting for underground depository of nuclear wastes has run into difficulties with poor exposure of the rock basement and radioactive contamination of the surface. The geological structure of this Early Paleozoic basement is too complex for extrapolations between drilling logs without surficial observation. In this context geochemical data interpretation can be especially valuable to compensate for the lack of geological information, using samples from drilling holes and sparse accessible outcrops. High indicative capacity of trace and rare elements made it possible to identify the oceanic island-arc origin of metamorphosed volcano-sedimentary formation which constitutes the bulk of the territory rock basement. Furthermore, the geochemical analysis has given some additional reasons for detailed subdivision of the formation fitness of rock suitable for underground disposal. More favorable are basic volcanics with regular distribution of chemical constituents. The authors consider less favorable tectonically deformed geological medium composed by more acid or heterogeneous rocks. Such a medium has been distinguished by presence of geochemical anomalies mostly related to subsequent intrusions or to permeable zones of tectonic dislocations.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Explicit correlation model of multi-source constraints for Re-design parts with complex curved surface

    NASA Astrophysics Data System (ADS)

    Jia, Zhenyuan; Wang, Fuji; Wang, Yongqing; Guo, Dongming

    2014-03-01

    In precision machining of complex curved surface parts with high performance, geometry accuracy is not the only constraint, but the performance should also be met. Performance of this kind of parts is closely related to the geometrical and physical parameters, so the final actual size and shape are affected by multiple source constraints, such as geometry, physics, and performance. These parts are rather difficult to be manufactured and new manufacturing method according to performance requirement is urgently needed. Based on performance and manufacturing requirements for complex curved surface parts, a new classification method is proposed, which divided the complex curved surface parts into two categories: surface re-design complex curved surface parts with multi-source constraints(PRCS) and surface unique complex curved surface parts with pure geometric constraints(PUCS). A correlation model is constructed between the performance and multi-source constraints for PRCS, which reveals the correlation between the performance and multi-source constraints. A re-design method is also developed. Through solving the correlation model of the typical part's performance-associated surface, the mapping relation between the performance-associated surface and the related removal amount is obtained. The explicit correlation model and the method for the corresponding related removal amount of the performance-associated surface are built based on the classification of surface re-design complex curved surface parts with multi-source constraints. Research results have been used in the actual processing of the typical parts such as radome, common bottom components, nozzle, et al., which shows improved efficiency and accuracy of the precision machining for the surface re-design parts with complex curved surface.

  11. Complexity of chaos in three cascaded vertical-cavity surface-emitting lasers

    NASA Astrophysics Data System (ADS)

    Hong, Yanhua; Quirce, Ana; Wang, Bingjie; Panajotov, Krassimir; Spencer, Paul S.

    2016-04-01

    The complexity of chaos generated in two systems has been studied experimentally. The complexity of the chaos is quantified by calculating average normalized permutation entropy (HS(P)). In the first system, a chaotic output from a master laser (ML) is injected into a CW slave laser (SL). The results show that the complexity of chaos generated in the SL decreases with absolute value of the frequency detuning Δf1, which means the complexity of the chaos is compromised with enhancing the bandwidth, as Δf1 is increased. The second system comprises three vertical-cavity surface-emitting lasers (VCSELs); the first VCSEL (used as ML) was rendered chaotic by optical feedback, the second VCSEL is used as intermediate laser (IL), which is rendered chaotic when it is subject to optical injection from the chaotic ML and the third VCSEL is used as a SL and is a subject of optical injection from the chaotic IL, thus entering chaotic dynamics. In this three-VCSEL system, small, intermediate and wide bandwidths of the injecting chaos signals, have been used to study the effect of the bandwidth of the injecting chaos on the complexity of chaos generated in the SL. The results show that the bandwidth of the chaotic injection beam does not impact the complexity of the chaos generated in the SL for positive frequency detuning; however, for large negative frequency detuning, the complexity of the chaos in the SL has been reduced significantly for the intermediate and lower bandwidth of the chaotic injection beam.

  12. Was Mineral Surface Complexity and Toxicity an Impetus for Evolution of Microbial Extracellular Polymeric Substances?

    NASA Astrophysics Data System (ADS)

    Sahai, N.; Xu, J.; Zhu, C.; Campbell, J.; Hickey, W.; Zhang, N.

    2011-12-01

    Modern ecological niches are teeming with an astonishing diversity of microbial life closely associated with mineral surfaces, highlighting the remarkable success of microorganisms in conquering the challenges and capitalizing on the benefits presented by the mineral-water interface. Such community-living is enabled by an extracellular, polymeric, biofilm matrix developed at cell surfaces. Despite the energetic penalties, biofilm formation capability likely evolved on early Earth because of crucial cell survival functions, of which recognized roles include facilitating cell-attachment at mineral surfaces, intercellular signaling and lateral gene transfer, protection from dessication in tidal pools, and screening toxic UV light and toxic soluble metals. Cell-attachment to mineral surfaces was likely critical for cell survival and function, but the potential toxicity of mineral surfaces towards cells and the complexities of the mineral-water-cell interface in promoting biofilm formation, have not been fully appreciated. We examined the effects of nanoparticulate oxides (amorphous SiO2, anatase β-TiO2, and γ-Al2O3) on EPS- and biofilm-producing wild-type strains and their isogenic knock-out mutants which are defective in EPS-producing ability. In detail, we used Gram-negative wild-type Pseudomonas aeruginosa PAO1 and its EPS knock-out mutant Δ-psl, and the Gram-positive wild-type Bacillus subtilis NCIB3610 and its EPS-knock-out mutant yhxBΔ. We conducted bacterial growth experiments in the presence of each oxide in order to determine the viability of each cell type relative to oxide-free controls. The amount of EPS generated in the presence of oxides was also quantified and qualitatively analyzed by fluorescent stains. The results indicated a previously unrecognized role for microbial extracellular polymeric substances (EPS) in shielding both Gram-negative and Gram-positive cells against the toxic effects of mineral surfaces. This role is distinct from the

  13. EXAFS Analyses of Innersphere Surface Complexations of Arsenate and Silicate on Natural Hydrous Ferric Oxides

    NASA Astrophysics Data System (ADS)

    Tommaseo, C. E.; Kersten, M.

    2002-12-01

    X-ray absorption spectroscopy (EXAFS) was used to determine the near range order of three elements (Fe, As, Si) on the surface of hydrous ferric oxide (HFO) from thermal water scales. Fe K-edge EXAFS analyses of the 2nd shell show a better fit including Si as backscattering neighbor. Validation of the Si-Fe bond was obtained by Si K-edge EXAFS spectra, where the light absorber element is surrounded favourably by much heavier second-shell elements. Least-squares fitting of the second-shell Fourier-filtered EXAFS spectrum in the k-range of 5-11 Å-1 yields in a Si-Fe distance of 3.10-3.13Å, and a Si-Si distance of 3.00Å. Both these interatomic distances and the coordination number N = 2 obtained for the Si-Fe shell are consistent with the formation of a corner-bridging bidentate binuclear (2C) surface complex on the HFO surface. The Si-Si bonds and existance of a vibrational band at 964 cm-1 in the infrared spectrum indicate polymerisation of the silicate on the HFO surface (Tommaseo and Kersten). As K-edge XANES analyses showed the As present in form of arsenate scavenged by the HFO phase. As and Si K-edge EXAFS analyses revealed both elements to compete for 2C surface complexation sites. A mean As-Fe distance of 3.03Å indicate an approx. equal distribution of arsenate between 2C (3.24Å) and another 1E (bidentate mononuclear surface complexation) sites (2.84Å). The average Fe-(O,OH) bond length of 2.09Å is compatible with a high proportion of distorted surficial FeIII(O,OH)6 octahedra in the colloidal HFO precipitates of the scale deposits. The slight distortion of the FeIII(O,OH)6 octahedra is consistent with the apparent strong binding of the 1E arsenate surface complexes (Manceau, 1995). The adverse effect of silicate would therefore be overpredicted without surface complexation models constructed to account for both surface functional groups. The Si K-edge EXAFS data provide also a basis for explaining at the molecular level the poisoning of HFO particle

  14. Surface structure of the Ag-In-(rare earth) complex intermetallics

    NASA Astrophysics Data System (ADS)

    Hars, S. S.; Sharma, H. R.; Smerdon, J. A.; Yadav, T. P.; Al-Mahboob, A.; Ledieu, J.; Fournée, V.; Tamura, R.; McGrath, R.

    2016-05-01

    We present a study of the surface structure of the Ag-In-RE (RE: rare-earth elements Gd, Tb, and Yb) complex intermetallics using scanning tunneling microscopy and low-energy electron diffraction. The surface of the Ag-In-Yb approximant prepared by sputter-annealing methods under ultrahigh-vacuum conditions produces a flat (100) surface with no facets. However, the Ag-In-Gd and Ag-In-Tb 1/1 approximants, which have a surface miscut of about 12∘ relative to the (100) plane, develop surface facets along various crystallographic directions. The structure of each facet can be explained as a truncation of the rhombic triacontahedral clusters, i.e., the main building blocks of these systems. Despite their differences in atomic structure, symmetry, and density, the facets show common features. The facet planes are In rich. The analysis of the nearest-neighbor atom distances suggests that In atoms form bonds with the RE atoms, which we suggest is a key factor that stabilizes even low-density facet planes.

  15. Evidence for Carbonate Surface Complexation during Forsterite Carbonation in Wet Supercritical Carbon Dioxide.

    PubMed

    Loring, John S; Chen, Jeffrey; Bénézeth, Pascale; Qafoku, Odeta; Ilton, Eugene S; Washton, Nancy M; Thompson, Christopher J; Martin, Paul F; McGrail, B Peter; Rosso, Kevin M; Felmy, Andrew R; Schaef, Herbert T

    2015-07-14

    Continental flood basalts are attractive formations for geologic sequestration of carbon dioxide because of their reactive divalent-cation containing silicates, such as forsterite (Mg2SiO4), suitable for long-term trapping of CO2 mineralized as metal carbonates. The goal of this study was to investigate at a molecular level the carbonation products formed during the reaction of forsterite with supercritical CO2 (scCO2) as a function of the concentration of H2O adsorbed to the forsterite surface. Experiments were performed at 50 °C and 90 bar using an in situ IR titration capability, and postreaction samples were examined by ex situ techniques, including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), focused ion beam transmission electron microscopy (FIB-TEM), thermal gravimetric analysis mass spectrometry (TGA-MS), and magic angle spinning nuclear magnetic resonance (MAS NMR). Carbonation products and reaction extents varied greatly with adsorbed H2O. We show for the first time evidence of Mg-carbonate surface complexation under wet scCO2 conditions. Carbonate is found to be coordinated to Mg at the forsterite surface in a predominately bidentate fashion at adsorbed H2O concentrations below 27 μmol/m(2). Above this concentration and up to 76 μmol/m(2), monodentate coordinated complexes become dominant. Beyond a threshold adsorbed H2O concentration of 76 μmol/m(2), crystalline carbonates continuously precipitate as magnesite, and the particles that form are hundreds of times larger than the estimated thicknesses of the adsorbed water films of about 7 to 15 Å. At an applied level, these results suggest that mineral carbonation in scCO2 dominated fluids near the wellbore and adjacent to caprocks will be insignificant and limited to surface complexation, unless adsorbed H2O concentrations are high enough to promote crystalline carbonate formation. At a fundamental level, the surface complexes and their dependence on adsorbed H2O

  16. Robotic path planning for non-destructive testing of complex shaped surfaces

    NASA Astrophysics Data System (ADS)

    Mineo, Carmelo; Pierce, Stephen Gareth; Wright, Ben; Nicholson, Pascual Ian; Cooper, Ian

    2015-03-01

    The requirement to increase inspection speeds for non-destructive testing (NDT) of composite aerospace parts is common to many manufacturers. The prevalence of complex curved surfaces in the industry provides significant motivation for the use of 6 axis robots for deployment of NDT probes in these inspections. A new system for robot deployed ultrasonic inspection of composite aerospace components is presented. The key novelty of the approach is through the accommodation of flexible robotic trajectory planning, coordinated with the NDT data acquisition. Using a flexible approach in MATLAB, the authors have developed a high level custom toolbox that utilizes external control of an industrial 6 axis manipulator to achieve complex path planning and provide synchronization of the employed ultrasonic phase array inspection system. The developed software maintains a high level approach to the robot programming, in order to ease the programming complexity for an NDT inspection operator. Crucially the approach provides a pathway for a conditional programming approach and the capability for multiple robot control (a significant limitation in many current off-line programming applications). Ultrasonic and experimental data has been collected for the validation of the inspection technique. The path trajectory generation for a large, curved carbon-fiber-reinforced polymer (CFRP) aerofoil component has been proven and is presented. The path error relative to a raster-scan tool-path, suitable for ultrasonic phased array inspection, has been measured to be within + 2mm over the 1.6 m2 area of the component surface.

  17. Electrochemical Instability of Phosphonate-Derivatized, Ruthenium(III) Polypyridyl Complexes on Metal Oxide Surfaces.

    PubMed

    Hyde, Jacob T; Hanson, Kenneth; Vannucci, Aaron K; Lapides, Alexander M; Alibabaei, Leila; Norris, Michael R; Meyer, Thomas J; Harrison, Daniel P

    2015-05-13

    The oxidative stability of the molecular components of dye-sensitized photoelectrosynthesis cells for solar water splitting remains to be explored systematically. We report here the results of an electrochemical study on the oxidative stability of ruthenium(II) polypyridyl complexes surface-bound to fluorine-doped tin oxide electrodes in acidic solutions and, to a lesser extent, as a function of pH and solvent with electrochemical monitoring. Desorption occurs for the Ru(II) forms of the surface-bound complexes with oxidation to Ru(III) enhancing both desorption and decomposition. Based on the results of long-term potential hold experiments with cyclic voltammetry monitoring, electrochemical oxidation to Ru(III) results in slow decomposition of the complex by 2,2'-bipyridine ligand loss and aquation and/or anation. A similar pattern of ligand loss was also observed for a known chromophore-catalyst assembly for both electrochemical water oxidation and photoelectrochemical water splitting. Our results are significant in identifying the importance of enhancing chromophore stability, or at least transient stability, in oxidized forms in order to achieve stable performance in aqueous environments in photoelectrochemical devices. PMID:25871342

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

    USGS Publications Warehouse

    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.

  19. Electron-phonon induced complex quasiparticles in the 1x1 H/W(110) surface.

    NASA Astrophysics Data System (ADS)

    Eiguren, Asier; Ambrosch-Draxl, Claudia

    2008-03-01

    We show that the solution of the complex Dyson equation for the electron-phonon problem induces several quasiparticle states for a given wave vector. The Dyson equation is considered in the full complex plane and it is solved without considering the imaginary part of the self-energy as an small parameter. By a first principle application of the formalism to the 1x1 H covered W(110) surface, we show that some aspects of the surface band splitting [Rotenberg et. al., Phys. Rev. Lett. 84, 2925 (2000)] can be traced back to electron-phonon coupling, where we present the energy and lifetimes of each quasiparticle. Despite this breakdown of the single quasi-particle picture, it is remarkable that the spectral functions are very well Represented by the predicted multiple quasi-particles. From these results, we can deduce that some of the features that previously where prescribed in ARPES spectra as incoherent structure could eventually be re-interpreted as contributions from additional quasi-particle states. Our method could also help to understand similar phenomena observed in high Tc cuprates and various other surfaces.

  20. An Evaluation of Fractal Surface Measurement Methods for Characterizing Landscape Complexity from Remote-Sensing Imagery

    NASA Technical Reports Server (NTRS)

    Lam, Nina Siu-Ngan; Qiu, Hong-Lie; Quattrochi, Dale A.; Emerson, Charles W.; Arnold, James E. (Technical Monitor)

    2001-01-01

    The rapid increase in digital data volumes from new and existing sensors necessitates the need for efficient analytical tools for extracting information. We developed an integrated software package called ICAMS (Image Characterization and Modeling System) to provide specialized spatial analytical functions for interpreting remote sensing data. This paper evaluates the three fractal dimension measurement methods: isarithm, variogram, and triangular prism, along with the spatial autocorrelation measurement methods Moran's I and Geary's C, that have been implemented in ICAMS. A modified triangular prism method was proposed and implemented. Results from analyzing 25 simulated surfaces having known fractal dimensions show that both the isarithm and triangular prism methods can accurately measure a range of fractal surfaces. The triangular prism method is most accurate at estimating the fractal dimension of higher spatial complexity, but it is sensitive to contrast stretching. The variogram method is a comparatively poor estimator for all of the surfaces, particularly those with higher fractal dimensions. Similar to the fractal techniques, the spatial autocorrelation techniques are found to be useful to measure complex images but not images with low dimensionality. These fractal measurement methods can be applied directly to unclassified images and could serve as a tool for change detection and data mining.

  1. Computational analysis of contact forces influence on cold forming processes in the dies with complex surfaces

    NASA Astrophysics Data System (ADS)

    Dragnea, D.; Lixandru, P.; Chereches, T.; Velicu, St.

    2016-08-01

    Interaction forces between the workpiece and the die appear during the cold forming process of metals in dies. Surface forces of high-intensity influence the mesh structure and internal structure of the finished piece by mechanical action. Frictional forces hinder the flow of the material in contact with the die walls, especially on surfaces of complex shape. Under certain conditions, the material can adhere to the wall of the die, leading to the blocking of the cold forming process. In order to highlight the influence of contact forces on cold forming processes in dies with complex surfaces there were used numerical simulation methods with finite elements. Numerical simulations of the process of axial cold forming in the die were carried out for analysis data acquisition necessary, in order to achieve HTD pulleys, for an ordinary range of friction coefficients. The analysis was directed to the gearing area of the HTD pulleys (head, flank and base of the tooth). The analysis highlighted the negative effects of friction forces on the shape and quality of the products and the need to use quality lubricants. Also, using the cold forming process they can be achieved substantial savings by redistribution of the material without removing it.

  2. Geochemical processes in landfills

    NASA Astrophysics Data System (ADS)

    Förstner, Ulrich; Kersten, Michael; Wienberg, Reinhard

    The present review focusses on the qualitative long-term perspectives of processes and mechanisms controlling the interactions of critical pollutants with organic and inorganic substrates both in "reactor landfills" and in deposits, which already consist of rock-like material ("final storage quality"). The behavior of pollutants in landfills is determined by the chemistry of interstitial solutions, i.e. by pH and redox conditions, and concentration of inorganic and organic ligands; in "reactor landfills" these conditions are widely variable as a result of biochemical reactions, while "final storage quality" implies less variations of chemical interactions. In both alternatives, however, prediction of short- and long-term effects on groundwater quality should be based on the proportion of "active species" of compounds ("mobility concept"). Qualitative assessment of potentially mobile pollutants may involve a controlled significative intensivation of important parameters such as pH-values. Using sequential extraction rearrangements of specific solid "phases" can be evaluated prior to the actual remobilisation of the pollutant into the dissolved phase. From a geochemical point of view the "reactor landfill" is characterized by labile conditions during the initial aerobic and acid anaerobic phases, the former mainly due to uncontrolled interactions with organic solutes. On the other hand, final storage quality, which is defined by the composition of earth crust material, in most cases is not attained by simple incineration of municipal waste, i.e. by reduction of organic fractions only. There is, in particular, the problem of easily soluble minerals, such as chlorides. Nonetheless the type of inorganic residue deposits will increasingly receive prevalence as a method of final storage for municipal wastes in the future.

  3. Cytochrome c Complexes with Cardiolipin Monolayer Formed under Different Surface Pressure.

    PubMed

    Marchenkova, Margarita A; Dyakova, Yulia A; Tereschenko, Elena Yu; Kovalchuk, Mikhail V; Vladimirov, Yury A

    2015-11-17

    The formation of the complex of cytochrome c (Cytc) with a phospholipid cardiolipin (CL) in mitochondria is a crucial event in apoptosis development. There are two viewpoints on the structure of the complex. (1) Cytc is bound on the surface of the lipid bilayer. (2) The complex is a hydrophobic nanoparticle Cytc-CL formed by Cytc molten globule, covered by CL monolayer.1 In the present work, we attempted to bridge the gap between these two structures. We investigated the interaction between Cytc and Langmuir monolayers of CL. The surface pressure increase during incorporation of Cytc into CL monolayer obeys the equation: π = π0 + Δπ∞[1 - exp(-βt)], where β is pseudo-first-order rate constant of Cytc binding, directly proportional to the initial Cytc concentration c0. Parameters Δπ∞ and the rate β measured in different conditions were virtually equal for natural bovine CL and peroxidation-resistant tetraoleoyl CL in all experiments. Surface area-surface pressure isotherms of Cytc alone and in combination with a CL monolayer were similar in shape. Apparently, the protein exposes hydrophilic groups to the water phase and hydrophobic to the air or to the hydrocarbon chains of CL. The 30% ethanol dramatically accelerated the adsorption of Cytc on the water surface. The protein-lipid surface films showed, in compression-expansion cycles, that hysteresis loops were observed always when Cytc present, reproducible in repeating cycles. Taken together, our data show that when incorporated in a lipid monolayer or after adsorption on the water-air interface, Cytc undergoes conformational transition. In that, one part of the globule sphere becomes predominantly hydrophobic and the other, hydrophilic and charged ("stratified" Cytc). We hypothesize that in CL-containing bilayer membranes, Cytc incorporation into the lipid monolayer would result in membrane folding with subsequent formation of either catalytically reactive "bubbles" inside the bilayer, formed by Cytc

  4. Ratioed scatter diagrams - An erotetic method for phase identification on complex surfaces using scanning Auger microscopy

    NASA Technical Reports Server (NTRS)

    Browning, R.

    1984-01-01

    By ratioing multiple Auger intensities and plotting a two-dimensional occupational scatter diagram while digitally scanning across an area, the number and elemental association of surface phases can be determined. This can prove a useful tool in scanning Auger microscopic analysis of complex materials. The technique is illustrated by results from an anomalous region on the reaction zone of a SiC/Ti-6Al-4V metal matrix composite material. The anomalous region is shown to be a single phase associated with sulphur and phosphorus impurities. Imaging of a selected phase from the ratioed scatter diagram is possible and may be a useful technique for presenting multiple scanning Auger images.

  5. 5-level polysilicon surface micromachine technology: Application to complex mechanical systems

    SciTech Connect

    Rodgers, M.S.; Sniegowski, J.J.

    1998-06-01

    The authors recently reported on the development of a 5-level poly-ilicon surface micromachine fabrication process consisting of four levels of mechanical poly plus an electrical interconnect layer. They are now reporting on the first components designed for and fabricated in this process. These are demonstration systems, which definitively show that five levels of polysilicon provide greater performance, reliability, and significantly increased functionality. This new technology makes it possible to realize levels of system complexity that have so far only existed on paper, while simultaneously adding to the robustness of many of the individual subassemblies.

  6. Potential Energy Surfaces and Charge Transfer of PAH-Sodium-PAH Complexes.

    PubMed

    Hjertenaes, Eirik; Andersson, Stefan; Koch, Henrik

    2016-09-19

    To further understanding of the role of sodium in carbon cathode degradation in Hall-Héroult cells, potential-energy surfaces and charge-transfer curves are presented for finite-size complexes of sodium intercalated between various polycyclic aromatic hydrocarbons. Calculations for lithium and potassium are included to highlight the disparate intercalation behaviour of the alkali metals in graphite intercalation compounds. Static energy barriers from DFT are used to compute macroscopic diffusion coefficients according to transition-state theory. Comparing the calculated diffusion coefficient to experimental values from the literature sheds light on the role of lattice diffusion of sodium-graphite intercalation compounds in sodium intrusion in graphitic carbon cathodes.

  7. Potential energy surface and bound states of the NH3-Ar and ND3-Ar complexes.

    PubMed

    Loreau, J; Liévin, J; Scribano, Y; van der Avoird, A

    2014-12-14

    A new, four-dimensional potential energy surface for the interaction of NH3 and ND3 with Ar is computed using the coupled-cluster method with single, double, and perturbative triple excitations and large basis sets. The umbrella motion of the ammonia molecule is explicitly taken into account. The bound states of both NH3-Ar and ND3-Ar are calculated on this potential for total angular momentum values from J = 0 to 10, with the inclusion of Coriolis interactions. The energies and splittings of the rovibrational levels are in excellent agreement with the extensive high-resolution spectroscopic data accumulated over the years in the infrared and microwave regions for both complexes, which demonstrates the quality of the potential energy surface.

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

    SciTech Connect

    Hao, Juan; Xu, Chunguang; Zhang, Lan

    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.

  9. On the reflectivity of complex mesh surfaces. [of space-deployable reflector antennas

    NASA Technical Reports Server (NTRS)

    Imbriale, William A.; Galindo-Israel, Victor; Rahmat-Samii, Yahya

    1991-01-01

    Poorer than expected surface reflectivity was observed in an early Tracking and Data Relay Satellite System antenna utilizing a tricot mesh weave. This poor reflectivity was determined to be caused by inadequate electrical contact at wire crossover points. A proper mathematical and numerical approach to assess the impact of wire junctions on reflectivity performance is developed. A mathematical method is presented for computing the surface reflectivity of complex mesh configurations like those on unfurlable-type spacecraft antennas. The method is based on the Floquet mode expansion to establish an integral equation for mesh wire currents. The equation is solved using the method of moments with triangular basis functions. It is observed that it is necessary to give special attention to the junction treatment among different branches of the mesh configurations. A vector junction current approach that resulted in satisfactory solutions for the current is described. The results of numerical simulations are compared against measured data and excellent agreement is observed.

  10. Surface-modified complex SU-8 microstructures for indirect optical manipulation of single cells.

    PubMed

    Aekbote, Badri L; Fekete, Tamás; Jacak, Jaroslaw; Vizsnyiczai, Gaszton; Ormos, Pál; Kelemen, Lóránd

    2016-01-01

    We introduce a method that combines two-photon polymerization (TPP) and surface functionalization to enable the indirect optical manipulation of live cells. TPP-made 3D microstructures were coated specifically with a multilayer of the protein streptavidin and non-specifically with IgG antibody using polyethylene glycol diamine as a linker molecule. Protein density on their surfaces was quantified for various coating methods. The streptavidin-coated structures were shown to attach to biotinated cells reproducibly. We performed basic indirect optical micromanipulation tasks with attached structure-cell couples using complex structures and a multi-focus optical trap. The use of such extended manipulators for indirect optical trapping ensures to keep a safe distance between the trapping beams and the sensitive cell and enables their 6 degrees of freedom actuation. PMID:26819816

  11. Surface-modified complex SU-8 microstructures for indirect optical manipulation of single cells

    PubMed Central

    Aekbote, Badri L.; Fekete, Tamás; Jacak, Jaroslaw; Vizsnyiczai, Gaszton; Ormos, Pál; Kelemen, Lóránd

    2015-01-01

    We introduce a method that combines two-photon polymerization (TPP) and surface functionalization to enable the indirect optical manipulation of live cells. TPP-made 3D microstructures were coated specifically with a multilayer of the protein streptavidin and non-specifically with IgG antibody using polyethylene glycol diamine as a linker molecule. Protein density on their surfaces was quantified for various coating methods. The streptavidin-coated structures were shown to attach to biotinated cells reproducibly. We performed basic indirect optical micromanipulation tasks with attached structure-cell couples using complex structures and a multi-focus optical trap. The use of such extended manipulators for indirect optical trapping ensures to keep a safe distance between the trapping beams and the sensitive cell and enables their 6 degrees of freedom actuation. PMID:26819816

  12. A model for sonar interrogation of complex bottom and surface targets in shallow-water waveguides.

    PubMed

    Giddings, Thomas E; Shirron, Joseph J

    2008-04-01

    Many problems of current interest in underwater acoustics involve low-frequency broadband sonar interrogation of objects near the sea surface or sea floor of a shallow-water environment. When the target is situated near the upper or lower boundary of the water column the acoustic interactions with the target objects are complicated by interactions with the nearby free surface or fluid-sediment interface, respectively. A practical numerical method to address such situations is presented. The model provides high levels of accuracy with the flexibility to handle complex, three-dimensional targets in range-independent environments. The model is demonstrated using several bottom target scenarios, with and without locally undulating seabeds. The impact of interface and boundary interactions is considered with an eye toward using the sonar return signal as the basis for acoustic imaging or spectral classification.

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

    USGS Publications Warehouse

    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.

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

    USGS Publications Warehouse

    Charlton, S.R.; Parkhurst, D.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. ?? 2011.

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

    NASA Astrophysics Data System (ADS)

    Charlton, Scott R.; Parkhurst, David L.

    2011-10-01

    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.

  16. HIFU scattering by the ribs: constrained optimisation with a complex surface impedance boundary condition

    NASA Astrophysics Data System (ADS)

    Gélat, P.; ter Haar, G.; Saffari, N.

    2014-04-01

    High intensity focused ultrasound (HIFU) enables highly localised, non-invasive tissue ablation and its efficacy has been demonstrated in the treatment of a range of cancers, including those of the kidney, prostate and breast. HIFU offers the ability to treat deep-seated tumours locally, and potentially bears fewer side effects than more established treatment modalities such as resection, chemotherapy and ionising radiation. There remains however a number of significant challenges which currently hinder its widespread clinical application. One of these challenges is the need to transmit sufficient energy through the ribcage to ablate tissue at the required foci whilst minimising the formation of side lobes and sparing healthy tissue. Ribs both absorb and reflect ultrasound strongly. This sometimes results in overheating of bone and overlying tissue during treatment, leading to skin burns. Successful treatment of a patient with tumours in the upper abdomen therefore requires a thorough understanding of the way acoustic and thermal energy is deposited. Previously, a boundary element (BE) approach based on a Generalised Minimal Residual (GMRES) implementation of the Burton-Miller formulation was developed to predict the field of a multi-element HIFU array scattered by human ribs, the topology of which was obtained from CT scan data [1]. Dissipative mechanisms inside the propagating medium have since been implemented, together with a complex surface impedance condition at the surface of the ribs. A reformulation of the boundary element equations as a constrained optimisation problem was carried out to determine the complex surface velocities of a multi-element HIFU array which generated the acoustic pressure field that best fitted a required acoustic pressure distribution in a least-squares sense. This was done whilst ensuring that an acoustic dose rate parameter at the surface of the ribs was kept below a specified threshold. The methodology was tested at an

  17. Joint body and surface wave tomography applied to the Toba caldera complex (Indonesia)

    NASA Astrophysics Data System (ADS)

    Jaxybulatov, Kairly; Koulakov, Ivan; Shapiro, Nikolai

    2016-04-01

    We developed a new algorithm for a joint body and surface wave tomography. The algorithm is a modification of the existing LOTOS code (Koulakov, 2009) developed for local earthquake tomography. The input data for the new method are travel times of P and S waves and dispersion curves of Rayleigh and Love waves. The main idea is that the two data types have complementary sensitivities. The body-wave data have good resolution at depth, where we have enough crossing rays between sources and receivers, whereas the surface waves have very good near-surface resolution. The surface wave dispersion curves can be retrieved from the correlations of the ambient seismic noise and in this case the sampled path distribution does not depend on the earthquake sources. The contributions of the two data types to the inversion are controlled by the weighting of the respective equations. One of the clearest cases where such approach may be useful are volcanic systems in subduction zones with their complex magmatic feeding systems that have deep roots in the mantle and intermediate magma chambers in the crust. In these areas, the joint inversion of different types of data helps us to build a comprehensive understanding of the entire system. We apply our algorithm to data collected in the region surrounding the Toba caldera complex (north Sumatra, Indonesia) during two temporary seismic experiments (IRIS, PASSCAL, 1995, GFZ, LAKE TOBA, 2008). We invert 6644 P and 5240 S wave arrivals and ~500 group velocity dispersion curves of Rayleigh and Love waves. We present a series of synthetic tests and real data inversions which show that joint inversion approach gives more reliable results than the separate inversion of two data types. Koulakov, I., LOTOS code for local earthquake tomographic inversion. Benchmarks for testing tomographic algorithms, Bull. seism. Soc. Am., 99(1), 194-214, 2009, doi:10.1785/0120080013

  18. Understanding the spatial complexity of surface hoar from slope to range scale

    NASA Astrophysics Data System (ADS)

    Hendrikx, J.

    2015-12-01

    Surface hoar, once buried, is a common weak layer type in avalanche accidents in continental and intermountain snowpacks around the World. Despite this, there is still limited understanding of the spatial variability in both the formation of, and eventual burial of, surface hoar at spatial scales which are of critical importance to avalanche forecasters. While it is relatively well understood that aspect plays an important role in the spatial location of the formation, and burial of these grain forms, due to the unequal distribution of incoming radiation, this factor alone does not explain the complex and often confusing spatial pattern of these grains forms throughout the landscape at different spatial scales. In this paper we present additional data from a unique data set including over two hundred days of manual observations of surface hoar at sixteen locations on Pioneer Mountain at the Yellowstone Club in southwestern Montana. Using this wealth of observational data located on different aspects, elevations and exposures, coupled with detailed meteorological observations, and detailed slope scale observation, we examine the spatial variability of surface hoar at this scale, and examine the factors that control its spatial distribution. Our results further supports our preliminary work, which shows that small-scale slope conditions, meteorological differences, and local scale lapse rates, can greatly influence the spatial variability of surface hoar, over and above that which aspect alone can explain. These results highlight our incomplete understanding of the processes at both the slope and range scale, and are likely to have implications for both regional and local scale avalanche forecasting in environments where surface hoar cause ongoing instabilities.

  19. Lunar and Planetary Science XXXV: Weird Martian Minerals: Complex Mars Surface Processes

    NASA Technical Reports Server (NTRS)

    2004-01-01

    The session "Complex Mars Surface" included the following reports:A Reappraisal of Adsorbed Superoxide Ion as the Cause Behind the Reactivity of the Martian Soils; Sub-Surface Deposits of Hydrous Silicates or Hydrated Magnesium Sulfates as Hydrogen Reservoirs near the Martian Equator: Plausible or Not?; Thermal and Evolved Gas Analysis of Smectites: The Search for Water on Mars; Aqueous Alteration Pathways for K, Th, and U on Mars; Temperature Dependence of the Moessbauer Fraction in Mars-Analog Minerals; Acid-Sulfate Vapor Reactions with Basaltic Tephra: An Analog for Martian Surface Processes; Iron Oxide Weathering in Sulfuric Acid: Implications for Mars; P/Fe as an Aquamarker for Mars; Stable Isotope Composition of Carbonates Formed in Low-Temperature Terrestrial Environments as Martian Analogs; Can the Phosphate Sorption and Occlusion Properties Help to Elucidate the Genesis of Specular Hematite on the Mars Surface?; Sulfate Salts, Regolith Interactions, and Water Storage in Equatorial Martian Regolith; Potential Pathways to Maghemite in Mars Soils: The Key Role of Phosphate; and Mineralogy, Abundance, and Hydration State of Sulfates and Chlorides at the Mars Pathfinder Landing Site.

  20. Influence of tailored MLI for complex surface geometries on heat transfer

    NASA Astrophysics Data System (ADS)

    Neumann, H.; Mayrhofer, R.; Richter, T.

    2015-12-01

    Complex, non-developable surfaces require a tailored multi-layer insulation (MLI) for lowest heat load. The most experiments showing the heat transfer through MLI are performed under quasi-ideal conditions determining the principle insulation quality. But the surface to be insulated in real cryostats implies feed-throughs and other non-developable surface parts. The thermal performance of MLI is degraded significantly at cutting points. To investigate this degrading effect a LN2-filled cylinder with a diameter of 219 mm and a length of 1820 mm was insulated with MLI and the heat load was measured by means of calorimetry. In addition the heat load to an insulated cylinder with eighteen branches was measured. Both cylinders have the same surface of 1.37 m2 for a comparison of the results. This article describes the experiments with different ways of tailoring the MLI for the cylinder with branches and discusses their results. It was shown that the cutting points at the branches have a significant degrading influence on the thermal performance of MLI.

  1. Chemistry-specific surface adsorption of the barnacle settlement-inducing protein complex

    PubMed Central

    Petrone, Luigi; Aldred, Nick; Emami, Kaveh; Enander, Karin; Ederth, Thomas; Clare, Anthony S.

    2015-01-01

    Gregarious settlement in barnacle larvae (cyprids) is induced by a contact pheromone, the settlement-inducing protein complex (SIPC). The SIPC has been identified both in the cuticle of adult barnacles and in the temporary adhesive secretion (footprint) of cyprids. Besides acting as a settlement inducer, the presence of the SIPC in footprints points to its additional involvement in the adhesion process. SIPC adsorption behaviour was therefore investigated on a series of self-assembled monolayers (SAMs) by surface plasmon resonance at the pH of seawater (8.3). Fibrinogen and α2-macroglobulin (A2M) (blood complement protease inhibitors with which the SIPC shares 29% sequence homology) were used in the adsorption experiments as positive and negative standards, respectively. The mass uptake of the SIPC was comparable to that of fibrinogen, with adsorption observed even on the protein-resistant oligo(ethylene glycol) surface. Notably, on the positively charged SAM the SIPC showed a kinetic overshoot, indicating a metastable configuration causing the amount of adsorbed protein to temporarily exceed its equilibrium value. A2M adsorption was low or negligible on all SAMs tested, except for the positively charged surface, indicating that A2M adsorption is mainly driven by electrostatics. Evaluation of SIPC non-specific adsorption kinetics revealed that it adsorbed irreversibly and non-cooperatively on all surfaces tested. PMID:25657832

  2. Chemistry-specific surface adsorption of the barnacle settlement-inducing protein complex.

    PubMed

    Petrone, Luigi; Aldred, Nick; Emami, Kaveh; Enander, Karin; Ederth, Thomas; Clare, Anthony S

    2015-02-01

    Gregarious settlement in barnacle larvae (cyprids) is induced by a contact pheromone, the settlement-inducing protein complex (SIPC). The SIPC has been identified both in the cuticle of adult barnacles and in the temporary adhesive secretion (footprint) of cyprids. Besides acting as a settlement inducer, the presence of the SIPC in footprints points to its additional involvement in the adhesion process. SIPC adsorption behaviour was therefore investigated on a series of self-assembled monolayers (SAMs) by surface plasmon resonance at the pH of seawater (8.3). Fibrinogen and α2-macroglobulin (A2M) (blood complement protease inhibitors with which the SIPC shares 29% sequence homology) were used in the adsorption experiments as positive and negative standards, respectively. The mass uptake of the SIPC was comparable to that of fibrinogen, with adsorption observed even on the protein-resistant oligo(ethylene glycol) surface. Notably, on the positively charged SAM the SIPC showed a kinetic overshoot, indicating a metastable configuration causing the amount of adsorbed protein to temporarily exceed its equilibrium value. A2M adsorption was low or negligible on all SAMs tested, except for the positively charged surface, indicating that A2M adsorption is mainly driven by electrostatics. Evaluation of SIPC non-specific adsorption kinetics revealed that it adsorbed irreversibly and non-cooperatively on all surfaces tested. PMID:25657832

  3. Auto-pick first breaks with complex raypaths for undulate surface conditions

    NASA Astrophysics Data System (ADS)

    An, Sheng-Pei; Hu, Tian-Yue; Cui, Yong-Fu; Duan, Wen-Sheng; Peng, Geng-Xin

    2015-03-01

    First-break picking is the key step in seismic data processing for surveying undulate surfaces, and directly influences the precision of near-surface modeling and effects of static corrections. The current first-break auto-picking methods may fail when the signal-to-noise ratio (SNR) is low for seismic data in the undulate area, and require labor and time intensive manual picking. This study develops an improved super-virtual interferometry (SVI) method that combines multichannel and multidomain quality control (MMQC) techniques to achieve auto-picked first breaks. The improved SVI method extends the SVI application to enhance the SNR for near-surface scattered waves for the first time, which allows for the SVI method to adapt to first breaks with complex raypaths by linear combination of refractions and near-surface scattered waves. Methods of inverse and multidomain interferometry are developed to effectively enhance the virtual records extracted by the SVI method. The deconvolution filter for waveforms is used to increase resolution and reduce false picks, while the MMQC technique is designed to auto-correct false picks and increase the stability of auto-picking first breaks. The robust technique developed in this study enables stable processing of large 3D seismic datasets. Higher quality results are obtained using the approach presented in this paper to actual field data from the mountain areas in western China, when compared to some commonly used commercial software.

  4. Dynamics of defects and dopants in complex systems: Silicon and oxide surfaces and interfaces

    NASA Astrophysics Data System (ADS)

    Kirichenko, Taras Alexandrovich

    2005-11-01

    Precise control of dopant redistribution and activation in the vicinity of the semiconductor-dielectric interface has become crucial for fabrication of deep sub-micron metal-oxide-semiconductor field-effect transistor devices. During the process of ion implantation and thermal oxidation a great number of native defects (such as vacancies and interstitials) can be created in the substrate. These defects are known to be mainly responsible for transient enhanced diffusion and electrical activation/deactivation of dopant impurities. In this work we seek to develop a detailed understanding of the exact mechanisms of defect annihilation, and dopant diffusion and clustering/dissolution in complex systems such as Si surfaces and amorphous-crystalline Si-Si and Si-SiO2 interfaces using density functional theory total energy calculations. Si(001) surface: (1) We examine structure, energetics, and bonding of vacancies and interstitials on the clean and terminated Si(001) surface and its subsurface layers. (2) We propose mechanism of vacancy stabilization at the surface and subsurface layers. (3) We find Si(001) surface to be an effective sink for vacancies and interstitials, irrespective of surface passivation. (4) We present diffusion pathways and barriers of vacancies at and in the vicinity of the clean surface. (5) We have demonstrated that the stability of native defects within the top-most three subsurface layers is greatly influenced by surface passivation. Amorphous-crystalline Si interface: (1) We present native defect configurations, energetics and the origin of their stabilization at amorphous-crystalline Si interface and in amorphous Si. (2) A continuous random network model is employed in the construction of a realistic a-c interface structures. (3) We propose the 'sponge-like' behavior of the amorphous phase toward native defects. Si/SiO2 interface: (1) We present stable Si interstitial structures at interface and in the oxide. (2) We propose mechanism of

  5. PALADYN, a comprehensive land surface-vegetation-carbon cycle model of intermediate complexity

    NASA Astrophysics Data System (ADS)

    Willeit, Matteo; Ganopolski, Andrey

    2016-04-01

    PALADYN is presented, a new comprehensive and computationally efficient land surface-vegetation-carbon cycle model designed to be used in Earth system models of intermediate complexity for long-term simulations and paleoclimate studies. The model treats in a consistent manner the interaction between atmosphere, terrestrial vegetation and soil through the fluxes of energy, water and carbon. Energy, water and carbon are conserved. The model explicitly treats permafrost, both in physical processes and as important carbon pool. The model distinguishes 9 surface types of which 5 are different vegetation types, bare soil, land ice, lake and ocean shelf. Including the ocean shelf allows to treat continuous changes in sea level and shelf area associated with glacial cycles. Over each surface type the model solves the surface energy balance and computes the fluxes of sensible, latent and ground heat and upward shortwave and longwave radiation. It includes a single snow layer. The soil model distinguishes between three different macro surface types which have their own soil column: vegetation and bare soil, ice sheet and ocean shelf. The soil is vertically discretized into 5 layers where prognostic equations for temperature, water and carbon are consistently solved. Phase changes of water in the soil are explicitly considered. A surface hydrology module computes precipitation interception by vegetation, surface runoff and soil infiltration. The soil water equation is based on Darcy's law. Given soil water content, the wetland fraction is computed based on a topographic index. Photosynthesis is computed using a light use efficiency model. Carbon assimilation by vegetation is coupled to the transpiration of water through stomatal conductance. The model includes a dynamic vegetation module with 5 plant functional types competing for the gridcell share with their respective net primary productivity. Each macro surface type has its own carbon pools represented by a litter, a fast

  6. Organic geochemical constraints on paleoelevation

    NASA Astrophysics Data System (ADS)

    Polissar, P. J.; Rowley, D. B.; Currie, B. S.; Freeman, K. H.

    2012-12-01

    The elevation history of the land surface is an important factor in the interpretation of past tectonic, climate and ecological processes. However, quantitative estimates of paleoelevation are difficult to produce and new techniques are needed. Organic geochemical approaches to quantifying paleoelevations provide a new perspective on this difficult task. The hydrogen isotopic composition of organic biomarker molecules synthesized by plants and algae is systematically related to the water used for growth. Organic molecules in ancient sediments can provide values for the isotopic composition of this water and thus elevation, provided the relationship between elevation and isotopic values is known. Molecular hydrogen isotope ratios from Cenozoic lake sediments on the Tibetan Plateau demonstrate the utility of a biomarker approach. Terrestrial plant-wax D/H values on Neogene sediments from the Namling-Oiyug Basin provide new paleoelevation estimates that compare well with previous studies. Plant wax D/H ratios paired with lacustrine carbonate oxygen isotope values from the Lunpola and Hoh-Xil basins illustrate how paired isotope systems can unravel the isotopic composition of precipitation from evaporative enrichment of lake waters. A potentially fruitful avenue for future research is illustrated by D/H analyses on older sediments from the Namling-Oiyug Basin. These sediments—like many that could be useful for paleoaltimetry—have experienced significant burial and heating. As temperatures approach the oil window it becomes possible to exchange hydrogen in both the extractable organic molecules (bitumen) and the insoluble organic residue (kerogen). The extent to which this exchange alters the original isotopic composition will determine the usefulness of D/H analyses on thermally mature organic matter. The potential payoff and pitfalls of D/H analyses on heated sediments is illustrated with thermally immature and mature samples from the Namling-Oiyug Basin.

  7. Interaction between zinc and freshwater and marine diatom species: Surface complexation and Zn isotope fractionation

    NASA Astrophysics Data System (ADS)

    Gélabert, A.; Pokrovsky, O. S.; Viers, J.; Schott, J.; Boudou, A.; Feurtet-Mazel, A.

    2006-02-01

    This work is devoted to characterization of zinc interaction in aqueous solution with two marine planktonic ( Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species ( Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption and electrophoretic measurements with surface complexation modeling and by assessing Zn isotopes fractionation during both long term uptake and short term adsorption on diatom cells and their frustules. Reversible adsorption experiments were performed at 25 and 5 °C as a function of exposure time (5 min to 140 h), pH (2 to 10), zinc concentration in solution (10 nM to 1 mM), ionic strength ( I = 0.001 to 1.0 M) and the presence of light. While the shape of pH-dependent adsorption edge is almost the same for all four species, the constant-pH adsorption isotherm and maximal Zn binding capacities differ by an order of magnitude. The extent of adsorption increases with temperature from 5 to 25 °C and does not depend on light intensity. Zinc adsorption decreases with increase of ionic strength suggesting competition with sodium for surface sites. Cell number-normalized concentrations of sorbed zinc on whole cells and their silica frustules demonstrated only weak contribution of the latter (10-20%) to overall zinc binding by diatom cell wall. Measurements of electrophoretic mobilities ( μ) revealed negative diatoms surface potential in the full range of zinc concentrations investigated (0.15-760 μmol/L), however, the absolute value of μ decreases at [Zn] > 15 μmol/L suggesting a change in surface speciation. These observations allowed us to construct a surface complexation model for Zn binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Zn complexation with carboxylate and silanol groups. Thermodynamic and structural parameters of this model are based on previous acid-base titration and spectroscopic results and allow

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

    NASA Astrophysics Data System (ADS)

    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

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

    PubMed

    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

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

    DOE PAGES

    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 feasibilitymore » 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.« less

  11. Chemical transformations drive complex self-assembly of uracil on close-packed coinage metal surfaces.

    PubMed

    Papageorgiou, Anthoula C; Fischer, Sybille; Reichert, Joachim; Diller, Katharina; Blobner, Florian; Klappenberger, Florian; Allegretti, Francesco; Seitsonen, Ari P; Barth, Johannes V

    2012-03-27

    We address the interplay of adsorption, chemical nature, and self-assembly of uracil on the Ag(111) and Cu(111) surfaces as a function of molecular coverage (0.3 to 1 monolayer) and temperature. We find that both metal surfaces act as templates and the Cu(111) surface acts additionally as a catalyst for the resulting self-assembled structures. With a combination of STM, synchrotron XPS, and NEXAFS studies, we unravel a distinct polymorphism on Cu(111), in stark contrast to what is observed for the case of uracil on the more inert Ag(111) surface. On Ag(111) uracil adsorbs flat and intact and forms close-packed two-dimensional islands. The self-assembly is driven by stable hydrogen-bonded dimers with poor two-dimensional order. On Cu(111) complex structures are observed exhibiting, in addition, a strong annealing temperature dependence. We determine the corresponding structural transformations to be driven by gradual deprotonation of the uracil molecules. Our XPS study reveals unambiguously the tautomeric signature of uracil in the contact layer and on Cu(111) the molecule's deprotonation sites. The metal-mediated deprotonation of uracil and the subsequent electron localization in the molecule determine important biological reactions. Our data show a dependence between molecular coverage and molecule-metal interaction on Cu(111), as the molecules tilt at higher coverages in order to accommodate a higher packing density. After deprotonation of both uracil N atoms, we observe an adsorption geometry that can be understood as coordinative anchoring with a significant charge redistribution in the molecule. DFT calculations are employed to analyze the surface bonding and accurately describe the pertaining electronic structure.

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

    PubMed

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

    2016-03-01

    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.

  13. Tetrathiafulvalene-Supported Triple-Decker Phthalocyaninato Dysprosium(III) Complex: Synthesis, Properties and Surface Assembly

    PubMed Central

    Gao, Feng; Zhang, Xue-Mei; Cui, Long; Deng, Ke; Zeng, Qing-Dao; Zuo, Jing-Lin

    2014-01-01

    Self-assembly of functional compounds into a prerequisite nanostructure with desirable dimension and morphology by controlling and optimizing intermolecular interaction attracts an extensive research interest for chemists and material scientist. In this work, a new triple-decker sandwich-type lanthanide complex with phthalocyanine and redox-active Schiff base ligand including tetrathiafulvalene (TTF) units has been synthesized, and characterized by single crystal X-ray diffraction analysis, absorption spectra, electrochemical and magnetic measurements. Interestingly, the non-centrosymmetric target complex displays a bias dependent selective adsorption on a solid surface, as observed by scanning tunneling microscopy (STM) at the single molecule level. Density function theory (DFT) calculations are utilized to reveal the formation mechanism of the molecular assemblies, and show that such electrical field dependent selective adsorption is regulated by the interaction between the external electric field and intrinsic molecular properties. Our results suggest that this type of multi-decker complex involving TTF units shows intriguing multifunctional properties from the viewpoint of structure, electric and magnetic behaviors, and fabrication through self-assembly. PMID:25088605

  14. Comparison of in situ uranium KD values with a laboratory determined surface complexation model

    USGS Publications Warehouse

    Curtis, G.P.; Fox, P.; Kohler, M.; Davis, J.A.

    2004-01-01

    Reactive solute transport simulations in groundwater require a large number of parameters to describe hydrologic and chemical reaction processes. Appropriate methods for determining chemical reaction parameters required for reactive solute transport simulations are still under investigation. This work compares U(VI) distribution coefficients (i.e. KD values) measured under field conditions with KD values calculated from a surface complexation model developed in the laboratory. Field studies were conducted in an alluvial aquifer at a former U mill tailings site near the town of Naturita, CO, USA, by suspending approximately 10 g samples of Naturita aquifer background sediments (NABS) in 17-5.1-cm diameter wells for periods of 3 to 15 months. Adsorbed U(VI) on these samples was determined by extraction with a pH 9.45 NaHCO3/Na2CO3 solution. In wells where the chemical conditions in groundwater were nearly constant, adsorbed U concentrations for samples taken after 3 months of exposure to groundwater were indistinguishable from samples taken after 15 months. Measured in situ K D values calculated from the measurements of adsorbed and dissolved U(VI) ranged from 0.50 to 10.6 mL/g and the KD values decreased with increasing groundwater alkalinity, consistent with increased formation of soluble U(VI)-carbonate complexes at higher alkalinities. The in situ K D values were compared with KD values predicted from a surface complexation model (SCM) developed under laboratory conditions in a separate study. A good agreement between the predicted and measured in situ KD values was observed. The demonstration that the laboratory derived SCM can predict U(VI) adsorption in the field provides a critical independent test of a submodel used in a reactive transport model. ?? 2004 Elsevier Ltd. All rights reserved.

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

    PubMed

    Famoso, Nicholas A; Davis, Edward Byrd

    2016-01-01

    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 significant (p = 0

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

    PubMed Central

    Davis, Edward Byrd

    2016-01-01

    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 significant (p = 0

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

    PubMed

    Famoso, Nicholas A; Davis, Edward Byrd

    2016-01-01

    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 significant (p = 0

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

    NASA Astrophysics Data System (ADS)

    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.

  19. GEOCHEMICAL MODELING OF ARSENIC SPECIATION AND MOBILIZATION: IMPLICATIONS FOR BIOREMEDIATION

    EPA Science Inventory

    Geochemical modeling techniques were used to examine the biogeochemical linkages between Fe, S, and As in shallow alluvial aquifers. We modeled: 1) the adsorption and desorption of As on the surface of hydrous ferric oxides (HFO’s) in stream beds under aerobic conditions; 2) red...

  20. Surface engineered gold nanoparticles through highly stable metal-surfactant complexes.

    PubMed

    Kim, Sunghwan; Jang, Youngjin; Yoon, Ki Youl; Park, Jongnam

    2016-02-15

    Monodispersed Au nanoparticles were synthesized by the reduction of Au-decyltrimethylammonium bromide (Au-DTAB), which was easily prepared via the reaction of HAuCl4 and DTAB. This Au-DTAB complex is highly stable in air and moisture, and suitable for large-scale synthesis of uniform-sized Au nanoparticles. The nanoparticles were characterized by transmission electron microscopy, optical absorption spectrometry, X-ray diffraction, and Fourier Transform infrared spectroscopy. The size of Au nanoparticles was controlled in the range of 5-10nm by changing the concentrations of reducing agent and Au precursor. The resulting Au nanoparticles were transferred to the aqueous phase after surface engineering using multidentate polymeric ligands with multiple imidazole functional groups. Polymeric imidazole ligands (PILs) demonstrated enhanced binding stability with the Au surface, and overcame the disadvantage of multidentate thiol ligand systems which have oxidative cross-linking and the formation of disulfide bonding. The colloidal stability of surface engineered Au nanoparticles with PILs was investigated by dynamic light scattering (DLS) characterization.

  1. The Interaction of Streptococcal Enolase with Canine Plasminogen: The Role of Surfaces in Complex Formation

    PubMed Central

    Balhara, Vinod; Deshmukh, Sasmit S.; Kálmán, László; Kornblatt, Jack A.

    2014-01-01

    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. PMID:24520380

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

    PubMed

    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.

  3. Advance Complex Liquid Nitriding of Stainless Steel AISI 321 Surface at 430 °C

    NASA Astrophysics Data System (ADS)

    Lin, Yuanhua; Wang, Jun; Zeng, Dezhi; Huang, Runbo; Fan, Hongyuan

    2013-09-01

    Liquid nitriding of type 321 austenite stainless steel was conducted at low temperature at 430 °C, using a type of a complex chemical heat-treatment; and the properties of the nitrided surface were evaluated. Experimental results revealed that a modified layer was formed on the surface with the thickness ranging from 2 to 30 μm varying with changing treatment time. When the stainless steel subjected to the advanced liquid nitriding less than 8 h at 430 °C, the main phase of the nitrided coating layer was the S phase generally. When the treatment time prolonged up to 16 h, S phase formed and partially transformed to CrN subsequently; and then the fine secondary CrN phase precipitated. All treatments performed in the current study can effectively improve the surface hardness. The nitrided layer thickness changed intensively with the increasing nitrided time. The growth of the nitride layer took place mainly by nitrogen diffusion according to the expected parabolic rate law. The highest hardness value obtained in this experiment was about 1400 Hv0.25. Low-temperature nitriding can improve the corrosion resistance of the 321 stainless steel against diluted vitriolic acid. The immerse test results revealed that the sample nitrided for 16 h had the best corrosion resistance than the others. SEM examinations indicated that after nitriding, the corrosion mechanisms of the steel had changed from serious general corrosion of untreated sample to selectivity corrosion of nitrided samples in the diluted vitriolic acid.

  4. The mineralogic evolution of the Martian surface through time: Implications from chemical reaction path modeling studies

    NASA Technical Reports Server (NTRS)

    Plumlee, G. S.; Ridley, W. I.; Debraal, J. D.; Reed, M. H.

    1993-01-01

    Chemical reaction path calculations were used to model the minerals that might have formed at or near the Martian surface as a result of volcano or meteorite impact driven hydrothermal systems; weathering at the Martian surface during an early warm, wet climate; and near-zero or sub-zero C brine-regolith reactions in the current cold climate. Although the chemical reaction path calculations carried out do not define the exact mineralogical evolution of the Martian surface over time, they do place valuable geochemical constraints on the types of minerals that formed from an aqueous phase under various surficial and geochemically complex conditions.

  5. Effect of complexing ligands on the adsorption of Cu(II) onto the silica gel surface. 2: Adsorption of Cu(II)-ligand complexes

    SciTech Connect

    Park, Y.J.; Jung, K.H.; Park, K.K.

    1995-06-15

    The effect of complexing ligands on the adsorption of Cu(II) onto silica gel was investigated in aqueous solution. The adsorption was conspicuously enhanced by 2,2{prime},6{prime},2{double_prime}-terpyridine, 2-pyridine methanol and 2-aminomethyl pyridine, as compared to non-complexed Cu{sup 2+} ions. This enhancement was attributed to both hydrophobic interaction in the low pH region and the formation of ternary surface complexes in the high pH region. It was attenuated by picolinic acid, salicylic acid, and 5-sulfosalicylic acid due to the competition of dissolved ligands and silanol groups with Cu{sup 2+} ions. In the presence of pyridine or 3,4-lutidine, the adsorption was slightly increased, as compared to non-complexed Cu{sup 2+} ions. In both cases, the adsorption at low pH was interpreted in terms of the type B ternary surface complex formation. For 2-pyridine methanol, the formation of cyclic ternary surface complexes was proposed. The Stern model was adopted for the treatment of the adsorption data in the present study.

  6. Geomorphological experiments for understanding cross-scale complexity of earth surface processes

    NASA Astrophysics Data System (ADS)

    Seeger, Manuel

    2016-04-01

    The shape of the earth's surface is the result of a complex interaction of different processes at different spatial and temporal scales. The challenging problem is, that process observation is rarely possible due to this different scales. In addition, the resulting landform often does not match the scale of process observation. But it is indispensable for the development of concepts of formation of landforms to identify and understand the involved processes and their interaction. To develop models it is even necessary to quantify them and their relevant parameters. Experiments are able to bridge the constraints of process observation mentioned above: it is possible to observe and quantify individual processes as well as complex process combinations up to the development of geomorphological units. The contribution aims at showing, based on soil erosion research, the possibilities of experimental methods for contributing to th understanding of geomorphological processes. A special emphasis is put on the linkage of conceptual understanding of processes, their measurement and the following development of models. The development of experiments to quantify relevant parameters will be shown, as well as the steps undertaken to bring them into the field taking into account the resulting increase of uncertainty in system parameters and results. It will be shown that experiments are even so able to produce precise measurements on individual processes as well as of complex combinations of parameters and processes and to identify their influence on the overall geomorphological dynamics. Experiments are therefore a methodological package able to check complex soil erosion processes at different levels of conceptualization and to generate data for their quantification. And thus, also a methodological concept to take more into account and to further develop in geomorphological science.

  7. Contaminant Organic Complexes: Their Structure and Energetics in Surface Decontamination Processes

    SciTech Connect

    Satish C. B. Myneni

    2005-12-13

    Siderophores are biological macromolecules (400-2000 Da) released by bacteria in iron limiting situations to sequester Fe from iron oxyhydroxides and silicates in the natural environment. These molecules contain hydroxamate and phenolate functional groups, and exhibit very high affinity for Fe{sup 3+}. While several studies were conducted to understand the behavior of siderophores and their application to the metal sequestration and mineral dissolution, only a few of them have examined the molecular structure of siderophores and their interactions with metals and mineral surfaces in aqueous solutions. Improved understanding of the chemical state of different functional moieties in siderophores can assist in the application of these biological molecules in actinide separation, sequestration and decontamination processes. The focus of our research group is to evaluate the (a) functional group chemistry of selected siderophores and their metal complexes in aqueous solutions, and (b) the nature of siderophore interactions at the mineral-water interfaces. We selected desferrioxamine B (desB), a hydroxamate siderophore, and its small structural analogue, acetohydroxamic acid (aHa), for this investigation. We examined the functional group chemistry of these molecules as a function of pH, and their complexation with aqueous and solid phase Fe(III). For solid phase Fe, we synthesized all naturally occurring Fe(III)-oxyhydroxides (goethite, lepidocrocite, akaganeite, feroxyhite) and hematite. We also synthesized Fe-oxides (goethite and hematite) of different sizes to evaluate the influence of particle size on mineral dissolution kinetics. We used a series of molecular techniques to explore the functional group chemistry of these molecules and their complexes. Infrared spectroscopy is used to specifically identify the variations in oxime group as a function of pH and Fe(III) complexation. Resonance Raman spectroscopy was used to evaluate the nature of hydroxamate binding in

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

    SciTech Connect

    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

  9. MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

    EPA Science Inventory

    Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

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

    DOEpatents

    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.

  11. A Non-Electrostatic Surface Complexation Approach to Modeling Radionuclide Migration at the Nevada Test Site: I. Iron Oxides and Calcite

    SciTech Connect

    Zavarin, M; Bruton, C J

    2004-12-17

    Reliable quantitative prediction of contaminant transport in subsurface environments is critical to evaluating the risks associated with radionuclide migration. As part of the Underground Test Area (UGTA) project, radionuclide transport away from various underground nuclear tests conducted in the saturated zone at the Nevada Test Site (NTS) is being examined. In the near-field environment, reactive transport simulations must account for changes in water chemistry and mineralogy as a function of time and their effect on radionuclide migration. Unlike the K{sub d} approach, surface complexation (SC) reactions, in conjunction with ion exchange and precipitation, can be used to describe radionuclide reactive transport as a function of changing environmental conditions. They provide a more robust basis for describing radionuclide retardation in geochemically dynamic environments. The interaction between several radionuclides considered relevant to the UGTA project and iron oxides and calcite are examined in this report. The interaction between these same radionuclides and aluminosilicate minerals is examined in a companion report (Zavarin and Bruton, 2004). Selection criteria for radionuclides were based on abundance, half-life, toxicity to human and environmental health, and potential mobility at NTS (Tompson et al., 1999). Both iron oxide and calcite minerals are known to be present at NTS in various locations and are likely to affect radionuclide migration from the near-field. Modeling the interaction between radionuclides and these minerals was based on surface complexation. The effectiveness of the most simplified SC model, the one-site Non-Electrostatic Model (NEM), to describe sorption under various solution conditions is evaluated in this report. NEM reactions were fit to radionuclide sorption data available in the literature, as well as sorption data recently collected for the UGTA project, and a NEM database was developed. For radionuclide-iron oxide sorption

  12. A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

    NASA Astrophysics Data System (ADS)

    Serrano, Susana; O'Day, Peggy A.; Vlassopoulos, Dimitri; García-González, Maria Teresa; Garrido, Fernando

    2009-02-01

    The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X - and Y -), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions. Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH

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

    USGS Publications Warehouse

    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

  14. The importance of spatial complexity in improving performance of groundwater-surface water models

    NASA Astrophysics Data System (ADS)

    McDonald, Karlie; Kolbe, Tamara; Dara, Rebwar; Weatherill, John; Hannah, David; Krause, Stefan

    2016-04-01

    Recent studies of the importance of nested smaller-scale processes at larger reach and catchment scales have sparked exciting discussions on the level of simplifications made in groundwater-surface water (GW-SW) modelling that may influence the ability to simulate interface processes realistically. The inclusion of high-resolution spatial heterogeneity in subsurface composition can alter hydrodynamics, such as flow paths, and residence time, and detect important locations for ecohydrological processes. Furthermore, the presence of obstructions and spatial complexity, such as woody debris, low permeability structures, and microbial accumulations, influences the replicability with which fluid forcing properties in the environment can be incorporated into hydrodynamic models of the GW-SW interface. In this paper, we address a fundamental question: Does increasing spatial complexity improve the performance of groundwater-surface water models across the GW-SW interface? A 3D model was developed to investigate groundwater flow paths and GW-SW exchange. The model was set up to test two comparative parameterisations: (1) homogeneous representation of the shallow subsurface and (2) heterogeneous subsurface geology utilising extensive core data and Ground Penetrating Radar (GPR) surveys of the area and in particular the streambed interface. Both the homogeneous and heterogeneous models were compared for residence time distributions and development of preferential flow paths. The two models were validated against continuous hydraulic head readings at piezometers and observation wells. The heterogeneous model predicted increased lateral flow with more complex preferential flow paths around low conductivity structures and differences in residence times within the site that was controlled by the subsurface structure and infiltration. The differences presented in this paper between the homogeneous and heterogeneous subsurface models indicate that increased spatial complexity in

  15. Exotic phenomena in 4f systems: From complex magnetism to surface conduction

    NASA Astrophysics Data System (ADS)

    Thomas, Sean Michael

    For materials synthesized with f-electron elements, the interaction between f-electrons and conduction electrons often leads to interesting physics. As the temperature is lowered, the f-electrons can hybridize with the conduction electrons in a process known as the Kondo effect. In a Kondo lattice material, the screening may become coherent at the so-called coherence temperature T*. The resulting material is often metallic, containing heavy bands with effective masses many times larger than the free electron mass. In some cases, the development of coherence leads to a filled heavy-electron band where the chemical potential lies within the hybridization gap, resulting in insulating behavior. CeAgBi2 is an antiferromagnetic compound (TN = 6.4 K) belonging to the former (metallic) case. The close energy scales of the Kondo coherence, antiferromagnetism, and crystal field levels results in complex physical properties. Transport measurements reveal a coupling between the different magnetic phases and Hall resistivity. As the field is increased, the antiferromagnetic transition temperature is suppressed to zero Kelvin. Typically, this is expected to result in a quantum critical point. However, due to strange transport behavior in the paramagnetic regime, the usual signatures of quantum criticality are hidden. SmB6 is a Kondo insulator due to the fact that the hybridization results in the opening of a gap. However, as the temperature is further lowered, the resistance saturates. Originally believed to be due to in-gap conduction states in the bulk, the true reason for the resistance saturation is a robust conducting surface state. Several theories predict that the surface state is a result of SmB6 belonging to a class of materials known as topological insulators. However, direct imaging of the spin-momentum locking of the surface states indicative of a topological insulator has proved elusive. Through transport and magnetic measurements, indirect evidence of the nature of

  16. Characterization of a complex near-surface structure using well logging and passive seismic measurements

    NASA Astrophysics Data System (ADS)

    Benjumea, Beatriz; Macau, Albert; Gabàs, Anna; Figueras, Sara

    2016-04-01

    We combine geophysical well logging and passive seismic measurements to characterize the near-surface geology of an area located in Hontomin, Burgos (Spain). This area has some near-surface challenges for a geophysical study. The irregular topography is characterized by limestone outcrops and unconsolidated sediments areas. Additionally, the near-surface geology includes an upper layer of pure limestones overlying marly limestones and marls (Upper Cretaceous). These materials lie on top of Low Cretaceous siliciclastic sediments (sandstones, clays, gravels). In any case, a layer with reduced velocity is expected. The geophysical data sets used in this study include sonic and gamma-ray logs at two boreholes and passive seismic measurements: three arrays and 224 seismic stations for applying the horizontal-to-vertical amplitude spectra ratio method (H/V). Well-logging data define two significant changes in the P-wave-velocity log within the Upper Cretaceous layer and one more at the Upper to Lower Cretaceous contact. This technique has also been used for refining the geological interpretation. The passive seismic measurements provide a map of sediment thickness with a maximum of around 40 m and shear-wave velocity profiles from the array technique. A comparison between seismic velocity coming from well logging and array measurements defines the resolution limits of the passive seismic techniques and helps it to be interpreted. This study shows how these low-cost techniques can provide useful information about near-surface complexity that could be used for designing a geophysical field survey or for seismic processing steps such as statics or imaging.

  17. The influence of surface characteristics on lapse rates and temperature profiles in areas of complex terrain

    NASA Astrophysics Data System (ADS)

    Pepin, N. C.; Pike, G.; Fower, D.; Schaefer, M.

    2012-12-01

    Temperatures near the ground are often decoupled from free-air equivalents, particularly in areas of complex relief and at high latitudes where cold air drainage occurs particularly when radiation balances become negative. This means that it is hard to predict spatial patterns of surface temperature in such regions. In this study several years of intensive field measurements in complex terrain in northern Finland (Kevo) and Sweden (Abisko) allow detailed examination of the interaction between land surface characteristics (including cryosphere), vegetation, and local/micro-climate in mountain basins. Temperature and vapour pressure were measured every 30 minutes for 5 years (2007-2012) at 60 sites at Kevo and for a winter season (September-June) at 52 sites in Abisko, ranging over 300/600 metres of elevation respectively. In Finland lapse rates vary considerably both seasonally and diurnally, the relative importance of seasonal and diurnal forcing changing throughout the year. The results show intense (up to +80 °C/km) and persistent inversion events during the winter months (NDJ) which are broken up by mechanical effects since there is no diurnal cycle. In the transition from winter into spring (FMA) these inversions still occur but increasing radiation imposes a diurnal pattern on their formation and destruction. As snow cover peaks in spring the interaction between surface albedo, land cover and radiation serves to amplify the diurnal cycle in lapse rates. Daytime lapse rates peak in spring because of an increase in albedo with elevation as dark trees give way to reflective snow. At night inversions rapidly reform. Summer lapse rates are modified (usually weakened) by the presence of open water at low elevations. In Abisko similar processes are shown to be at work, although since the valley system is more open and at a larger spatial scale, the range of lapse rate variability is slightly less and the influence of surface characteristics more subdued. Taken

  18. Exploring the distribution of copper-Schiff base complex covalently anchored onto the surface of mesoporous MCM 41 silica

    SciTech Connect

    Singh, Udayshankar G. . E-mail: usingh@engr.ucsb.edu; Williams, Ruth T. . E-mail: r.t.williams@open.ac.uk; Hallam, Keith R. . E-mail: k.r.hallam@bristol.ac.uk; Allen, Geoffrey C. . E-mail: g.c.allen@bristol.ac.uk

    2005-11-15

    A series of copper-Schiff base MCM 41 materials, synthesized by post-synthetic grafting, was studied by X-ray photoelectron spectroscopy (XPS) and nitrogen sorption (77 K) to explore distribution of the copper-Schiff base complex immobilized on the porous Si-MCM 41. Additional information on the physico-chemical properties of the functionalized materials was obtained by powder X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), CHN microanalysis, FTIR spectroscopy, {sup 29}Si and {sup 13}C CP MAS NMR spectroscopy. The effect of copper-Schiff base complex loading and reaction times on the surface properties of Si-MCM 41 (surface area and pore parameters) in addition to its distribution within the Si-MCM 41 was explored by nitrogen sorption and XPS coupled with argon etching. Argon etching of a surface to a depth of 45 A confirmed that the copper-Schiff base complex was distributed both on the external surface (pore end) and within the pores of Si-MCM 41. The amount of complex located in the pores at this depth was about one-third of the amount detected on the external surface of MCM 41. Nitrogen sorption isotherms measured at 77 K confirmed the reduction in total pore volume and surface area was the result of pore narrowing of Si-MCM 41 following grafting of complex in the 8 h samples. A significant decrease in surface area and pore volume for the 20 h sample (longer reaction time), with the highest copper loading (0.65 mmol g{sup -1}), confirmed pore blocking in this material. The uneven distribution of the copper complex between the external and internal surface of Si-MCM 41 was attributed to the bulky nature of the complex, which restricted access to the pores.

  19. Surface-enhanced resonance Raman spectroscopy of iron-dopamine complexes

    NASA Astrophysics Data System (ADS)

    Kowalchyk, Will K.; Davis, Kevin L.; Morris, Michael D.

    1995-01-01

    Surface-enhanced resonance Raman spectroscopy (SERRS) at silver colloids is used to detect the catecholamines, 3-hydroxytyramine (dopamine) and 3,4-dihydroxyphenylacetic acid (DOPAC), in a modified Ringer's solution. Catecholamines form very strong complexes with iron(III) in solution ( Kf > 10 40) and exhibit a broad ligand-to-metal charge-transfer (LMCT) absorption in the visible (˜ 500 nm). Resonance enhancement is achieved by excitation at 532 nm from a frequency doubled Nd:YAG laser with high quality spectra attainable in 1 s. Maximum SERRS signal is observed when basic buffer is added to a dopamine sample containing 50 × 10 -6 M ferric ion. Dopamine concentrations in the nanomolar (resting level) range are obtained using this technique.

  20. Sanitary study of surface water and of the beach of a water sports and leisure complex.

    PubMed Central

    Chabasse, D.; Laine, P.; Simitzis-Le-Flohic, A. M.; Martineau, B.; el Hourch, M.; Becaud, J. P.

    1986-01-01

    This report presents the parasitological, bacteriological, mycological and physicochemical data obtained from both surface water and beach sand of a lake used for water sports. These show that the lake is contaminated in both winter and spring by water which overflows from the River Maine, and is self-purified by a mechanism of 'lagunage'. In summer signs of pollution are at their lowest level although use of the complex is at its peak. Conversely, the amoebic flora, which is independent of the usual criteria of pollution, predominates in summer, and serves as a marker for the need for increased surveillance. The sand of the beaches does not appear to show any infectious hazard. Environmental pressure will doubtless change these data over a period of time, and it is planned to monitor this. PMID:3734425

  1. Cargo surface hydrophobicity is sufficient to overcome the nuclear pore complex selectivity barrier.

    PubMed

    Naim, Bracha; Zbaida, David; Dagan, Shlomi; Kapon, Ruti; Reich, Ziv

    2009-09-16

    To fulfil their function, nuclear pore complexes (NPCs) must discriminate between inert proteins and nuclear transport receptors (NTRs), admitting only the latter. This specific permeation is thought to depend on interactions between hydrophobic patches on NTRs and phenylalanine-glycine (FG) or related repeats that line the NPC. Here, we tested this premise directly by conjugating different hydrophobic amino-acid analogues to the surface of an inert protein and examining its ability to cross NPCs unassisted by NTRs. Conjugation of as few as four hydrophobic moieties was sufficient to enable passage of the protein through NPCs. Transport of the modified protein proceeded with rates comparable to those measured for the innate protein when bound to an NTR and was relatively insensitive both to the nature and density of the amino acids used to confer hydrophobicity. The latter observation suggests a non-specific, small, and plant interaction network between cargo and FG repeats.

  2. An artificial processivity clamp made with streptavidin facilitates oriented attachment of polymerase–DNA complexes to surfaces

    PubMed Central

    Williams, John G. K.; Steffens, David L.; Anderson, Jon P.; Urlacher, Teresa M.; Lamb, Donald T.; Grone, Daniel L.; Egelhoff, Jolene C.

    2008-01-01

    Single molecule analysis of individual enzymes can require oriented immobilization of the subject molecules on a detection surface. As part of a technology development project for single molecule DNA sequencing, we faced the multiple challenges of immobilizing both a DNA polymerase and its DNA template together in an active, stable complex capable of highly processive DNA synthesis on a nonstick surface. Here, we report the genetic modification of the archaeal DNA polymerase 9°N in which two biotinylated peptide ‘legs’ are inserted at positions flanking the DNA-binding cleft. Streptavidin binding on either side of the cleft both traps the DNA template in the polymerase and orients the complex on a biotinylated surface. We present evidence that purified polymerase–DNA–streptavidin complexes are active both in solution and immobilized on a surface. Processivity is improved from <20 nt in the unmodified polymerase to several thousand nucleotides in the engineered complexes. High-molecular weight DNA synthesized by immobilized complexes is observed moving above the surface even as it remains tethered to the polymerase. Pre-formed polymerase–DNA–streptavidin complexes can be stored frozen and subsequently thawed without dissociation or loss of activity, making them convenient for use in single molecule analysis. PMID:18723573

  3. An artificial processivity clamp made with streptavidin facilitates oriented attachment of polymerase-DNA complexes to surfaces.

    PubMed

    Williams, John G K; Steffens, David L; Anderson, Jon P; Urlacher, Teresa M; Lamb, Donald T; Grone, Daniel L; Egelhoff, Jolene C

    2008-10-01

    Single molecule analysis of individual enzymes can require oriented immobilization of the subject molecules on a detection surface. As part of a technology development project for single molecule DNA sequencing, we faced the multiple challenges of immobilizing both a DNA polymerase and its DNA template together in an active, stable complex capable of highly processive DNA synthesis on a nonstick surface. Here, we report the genetic modification of the archaeal DNA polymerase 9 degrees N in which two biotinylated peptide 'legs' are inserted at positions flanking the DNA-binding cleft. Streptavidin binding on either side of the cleft both traps the DNA template in the polymerase and orients the complex on a biotinylated surface. We present evidence that purified polymerase-DNA-streptavidin complexes are active both in solution and immobilized on a surface. Processivity is improved from <20 nt in the unmodified polymerase to several thousand nucleotides in the engineered complexes. High-molecular weight DNA synthesized by immobilized complexes is observed moving above the surface even as it remains tethered to the polymerase. Pre-formed polymerase-DNA-streptavidin complexes can be stored frozen and subsequently thawed without dissociation or loss of activity, making them convenient for use in single molecule analysis. PMID:18723573

  4. Understanding the Hydrological Controls on the Water Chemistry at the Watershed Scale Using an Integrated Hydro-Thermo-Geochemical Model PIHM-RT

    NASA Astrophysics Data System (ADS)

    Bao, C.; Li, L.; Shi, Y.; Qiao, C.; Sullivan, P. L.; Brantley, S. L.; Duffy, C.

    2013-12-01

    Hydrological and geochemical processes are intricately coupled at the watershed scale. Despite recent advances, modeling the complex hydro-thermo-geochemical interactions at the watershed scale has been challenging. Many efforts have been put forward to solve the well-known puzzles such as the 'double paradox ' raised by Kirchner either mechanistically or through simplified numerical modeling. However, a major gap remains in explicitly modeling and integrating these processes at the watershed scale. This work presents an integrated approach to understanding and quantifying the hydrologic controls on water chemistry at the watershed scale. A fully coupled finite volume hydro -thermo-geochemical model, PIHM-RT (Penn State Integrated Hydrologic Model -Reactive Transport) has been developed based on the land surface hydrologic model, Flux-PIHM. Flux-PIHM is capable of simulating the terrestrial water cycle and the surface energy balance (SEB) to reproduce the spatially distributed observations of water, temperature, and saturation . Adding the reactive transport module enables explicit modeling of the evolving water chemistry, which is controlled by hydrologic processes and geochemical reactions. The reactions include mineral dissolution, precipitation and ion exchange. PIHM-RT utilizes an a priori database EQ3EQ6 that is widely used for geochemical thermodynamics and kinetics. The RT module utilizes an operator splitting scheme described in Zysset et al. (1994), to solve for the advection-dispersion-reaction equation (ADR). The advection dispersion equation was solved using the Euler forward method and the reaction process was solved implicitly. In addition, because the reaction and transport processes differ significantly between the unsaturated and saturated zones, we implemented a volume explicit mass conservation law to account for the variable depth of groundwater and the mixing process involved at the boundary between the saturated and unsaturated zone. The use

  5. Geochemical controls on groundwater chemistry in shales

    SciTech Connect

    Von Damm, K.L.

    1989-01-01

    The chemistry of groundwaters is one of the most important parameters in determining the mobility of species within a rock formation. A three pronged approach was used to determine the composition of, and geochemical controls, on groundwaters specifically within shale formations: (1) available data were collected from the literature, the US Geological Survey WATSTORE data base, and field sampling, (2) the geochemical modeling code EQ3/6 was used to simulate interaction of various shales and groundwaters, and (3) several types of shale were reacted with synthetic groundwaters in the laboratory. The comparison of model results to field and laboratory data provide a means of validating the models, as well as a means of deconvoluting complex field interactions. Results suggest that groundwaters in shales have a wide range in composition and are primarily of the Na-Cl-HCO/sub 3/- type. The constancy of the Na:Cl (molar) ratio at 1:1 and the Ca:Mg ratio from 3:1 to 1:1 suggests the importance of halite and carbonates in controlling groundwater compositions. In agreement with the reaction path modeling, most of the groundwaters are neutral to slightly alkaline at low temperatures. Model and experimental results suggest that reaction (1) at elevated temperatures, or (2) in the presence of oxygen will lead to more acidic conditions. Some acetate was found to be produced in the experiments; depending on the constraints applied, large amounts of acetate were produced in the model results. 13 refs., 1 tab.

  6. Potential energy surface of the CO2-N2 van der Waals complex

    NASA Astrophysics Data System (ADS)

    Nasri, Sameh; Ajili, Yosra; Jaidane, Nejm-Eddine; Kalugina, Yulia N.; Halvick, Philippe; Stoecklin, Thierry; Hochlaf, Majdi

    2015-05-01

    Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO2-N2 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 CO2. In addition, we located a second isomer and two transition states in the ground state PES of CO2-N2. All of them lay below the CO2 + N2 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 N2, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C2v structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

  7. Evolutionarily conserved Galphabetagamma binding surfaces support a model of the G protein-receptor complex.

    PubMed Central

    Lichtarge, O; Bourne, H R; Cohen, F E

    1996-01-01

    The pivotal role of G proteins in sensory, hormonal, inflammatory, and proliferative responses has provoked intense interest in understanding how they interact with their receptors and effectors. Nonetheless, the locations of the receptors and effector binding sites remain poorly characterized, although nearly complete structures of the alphabetagamma heterotrimeric complex are available. Here we apply evolutionary trace (ET) analysis [Lichtarge, O., Bourne, H. R. & Cohen, F. E. (1996) J. Mol. Biol. 257, 342-358] to propose plausible locations for these sites. On each subunit, ET identifies evolutionarily selected surfaces composed of residues that do not vary within functional subgroups and that form spatial clusters. Four clusters correctly identify subunit interfaces, and additional clusters on Galpha point to likely receptor or effector binding sites. Our results implicate the conformationally variable region of Galpha in an effector binding role. Furthermore the range of predicted interactions between the receptor and Galphabetagamma, is sufficiently limited that we can build a low resolution and testable model of the receptor-G protein complex. Images Fig. 1 Fig. 2 PMID:8755504

  8. Crystal structures and Hirshfeld surface analysis calculations of mercury(II) complexes with a diiminopyridine ligand

    NASA Astrophysics Data System (ADS)

    Hosseini, Seyed Ali; Mahmoudi, Ghodrat; Garczarek, Piotr; Hazendonk, Paul; Abedi, Marjan; Servati Gargari, Masoumeh

    2016-02-01

    The reaction of a diiminopyridine ligand, N,N‧-bis(phenyl(pyridin-2-yl)methylene)propane-1,3-diamine (L), with mercury(II) salts gave two complexes namely [Hg(L)Cl]·0.5[Hg2Cl6] (1) and [Hg(L)(μ-I)HgI3] (2), which were characterized by XRD, NMR and FTIR. The crystal structure of 1 consists of discrete units of [Hg(L)CI]+cations and [Hg2C16]2- anions in the ratio 2:1. The coordination of mercury in the cation is approximately square pyramidal (sp), the metal center is chelated in a tetradentate manner by the ligand and further coordinated by one chlorine atom. In 2 the packing can be described as units of μ-I-connected square pyramidal (sp) and tetrahedral Hg complexes. The sp coordination around the metal atom is defined by the N4 donor set of the ligand and one bridging iodide. The hydrogen-chlorine donor-accepter interactions in 1 stabilize an infinite 1-D chain; however, such interactions were not observed in 2. Analysis of their Hirshfeld surfaces indicates that the molecules in 1 and 2 are packed predominately by means of van der Waals forces, 'edge to face' aromatic ring packing and weak C-H··X donor-acceptor interactions.

  9. Ab initio potential energy surface and bound states for the Kr-OCS complex.

    PubMed

    Feng, Eryin; Sun, Chunyan; Yu, Chunhua; Shao, Xi; Huang, Wuying

    2011-09-28

    The first ab initio potential energy surface of the Kr-OCS complex is developed using the coupled-cluster singles and doubles with noniterative inclusion of connected triples [CCSD(T)]. The mixed basis sets, aug-cc-pVTZ for the O, C, and S atom, and aug-cc-pVQZ-PP for the Kr atom, with an additional (3s3p2d1f) set of midbond functions are used. A potential model is represented by an analytical function whose parameters are fitted numerically to the single point energies computed at 228 configurations. The potential has a T-shaped global minimum and a local linear minimum. The global minimum occurs at R = 7.146 a(0), θ = 105.0° with energy of -270.73 cm(-1). Bound state energies up to J = 9 are calculated for three isotopomers (82)Kr-OCS, (84)Kr-OCS, and (86)Kr-OCS. Analysis of the vibrational wavefunctions and energies suggests the complex can exist in two isomeric forms: T-shaped and quasi-linear. The calculated transition frequencies and spectroscopic constants of the three isotopomers are in good agreement with the experimental values.

  10. Recovery of a cell surface fetal antigen from circulating immune complexes of melanoma patients.

    PubMed

    Wong, J H; Aguero, B; Gupta, R K; Morton, D L

    1988-01-01

    A well-characterized 69.5 x 10(3) dalton glycoprotein fetal antigen (FA), isolated from the spent culture medium of a melanoma cell line, UCLA-SO-14 (M14), was utilized to characterize the antigen component of circulating immune complexes (CIC) from melanoma patients. Ten serum samples from five patients with stage II melanoma at 1 and 4 months prior to the clinical detection of recurrent disease were selected for study. The CIC were dissociated with low pH and ultrafiltered through a 100 x 10(3) dalton exclusion limit membrane. The low pH treatment resulted in an increase in antibody titer in eight of ten serum samples. The antibody activity in membrane immunofluorescence was quantitatively inhibited by the filtered antigen fraction and purified FA, suggesting the presence of anti-FA antibodies in the treated serum, which possibly were complexed with FA in the untreated sample. As determined by competitive inhibition in an enzyme-linked immunosorbent assay, the filtrate (antigen fraction) contained an antigen that was immunologically similar to FA. These results clearly demonstrate that FA, expressed on the cell surface of melanoma cells, is present in CIC of selected melanoma patients.

  11. Modeling the surface complexation of calcium at the rutile-water interface to 250°C

    NASA Astrophysics Data System (ADS)

    Ridley, Moira K.; Machesky, Michael L.; Wesolowski, David J.; Palmer, Donald A.

    2004-01-01

    The adsorption behavior of metal-(hydr)oxide surfaces can be described and rationalized using a variety of surface complexation models. However, these models do not uniquely describe experimental data unless some additional insight into actual binding mechanisms for a given system is available. This paper presents the results of applying the MUlti SIte Complexation or MUSIC model, coupled with a Stern-based three layer description of the electric double layer, to Ca 2+ adsorption data on rutile surfaces from 25 to 250°C in 0.03 and 0.30 m NaCl background electrolyte. Model results reveal that the tetradentate adsorption configuration found for Sr 2+ adsorbed on the rutile (110) surface in the in situ X-ray standing wave experiments of Fenter et al. (2000) provides a good fit to all Ca 2+ adsorption data. Furthermore, it is also shown that equally good fits result from other plausible adsorption complexes, including various monodentate and bidentate adsorption configurations. These results amply demonstrate the utility of in situ spectroscopic data to constrain surface complexation modeling, and the ability of the MUSIC model approach to accommodate this spectroscopic information. Moreover, this is the first use of any surface complexation model to describe multivalent ion adsorption systematically into the hydrothermal regime.

  12. Interfacial phenomena at a surface of individual and complex fumed nanooxides.

    PubMed

    Gun'ko, V M; Turov, V V; Zarko, V I; Goncharuk, O V; Pakhlov, E M; Skubiszewska-Zięba, J; Blitz, J P

    2016-09-01

    Investigations of interfacial and temperature behaviors of nonpolar and polar adsorbates interacting with individual and complex fumed metal or metalloid oxides (FMO), initial and subjected to various treatments or chemical functionalization and compared to such porous adsorbents as silica gels, precipitated silica, mesoporous ordered silicas, filled polymeric composites, were analyzed. Complex nanooxides include core-shell nanoparticles, CSNP (50-200nm in size) with titania or alumina cores and silica or alumina shells in contrast to simple and smaller nanoparticles of individual FMO. CSNP could be destroyed under high-pressure cryogelation (HPCG) or mechanochemical activation (MCA). These treatments affect the structure of aggregates of nanoparticles and agglomerates of aggregates, resulting in their becoming more compacted. The analysis shows that complex FMO could be more sensitive to external actions than simple nanooxides such as fumed silica. Any treatment of 'soft' FMO affects the interfacial and temperature behaviors of polar and nonpolar adsorbates. Rearrangement of secondary particles and surface functionalization affects the freezing-melting point depression of adsorbates. For some adsorbates, open hysteresis loops became readily apparent in adsorption-desorption isotherms. Clustering of adsorbates bound in textural pores in aggregates of nanoparticles (i.e., voids between nanoparticles in secondary structures) causes reduced changes in enthalpy during phase transitions (freezing, fusion, evaporation). Freezing point depression and melting point elevation cause significant hysteresis freezing-melting effects for adsorbates bound to FMO in the textural pores. Relaxation phenomena for both low- and high-molecular weight adsorbates or filled polymeric composites are affected by the morphology of primary particles, structural organization of secondary particles of differently treated or functionalized FMO, content of adsorbates, co-adsorption order, and

  13. Electronic state of vortices in YBa2Cu3Oy investigated by complex surface impedance measurements

    NASA Astrophysics Data System (ADS)

    Tsuchiya, Yoshishige; Iwaya, Katsuya; Kinoshita, Kentarou; Hanaguri, Tetsuo; Kitano, Haruhisa; Maeda, Atsutaka; Shibata, Kenji; Nishizaki, Terukazu; Kobayashi, Norio

    2001-05-01

    The electromagnetic response to microwaves in the mixed state of YBa2Cu3Oy (YBCO) was measured in order to investigate the electronic state inside and outside the vortex core. The magnetic-field dependence of the complex surface impedance at low temperatures was in good agreement with a general vortex dynamics description assuming that the field-independent viscous damping force and the linear restoring force were acting on the vortices. In other words, both real and imaginary parts of the complex resistivity, ρ1, and ρ2, were linear in B. This is explained by theories for d-wave superconductors. Using analysis based on the Coffey-Clem description of the complex penetration depth, we estimated that the vortex viscosity η at 10 K was (4-5)×10-7 Ns/m2. This value corresponds to ω0τ~0.3-0.5, where ω0 and τ are the minimal gap frequency and the quasiparticle lifetime in the vortex core, respectively. These results suggest that the vortex core in YBCO is not in the deeply superclean regime but in the moderately clean regime. Investigation of the moderately clean vortex core in high-temperature superconductors is significant because physically new effects may be expected due to d-wave characteristics and to the quantum nature of cuprate superconductors. The behavior of Zs as a function of B across the first order transition (FOT) of the vortex lattice was also investigated. Unlike Bi2Sr2CaCu2Oy (BSCCO), no distinct anomaly was observed around the FOT in YBCO. Our results suggest that the rapid increase of Xs due to the change of superfluid density at the FOT would be observed only in highly anisotropic two-dimensional vortex systems like BSCCO. We discuss these results in terms of the difference of the interlayer coupling and the energy scale between the two materials.

  14. Paramagnetic complexes of 9,10-anthraquinone on zeolite surfaces and their thermal transformations

    NASA Astrophysics Data System (ADS)

    Fionov, A. V.; Nekhaev, A. I.; Shchapin, I. Yu.; Maksimov, A. L.; Lunin, V. V.

    2013-12-01

    The concentration of one-electron transfer sites on the surface of H-ZSM-5, H-Y, H-mordenite, and H-β zeolites was measured by EPR using 9,10-antrhraquinone as a probe. It has been found that the hyperfine structure from four protons typical for one-centered complexes of anthraquinone with one acidic site was observed in the EPR spectra after anthraquinone interaction with a zeolite surface in the temperature range of 373 to 423 K. It has been established that an elevated temperature of 473 K promoted the decomposition of the adsorbed anthraquinone and the disappearance of the hyperfine structure. It has been shown that the thermal instability of anthraquinone adsorbed on zeolites changed in the series H-β > H-Y > H-ZSM-5 ˜ H-mordenite; the coke-forming ability of zeolites with regard to n-decane at 443 K changed in a similar manner. It has been established that the presence of air promoted coke-forming processes upon interaction between n-decane and zeolites.

  15. An ultrahigh vacuum compatible sample holder for studying complex metal surfaces.

    PubMed

    Dhaka, R S; Shukla, A K; Maniraj, M; D'Souza, S W; Nayak, J; Barman, S R

    2010-04-01

    We present a design of a compact and versatile sample holder meant for studying complex (ternary) metallic crystals that require sputtering and annealing to high temperatures under ultrahigh vacuum (10(-10) mbar range) for obtaining the clean, ordered and stoichiometric surface. A resistive heater is fixed to the sample holder and not to the sample plate, and thus can be thoroughly degassed initially to high temperatures without heating the sample. The heater, which is mounted vertically on the sample holder frame, slides into the sample plate of rectangular cross-section during sample transfer. For efficient cooling that is required for adlayer deposition, Cu braids can be pressed on the sample plate from both sides through a screw mechanism. The sample holder has 5 degrees of freedom including a tilt rotation. The sample holder has been used to study different metal surfaces such as ferromagnetic shape memory alloys, alkali metal and Mn adlayers on Al-Pd-Mn quasicrystal, aluminum metal, and Al-Mn alloys. Here, our recent results on temperature dependent low energy electron diffraction study of Ni(2)MnGa(100) are presented.

  16. Cycloheptaamylose-dansyl chloride complex as a fluorescent label of surface membranes in living ciliates.

    PubMed

    Wyroba, E; Bottiroli, G; Giordano, P

    1981-12-01

    Labelling of surface membrane of living ciliates: Paramecium aurelia and Tetrahymena pyriformis with fluorescent compound--cycloheptaamylose-dansyl chloride complex (CDC) has been achieved. Fluorescence micrographs of the dried samples showed specific localization of CDC on the cell membrane without any intracellular penetration. On the contrary the ciliates which have been dead during labelling revealed a non-specific fluorescence of their whole bodies. Microspectrofluorimetric analysis of labelled Paramecium cells was performed with Leitz microspectrograph. Spectrum of fluorescence emission measured over the cell membrane level had maximum at 450 nm. Strikingly, the emission maximum of the cells dead at the moment of labelling was shifted 10 nm to a longer wavelength. The rate of photofading measured in this case was almost 3-fold higher than for the ciliates labelled as living ones. Fluorescence excitation spectra did not show any difference in the peak position. Thus CDC staining appears to be an useful method of supravital labelling of cell surface enabling also to distinguish--on the basis of spectral characteristics--the ciliates being alive from those dead at the moment of fluorochrome binding.

  17. [Role of polymer complexes in the formation of biofilms by corrosive bacteria on steel surfaces].

    PubMed

    Purish, L M; Asaulenko, L G; Abdulina, D R; Vasil'ev, V N; Iutinskaia, G A

    2012-01-01

    The composition of exopolymer complexes (EPCs), synthesized by the monocultures Desulfovibrio sp. 10, Bacillus subtilis 36, and Pseudomonas aeruginosa 27 and by microbial associations involved in the corrosion of metal surfaces has been studied. An analysis of the monosaccharide composition of carbohydrate components, as well as the fatty acid composition of the lipid part of EPCs, was carried out by gas-liquid chromatography (GLC). It was found that bacteria in biofilms synthesized polymers; this process was dominated by glucose, while the growth of bacteria in a suspension was marked by a high rhamnose content. Hexouronic acids and hexosamine have been revealed as a part of B. subtilis 36 and P. aeruginosa 27 EPCs. Qualitative differences were revealed in the fatty acid composition ofexopolymers in biofilms and in a bacterial suspension. It was shown that the transition to a biofilm form of growth led to an increase in the unsaturation degree of fatty acids in the exopolymers of associative cultures. The results can be used to develop methods to control microbial corrosion of metal surfaces.

  18. The IEM2M rough-surface scattering model for complex-permittivity scattering media

    NASA Astrophysics Data System (ADS)

    Álvarez-Pérez, José L.

    2012-05-01

    The integral equation model (IEM) was developed in the late 1980s and arguably became the most cited and implemented rough-surface scattering model in the field of radar remote sensing for Earth observation. It was derived by applying a second-order iteration in the incident electromagnetic field to the integral equations of the surface fields as given by Poggio and Miller. It is thus an extension of the first-order, Born approximation of these equations that produce the classical Kirchhoff approximation. The IEM has been subject to numerous amendments and variations over the last 20 years due to the imperfect introduction and handling of the Weyl representation of the spherical wave in its first version. The work presented here is a further development of the contribution made by the same author in 2001 (IEM2M), which was the first version of IEM able to blend analytically both the Kirchhoff and the small-perturbation approximations for the bistatic case. The improvement reported in this article is concerned with the inclusion of evanescent waves in the formulation of the model and the extension of the range of applicability of the second-order scattering terms to interfaces with complex-permittivity scattering media.

  19. Yeast surface display of a noncovalent MHC class II heterodimer complexed with antigenic peptide.

    PubMed

    Boder, Eric T; Bill, Jerome R; Nields, Andrew W; Marrack, Philippa C; Kappler, John W

    2005-11-20

    Microbial protein display technologies have enabled directed molecular evolution of binding and stability properties in numerous protein systems. In particular, dramatic improvements to antibody binding affinity and kinetics have been accomplished using these tools in recent years. Examples of successful application of display technologies to other immunological proteins have been limited to date. Herein, we describe the expression of human class II major histocompatibility complex allele (MHCII) HLA-DR4 on the surface of Saccharomyces cerevisiae as a noncovalently associated heterodimer. The yeast-displayed MHCII is fully native as assessed by binding of conformationally specific monoclonal antibodies; failure of antibodies specific for empty HLA-DR4 to bind yeast-displayed protein indicates antigenic peptide is bound. This report represents the first example of a noncovalent protein dimer displayed on yeast and of successful display of wild-type MHCII. Results further point to the potential for using yeast surface display for engineering and analyzing the antigen binding properties of MHCII.

  20. Self-assembled monolayer and multilayer formation using redox-active Ru complex with phosphonic acids on silicon oxide surface

    NASA Astrophysics Data System (ADS)

    Ishida, Takao; Terada, Kei-ichi; Hasegawa, Kiichi; Kuwahata, Hironao; Kusama, Kazunori; Sato, Ryo; Nakano, Miki; Naitoh, Yasuhisa; Haga, Masa-aki

    2009-08-01

    The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO 2 surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO 2 surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO 2 surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO 2 surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO 2 surface. We found the film growth reached a saturation point after 6 layers on the SiO 2 surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer.

  1. The effect of sterilization on biological, organic geochemical and morphological information in natural samples

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Kvenvolden, K. A.; Philpott, D. E.

    1974-01-01

    The loss of biological, organic geochemical, and morphological science information that may occur should a Mars surface sample be sterilized prior to return to earth is examined. Results of experimental studies are summarized.

  2. A multiscale approach to assess the complex surface of polyurethane catheters and the effects of a new plasma decontamination treatment on the surface properties.

    PubMed

    Mrad, Omar; Saunier, Johanna; Aymes-Chodur, Caroline; Rosilio, Véronique; Bouttier, Sylvie; Agnely, Florence; Aubert, Pascal; Vigneron, Jacky; Etcheberry, Arnaud; Yagoubi, Najet

    2010-12-01

    Polyurethane catheters made of Pellethane 2363-80AE® were treated with a low temperature plasma developed for the decontamination of reusable polymer devices in hospitals. We investigated the modifications of the polymer surface by studying the topographic modifications, the chemical modifications, and their consequences on the wettability and bacterial adhesion. This study showed that plasma treatment modified the topography and grafted oxygen and nitrogen species onto the surface, resulting in an increase in the surface polarity. This effect could be correlated to the number of nitrogen atoms interacting with the surface. Moreover, this study demonstrated the significance of multiscale heterogeneities, and the complexity of industrial medical devices made from polymers. Their surface can be heterogeneous, and they contain additives that can migrate and change the surface composition. PMID:20920389

  3. Geochemical characterisation of northern Norwegian fjords sediments: A source to sink study

    NASA Astrophysics Data System (ADS)

    Faust, Johan; Knies, Jochen; Scheiber, Thomas

    2016-04-01

    To provide a better understanding of the weathering, transportation and sedimentation processes in a complex fjord system forty-four surface sediment samples plus three sediment cores were recovered from the Vestfjord, Ofotfjord and Tysfjord in northern Norway. We analysed the elemental composition, Corg, bulk mineral composition, CaCO3, grain size and C, Nd, Sr and Hf isotopes. We found that the Vestfjord, Ofotfjord and Tysfjord can be characterised and separated by distinct geochemical signatures of the surface sediment samples e.g. in the distribution of REE and the relation between grain size and Ni, Fe and K. These variations are related to differences in the hinterland bedrock composition. The bedrock in the drainage area of these fjords consist mainly of para- and orthogneiss. Onshore soil and bedrock geochemistry data show that the orthogneiss can be distinguished from the paragneiss by the different content of Th, K, Mg, Ni and Fe. Moreover, a limestone formation rich in dolomite can be traced in the fjord system using the calcite/dolomite ratio. The investigation of the sediment cores shows that these parameters can be used as a geochemical fingerprint to trace the different rock types throughout the entire Holocene. This finding will also help to gain more knowledge about the timing of the past deglaciation and sea level variations in northern Norway.

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

    SciTech Connect

    Chen, Wilfred

    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

  5. FRET efficiency in surface complexes of CdSe/ZnS quantum dots with azo-dyes

    NASA Astrophysics Data System (ADS)

    Annas, Kirill I.; Gromova, Yuliya A.; Orlova, Anna O.; Maslov, Vladimir G.; Fedorov, Anatoly V.; Baranov, Alexander V.

    2016-04-01

    Photoinduced dissociation of surface complexes of CdSe/ZnS quantum dots with azo-dye 1-(2- pyridylazo)-2-naphthol (PAN) was investigated. It was shown that the Förster resonance energy transfer contributes in the complexes photodissociation rate, which depends on resonance condition between electronic levels of donor (quantum dots) and acceptor (azo-dye) and donor photoluminescent quantum yield. It has allowed to estimate energy transfer efficiency in the complexes and disclosed a new nonradiative channel that has minor contribution in the deactivation of excited states of quantum dots in the complexes.

  6. Is formamide a geochemically plausible prebiotic solvent?

    PubMed

    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. PMID:27253848

  7. Geochemical Exploration Techniques Applicable in the Search for Copper Deposits

    USGS Publications Warehouse

    Chaffee, Maurice A.

    1975-01-01

    media. Samples of ice and snow have been used for limited geochemical surveys. Both geobotanical and biogeochemical surveys have been successful in locating copper deposits in many parts of the world. Micro-organisms, including bacteria and algae, are other unproved media that should be studied. Animals can be used in geochemical-prospecting programs. Dogs have been used quite successfully to sniff out hidden and exposed sulfide minerals. Tennite mounds are commonly composed of subsurface material, but have not as yet proved to be useful in locating buried mineral deposits. Animal tissue and waste products are essentially unproved but potentially valuable sampling media. Knowledge of the location of areas where trace-element-associated diseases in animals and man are endemic as well as a better understanding of these diseases, may aid in identifying regions that are enriched in or depleted of various elements, including copper. Results of analyses of gases in the atmosphere are proving valuable in mineral-exploration surveys. Studies involving metallic compounds exhaled by plants into the atmosphere, and of particulate matter suspended in the atmosphere are reviewed these methods may become important in the future. Remote-sensing techniques are useful for making indirect measurements of geochemical responses. Two techniques applicable to geochemical exploration are neutron-activation analysis and gamma-ray spectrometry. Aerial photography is especially useful in vegetation surveys. Radar imagery is an unproved but potentially valuable method for use in studies of vegetation in perpetually clouded regions. With the advent of modern computers, many new techniques, such as correlation analysis, regression analysis, discriminant analysis, factor analysis, cluster analysis, trend-surface analysis, and moving-average analysis can be applied to geochemical data sets. Selective use of these techniques can provide new insights into the interpretatio

  8. Using AFM to probe the complexation of DNA with anionic lipids mediated by Ca(2+): the role of surface pressure.

    PubMed

    Luque-Caballero, Germán; Martín-Molina, Alberto; Sánchez-Treviño, Alda Yadira; Rodríguez-Valverde, Miguel A; Cabrerizo-Vílchez, Miguel A; Maldonado-Valderrama, Julia

    2014-04-28

    Complexation of DNA with lipids is currently being developed as an alternative to classical vectors based on viruses. Most of the research to date focuses on cationic lipids owing to their spontaneous complexation with DNA. Nonetheless, recent investigations have revealed that cationic lipids induce a large number of adverse effects on DNA delivery. Precisely, the lower cytotoxicity of anionic lipids accounts for their use as a promising alternative. However, the complexation of DNA with anionic lipids (mediated by cations) is still in early stages and is not yet well understood. In order to explore the molecular mechanisms underlying the complexation of anionic lipids and DNA we proposed a combined methodology based on the surface pressure-area isotherms, Gibbs elasticity and Atomic Force Microscopy (AFM). These techniques allow elucidation of the role of the surface pressure in the complexation and visualization of the interfacial aggregates for the first time. We demonstrate that the DNA complexes with negatively charged model monolayers (DPPC/DPPS 4 : 1) only in the presence of Ca(2+), but is expelled at very high surface pressures. Also, according to the Gibbs elasticity plot, the complexation of lipids and DNA implies a whole fluidisation of the monolayer and a completely different phase transition map in the presence of DNA and Ca(2+). AFM imaging allows identification for the first time of specific morphologies associated with different packing densities. At low surface coverage, a branched net like structure is observed whereas at high surface pressure fibers formed of interfacial aggregates appear. In summary, Ca(2+) mediates the interaction between DNA and negatively charged lipids and also the conformation of the ternary system depends on the surface pressure. Such observations are important new generic features of the interaction between DNA and anionic lipids. PMID:24668321

  9. Surface Complexation Modeling of U(VI) Adsorption onto Savannah River Site Sediments

    NASA Astrophysics Data System (ADS)

    Dong, W.; Wan, J.; Tokunaga, T. K.; Denham, M.; Davis, J.; Hubbard, S. S.

    2011-12-01

    The Savannah River Site (SRS) was a U.S. Department of Energy facility for plutonium production during the Cold War. Waste plumes containing low-level radioactivity and acidic waste solutions were discharged to a series of unlined seepage basins in the F-Area of the SRS from 1955 to 1988. Although the site has undergone many years of active remediation, the groundwater remains acidic, and the concentrations of U and other radionuclides are still significantly higher than their Maximum Contaminant Levels (MCLs). The objective of this effort is to understand and predict U(VI) mobility in acidic waste plumes through developing surface complexation models (SCMs). Laboratory batch experiments were conducted to evaluate U adsorption behavior over the pH range of 3.0 to 9.5. Ten sorbent samples were selected including six contaminated sediment samples from three boreholes drilled within the plume and along the groundwater flow direction, two uncontaminated (pristine) sediment samples from a borehole outside of the plume, and two reference minerals, goethite and kaolinite (identified as the dominant minerals in the clay size fraction of the F-Area sediments). The results show that goethite and kaolinite largely control U partitioning behavior. In comparison with the pristine sediment, U(VI) adsorption onto contaminated sediments exhibits adsorption edges shifted toward lower pH by about 1.0 unit (e.g., from pH≈4.5 to pH≈3.5). We developed a SCMs based component additivity (CA) approach, which can successfully predict U(VI) adsorption onto uncontaminated SRS sediments. However, application of the same SCMs based CA approach to contaminated sediments resulted in underestimates of U(VI) adsorption at acidic pH conditions. The model sensitivity analyses indicate that both goethite and kaolinite surfaces co-contributed to U(VI) adsorption under acidic pH conditions. In particular, the exchange sites of clay minerals might play an important role in adsorption of U(VI) at p

  10. Microbiological and geochemical characterization of fluvially deposited sulfidic mine tailings

    PubMed

    Wielinga; Lucy; Moore; Seastone; Gannon

    1999-04-01

    The fluvial deposition of mine tailings generated from historic mining operations near Butte, Montana, has resulted in substantial surface and shallow groundwater contamination along Silver Bow Creek. Biogeochemical processes in the sediment and underlying hyporheic zone were studied in an attempt to characterize interactions consequential to heavy-metal contamination of shallow groundwater. Sediment cores were extracted and fractionated based on sediment stratification. Subsamples of each fraction were assayed for culturable heterotrophic microbiota, specific microbial guilds involved in metal redox transformations, and both aqueous- and solid-phase geochemistry. Populations of cultivable Fe(III)-reducing bacteria were most prominent in the anoxic, circumneutral pH regions associated with a ferricrete layer or in an oxic zone high in organic carbon and soluble iron. Sulfur- and iron-oxidizing bacteria were distributed in discrete zones throughout the tailings and were often recovered from sections at and below the anoxic groundwater interface. Sulfate-reducing bacteria were also widely distributed in the cores and often occurred in zones overlapping iron and sulfur oxidizers. Sulfate-reducing bacteria were consistently recovered from oxic zones that contained high concentrations of metals in the oxidizable fraction. Altogether, these results suggest a highly varied and complex microbial ecology within a very heterogeneous geochemical environment. Such physical and biological heterogeneity has often been overlooked when remediation strategies for metal contaminated environments are formulated.

  11. The merozoite surface protein 1 complex is a platform for binding to human erythrocytes by Plasmodium falciparum.

    PubMed

    Lin, Clara S; Uboldi, Alessandro D; Marapana, Danushka; Czabotar, Peter E; Epp, Christian; Bujard, Hermann; Taylor, Nicole L; Perugini, Matthew A; Hodder, Anthony N; Cowman, Alan F

    2014-09-12

    Plasmodium falciparum is the causative agent of the most severe form of malaria in humans. The merozoite, an extracellular stage of the parasite lifecycle, invades erythrocytes in which they develop. The most abundant protein on the surface of merozoites is merozoite surface protein 1 (MSP1), which consists of four processed fragments. Studies indicate that MSP1 interacts with other peripheral merozoite surface proteins to form a large complex. Successful invasion of merozoites into host erythrocytes is dependent on this protein complex; however, the identity of all components and its function remain largely unknown. We have shown that the peripheral merozoite surface proteins MSPDBL1 and MSPDBL2 are part of the large MSP1 complex. Using surface plasmon resonance, we determined the binding affinities of MSPDBL1 and MSPDBL2 to MSP1 to be in the range of 2-4 × 10(-7) m. Both proteins bound to three of the four proteolytically cleaved fragments of MSP1 (p42, p38, and p83). In addition, MSPDBL1 and MSPDBL2, but not MSP1, bound directly to human erythrocytes. This demonstrates that the MSP1 complex acts as a platform for display of MSPDBL1 and MSPDBL2 on the merozoite surface for binding to receptors on the erythrocyte and invasion.

  12. Antibody responses to the merozoite surface protein-1 complex in cerebral malaria patients in India

    PubMed Central

    Lucchi, Naomi W; Tongren, Jon Eric; Jain, Vidhan; Nagpal, Avinash C; Kauth, Christian W; Woehlbier, Ute; Bujard, Hermann; Dash, Aditya P; Singh, Neeru; Stiles, Jonathan K; Udhayakumar, Venkatachalam

    2008-01-01

    Background Plasmodium falciparum infection causes cerebral malaria (CM) in a subset of patients with anti-malarial treatment protecting only about 70% to 80% of patients. Why a subset of malaria patients develops CM complications, including neurological sequelae or death, is still not well understood. It is believed that host immune factors may modulate CM outcomes and there is substantial evidence that cellular immune factors, such as cytokines, play an important role in this process. In this study, the potential relationship between the antibody responses to the merozoite surface protein (MSP)-1 complex (which consists of four fragments namely: MSP-183, MSP-130, MSP-138 and MSP-142), MSP-636 and MSP-722 and CM was investigated. Methods Peripheral blood antibody responses to recombinant antigens of the two major allelic forms of MSP-1 complex, MSP-636 and MSP-722 were compared between healthy subjects, mild malaria patients (MM) and CM patients residing in a malaria endemic region of central India. Total IgG and IgG subclass antibody responses were determined using ELISA method. Results The prevalence and levels of IgG and its subclasses in the plasma varied for each antigen. In general, the prevalence of total IgG, IgG1 and IgG3 was higher in the MM patients and lower in CM patients compared to healthy controls. Significantly lower levels of total IgG antibodies to the MSP-1f38, IgG1 levels to MSP-1d83, MSP-119 and MSP-636 and IgG3 levels to MSP-1f42 and MSP-722 were observed in CM patients as compared to MM patients. Conclusion These results suggest that there may be some dysregulation in the generation of antibody responses to some MSP antigens in CM patients and it is worth investigating further whether perturbations of antibody responses in CM patients contribute to pathogenesis. PMID:18601721

  13. A combined geochemical and hydrological approach for understanding macronutrient sources

    NASA Astrophysics Data System (ADS)

    Lapworth, Dan J.; Gooddy, Daren C.; Kent, Flo; Heaton, Tim H. E.; Cole, Steven J.; Allen, Debbie

    2013-09-01

    This study employed complementary geochemical techniques and distributed hydrological modelling to investigate multiple sources of catchment macronutrients and characterise their changes in contrasting storm and baseflow conditions. This approach was demonstrated for the Beult catchment in the county of Kent (England), a designated Site of Special Scientific Interest (SSSI) indentified as failing to meet water quality standards for key nutrients under the Water Framework Directive. Significant changes in nutrient stoichiometry and bioavailability are observed for surface waters under contrasting flow regimes. Soluble reactive phosphorus (SRP) concentrations are approximately twice as high during baseflow compared to high flow, while the inverse is true for particulate, colloidal and dissolved hydrolysable phosphorus, dissolved organic carbon and nitrate. Nitrogen (N):phosphorus (P) ratios are lower during baseflow for most surface waters impacted by diffuse sources of pollution. Fluorescence indices of dissolved organic matter (DOM) show that waste water inputs may be locally important sources of more complex low molecular weight DOM, particularly during baseflow. Nitrate N and O isotope signatures, combined with other dissolved chemical tracers, confirm the dominance of wastewater N inputs at sites downsteam of sewerage treatment works during baseflow, with a shift towards the soil N pool in surface waters across the catchment during high flow. Distributed hydrological modelling using the Grid-to-Grid model reveal areas with the greatest runoff also export higher N and P concentrations, and hence deliver a greater flux of macronutrients, while forested areas with low nutrient concentrations reduce runoff and nutrient fluxes. During periods of high runoff, nested sampling indicates that nutrient fluxes scale with catchment area. This combined approach enables a more thorough assessment of the macronutrient sources and dynamics, better informing management options

  14. Effect of Grain Size on Uranium(VI) Surface Complexation Kinetics and Adsorption Additivity

    SciTech Connect

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

    2011-07-27

    Laboratory experiments were performed to investigate the contribution of variable grain sizes to uranium adsorption/desorption in a sediment collected 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 (0.05-0.2 mm), and clay/silt fraction (< 0.05mm). For each size fraction and their composite (sediment), batch experiments were performed to determine uranium adsorption isotherms, and stirred flow-cell experiments were conducted to derive kinetic data of uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size-specific, reflecting the 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. Our analysis also showed that uranium adsorption site concentration estimated from the adsorption isotherms was 3 orders of magnitude less than a site concentration estimated from sediment surface area and generic site density. 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.

  15. Geochemical cycles of atmospheric gases

    NASA Technical Reports Server (NTRS)

    Walker, J. C. G.; Drever, J. I.

    1988-01-01

    The processes that control the atmosphere and atmospheric changes are reviewed. The geochemical cycles of water vapor, nitrogen, carbon dioxide, oxygen, and minor atmospheric constituents are examined. Changes in atmospheric chemistry with time are discussed using evidence from the rock record and analysis of the present atmosphere. The role of biological evolution in the history of the atmosphere and projected changes in the future atmosphere are considered.

  16. The geochemical record in rock glaciers

    USGS Publications Warehouse

    Steig, E.J.; Fitzpatrick, J.J.; Potter, N.; Clark, D.H.

    1998-01-01

    A 9.5 m ice core was extracted from beneath the surficial debris cover of a rock glacier at Galena Creek, northwestern Wyoming. The core contains clean, bubble-rich ice with silty debris layers spaced at roughly 20 cm intervals. The debris layers are similar in appearance to those in typical alpine glaciers, reflecting concentration of debris by melting at the surface during the summer ablation season. Profiles of stable isotope concentrations and electrical conductivity measurements provide independent evidence for melting in association with debris layers. These observations are consistent with a glacial origin for the ice, substantiating the glacigenic model for rock glacier formation. The deuterium excess profile in the ice indicates that the total depth of meltwater infiltration is less than the thickness of one annual layer, suggesting that isotope values and other geochemical signatures are preserved at annual resolution. This finding demonstrates the potential for obtaining useful paleoclimate information from rock glacier ice.

  17. Current trend in fabrication of complex morphologically tunable superhydrophobic nano scale surfaces

    NASA Astrophysics Data System (ADS)

    Abdulhussein, Ali T.; Kannarpady, Ganesh K.; Wright, Andrew B.; Ghosh, Anindya; Biris, Alexandru S.

    2016-10-01

    Superhydrophobic surfaces are found in nature and possess several fascinating properties, including the ability to self-clean. A typical superhydrophobic surface has micro/nanostructure roughness and low surface energy, which combine to give it its unusual anti-wetting properties. Because of their unique capabilities, these surfaces have interested scientists in research and industry fields for years. In recent decades, researchers have developed a number of synthetic methods for producing novel superhydrophobic surfaces that mimic natural surfaces. These synthetic surfaces have been widely applied on different types of substrates for potential widespread, practical applications. This review article focuses on these advances in fabricating manmade superhydrophobic surfaces.

  18. Technical Report: Contaminant Organic Complexes: Their structure and energetics in surface decontamination

    SciTech Connect

    Samuel J. Traina; Shankar Sharma

    2007-04-22

    The Department of Energy has a goal of decontaminating an estimated 180,000 metric tons of metal wastes in various surplus facilities. Uranium (U) and other radioactive actinides and lanthanides are embedded within the mixed oxide structures of the passivity layers of corroded iron and steel. These toxic metals can be dissolved out of the surface layers by a naturally occurring bacterial siderophore called Desferrioxamine B (DFB). DFB is a trihydroxamate ligand with one amine (pK1 =10.89) and three hydroxamate groups (pK2 =9.70, pK3 =9.03, and pK4 =8.30), which chelates with metals through hydroxamate coordination. Complexation of DFB with U can be utilized in decontamination strategy of the passivity layers. Therefore, we have been studying reactions of uranyl U(VI) with zerovalent iron (Fe0) followed by dissolution by DFB. The objectives were to determine the structure and speciation of solution and solid phases of U and to assess the effectiveness of DFB in U dissolution.

  19. Tracing origins of complex pharmaceutical preparations using surface desorption atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Zhang, Xinglei; Jia, Bin; Huang, Keke; Hu, Bin; Chen, Rong; Chen, Huanwen

    2010-10-01

    A novel strategy to trace the origins of commercial pharmaceutical products has been developed based on the direct chemical profiling of the pharmaceutical products by surface desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS). Besides the unambiguous identification of active drug components, various compounds present in the matrixes are simultaneously detected without sample pretreatment, providing valuable information for drug quality control and origin differentiation. Four sources of commercial amoxicillin products made by different manufacturers have been successfully differentiated. This strategy has been extended to secerning six sources of Liuwei Dihuang Teapills, which are herbal medicine preparations with extremely complex matrixes. The photolysis status of chemical drug products and the inferior natural herd medicine products prepared with different processes (e.g., extra heating) were also screened using the method reported here. The limit of detection achieved in the MS/MS experiments was estimated to be 1 ng/g for amoxicillin inside the capsule product. Our experimental data demonstrate that DAPCI-MS is a useful tool for rapid pharmaceutical analysis, showing promising perspectives for tracking the entire pharmaceutical supply chain to prevent counterfeit intrusions.

  20. Usp12 stabilizes the T-cell receptor complex at the cell surface during signaling

    PubMed Central

    Jahan, Akhee S.; Lestra, Maxime; Swee, Lee Kim; Fan, Ying; Lamers, Mart M.; Tafesse, Fikadu G.; Theile, Christopher S.; Spooner, Eric; Bruzzone, Roberto; Ploegh, Hidde L.; Sanyal, Sumana

    2016-01-01

    Posttranslational modifications are central to the spatial and temporal regulation of protein function. Among others, phosphorylation and ubiquitylation are known to regulate proximal T-cell receptor (TCR) signaling. Here we used a systematic and unbiased approach to uncover deubiquitylating enzymes (DUBs) that participate during TCR signaling in primary mouse T lymphocytes. Using a C-terminally modified vinyl methyl ester variant of ubiquitin (HA-Ub-VME), we captured DUBs that are differentially recruited to the cytosol on TCR activation. We identified ubiquitin-specific peptidase (Usp) 12 and Usp46, which had not been previously described in this pathway. Stimulation with anti-CD3 resulted in phosphorylation and time-dependent translocation of Usp12 from the nucleus to the cytosol. Usp12−/− Jurkat cells displayed defective NFκB, NFAT, and MAPK activities owing to attenuated surface expression of TCR, which were rescued on reconstitution of wild type Usp12. Proximity-based labeling with BirA-Usp12 revealed several TCR adaptor proteins acting as interactors in stimulated cells, of which LAT and Trat1 displayed reduced expression in Usp12−/− cells. We demonstrate that Usp12 deubiquitylates and prevents lysosomal degradation of LAT and Trat1 to maintain the proximal TCR complex for the duration of signaling. Our approach benefits from the use of activity-based probes in primary cells without any previous genome modification, and underscores the importance of ubiquitin-mediated regulation to refine signaling cascades. PMID:26811477

  1. Laser-induced periodic surface structures of thin, complex multi-component films

    NASA Astrophysics Data System (ADS)

    Reif, Juergen; Varlamova, Olga; Ratzke, Markus; Uhlig, Sebastian

    2016-04-01

    Femtosecond laser-induced regular nanostructures are generated on a complex multilayer target, namely a piece of a commercial, used hard disk memory. It is shown that after single-shot 800-nm irradiation at 0.26 J/cm2 only the polymer cover layer and—in the center—a portion of the magnetic multilayer are ablated. A regular array of linearly aligned spherical 450-nm features at the uncovered interface between cover and magnetic layers appears not to be produced by the irradiation. Only after about 10 pulses on one spot, classical ripples perpendicular to the laser polarization with a period of ≈700 nm are observed, with a modulation between 40 nm above and 40 nm below the pristine surface and an ablation depth only slightly larger than the thickness of the multilayer magnetic film. Further increase of the pulse number does not result in deeper ablation. However, 770-nm ripples become parallel to the polarization and are swelling to more than 120 nm above zero, much more than the full multilayer film thickness. In the spot periphery, much shallower 300-nm ripples are perpendicular to the strong modulation and the laser polarization. Irradiation with 0.49-J/cm2 pulses from an ultrafast white-light continuum results—in the spot periphery—in the formation of 200-nm ripples, only swelling above zero after removal of the polymer cover, without digging into the magnetic film.

  2. Validation of the WATEQ4 geochemical model for uranium

    SciTech Connect

    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/sub 2/(OH)/sub 2/ . H/sub 2/O), UO/sub 2/(OH)/sub 2/, and rutherfordine ((UO/sub 2/CO/sub 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.

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

    NASA Astrophysics Data System (ADS)

    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

  4. Complex coordinate implementation in the curvilinear coordinate method: application to plane-wave diffraction by nonperiodic rough surfaces.

    PubMed

    Edee, Kofi; Granet, Gérard; Plumey, Jean-Píerre

    2007-04-01

    We investigate the electromagnetic modeling of plane-wave diffraction by nonperiodic surfaces by using the curvilinear coordinate method (CCM). This method is often used with a Fourier basis expansion, which results in the periodization of both the geometry and the electromagnetic field. We write the CCM in a complex coordinate system in order to introduce the perfectly matched layer concept in a simple and efficient way. The results, presented for a perfectly conducting surface, show the efficiency of the model.

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

    NASA Astrophysics Data System (ADS)

    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

  6. Re-Inversion of Surface Electrical Resistivity Tomography Data from the Hanford Site B-Complex

    SciTech Connect

    Johnson, Timothy C.; Wellman, Dawn M.

    2013-05-01

    This report documents the three-dimensional (3D) inversion results of surface electrical resistivity tomography (ERT) data collected over the Hanford Site B-Complex. The data were collected in order to image the subsurface distribution of electrically conductive vadose zone contamination resulting from both planned releases of contamination into subsurface infiltration galleries (cribs, trenches, and tile fields), as well as unplanned releases from the B, BX, and BY tank farms and/or associated facilities. Electrically conductive contaminants are those which increase the ionic strength of pore fluids compared to native conditions, which comprise most types of solutes released into the subsurface B-Complex. The ERT data were collected and originally inverted as described in detail in report RPP-34690 Rev 0., 2007, which readers should refer to for a detailed description of data collection and waste disposal history. Although the ERT imaging results presented in that report successfully delineated the footprint of vadose zone contamination in areas outside of the tank farms, imaging resolution was not optimized due to the inability of available inversion codes to optimally process the massive ERT data set collected at the site. Recognizing these limitations and the potential for enhanced ERT characterization and time-lapse imaging at contaminated sites, a joint effort was initiated in 2007 by the U.S. Department of Energy – Office of Science (DOE-SC), with later support by the Office of Environmental Management (DOE-EM), and the U.S. Department of Defense (DOD), to develop a high-performance distributed memory parallel 3D ERT inversion code capable of optimally processing large ERT data sets. The culmination of this effort was the development of E4D (Johnson et al., 2010,2012) In 2012, under the Deep Vadose Zone Applied Field Research Initiative (DVZ-AFRI), the U.S. Department of Energy – Richland Operations Office (DOE-RL) and CH2M Hill Plateau Remediation

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Geochemical Responses to Anthropogenic and Natural Influences in Ebinur Lake Sediments of Arid Northwest China.

    PubMed

    Ma, Long; Wu, Jinglu; Abuduwaili, Jilili; Liu, Wen

    2016-01-01

    Geochemical concentrations were extracted for a short sediment core from Ebinur Lake, located in arid northwest China, and mathematical methods were used to demonstrate the complex pattern of the geochemical anomalies resulting from the temporal changes in natural and anthropogenic forces on the lake sediments. The first element assemblage (C1) (aluminum, potassium, iron, magnesium, beryllium, etc.) was predominantly terrigenous; among the assemblage, total phosphorus and titanium were generally consistent with aluminum except with regards to their surface sequences, which inferred the differences of source regions for terrigenous detrital material led to this change around ca. 2000AD. The second assemblage (C2) (calcium and strontium) was found to have a negative relationship with aluminum through a cluster analysis. The third assemblage (C3) included sodium and magnesium, which were influenced by the underwater lake environment and deposited in the Ebinur depression. The concentration ratio of C1/(C1+C2) was used as an indicator for denudation amount of detrital materials, which was supported by the values of magnetic susceptibility. The enrichment factors for heavy metals suggested that the influence of human activities on heavy-metal enrichment in Ebinur Lake region was not severe over the past century. Prior to the 1960s, geochemical indicators suggested a stable lacustrine environment with higher water levels. Beginning in the 1960s, high agricultural water demand resulted in rapid declines in lake water level, with subsequent increases of lake water salinity, as evidenced by enhanced sodium concentration in lake core sediments. During this period, anthropogenic activity also enhanced the intensity of weathering and the denudation of the Ebinur watershed. PMID:27176765

  9. Geochemical Responses to Anthropogenic and Natural Influences in Ebinur Lake Sediments of Arid Northwest China

    PubMed Central

    Wu, Jinglu; Abuduwaili, Jilili; Liu, Wen

    2016-01-01

    Geochemical concentrations were extracted for a short sediment core from Ebinur Lake, located in arid northwest China, and mathematical methods were used to demonstrate the complex pattern of the geochemical anomalies resulting from the temporal changes in natural and anthropogenic forces on the lake sediments. The first element assemblage (C1) (aluminum, potassium, iron, magnesium, beryllium, etc.) was predominantly terrigenous; among the assemblage, total phosphorus and titanium were generally consistent with aluminum except with regards to their surface sequences, which inferred the differences of source regions for terrigenous detrital material led to this change around ca. 2000AD. The second assemblage (C2) (calcium and strontium) was found to have a negative relationship with aluminum through a cluster analysis. The third assemblage (C3) included sodium and magnesium, which were influenced by the underwater lake environment and deposited in the Ebinur depression. The concentration ratio of C1/(C1+C2) was used as an indicator for denudation amount of detrital materials, which was supported by the values of magnetic susceptibility. The enrichment factors for heavy metals suggested that the influence of human activities on heavy-metal enrichment in Ebinur Lake region was not severe over the past century. Prior to the 1960s, geochemical indicators suggested a stable lacustrine environment with higher water levels. Beginning in the 1960s, high agricultural water demand resulted in rapid declines in lake water level, with subsequent increases of lake water salinity, as evidenced by enhanced sodium concentration in lake core sediments. During this period, anthropogenic activity also enhanced the intensity of weathering and the denudation of the Ebinur watershed. PMID:27176765

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

    PubMed Central

    2010-01-01

    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 displayed with efficiencies

  11. 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

    USGS Publications Warehouse

    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

  12. Immune complex receptors on cell surfaces. II. Cytochemical evaluation of their abundance on different immune cells: distribution, uptake, and regeneration.

    PubMed Central

    McKeever, P. E.; Garvin, A. J.; Hardin, D. H.; Spicer, S. S.

    1976-01-01

    A recently developed method for ultrastructural demonstration of cell surface receptors for immune complexes is applied to evaluation of these receptors on various cell types. The method entailing incubation with a complex of horesradish peroxidase (HRP) and antibody to HRP (anti-HRP) disclosed dense foci indicative of immune complex receptors distributed at 30- to 120-mmu intervals over macrophage surfaces. Invaginations, loop-like evaginations, and pinocytotic vasicles stained prominently. The number of stained immune complex receptors averaged 200,000 per oil-induced macrophage and 120,000 per noninduced macrophage, as determined from counts of focal deposits in electron micrographs. Receptor periodicity on giant cells present in oil-induced exudates resembled that on macrophages, but the larger giant cells contained an estimated 1.5 million sites. Although receptor periodicity on eosinophils and neutrophils equaled that on macrophages, the staining was lighter and was interrupted by intervals of unstained membrane. Neutrophils averaged 28,000 and eosinophils 35,000 receptors per cell, whereas those lymphocytes with receptors averaged 3,500 per cell. Viable cells incubated with anti-HRP sequentially exhibited about half as many reactive sites as did cells incubated with immune complex. When warmed to 37 C, viable macrophages and eosinophils pinocytosed soluble immune complexes almost completely within 30 minutes and phagocytosed insoluble complexes more slowly. The endocytosed soluble immune complexes were sequestered within tubulovesicular structures in addition to the expected phagocytic vacuoles. Receptors appeared fully active on macrophages that were restained with soluble, cold immune complex after they had endocytosed immune complex in the course of a 30-minute warming interval. Images Figure 16 Figures 2 and 3 Figures 4-6 Figure 7 Figures 8-11 Figure 1 Figure 12 Figure 13 Figures 14 and 15 PMID:60883

  13. High-Resolution and Specific Detection of Bacteria on Complex Surfaces Using Nanoparticle Probes and Electron Microscopy

    PubMed Central

    Ye, Jun; Nielsen, Shaun; Joseph, Stephen; Thomas, Torsten

    2015-01-01

    The study of the interaction of bacteria with surfaces requires the detection of specific bacterial groups with high spatial resolution. Here, we describe a method to rapidly and efficiently add nanogold particles to oligonucleotide probes, which target bacterial ribosomal RNA. These nanogold-labeled probes are then used in an in situ hybridization procedure that ensures both cellular integrity and high specificity. Electron microscopy subsequently enables the visualization of specific cells with high local precision on complex surface structures. This method will contribute to an increased understanding of how bacteria interact with surface structures on a sub-micron scale. PMID:26018431

  14. High-resolution and specific detection of bacteria on complex surfaces using nanoparticle probes and electron microscopy.

    PubMed

    Ye, Jun; Nielsen, Shaun; Joseph, Stephen; Thomas, Torsten

    2015-01-01

    The study of the interaction of bacteria with surfaces requires the detection of specific bacterial groups with high spatial resolution. Here, we describe a method to rapidly and efficiently add nanogold particles to oligonucleotide probes, which target bacterial ribosomal RNA. These nanogold-labeled probes are then used in an in situ hybridization procedure that ensures both cellular integrity and high specificity. Electron microscopy subsequently enables the visualization of specific cells with high local precision on complex surface structures. This method will contribute to an increased understanding of how bacteria interact with surface structures on a sub-micron scale.

  15. Integrating seasonal optical and thermal infrared spectra to characterize urban impervious surfaces with extreme spectral complexity: a Shanghai case study

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Yao, Xinfeng; Ji, Minhe

    2016-01-01

    Despite recent rapid advancement in remote sensing technology, accurate mapping of the urban landscape in China still faces a great challenge due to unusually high spectral complexity in many big cities. Much of this complication comes from severe spectral confusion of impervious surfaces with polluted water bodies and bright bare soils. This paper proposes a two-step land cover decomposition method, which combines optical and thermal spectra from different seasons to cope with the issue of urban spectral complexity. First, a linear spectral mixture analysis was employed to generate fraction images for three preliminary endmembers (high albedo, low albedo, and vegetation). Seasonal change analysis on land surface temperature induced from thermal infrared spectra and coarse component fractions obtained from the first step was then used to reduce the confusion between impervious surfaces and nonimpervious materials. This method was tested with two-date Landsat multispectral data in Shanghai, one of China's megacities. The results showed that the method was capable of consistently estimating impervious surfaces in highly complex urban environments with an accuracy of R2 greater than 0.70 and both root mean square error and mean average error less than 0.20 for all test sites. This strategy seemed very promising for landscape mapping of complex urban areas.

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

    SciTech Connect

    Kostyrko, T. Ślusarski, T.

    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.

  17. Using object-based analysis to derive surface complexity information for improved filtering of airborne laser scanning data

    NASA Astrophysics Data System (ADS)

    Yan, Menglong; Blaschke, Thomas; Tang, Hongzhao; Xiao, Chenchao; Sun, Xian; Zhang, Daobing; Fu, Kun

    2016-03-01

    Airborne laser scanning (ALS) is a technique used to obtain Digital Surface Models (DSM) and Digital Terrain Models (DTM) efficiently, and filtering is the key procedure used to derive DTM from point clouds. Generating seed points is an initial step for most filtering algorithms, whereas existing algorithms usually define a regular window size to generate seed points. This may lead to an inadequate density of seed points, and further introduce error type I, especially in steep terrain and forested areas. In this study, we propose the use of objectbased analysis to derive surface complexity information from ALS datasets, which can then be used to improve seed point generation.We assume that an area is complex if it is composed of many small objects, with no buildings within the area. Using these assumptions, we propose and implement a new segmentation algorithm based on a grid index, which we call the Edge and Slope Restricted Region Growing (ESRGG) algorithm. Surface complexity information is obtained by statistical analysis of the number of objects derived by segmentation in each area. Then, for complex areas, a smaller window size is defined to generate seed points. Experimental results show that the proposed algorithm could greatly improve the filtering results in complex areas, especially in steep terrain and forested areas.

  18. Heavy metal desorption kinetic as affected by of anions complexation onto manganese dioxide surfaces.

    PubMed

    Zaman, Muhammad Iqbal; Mustafa, Syed; Khan, Sadullah; Xing, Baoshan

    2009-10-01

    Oxides of Fe, Al, and Mn have been studied extensively for heavy metals fixation in soil. However, little is known about the effect of anions on the desorption processes of these metals, especially from manganese dioxide. The purpose of this study was to examine the influence of residence time, temperature, and interacting anions on desorption of Pb(2+), Cd(2+) and Cu(2+) from MnO(2). MnO(2) was characterized by different experimental techniques prior to desorption studies. The sorption-desorption studies were conducted for Pb(2+), Cu(2+), and Cd(2+) ions in the presence of different electrolytes and at different temperature in the range 293-323 K. For all the sorption experiments, Pb(2+) sorption was the greatest and almost 100% sorption occurred in the presence of 0.001 M potassium phosphate. The sorption of metals under investigation followed the order Pb(2+)>Cu(2+)>Cd(2+), whereas the desorption order was Cd(2+)>Cu(2+)>Pb(2+) in 0.01 M potassium nitrate and sulphate. Only a small quantity of desorbed Pb was detected, even at the low value of pH 3. These results indicated the stability of lead phosphate precipitates or that phosphate treatment imparted stability to the ternary complexes formed at the MnO(2) surface. The detailed desorption kinetics were conducted only for Cd(2+) in 0.01 M potassium nitrate or 0.001 M phosphate at pH values of 3 and 4 in the temperature range 303-323 K. A substantial decrease in Cd(2+) desorption was noted with increasing pH and temperature and the desorption process reached equilibration in 3h at pH 4. However, at pH 3 the desorption fluctuated, which is probably due the dissolution of the solid at such low pH values.

  19. Model complexity in carbon sequestration:A design of experiment and response surface uncertainty analysis

    NASA Astrophysics Data System (ADS)

    Zhang, Y.; Li, S.

    2014-12-01

    Geologic carbon sequestration (GCS) is proposed for the Nugget Sandstone in Moxa Arch, a regional saline aquifer with a large storage potential. For a proposed storage site, this study builds a suite of increasingly complex conceptual "geologic" model families, using subsets of the site characterization data: a homogeneous model family, a stationary petrophysical model family, a stationary facies model family with sub-facies petrophysical variability, and a non-stationary facies model family (with sub-facies variability) conditioned to soft data. These families, representing alternative conceptual site models built with increasing data, were simulated with the same CO2 injection test (50 years at 1/10 Mt per year), followed by 2950 years of monitoring. Using the Design of Experiment, an efficient sensitivity analysis (SA) is conducted for all families, systematically varying uncertain input parameters. Results are compared among the families to identify parameters that have 1st order impact on predicting the CO2 storage ratio (SR) at both end of injection and end of monitoring. At this site, geologic modeling factors do not significantly influence the short-term prediction of the storage ratio, although they become important over monitoring time, but only for those families where such factors are accounted for. Based on the SA, a response surface analysis is conducted to generate prediction envelopes of the storage ratio, which are compared among the families at both times. Results suggest a large uncertainty in the predicted storage ratio given the uncertainties in model parameters and modeling choices: SR varies from 5-60% (end of injection) to 18-100% (end of monitoring), although its variation among the model families is relatively minor. Moreover, long-term leakage risk is considered small at the proposed site. In the lowest-SR scenarios, all families predict gravity-stable supercritical CO2 migrating toward the bottom of the aquifer. In the highest

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

    NASA Astrophysics Data System (ADS)

    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

  1. Complexation of β-cyclodextrin with a gemini surfactant studied by isothermal titration microcalorimetry and surface tensiometry.

    PubMed

    Benkő, Mária; Király, László A; Puskás, Sándor; Király, Zoltán

    2014-06-17

    We report on the inclusion complex formation of β-cyclodextrin (βCD) with a cocogem surfactant (counterion-coupled gemini surfactant; (bis(4-(2-alkyl)benzenesulfonate)-Jeffamine salt, abbreviated as ABSJ), studied by isothermal titration calorimetry (ITC) and surface tension (SFT) measurements. We measured the critical micelle concentration (cmc) of ABSJ in water by the two experimental techniques in the temperature range 283-343 K, and determined the thermodynamic parameters of the complex formation directly by ITC and indirectly by the SFT. The stoichiometry (N), the binding constant (K), and the enthalpy of complexation were determined, and the Gibbs free energy and the entropy term were calculated from the experimental data. A novel method is presented for the determination of N and K by using surface tensiometry.

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

    SciTech Connect

    Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    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. The RSV F and G glycoproteins interact to form a complex on the surface of infected cells

    SciTech Connect

    Low, Kit-Wei; Tan, Timothy; Ng, Ken; Tan, Boon-Huan; Sugrue, Richard J.

    2008-02-08

    In this study, the interaction between the respiratory syncytial virus (RSV) fusion (F) protein, attachment (G) protein, and small hydrophobic (SH) proteins was examined. Immunoprecipitation analysis suggested that the F and G proteins exist as a protein complex on the surface of RSV-infected cells, and this conclusion was supported by ultracentrifugation analysis that demonstrated co-migration of surface-expressed F and G proteins. Although our analysis provided evidence for an interaction between the G and SH proteins, no evidence was obtained for a single protein complex involving all three of the virus proteins. These data suggest the existence of multiple virus glycoprotein complexes within the RSV envelope. Although the stimulus that drives RSV-mediated membrane fusion is unknown, the association between the G and F proteins suggest an indirect role for the G protein in this process.

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

    PubMed

    de la Llave, Ezequiel; Herrera, Santiago E; Adam, Catherine; Méndez De Leo, Lucila P; Calvo, Ernesto J; Williams, Federico J

    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. PMID:26567676

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

    NASA Astrophysics Data System (ADS)

    de la Llave, Ezequiel; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    2015-11-01

    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.

  6. Mechanism of Bacterial Cell-Surface Attachment Revealed by the Structure of Cellulosomal Type II Cohesin-dockerin Complex

    SciTech Connect

    Adams,J.; Pal, G.; Jia, Z.; Smith, S.

    2006-01-01

    Bacterial cell-surface attachment of macromolecular complexes maintains the microorganism in close proximity to extracellular substrates and allows for optimal uptake of hydrolytic byproducts. The cellulosome is a large multienzyme complex used by many anaerobic bacteria for the efficient degradation of plant cell-wall polysaccharides. The mechanism of cellulosome retention to the bacterial cell surface involves a calcium-mediated protein-protein interaction between the dockerin (Doc) module from the cellulosomal scaffold and a cohesin (Coh) module of cell-surface proteins located within the proteoglycan layer. Here, we report the structure of an ultra-high-affinity (K{sub a} = 1.44 x 10{sup 10} M{sup 1-}) complex between type II Doc, together with its neighboring X module from the cellulosome scaffold of Clostridium thermocellum, and a type II Coh module associated with the bacterial cell surface. Identification of X module-Doc and X module-Coh contacts reveal roles for the X module in Doc stability and enhanced Coh recognition. This extremely tight interaction involves one face of the Coh and both helices of the Doc and comprises significant hydrophobic character and a complementary extensive hydrogen-bond network. This structure represents a unique mechanism for cell-surface attachment in anaerobic bacteria and provides a rationale for discriminating between type I and type II Coh modules.

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

    NASA Astrophysics Data System (ADS)

    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

  8. SUMMARY OF GEOCHEMICAL TRANSPORT EXPERIMENTS AND MODELS FOR SOLUTE-SEDIMENT INTERACTIONS IN STREAMS.

    USGS Publications Warehouse

    Bencala, Kenneth E.; Zellweger, Gary W.; McKnight, Diane; Kennedy, Vance C.; Jackman, Alan P.

    1985-01-01

    A variety of in-stream experiments have been conducted in small, mountain streams to investigate in-stream solute transport, interactions between surface and subsurface flows, and geochemical interactions between solutes and sediments. Models for cation transport have been developed. The emphasis has been on attempting to demonstrate the relative roles of physical transport processes and geochemical reactions. A summary of experiments conducted in three streams is presented.

  9. Boric acid adsorption on humic acids: Ab initio calculation of structures, stabilities, 11B NMR and 11B, 10B isotopic fractionations of surface complexes

    NASA Astrophysics Data System (ADS)

    Tossell, J. A.

    2006-10-01

    Boric acid, B(OH) 3, forms complexes in aqueous solution with a number of bidentate O-containing ligands, HL -, where H 2L is C 2O 4H 2 (oxalic acid), C 3O 4H 4 (malonic acid), C 2H 6O 2 (ethylene glycol), C 6H 6O 2 (catechol), C 10H 8O 2 (dioxynaphthalene) and C 2O 3H 4 (glycolic acid). McElligott and Byrne [McElligott, S., Byrne, R.H., 1998. Interaction of B(OH)30 and HCO3- in seawater: Formation of B(OH)CO3-. Aquat. Geochem.3, 345-356.] have also found B(OH) 3 to form an aqueous complex with HCO3-1. Recently Lemarchand et al. [Lemarchand, E., Schott, J., Gaillardeet, J., 2005. Boron isotopic fractionation related to boron sorption on humic acid and the structure of surface complexes formed. Geochim. Cosmochim. Acta69, 3519-3533] have studied the formation of surface complexes of B(OH) 3 on humic acid, determining 11B NMR shifts and fitted values of formation constants, and 11B, 10B isotope fractionations for a number of surface complexation models. Their work helps to clarify both the nature of the interaction of boric acid with the functional groups in humic acid and the nature of some of these coordinating sites on the humic acid. The determination of isotope fractionations may be seen as a form of vibrational spectroscopy, using the fractionating element as a local probe of the vibrational spectrum. We have calculated quantum mechanically the structures, stabilities, vibrational spectra, 11B NMR spectra and 11B, 10B isotope fractionations of a number of complexes B(OH) 2L - formed by reactions of the type: B(OH)3+HL-⇒B(OH)2L+HO using a 6-311G(d,p) basis set and the B3LYP method for determination of structures, vibrational frequencies and isotopic fractionations, the highly accurate Complete Basis Set-QB3 method for calculating the free energies and the GIAO HF method with a 6-311+G(2d,p) basis for the NMR shieldings. The calculations indicate that oxalic acid, malonic acid, catechol and glycolic acid all form stable complexes (Δ G < 0 for Reaction (1

  10. Imposing land-surface fluxes at an immersed boundary for improved simulations of atmospheric flow over complex terrain

    SciTech Connect

    Lundquist, K A; Chow, F K; Lundquist, J K; Mirocha, J D

    2008-06-05

    Boundary layer flows are greatly complicated by the presence of complex terrain which redirects mean flow and alters the structure of turbulence. Surface fluxes of heat and moisture provide additional forcing which induce secondary flows, or can dominate flow dynamics in cases with weak mean flows. Mesoscale models are increasingly being used for numerical simulations of boundary layer flows over complex terrain. These models typically use a terrain-following coordinate transformation, but these introduce numerical errors over steep terrain. An alternative is to use an immersed boundary method which alleviates errors associated with the coordinate transformation by allowing the terrain to be represented as a surface which arbitrarily passes through a Cartesian grid. This paper describes coupling atmospheric physics models to an immersed boundary method implemented in the Weather Research and Forecasting (WRF) model in previous work [Lundquist et al., 2007]. When the immersed boundary method is used, boundary conditions must be imposed on the immersed surface for velocity and scalar surface fluxes. Previous algorithms, such as those used by Tseng and Ferziger [2003] and Balaras [2004], impose no-slip boundary conditions on the velocity field at the immersed surface by adding a body force to the Navier-Stokes equations. Flux boundary conditions for the advection-diffusion equation have not been adequately addressed. A new algorithm is developed here which allows scalar surface fluxes to be imposed on the flow solution at an immersed boundary. With this extension of the immersed boundary method, land-surface models can be coupled to the immersed boundary to provide realistic surface forcing. Validation is provided in the context of idealized valley simulations with both specified and parameterized surface fluxes using the WRF code. Applicability to real terrain is illustrated with a fully coupled two-dimensional simulation of the Owens Valley in California.