Science.gov

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 of U(VI) sorption to Hanford sediment with varying geochemical conditions

    SciTech Connect

    Um, Wooyong; Serne, R. Jeffrey; Krupka, Kenneth M.

    2007-04-11

    A series of U(VI) adsorption experiments with varying pH, ionic strength, concentrations of dissolved U(VI) and carbonate was conducted to provide a more realistic database for U(VI) adsorption onto near-field vadose zone sediments at the proposed Integrated Disposal Facility (IDF) on the Hanford Site. The distribution coefficient, Kd, for U(VI) in predicted “pure” glass leachate is 0 mL/g because the glass leachate has high sodium and carbonate concentrations and high pH. The zero adsorption result suggests that uranium will exhibit no retardation when the subsurface geochemistry is controlled by glass leachate. However, U(VI) can be sequestrated even when the pH, carbonate and sodium concentrations reached levels similar to “pure” glass leachate, because U(VI) coprecipitates with calcite. When glass leachate interacts with existing porewater or surrounding sediments, sorption is observed and the numerical value of the U(VI) Kd varies significantly. A non-electrostatic, general composite approach for surface complexation modeling was applied and a combination of two U(VI) surface species, monodentate (SOUO2+) and bidentate (SO2UO2(CO3)2-), simulated very well the measured U(VI) adsorption data. The general composite surface complexation model, compared to the constant or single-valued Kd model, more accurately predicted U(VI) adsorption under the varying geochemical conditions expected at the IDF.

  3. Geochemical processes at mineral surfaces

    SciTech Connect

    Davis, J.A.; Hayes, K.F.

    1986-01-01

    This volume includes 32 papers which were presented at a symposium on geochemical processes at mineral-water interfaces in 1985 and which bring to bear on this area a very wide range of expertise. The discontinuities in properties which occur at the mineral-water interface have profound effects on the movement of naturally occurring ions. Weathering and precipitation processes control the concentrations and speciation of ions in natural waters and the movements of these within the hydrosphere; both classes of processes take place at mineral-water interfaces. After an introductory overview, the book is divided into seven major sections, each dealing with one of the aspects of the processes occurring at the mineral-water interface. Five papers deal with the physical properties of the mineral-water interface; these represent a well-balanced mix of experimental and theoretical (mathematical modeling) work. Adsorption phenomena are dealt with in another five papers; these are largely experimental in character. Ion-exchange processes are discussed in four papers, one of which addresses the use of relaxation methods to study ion exchange kinetics at the microscopic level. Spectroscopic techniques (including electron-spin resonance and Moessbauer spectroscopy) are utilized in four papers. Chemical reactions, mainly redox processes, at mineral-water interfaces are treated in four papers, one of which deals with non-biological organic reactions. Solid-solution formation and equilibria are the subjects of another set of four articles, and the last group of papers deals with the processes involved in precipitation and dissolution, including weathering.

  4. Uranium (VI) sorption onto selected mineral surfaces: Key geochemical parameters

    SciTech Connect

    Pabalan, R.T.; Bertetti, F.P.; Prikryl, J.D.; Turner, D.R.

    1996-10-01

    Batch U(VI) sorption experiments were conducted using quartz, montmorillonite, clinoptilolite, and {alpha}-alumina to determine the key geochemical parameters that influence sorption onto mineral surfaces. The experiments were done at different initial U concentration, pH, M/V, and ionic strength, and at ambient and elevated PCO{sub 2} (10{sup -3.5} and 10{sup -2.0} atm, respectively). The results show that U(VI) sorption on all the minerals studied reaches a maximum at near-neutral pH ({approximately}6.3-6.8) and decreases sharply towards more acidic or alkaline conditions. The pH range where U sorption occurs corresponds to the predominance field of aqueous monomeric U(VI)-hydroxy complexes. Sorption is inhibited at high pH and PCO{sub 2} due to formation of aqueous U(VI)-carbonate complexes. For montmorillonite and clinoptilolite, ion-exchange was suppressed due to the relatively high ionic strength of the solutions. Surface charge properties of the sorbent are inferred to be relatively unimportant factors in U(VI) sorption. Sorption data plotted in terms of K{sub d} show that M/V ratio has little influence on the distribution of U(VI) between the solid and aqueous phases. Modeling of the sorption behavior of U(VI) was performed using a surface complexation approach (Diffuse-Layer Model).

  5. Microstructural and geochemical evolution of sliding surfaces in landslides

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    The formation of basal sliding surfaces in mass movements is known to be associated with chemical and physical alteration of rock and regolith. To evaluate its microstructural and geochemical evolution we collected samples from the host rock to the sliding surface and adjacent deposits within landslides in Kirgizstan and central China. The sample locations represent different morphological and geological conditions to evaluate if the weakness of the sliding surface derives from general factors such as (micro)structural or mineralogical changes within the landslide body. Based on qualitative and quantitative geochemical analysis we could not find neither indication for notable weathering of the parent bedrock nor accumulation of clay minerals along the sliding surface to explain its reduced shear strength in the investigated near-surface landslides. The cataclasites are mainly composed of quartz, illite, calcite, kaolinite and feldspar with grain sizes between 5 μm down to < 50 nm. XRD and XRF data show no increase in Al2O3, Fe2O3 or decrease in SiO2, CaO or MgO contents towards the sliding surface, pointing to alteration processes. Transmission electron microscopy and focused ion beam technique for TEM sample preparation were used to compare the microstructures. It clearly revealed a severe reduction of grain size, and increase of pore space due to grain comminution by creeping and moving processes, indicating that elevated pore pressures are the main reason for the weakness of the sliding surfaces in shallow landslides. The comminution process within sliding surface formation seems to be comparable to fault gauge formation.

  6. 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 ...

  7. 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.

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

    PubMed

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

    2016-06-01

    The bioavailability of metals was estimated in three river sediments (Sensée, Scarpe, and Deûle Rivers) impacted by different levels of Cu, Cd, Pb, and Zn (Northern France). For that, a combination of geochemistry and biological responses (bacteria and chironomids) was used. The results obtained illustrate the complexity of the notion of "bioavailability." Indeed, geochemical indexes suggested a low toxicity, even in surface sediments with high concentrations of total metals and a predicted severe effect levels for the organisms. This was also suggested by the abundance of total bacteria as determined by DAPI counts, with high bacterial cell numbers even in contaminated areas. However, a fraction of metals may be bioavailable as it was shown for chironomid larvae which were able to accumulate an important quantity of metals in surface sediments within just a few days.We concluded that (1) the best approach to estimate bioavailability in the selected sediments is a combination of geochemical and biological approaches and that (2) the sediments in the Deûle and Scarpe Rivers are highly contaminated and may impact bacterial populations but also benthic invertebrates. PMID:26884242

  9. The geochemical composition of the terrestrial surface (without soils) and comparison with the upper continental crust

    NASA Astrophysics Data System (ADS)

    Hartmann, Jens; Dürr, Hans H.; Moosdorf, Nils; Meybeck, Michel; Kempe, Stephan

    2012-01-01

    The terrestrial surface, the "skin of the earth", is an important interface for global (geochemical) material fluxes between major reservoirs of the Earth system: continental and oceanic crust, ocean and atmosphere. Because of a lack in knowledge of the geochemical composition of the terrestrial surface, it is not well understood how the geochemical evolution of the Earth's crust is impacted by its properties. Therefore, here a first estimate of the geochemical composition of the terrestrial surface is provided, which can be used for further analysis. The geochemical average compositions of distinct lithological classes are calculated based on a literature review and applied to a global lithological map. Comparison with the bulk composition of the upper continental crust shows that the geochemical composition of the terrestrial surface (below the soil horizons) is significantly different from the assumed average of the upper continental crust. Specifically, the elements Ca, S, C, Cl and Mg are enriched at the terrestrial surface, while Na is depleted (and probably K). Analysis of these results provide further evidence that chemical weathering, chemical alteration of minerals in marine settings, biogeochemical processes (e.g. sulphate reduction in sediments and biomineralization) and evaporite deposition are important for the geochemical composition of the terrestrial surface on geological time scales. The movement of significant amounts of carbonate to the terrestrial surface is identified as the major process for observed Ca-differences. Because abrupt and significant changes of the carbonate abundance on the terrestrial surface are likely influencing CO2-consumption rates by chemical weathering on geological time scales and thus the carbon cycle, refined, spatially resolved analysis is suggested. This should include the recognition of the geochemical composition of the shelf areas, now being below sea level.

  10. 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.

  11. Distinguishing between two reservir oil types using surface geochemical modeling methods

    SciTech Connect

    Silliman, A.H.; Harrington, P.A.

    1996-08-01

    A passive soil gas surface geochemical survey was conducted in a frontier basin in Latin America. The survey was conducted in two phases in the early 1990s. Hydrocarbon data in the mass range from C{sub 2} to C{sub 11} was acquired. The data were analyzed by thermal desorption mass spectrometry. Geochemical interpretation and modeling of this data were performed using principal components analysis. During the first phase, a generic oil model was developed which mapped multiple geochemical anomalies in the basin. Subsequent drilling found that these anomalies were associated with two types of oil, a high gravity oil and a low gravity oil. During the second phase, the previous survey was expanded. The objective of the second phase was to define areas of high gravity oil influence only. Geochemical models were developed to separate areas of high gravity oil influence from low gravity oil influence. Subsequent drilling on two anomalies confirmed the presence of high gravity oil accumulations. This project illustrates the ability of passive soil gas geochemistry to distinguish between two different types of oil at depth using geochemical modeling techniques. This project also demonstrates the effectiveness of integrating multiple phases of geochemical sampling in an exploration program.

  12. 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.

  13. 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.

  14. Application of statistical quality control measures for near-surface geochemical petroleum exploration

    NASA Astrophysics Data System (ADS)

    Belt, John Q.; Rice, Gary K.

    2002-02-01

    There are four major quality control measures that can apply to geochemical petroleum exploration data: statistical quality control charts, data reproducibility-Juran approach, ethane composition index, and hydrocarbon cross plots. Statistical quality control, or SQC, charts reflect the quality-performance of the analytical process composed of equipment, instrumentation, and operator technique. An unstable process is detected through assignable causes using SQC charts. Knowing data variability is paramount to tying geochemical data over time for in-fill samples and/or project extensions. The Juran approach is a statistical tool used to help determine the ability of a process to maintain itself within the limits of set specifications for reproducing geochemical data. Ethane composition index, or ECI, is a statistical calculation based on near-surface, light hydrocarbon measurements that help differentiate thermogenic, petroleum sources at depth. The ECI data are integrated with subsurface geological information, and/or seismic survey data to determine lower-risk drilling locations. Hydrocarbon cross plots are visual correlation techniques that compare two hydrocarbons within a similar hydrocarbon suite (e.g., ethane versus propane, benzene versus toluene, or 2-ring aromatics versus 3-ring aromatics). Cross plots help determine contamination, multiple petroleum sources, and low-quality data versus high-quality data indigenous to different geochemical exploration tools. When integrated with geomorphology, subsurface geology, and seismic survey data high-quality geochemical data provides beneficial information for developing a petroleum exploration model. High-quality data is the key to the successful application of geochemistry in petroleum exploration modeling. The ability to produce high-quality, geochemical data requires the application of quality control measures reflective of a well managed ISO 9000 quality system. Statistical quality control charts, Juran

  15. 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.

  16. 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.

  17. 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

  18. 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).

  19. 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

  20. 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.

  1. Geochemical composition of Trondheimsfjord surface sediments: Sources and spatial variability of marine and terrigenous components

    NASA Astrophysics Data System (ADS)

    Faust, Johan C.; Knies, Jochen; Slagstad, Trond; Vogt, Christoph; Milzer, Gesa; Giraudeau, Jacques

    2014-10-01

    High sedimentation rates in fjords provide excellent possibilities for high resolution sedimentary and geochemical records over the Holocene. As a baseline for an improved interpretation of geochemical data from fjord sediment cores, this study aims to investigate the inorganic/organic geochemistry of surface sediments and to identify geochemical proxies for terrestrial input and river discharge in the Trondheimsfjord, central Norway. Sixty evenly distributed surface sediment samples were analysed for their elemental composition, total organic carbon (Corg), nitrogen (Norg) and organic carbon stable isotopes (δ13Corg), bulk mineral composition and grain size distribution. Our results indicate carbonate marine productivity to be the main CaCO3 source. Also, a strong decreasing gradient of marine-derived organic matter from the entrance towards the fjord inner part is consistent with modern primary production data. We show that the origin of the organic matter as well as the distribution of CaCO3 in Trondheimsfjord sediments can be used as a proxy for the variable inflow of Atlantic water and changes in river runoff. Furthermore, the comparison of grain size independent Al-based trace element ratios with geochemical analysis from terrigenous sediments and bedrocks provides evidence that the distribution of K/Al, Ni/Al and K/Ni in the fjord sediments reflect regional sources of K and Ni in the northern and southern drainage basin of the Trondheimsfjord. Applying these findings to temporally well-constrained sediment records will provide important insights into both the palaeoenvironmental changes of the hinterland and the palaeoceanographic modifications in the Norwegian Sea as response to rapid climate changes and associated feedback mechanisms.

  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. 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

  4. Trace metals in surface sediments of the Taiwan Strait: geochemical characteristics and environmental indication.

    PubMed

    Gao, Xuelu; Zhou, Fengxia; Lui, Hon-Kit; Lou, Jiann-Yuh; Chen, Chen-Tung Arthur; Zhuang, Wen

    2016-06-01

    The concentration and geochemical fractionation of six trace metals related with environmental quality assessment, namely Cd, Cr, Cu, Ni, Pb, and Zn, in 30 surface sediments from both inshore and offshore areas of the Taiwan Strait were measured to investigate their distribution characteristics, evaluate their potential mobility, and assess their pollution status. The geoaccumulation index results indicated that, on average, the studied metals presented an order of Cd > Pb > Ni > Zn > Cu > Cr and were practically in uncontaminated status except Cd. The results of the sequential extraction analysis indicated that, on average, the studied metals were mostly accumulated in residual fraction except Cd whose concentration was the highest in the acid soluble fraction presenting a high risk to the environment, and their mobility decreased in the sequence of Cd > Pb > Ni > Cu > Zn > Cr. Based on the mean probable effect level quotients, the combination of the studied metals had an 8 % probability of being toxic at two sampling sites and had a 21 % probability of being toxic at the rest of sites. The spatial distribution of the studied metals in total concentrations and different geochemical fractions corroborated the previous findings about the possible sediment transportation routes in and around the Taiwan Strait. PMID:26514571

  5. Metamorphic and geochemical evolution of an amphibolite layer in the Chugach Metamorphic Complex (Alaska)

    NASA Astrophysics Data System (ADS)

    Bruand, E.; Gasser, D.; Stuewe, K.

    2010-12-01

    The Chugach Metamorphic Complex (CMC) is an Eocene high temperature- low to medium pressure complex located in an accretionary prism (Southern Alaska). This complex is more than 300 km long, made up of metasediments associated with an amphibolite layer (~ 10m to several km width) in its southern part. Based on the study of some part of this amphibolite layer, Lull and Plafker (1990) suggested that its geometry was due to the subduction of an intraplate island arc parallel to the Alaskan margin. However following their data, the assumption was highly hypothetic. West of our study area (>150km), another “metabasalt layer” composed by pillow basalts, gabbros and sheeted dikes is described in a southern accreted terrane (Prince William terrane). Some workers suggested a possible link between the origin of these ophiolites and the metabasalt layer extended from Valdez to south of Yakutat (our study area). They argued that these metabasalts or at least the western part (Valdez location) could reflect melt emplaced into the accretionary prism and generated upward to an asthenospheric window link with the subduction of a ridge. Thus the presence of this amphibolite layer in southern Alaska is matter of debate. Therefore, in this contribution, we detailed a petrologic and geochemical study of the amphibolite layer to reconstruct the metamorphic history of this strip using thermobarometry and pseudosection modelling (THERMOCALC). Petrological observations reveal a metamorphic peak assemblage composed by hb-pl±qtz-ilm/hem/mag and PT estimates about 650-750°C and 6-8 kb. Retrograde feature are symbolised by epidote, actinolite, chlorite, albite and sphene and seem to crystallise at temperature below 450°C. The amphibolite show REE and trace elements patterns characteristic for an altered metabasalt (U and Ba positive anomalies) as well as local contaminations by sediments (Pb and Sr positive anomalies). Pressure-temperature results are compared to a recent study on the

  6. 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.

  7. 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.

  8. 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.

  9. Combined geological and surface geochemical methods discovered Agaritta and Brady Creek Fields, Concho County, Texas

    SciTech Connect

    Saunders, D.F.; Burson, K.R.; Thompson, C.K. ); Brown, J.J. )

    1993-07-01

    From December 1987 to March 1991, 25 prospects in the lower King sand (Upper Pennsylvanian Cisco) play in Concho County, Texas, were tested by several operators. They used combinations of subsurface geology, reconnaissance airborne gas sensing, surface radiometrics, soil magnetic susceptibility, and soil-gas hydrocarbon measurements to define prospects. Six new King sand discoveries or extensions and three deeper Goen discoveries resulted in a 36% exploratory success rate. The total exploration and development cost was approximately $0.67/bbl of proven producing oil reserves. Final locations for the discovery wells on each of the nine successful prospects were selected primarily on the basis of combined subsurface geology and surface geochemical data. As examples, we present information about the discovery of Brady Creek and Agaritta fields. Agaritta field is one of the two largest of the new-field discoveries, with estimated proven producing recoverable reserves of 6 million bbl of oil. Its discovery was based on a combination of (1) regional subsurface geologic projection, (2) airborne hydrocarbon sensing, (3) interstitial soil-gas hydrocarbon data, (4) soil magnetic-susceptibility measurements, and (5) surface potassium and uranium concentrations measured by gamma-ray spectrometry.

  10. Combined geological and surface geochemical methods discover King Sand production, Concho County, Texas

    SciTech Connect

    Thompson, C.K; Burson, K.R.; Saunders, D.F. ); Brown, J.J. )

    1991-03-01

    From December, 1987 to September, 1990, 16 prospects within the current confines of the Lower King (Upper Pennsylvanian Cisco age) Sand Play in Concho County, Texas, were tested by several operators on locations found by various combinations of subsurface geology, reconnaissance surface radiometrics, and soil gas hydrocarbon leads A 37.5% exploratory success rate has resulted in six new field discoveries or extensions with a total exploration and development cost of less than $0.50 per barrel of proven oil reserves. The average recoverable reserves per new field discovery are estimated to be 2.6 Mbbl of oil, and the average recoverable reserves per well are estimated to be 285,000 bbl at a depth of 2200 ft. Five of the six new field discoveries were based primarily on surface geochemical data. The sixth discovery, a southeast extension to the Lonesome Dove II field, was found on the basis of subsurface geology. The Agaritta field is one of the two largest of the new field discoveries with estimated proven (producing and undeveloped) recoverable reserves of 6 Mbbl of oil as of September, 1990. Its discovery was based on a combination of (1) detailed interstitial soil gas hydrocarbon data, (2) soil magnetic susceptibility measurements, and (3) surface potassium and uranium concentrations measured by gamma-ray spectrometry applied over two leads based on reconnaissance radiometrics. What initially appeared to be two separate prospects spaced over 7000 ft apart has since developed into one large field.

  11. 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.

  12. 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

  13. An index of floodplain surface complexity

    NASA Astrophysics Data System (ADS)

    Scown, M. W.; Thoms, M. C.; De Jager, N. 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.

  14. An index of floodplain surface complexity

    NASA Astrophysics Data System (ADS)

    Scown, M. W.; Thoms, M. C.; De Jager, N. R.

    2015-04-01

    Floodplain surface topography is an important component of floodplain ecosystems. It is the primary physical template upon which ecosystem processes are acted out. 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 the two key indicators of complexity; variability in surface geometry (VSG) and the spatial organization of surface conditions (SOC) and was determined at three sampling scales. Relationships between these measures of spatial complexity and environmental drivers, namely; flow variability (mean daily discharge [Q], the coefficient of variation of daily discharge [QCV], the coefficient of variation of mean annual discharge [QCVAnn], the coefficient of variation of maximum annual discharge [QCVMax]), sediment yield (SY), valley slope (Vs), and floodplain width (Fpw) were examined. FSC, VSG, and SOC varied between the eight floodplains and this was dependent upon sampling scale. All complexity values declined with increasing Fpw in either a power, logarithmic, or exponential function. There was little change in surface complexity with floodplain widths greater than 10 km. VSG was significantly related to SY and no significant relationships were determined between any of the hydrological variables and floodplain surface complexity.

  15. 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. PMID:16124310

  16. 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

  17. 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

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. Metal complexes as "protein surface mimetics".

    PubMed

    Hewitt, Sarah H; Wilson, Andrew J

    2016-07-28

    A key challenge in chemical biology is to identify small molecule regulators for every single protein. However, protein surfaces are notoriously difficult to recognise with synthetic molecules, often having large flat surfaces that are poorly matched to traditional small molecules. In the surface mimetic approach, a supramolecular scaffold is used to project recognition groups in such a manner as to make multivalent non-covalent contacts over a large area of protein surface. Metal based supramolecular scaffolds offer unique advantages over conventional organic molecules for protein binding, including greater stereochemical and geometrical diversity conferred through the metal centre and the potential for direct assessment of binding properties and even visualisation in cells without recourse to further functionalisation. This feature article will highlight the current state of the art in protein surface recognition using metal complexes as surface mimetics. PMID:27353704

  4. 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. PMID:24863364

  5. 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

  6. Growth and Characterization of Complex Mineral Surfaces

    SciTech Connect

    P. Meakin; E. Jettestuen; B. Jamtveit; Y. Y. Podladchikov; S. deVilliers; H. E. F. Amundsen

    2006-09-01

    Precipitation of mineral aggregates near the Earth's surface or in subsurface fractures and cavities often produces complex microstructures and surface morphologies. Here we demonstrate how a simple surface normal growth (SNG) process may produce microstructures and surface morphologies very similar to those observed in some natural carbonate systems. A simple SNG model was used to fit observed surfaces, thus providing information about the growth history and also about the frequency and spatial distribution of nucleation events during growth. The SNG model can be extended to systems in which the symmetry of precipitation is broken, for example by fluid flow. We show how a simple modification of the SNG model in which the local growth rate depends on the distance from a fluid source and the local slope or fluid flow rate, produces growth structures with many similarities to natural travertine deposits.

  7. 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

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

    USGS Publications Warehouse

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

    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.

  9. 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.

  10. 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

  11. Petrological and geochemical constraints on the origin of adakites in the Garibaldi Volcanic Complex, southwestern British Columbia, Canada

    NASA Astrophysics Data System (ADS)

    Fillmore, Julie; Coulson, Ian M.

    2013-07-01

    The Garibaldi Volcanic Complex (GVC) is located in southwestern British Columbia and comprises two related but distinct volcanic fields: the Garibaldi Lake and the Mount Garibaldi volcanic fields. The rocks of the GVC range from basalt to rhyolite, and analyses of samples from both fields distinguish these as adakites. The GVC magmas have high Sr/Y, Mg#, and Al2O3; low K2O/Na2O; and fractionated rare earth element compositions. Models of adakite genesis fall into two main groups: slab melting and non-slab melting. Adakites generated by slab melting commonly occur from young subducting crust (≤25 Ma) and are felsic partial melts of the subducting slab that interact with the mantle wedge during ascent. Non-slab melting models vary widely and include basalt fractionation, assimilation, fractional crystallization processes and partial melting of mafic lower crust. Data from the GVC are too limited to fully elucidate the mechanisms of adakite genesis; however, the petrographical and geochemical characteristics of the GVC rocks in this study do not refute an origin by slab partial melts. Variations in trace elements that reflect non-adakitic values (e.g., low La, low Cr) are likely the result of magma mixing at shallow depths within the magma reservoirs of each center, for which there is mineralogical and textural evidence. The adakite rocks of the GVC share geochemical traits akin to both low-SiO2 adakite (LSA) and high-SiO2 adakite (HSA) groups, though additional data are needed to investigate whether LSA- or HSA-type dominates within the GVC, and by extension, which should be the preferred model of adakite genesis.

  12. Colloidal Nanocrystals Fluoresced by Surface Coordination Complexes

    PubMed Central

    Wang, Guan; Ji, Jianwei; Zhang, Xinwen; Zhang, Yan; Wang, Qiangbin; You, Xiaozeng; Xu, Xiangxing

    2014-01-01

    Colloidal Nanocrystals (NCs) with fluorescence originating from surface complexes are successfully prepared. The components of these NCs range from insulator, semiconductor to metal, with either pure phase, doped or core/shell structures. The photoluminescence of these NCs can be reversibly tuned across the visible to infrared spectrum, and even allow multi-color emission. A light emitting device is fabricated and a new in vivo cell imaging method is performed to demonstrate the power of this technology for emerging applications. PMID:24970242

  13. Geochemical and age-related heterogeneity of accessory zircon from Novopavlovsk complex of the Ukrainian shield

    NASA Astrophysics Data System (ADS)

    Bibikova, E. V.; Senin, V. G.; Legkova, G. A.

    1991-10-01

    The paper presents electronic-microprobe results on the distribution of major elements (Zr and Si) and trace elements (Hf, Y, P, U, Pb, Ca, and Fe) in samples of zircon from the most ancient rocks of the Novopavlovsk complex (Ukranian shield) that were dated previously by the U-Th-Pb isotope method. The combined use of the two methods made it possible to explain the genesis of the accessory zircons in these rocks and to interpret dated events. It is shown that the tonalites of the Novopavlovsk complex were formed about 3650 million years ago, together with the basic-ultrabasic formations, followed by an increased metasomatic generation of zircons in these formations.

  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. 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

  16. 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

  17. 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.

  18. 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

  19. Contributions of natural arsenic sources to surface waters on a high grade arsenic-geochemical anomaly (French Massif Central).

    PubMed

    Bossy, A; Grosbois, C; Hendershot, W; Beauchemin, S; Crouzet, C; Bril, H

    2012-08-15

    The subwatershed studied drains a non-exploited area of the St-Yrieix-la-Perche gold mining district (French Massif Central) and it is located on an arsenic (As) geochemical anomaly. In this context, it is important to know the geochemical processes involved in the transfer of As from solid environmental compartments to the aquatic system. The stream showed a temporal variation of dissolved As (As(d)) content from 69.4 μg.L(-1) in the low flow period to 7.5 μg.L(-1) in the high flow period. Upstream, ground- and wetland waters had As(d) concentrations up to 215 and 169 μg.L(-1), respectively. The main representative As sources were determined at the subwatershed scale with in-situ monitoring of major and trace element contents in different waters and single extraction experiments. The As sources to stream water could be regrouped into two components: (i) one As-rich group (mainly in the low flow period) with groundwater, gallery exploration outlet waters and wetland waters, and (ii) one As-poor group (mainly in the high flow period) with rainwaters and soil solutions. In the soil profile, As(d) showed a significant decrease from 52.4 μg.L(-1) in the 0-5 cm superficial soil horizon to 14.4 μg.L(-1) in the 135-165 cm deep soil horizon. This decrease may be related to pedogenic processes and suggests an evolution of As-bearing phase stability through the soil profile. Quantification of As(d) fluxes at the subwatershed scale showed that groundwater was the major input (>80%) of As(d) to surface water. Moreover, natural weathering of the As-rich solid phases showed an impact on the As release, mainly from superficial soil horizons with runoff contributing about 5% to As input in surface water. PMID:22750171

  20. 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.

  1. A geochemical and stable isotope investigation of groundwater/surface-water interactions in the Velenje Basin, Slovenia

    NASA Astrophysics Data System (ADS)

    Kanduč, Tjaša; Grassa, Fausto; McIntosh, Jennifer; Stibilj, Vekoslava; Ulrich-Supovec, Marija; Supovec, Ivan; Jamnikar, Sergej

    2014-06-01

    The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water-rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO3 -, Ca2+, Mg2+ and δ13CDIC indicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ18O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg2+, Na+, Ca2+, K+, and Si, and has high alkalinity and δ13CDIC values, with low SO4 2- and NO3 - concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in 18O and 2H, and have 3H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.

  2. 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

  3. 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.

  4. 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

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

    NASA Astrophysics Data System (ADS)

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

    2013-02-01

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

  6. Geochemical and geochronologic analysis of the plutonic basement of the Tacaná Volcano Complex, Chiapas México.

    NASA Astrophysics Data System (ADS)

    Paul William, L.

    2006-12-01

    The Tacana Volcano Complex (TVC) is located on the border between the State of Chiapas, southern Mexico, and Guatemala. This volcanic complex has been described as the last volcano in the northwest part of the Central American Volcanic Arc (CAVA). The region where the TVC was emplaced is influenced by the transpressional boundary formed by the shear movement between the North American and Caribbean Plates and the compressive stress by the subduction of the Cocos Plate under the North American Plate. The most recently study about TVC was by García-Palomo et al. (2004), who summarized the chronology of the TVC from basement formation to its recent activity and report that the active TVC lies on igneous basement rocks that were formed by two magmatic processes during the Mesozoic and Cenozoic. In this work, we present the results of detailed petrographic, geochemical and geochronologic analyses obtained from plutonic rocks in the basement of the TVC zone. The results show that t this basement (granites: SiO2 of 64.64 to 65.29 wt%, granodiorites: SiO2 of 60.18 wt%, and gabbros: SiO2 of 51.67 wt%) belongs to the suite of plutonic rocks of an orogenic environment. The granites are classified as both S-type peraluminosus granites derived form partial melting of continental crust, characterized by minerals such as quartz, k-feldspar, biotite, hornblende and some Fe-Ti oxides and I-type metaluminous granites derived from subduction processes with the main mineral phases being quartz, k-feldspar, hornblende, biotite and Fe-Ti oxides. The ages thus far obtained (K- Ma to 12.65 +/- 0.08 Ma) suggest that there were at least nine periods of magmatic activity that produced granitic and mafic magmas. Reference: Garcia-Palomo, A., Macias, J.L., Arce, J.L., Mora, J.C., Hughes, S., Saucedo, R., Espindola, J.M., Escobar, R., and Layer, P., (2004). GSA Special Paper 412, p 39-57.

  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. 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

  9. 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

  10. Neutral surface layer turbulence over complex terrain

    SciTech Connect

    Bowen, B.M.

    1995-09-01

    Accurate turbulence estimates are important input to atmospheric dispersion models since they characterize downwind dispersion and hence, potential pollutant concentrations. When only basic wind information is available, an atmospheric modeler must first estimate roughness length (z{sub 0},) at the location of interest, ({mu}*) from similarity theory using average wind speed ({mu}) and z{sub 0}, and finally apply experimentally derived relationships to determine the turbulence intensities. Even when turbulence coefficients are measured, the turbulence profile must be estimated in the surface layer, using, for example, the power law recommended in a US Environmental Protection Agency guidance document. In this study, turbulent intensities and wind profiles are analyzed in eight direction sectors during near neutral stability. ``Local`` and ``regional`` roughness lengths are calculated from wind speed profiles and from longitudinal turbulence intensities ({sigma}{sub {mu}}) at both sites. With ``regional`` roughness length, complex terrain features are in effect the roughness elements. Profiles of median, 15-minute averaged turbulence intensities {sigma}{sub {mu}}, {sigma}{sub {nu}} and {sigma}{sub w} are calculated at both sites. Profiles of median {sigma}{sub {theta}} and {sigma}{sub {phi}} are also calculated using four mean values of regional z{sub 0} at both sites. Finally, differences between widely-used turbulence relationships and the relationships determined in this study, and their possible effect on model results, are discussed.

  11. Combined geological and surface geochemical methods discover Agaritta and Brady Creek fields, Concho County, Texas

    SciTech Connect

    Saunders, D.F.; Burson, K.R.; Thompson, C.K. ); Brown, J.J. )

    1992-04-01

    From December 1987 to March 1991, 25 prospects in the lower King Sandstone (Upper Pennsylvanian Cisco) play in Concho County, Texas, were tested by several operators. They used combinations of subsurface geology, reconnaissance airborne gas sensing, surface radiometrics, soil magnetic susceptibility, and soil gas hydrocarbon measurements to define prospects. Six new King Sandstone field discoveries or extensions and three deeper pay Goen Limestone field discoveries resulted in a 36% exploratory success rate. The total exploration and development cost was approximately $0.67 per bbl of proven producing oil reserves. As examples, the authors present the discovery of Brady Creek and Agaritta fields. Agaritta field is one of the two largest of the new field discoveries with estimated proven producing recoverable reserves of 6,000,000 BO. Its discovery was based on a combination of (1) airborne hydrocarbon sensing, (2) interstitial soil gas hydrocarbon data, (3) soil magnetic susceptibility measurements, and (4) surface potassium and uranium concentrations measured by gamma-ray spectrometry. Interstitial soil gas hydrocarbon anomalies combined with soil magnetic susceptibility anomalies provided the best detailed surface guidance to Agaritta field. These were supported locally by radiometric anomalies. The Brady Creek field is interpreted to be a possible crevasse splay deposit. The Aggaritta field is interpreted to be a point bar deposit. Both fields are stratigraphic traps.

  12. 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

  13. Heavy metal assessment using geochemical and statistical tools in the surface sediments of Vembanad Lake, Southwest Coast of India.

    PubMed

    Selvam, A Paneer; Priya, S Laxmi; Banerjee, Kakolee; Hariharan, G; Purvaja, R; Ramesh, R

    2012-10-01

    The geochemical distribution and enrichment of ten heavy metals in the surface sediments of Vembanad Lake, southwest coast of India was evaluated. Sediment samples from 47 stations in the Lake were collected during dry and wet seasons in 2008 and examined for heavy metal content (Al, Fe, Mn, Cr, Zn, Ni, Pb, Cu, Co, Cd), organic carbon, and sediment texture. Statistically significant spatial variation was observed among all sediment variables, but negligible significant seasonal variation was observed. Correlation analysis showed that the metal content of sediments was mainly regulated by organic carbon, Fe oxy-hydroxides, and grain size. Principal component analysis was used to reduce the 14 sediment variables into three factors that reveal distinct origins or accumulation mechanisms controlling the chemical composition in the study area. Pollution intensity of the Vembanad Lake was measured using the enrichment factor and the pollution load index. Severe and moderately severe enrichment of Cd and Zn in the north estuary with minor enrichment of Pb and Cr were observed, which reflects the intensity of the anthropogenic inputs related to industrial discharge into this system. The results of pollution load index reveal that the sediment was heavily polluted in northern arm and moderately polluted in the extreme end and port region of the southern arm of the lake. A comparison with sediment quality guideline quotient was also made, indicating that there may be some ecotoxicological risk to benthic organisms in these sediments. PMID:22068311

  14. The cancrinite-syenite/carbonatite complex of Lueshe, Kivu/NE-Zaire: petrographic and geochemical studies and its economic significance

    NASA Astrophysics Data System (ADS)

    Maravic, H. v.; Morteani, G.; Roethe, G.

    The Luesche cancrinite-syenite/carbonatite complex is located in NE-Zaire about 50 km SSW of Lake Edward. The alkaline rocks have intruded metamorphic rocks of Burundian age (1.100 m.y.). The country rocks are quartzites and mica schists bearing chlorite, garnet, Kyanite and staurolite, which indicates P-T conditions of some 4 kbar and 430-500°C, maximum 6 kbar and 620°C. The K/Ar age of the biotites from the carbonatite is found to be 516 m.y. The core of the alkaline complex is composed of cancrinite-syenites which vary from place to place with respect to the contents of garnet, amphibole, aegirine, sodalite and cancrinite. Significant variations of the pyrochlore content are also observed. The core is surrounded by fine grained calcitic carbonatite (alvikite) which often shows a banded texture and grades into coarse grained calcitic carbonatite (søvite). In the SE of the søvite ring there is a separate dolomitic carbonatite body (beforsite) while at the contacts between the alkaline rocks and the country rocks a wide range of low to high grade fenites enriched in Na or K occurs. Within the alkaline complex the highest niobium values are found associated with metasomatic rocks of the contact zones such as carbosyenites, pyroxentic rocks and fenites. The main niobium mineral is a Ca, Na-pyrochlore enriched in Ti and/or Sr. The geochemical distribution patterns of the major elements as well as of the trace elements, especially the REE, suggests that the carbonatites are of primary magmatic origin derived from mantle material which was affected by later remobilizations, most likely as a result of postmagmatic hydrothermal solutions. Regarding the cancrinite-syenites, there is no evidence for a comagmatic formation with the carbonatites. They are rather of subcrustal origin; formed in the course of various metasomatic processes where the alkalic carbonate melts or volatile carbonate phases interacted with the metamorphic country rocks to form rheomorphic syenites

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. APPLICATION OF SURFACE COMPLEXATION MODELS TO SOIL SYSTEMS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Chemical surface complexation models were developed to describe potentiometric titration and ion adsorption data on oxide minerals. These models provide molecular descriptions of adsorption using an equilibrium approach that defines surface species, chemical reactions, mass and charge balances and ...

  20. Organic-geochemical proxies of sea surface temperature in surface sediments of the tropical eastern Indian Ocean

    NASA Astrophysics Data System (ADS)

    Chen, Wenwen; Mohtadi, Mahyar; Schefuß, Enno; Mollenhauer, Gesine

    2014-06-01

    In this study we reconstruct sea surface temperatures (SSTs) using two lipid-based biomarker proxies (alkenone unsaturation index U37K‧ and TEX86 index based on glycerol dibiphytanyl glycerol tetraethers) in 36 surface sediment samples from the Indonesian continental margin off west Sumatra and south of Java and the Lesser Sunda Islands. Comparison of measured temperatures (World Ocean Atlas 09) to reconstructed temperatures suggests that SST estimates based on U37K‧ reflect the SE monsoon SST in the upwelling area south of Java and the Lesser Sunda Islands. Estimates based on TEX86 using the calibration for temperatures >20 °C (TEX86H) are up to 2 °C lower than U37K‧-based SSTs. This offset is possibly related to either one or a combination of two factors: (i) the depth habitats of the source organisms and (ii) different seasonal production and/or seasonality of export associated with phytoplankton blooming triggered by primary productivity. In the non-upwelling area off west Sumatra, the alkenone-based SSTs are cooler than measured temperatures during the entire year, likely reflecting the limitations of the U37K‧ proxy beyond 28 °C, while reconstructed temperatures based on TEX86H are consistent with mean annual SST.

  1. 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.

  2. 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

  3. 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.

  4. Soft Landing of Complex Molecules on Surfaces

    SciTech Connect

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

    2011-07-01

    Mass spectrometry is a versatile technique for identification and structural characterization of large molecules. The advent of soft ionization techniques such as electrospray (ESI) (1-2) has enabled ionization of a wide variety of complex molecules without significant \\fragmentation while non-thermal ion sources such as laser vaporization (3-4) and magnetron sputtering (5-6) have provided access to materials that cannot, currently, be produced through conventional techniques. Most mass spectrometry studies rely on ionization of a molecule of interest or a complex mixture followed by mass analysis. Alternatively, mass spectrometry may be used as a preparatory technique, in which mass-selected ions are deposited onto solid supports or into liquid materials (7-18). Preparatory mass spectrometry offers several unique advantages for deposition of complex molecules on substrates including the ability to generate high-purity uniform films (19-20), unprecedented selectivity and specificity of preparation of deposited species (11, 21-22), the ability to focus and pattern an ion beam (23-24), and flexibility in both ion formation (1, 3, 25-26) and mass selection (27-32) processes. This review will highlight applications of mass-selected deposition of complex molecules for selective immobilization of biological molecules and catalytically active complexes on substrates.

  5. 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.

  6. A geochemical constraint on the formation process of a manganese carbonate nodule in the siliceous mudstone of the Jurassic accretionary complex in the Mino Belt, Japan

    NASA Astrophysics Data System (ADS)

    Nakada, Ryoichi; Shirai, Taka'aki; Takahashi, Satoshi; Suzuki, Noritoshi; Ogawa, Kazuhiro; Takahashi, Yoshio

    2014-12-01

    Manganese (Mn) carbonate nodules, which differ from seafloor Mn nodules mainly composed of MnO2, are occasionally embedded in the form of a lens shape in the Jurassic accretionary complexes, such as the Mino Belt in Japan. The interpretation of the formation process of Mn carbonate is still controversial, particularly concerning whether the Mn carbonate was formed primarily or secondarily. In this study, a fresh Mn carbonate nodule incorporated into the red siliceous mudstone was collected for geochemical and sedimentological analysis. The optical observation of thin sections indicates that the Mn carbonate nodules are composed of abraded grains of rhodochrosite spherule with radiolarians and are sedimentary embedded in siliceous mudstone. Microfossil radiolarians from the Mn carbonate nodules and the host red siliceous mudstone are dated as the Bajocian, but the radiolarians in the nodules are somewhat older than those in the host red siliceous mudstone. Geochemical analysis using the X-ray absorption near-edge structure on Ce indicates the dominance of trivalent Ce at present, despite the observation of a positive Ce anomaly in the PAAS-normalized REE pattern of Mn carbonate. The REE adsorption experiment on synthesized MnCO3 does not show any distinctive positive Ce anomaly, and a thermodynamic calculation suggests the possible coexistence of rhodochrosite and spontaneous oxidation of Ce. A leaching experiment that can selectively decompose the carbonate phase demonstrated no Ce anomaly in the carbonate phase of the Mn carbonate and a poor contribution to the bulk REE concentration. The carbon isotope data of Mn carbonate nodule implied the dominance of inorganic marine carbonate origin with small contribution of organic decomposition. The most plausible account of all of the observational and geochemical results is that the rhodochrosite grains were primarily formed on the depositional site and subsequently transferred to a different site, where siliceous

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

    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 2OH), 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 in

  8. 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

  9. 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.

  10. Geochemical processes in ground water resulting from surface mining of coal at the Big Sky and West Decker Mine areas, southeastern Montana

    USGS Publications Warehouse

    Clark, D.W.

    1995-01-01

    A potential hydrologic effect of surface mining of coal in southeastern Montana is a change in the quality of ground water. Dissolved-solids concen- trations in water in spoils aquifers generally are larger than concentrations in water in the coal aquifers they replaced; however, laboratory experiments have indicated that concentrations can decrease if ground water flows from coal-mine spoils to coal. This study was conducted to determine if decreases in concentrations occur onsite and, if so, which geochemical processes caused the decreases. Solid-phase core samples of spoils, unmined over- burden, and coal, and ground-water samples were collected from 16 observation wells at two mine areas. In the Big Sky Mine area, changes in ground- water chemistry along a flow path from an upgradient coal aquifer to a spoils aquifer probably were a result of dedolomitization. Dissolved-solids concentrations were unchanged as water flowed from a spoils aquifer to a downgradient coal aquifer. In the West Decker Mine area, dissolved-solids concentrations apparently decreased from about 4,100 to 2,100 milligrams per liter as water moved along an inferred flow path from a spoils aquifer to a downgradient coal aquifer. Geochemical models were used to analyze changes in water chemistry on the basis of results of solid-phase and aqueous geochemical characteristics. Geochemical processes postulated to result in the apparent decrease in dissolved-solids concentrations along this inferred flow path include bacterial reduction of sulfate, reverse cation exchange within the coal, and precipitation of carbonate and iron-sulfide minerals.

  11. 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.

  12. Complex land surface phenologies of moisture status

    NASA Astrophysics Data System (ADS)

    Henebry, G. M.; Doubkova, M.

    2006-12-01

    Making cross-scale linkages from experimental plots or flux tower footprints to regional and continental extents is made difficult by disparate spatial and temporal scales between process and observation. While exchanges between the vegetated land surface and the atmospheric boundary layer are continual, sampling and observations are typically intermittent in time and limited across space. Remote sensing of reflected sunlight has proven useful to track ecological dynamics. These observations are, however, restricted to daytime and often obscured by cloud cover, necessitating production of multi-date composites. The current generation of passive microwave radiometers can observe the land surface both day and night regardless of cloudiness, albeit at a spatial resolution coarser than typically used in ecological remote sensing. Datastreams from the AMSR-E (Advanced Microwave Scanning Radiometer-EOS) onboard NASA's Aqua platform are processed daily at the National Snow and Ice Data Center (NSIDC) into various products, including global retrievals of surficial soil moisture and vegetation water content based on microwave brightness temperatures observed at multiple frequencies. Due to sensor orbit and swath width, gaps occur at the lower latitudes in daily products. We have further processed the product-streams from the descending (01:30) and ascending (13:30) orbits into separate smoothed daily composites using an 8-day retrospective moving average. Of particular interest for synoptic ecology is the diel difference in vegetation water content. When the difference between the pre-dawn and the early afternoon values is positive, it suggests that the supply of moisture from the root zone is not able to keep pace with evapotranspiration during the day, but the soil and canopy moisture equalize overnight. Time series of the diel difference show rapid changes in moisture status in response to precipitation events and dry spells. What constitutes the appropriate baseline

  13. 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.

  14. Geochemical features of metabasic rocks from an Early to Middle Jurassic Accretionary Complex (Refahiye metamorphics, Eastern Pontides, NE Turkey): Implications for Late Jurassic-Early Cretaceous magmatic lull

    NASA Astrophysics Data System (ADS)

    Göçmengil, G.; Topuz, G.; Çelik, Ö. F.; Altıntaş, Ä.°. E.; Özkan, M.

    2012-04-01

    The Refahiye metamorphics (Eastern Pontides, NE Turkey) represent a metamorphosed accretionary complex of Early to Middle Jurassic age and occur as an interleave between coeval ophiolite. This Early to Middle Jurassic metamorphics and ophiolites are bound by a Permo-Triassic accretionary complex in the north and a Late Cretaceous accretionary complex in the south. The Refahiye metamorphics are made up of greenschist, marble, serpentine, phyllite and subordinately amphibolite, micaschist, eclogite and metachert knockers. The Jurassic and Late Cretaceous accretionary complexes in Eastern Mediterranean are related to the consumption of a Mesozoic ocean, the so-called Neo-Tethys. Regional geology in the Eastern Pontides indicate that the Early to Middle Jurassic and Late Cretaceous times correspond to volumious igneous activity, while Late Jurassic and Early Cretaceous time to an igneous lull. Here we present whole-rock geochemical data on metabasic rocks from the Refahiye accretionary complex, and discuss these data in terms of accreted material and its implications for the Jurassic evolution of the Eastern Pontides. All the metabasic rocks are well recrystallized, free of any relict texture and are variably hydrated (LOI ~ 1.3-5.1 wt%). Some samples are characterized by the unusually high-Al2O3 contents (up to 20.8 wt%) suggestive of derivation from high-Al basalts. Geochemically three distinct metabasic group are distinguished, on the basis of fluid immobile HFSEs and REEs. Group I is characterized by moderately to strongly fractionated REE patterns [(La/Yb)cn ~8-18], absence of any Nb-Ta anomaly in multi element variation diagrams and high Ti and low Zr/Nb ratios (3.68-5.72), corresponding to unorogenic alkaline basalts (ocean island basalt). Group II characterized by moderately fractionated REE ratios [(La/Yb)cn ~0.6-2.6], absence of any Nb-Ta anomaly, resembling unorogenic tholeiitic basalts (E and N-MORB). Group III on the other hand, displays unfractionated

  15. 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

  16. 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

  17. Geochemical characterization of a Quaternary monogenetic volcano in Erciyes Volcanic Complex: Cora Maar (Central Anatolian Volcanic Province, Turkey)

    NASA Astrophysics Data System (ADS)

    Gencalioglu-Kuscu, Gonca

    2011-11-01

    Central Anatolian Volcanic Province (CAVP) is a fine example of Neogene-Quaternary post-collisional volcanism in the Alpine-Mediterranean region. Volcanism in the Alpine-Mediterranean region comprises tholeiitic, transitional, calc-alkaline, and shoshonitic types with an "orogenic" fingerprint. Following the orogenic volcanism, subordinate, within-plate alkali basalts ( sl) showing little or no orogenic signature are generally reported in the region. CAVP is mainly characterized by widespread calc-alkaline andesitic-dacitic volcanism with orogenic trace element signature, reflecting enrichment of their source regions by subduction-related fluids. Cora Maar (CM) located within the Erciyes pull-apart basin, is an example to numerous Quaternary monogenetic volcanoes of the CAVP, generally considered to be alkaline. Major and trace element geochemical and geochronological data for the CM are presented in comparison with other CAVP monogenetic volcanoes. CM scoria is basaltic andesitic, transitional-calc-alkaline in nature, and characterized by negative Nb-Ta, Ba, P and Ti anomalies in mantle-normalized patterns. Unlike the "alkaline" basalts of the Mediterranean region, other late-stage basalts from the CAVP monogenetic volcanoes are classified as tholeiitic, transitional and mildly alkaline. They display the same negative anomalies and incompatible element ratios as CM samples. In this respect, CM is comparable to other CAVP monogenetic basalts ( sl), but different from the Meditterranean intraplate alkali basalts. Several lines of evidence suggest derivation of CM and other CAVP monogenetic basalts from shallow depths within the lithospheric mantle, that is from a garnet-free source. In a wider regional context, CAVP basalts ( sl) are comparable to Apuseni (Romania) and Big Pine (Western Great Basin, USA) volcanics, except the former have depleted Ba contents. This is a common feature for the CAVP volcanics and might be related to crustal contamination or source

  18. 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

  19. Surface complexation modeling of inositol hexaphosphate sorption onto gibbsite.

    PubMed

    Ruyter-Hooley, Maika; Larsson, Anna-Carin; Johnson, Bruce B; Antzutkin, Oleg N; Angove, Michael J

    2015-02-15

    The sorption of Inositol hexaphosphate (IP6) onto gibbsite was investigated using a combination of adsorption experiments, (31)P solid-state MAS NMR spectroscopy, and surface complexation modeling. Adsorption experiments conducted at four temperatures showed that IP6 sorption decreased with increasing pH. At pH 6, IP6 sorption increased with increasing temperature, while at pH 10 sorption decreased as the temperature was raised. (31)P MAS NMR measurements at pH 3, 6, 9 and 11 produced spectra with broad resonance lines that could be de-convoluted with up to five resonances (+5, 0, -6, -13 and -21ppm). The chemical shifts suggest the sorption process involves a combination of both outer- and inner-sphere complexation and surface precipitation. Relative intensities of the observed resonances indicate that outer-sphere complexation is important in the sorption process at higher pH, while inner-sphere complexation and surface precipitation are dominant at lower pH. Using the adsorption and (31)P MAS NMR data, IP6 sorption to gibbsite was modeled with an extended constant capacitance model (ECCM). The adsorption reactions that best described the sorption of IP6 to gibbsite included two inner-sphere surface complexes and one outer-sphere complex: ≡AlOH + IP₆¹²⁻ + 5H⁺ ↔ ≡Al(IP₆H₄)⁷⁻ + H₂O, ≡3AlOH + IP₆¹²⁻ + 6H⁺ ↔ ≡Al₃(IP₆H₃)⁶⁻ + 3H₂O, ≡2AlOH + IP₆¹²⁻ + 4H⁺ ↔ (≡AlOH₂)₂²⁺(IP₆H₂)¹⁰⁻. The inner-sphere complex involving three surface sites may be considered to be equivalent to a surface precipitate. Thermodynamic parameters were obtained from equilibrium constants derived from surface complexation modeling. Enthalpies for the formation of inner-sphere surface complexes were endothermic, while the enthalpy for the outer-sphere complex was exothermic. The entropies for the proposed sorption reactions were large and positive suggesting that changes in solvation of species play a major role in driving

  20. 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

  1. 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.

  2. Uniform surface complexation approaches to radionuclide sorption modeling

    SciTech Connect

    Turner, D.R.; Pabalan, R.T.; Muller, P.; Bertetti, F.P.

    1995-12-01

    Simplified surface complexation models, based on a uniform set of model parameters have been developed to address complex radionuclide sorption behavior. Existing data have been examined, and interpreted using numerical nonlinear least-squares optimization techniques to determine the necessary binding constants. Simplified modeling approaches have generally proven successful at simulating and predicting radionuclide sorption on (hydr)oxides and aluminosilicates over a wide range of physical and chemical conditions.

  3. 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.

  4. 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

  5. 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

  6. Evolution of Palaeoproterozoic mafic intrusions located within the thermal aureole of the Sudbury Igneous Complex, Canada: Isotopic, geochronological and geochemical evidence

    NASA Astrophysics Data System (ADS)

    Prevec, Stephen A.; Baadsgaard, Halfdan

    2005-07-01

    Impact cratering and their resultant geological phenomena are recognised as significant factors in the lithological and biologic evolution of the earth. Age-dating of impact events is critical in correlating cause and effects for these catastrophic processes. The Falconbridge and Drury Township (Twp) intrusions were emplaced at the contact between Neoarchaean basement and Palaeoproterozoic volcanosedimentary rocks, and also lie at the southeast and southwest edges of the Sudbury Igneous Complex (SIC), within its thermal contact aureole. The Falconbridge Twp intrusion is dated at 2441 ± 3 Ma by U-Pb zircon, with evidence of Archaean inheritance from its host granitoids. Granitoids from the southernmost Abitibi Subprovince are dated here between 2670 ± 11 Ma for an undeformed Algoman granite, and 2696 ± 18 Ma for a foliated granitoid, consistent with existing data from the Abitibi Greenstone Belt and from the Wawa Subprovince. Major and trace element geochemical evidence, common-Pb isotopic compositions, and ɛNd2440 values between 0 and -1 are all consistent with a Palaeoproterozoic origin for the Falconbridge Twp intrusion, and support inclusion in the East Bull Lake-type suite of leucogabbroic plutons and sills. In contrast, the Drury Twp intrusion gives a U-Pb zircon age of 1859 ± 13 Ma, coincident with the date of SIC-emplacement. While the major and trace element compositions are comparable to the Falconbridge data, the Drury displays significant heterogeneity in ɛNd2440, with values ranging from +3.7 to -0.1, and contains more radiogenic Pb isotopic compositions. Field, geochemical and isotopic evidence clearly distinguishes this intrusion from constituents of the SIC itself, and indicates that the Drury too is a Palaeoproterozoic intrusion. This requires that apparently unshocked, undeformed magmatic-looking zircon has been grown or reset in a postmagmatic setting. This has significant implications for the identification of mantle-derived magmas and

  7. 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

  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. 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).

  10. 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

  11. The Guarguaraz Complex and the Neoproterozoic-Cambrian evolution of southwestern Gondwana: Geochemical signatures and geochronological constraints

    NASA Astrophysics Data System (ADS)

    López de Azarevich, Vanina L.; Escayola, Mónica; Azarevich, Miguel B.; Pimentel, Márcio M.; Tassinari, Colombo

    2009-12-01

    The Guarguaraz Complex, in western Argentina, comprises a metasedimentary assemblage, associated with mafic sills and ultramafic bodies intruded by basaltic dikes, which are interpreted as Ordovician dismembered ophiolites. Two kinds of dikes are recognized, a group associated with the metasediments and the other ophiolite-related. Both have N-MORB signatures, with ɛNd between +3.5 and +8.2, indicating a depleted source, and Grenville model ages between 0.99 and 1.62 Ga. A whole-rock Sm-Nd isochron yielded an age of 655 ± 76 Ma for these mafic rocks, which is compatible with cianobacteria and acritarchae recognized in the clastic metasedimentary platform sequences, that indicate a Neoproterozoic (Vendian)-Cambrian age of deposition. The Guarguaraz metasedimentary-ophiolitic complex represents, therefore, a remnant of an oceanic basin developed to the west of the Grenville-aged Cuyania terrane during the Neoproterozoic. The southernmost extension of these metasedimentary sequences in Cordón del Portillo might represent part of this platform and not fragments of the Chilenia terrane. An extensional event related to the fragmentation of Rodinia is represented by the mafic and ultramafic rocks. The Devonian docking of Chilenia emplaced remnants of ocean floor and slices of the Cuyania terrane (Las Yaretas Gneisses) in tectonic contact with the Neoproterozoic metasediments, marking the Devonian western border of Gondwana.

  12. Geochemical and isotopic (Sr, C, O) data from the alkaline complex of Grønnedal-ĺka (South Greenland): evidence for unmixing and crustal contamination

    NASA Astrophysics Data System (ADS)

    Taubald, H.; Morteani, G.; Satir, M.

    The alkaline intrusion of Grønnedal-ĺka (South Greenland) is the oldest of the ten major rift-related plutonic complexes of southern Greenland that intruded during the Gardar period between 1330 and 1150 Ma into the 2.6-Ga-old gneisses and metasediments of the Ketilidian basement. The Grønnedal-ĺka alkaline intrusion consists of carbonatites, silicocarbonatites, transitional carbonatites and nepheline-bearing syenites. The silicocarbonatites exhibit locally ocellar textures that are typical for immiscibility processes. A 87Sr/86Sr initial ratio of about 0.703184 major and trace element compositions-including REE and C-, and O-isotope data from 15 carbonatite, 12 silicocarbonatite, 10 transitional carbonatite and 8 syenite and samples-provide evidence for minor crustal contamination of the mantle-derived magma that generated by unmixing carbonatites, silicocarbonatites and syenites. A scatter in major and trace element contents and isotope ratios is related to late- to post-magmatic alteration processes. The Grønnedal-ĺka silicocarbonatites are one of the rather rare cases in which unmixing of a highly alkaline mantle-derived magma into an alkalisilicate and a carbonatitic magma-fraction under plutonic conditions is well documented by textural and geochemical data.

  13. 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. PMID:17935419

  14. 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

  15. Ab-initio structure, energy and stable Fe isotope equilibrium fractionation of some geochemically relevant H-O-Fe complexes

    NASA Astrophysics Data System (ADS)

    Ottonello, Giulio; Zuccolini, Marino Vetuschi

    2009-11-01

    The hexa-aqua complexes [Fe(H 2O) 6-m-n(OH) n] (2-n)+n = 0 → 3, m = 0 → 6 - n; [Fe(H 2O) 6-m-n(OH) n] (3-n)+n = 0 → 4, m = 0 → 6 - n were investigated by ab-initio methods with the aim of determining their ground-state geometries, total energies and vibrational properties by treating their inner solvation shell as part of their gaseous precursor (or " hybrid approach"). After a gas-phase energy optimization within the Density Functional Theory (DFT), the molecules were surrounded by a dielectric representing the Reaction Field through an implicit Polarized Continuum Model (PCM). The exploration of several structural ligand arrangements allowed us to quantify the relative stabilities of the various ionic species and the role of the various forms of energy (solute-solvent electronic interaction, cavitation, dispersion, repulsion, liberation free energy) that contribute to stabilize the aqueous complexes. A comparison with experimental thermochemistries showed that ab-initio gas-phase + solvation energies are quite consistent with experimental evidence and allow the depiction of the most stable form in solution and the eventual configurational disorder of water/hydroxyl species around central cations. A vibrational analysis performed on the 54Fe, 56Fe, 57Fe and 58Fe isotopomers indicated important separative effects systematically affected by the extent of deprotonation. The role of the system's redox state (fO 2) and acidity (pH) on the isotopic imprinting of the aqueous species in solution was investigated by coupling the separative effects with speciation calculations. The observed systematics provided a tool of general utility in the interpretation of the iron isotopic signature of natural waters. Applications to the interpretation of isotopic fractionation in solution dictated by redox equilibria and to the significance of the Fe-isotopic imprinting of Banded Iron Formations are given. With "gaseous precursor" it is intended here the isolated gaseous

  16. 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

  17. 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.

  18. Prelimilary Geological and Geochemical Data from the Cangaldag Complex (Kastamonu-Turkey): Implications for the Geodynamic Evolution of the Central Pontides

    NASA Astrophysics Data System (ADS)

    Cimen, Okay; Sayit, Kaan; Goncuoglu, M. Cemal

    2015-04-01

    The Cangaldag Complex, one of the tectonic units lying in the Central Pontides of the Sakarya Composite Terrane, comprises variably deformed and metamorphosed rocks of mostly magmatic origin. These lithologies include both extrusive and intrusive varieties as well as volcaniclastic types, with a wide range of compositions from felsic to mafic. Petrographically the complex consists of diverse rock types, including basalt, tuff, diabase, gabbro, andesite, and rhyo-dacite. The mafic lithologies generally appear to be affected by greenschist facies metamorphism with typical assemblage of ab+act+chl+ep. A well-developed schistosity is observed in some cases. The dacitic types are generally slightly metamorphic, displaying porphyritic textures with quartz and feldspar phenocrysts embedded in a fine-grained groundmass. Mylonitic varieties of this type are also found. On the basis of geochemistry, the Cangaldag samples are of sub-alkaline character and represented by both primitive and evolved members. All rock types are variably depleted in Nb compared to LREE, similar to the lavas from subduction-related tectonic settings. In N-MORB normalized plots, the primitive members are separated into 3 groups on the basis of levels of enrichment. The first group display highly depleted characteristics akin to boninitic lavas. The second group is relatively enriched compared to the first group but still depleted than N-MORB. The third group, however, is the most enriched among the three, whose level of enrichment is around N-MORB. The overall geochemical features suggest that the Cangaldag meta-igneous rocks have been generated in an intra-oceanic system with the involvement of a subduction-modified mantle source. The chemistry of the primitive members further indicate that the melt generation within the Cangaldag Unit probably occurred on both arc and back-arc regions of the Intra-Pontide supra-subduction zone.

  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. 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.

  1. Universal spreading of water drops on complex surfaces.

    PubMed

    Stapelbroek, B B J; Jansen, H P; Kooij, E S; Snoeijer, J H; Eddi, A

    2014-04-21

    A drop of water spreads very rapidly just after it is gently deposited on a solid surface. Here we experimentally investigate how these early stages of spreading are influenced by different types of surface complexity. In particular, we consider micro-textured substrates, chemically striped substrates and soft substrates. For all these complex substrates, it is found that there always exists an inertial regime where the radius r of the wetted area grows as r ∼ t(1/2). For perfectly wetting substrates, this regime extends over several decades in time, whereas we observe a deviation from a pure power-law for partially wetting substrates. Our experiments reveal that even the cross-over from the 1/2 power law to the final equilibrium radius displays a universal dynamics. This cross-over is governed only by the final contact angle, regardless of the details of the substrate. PMID:24647615

  2. 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

  3. 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.

  4. 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. PMID:26899028

  5. 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.

  6. Characterization of surface complexes in enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Roy, D.; Furtak, T. E.

    1984-11-01

    An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl- ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl- ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl+ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl-/Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

  7. Characterization of surface complexes in enhanced Raman scattering

    SciTech Connect

    Roy, D.; Furtak, T.E.

    1984-11-01

    An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl/sup -/ ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl/sup -/ ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl/sup +/ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl/sup -//Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

  8. 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

  9. 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 .

  10. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1991-01-01

    Adsorbing organometallic molecules onto the surfaces of inorganic supports such as Al{sub 2}O{sub 3}, MgCl{sub 2}, SiO{sub 2}, etc. can result in dramatic enhancements in catalytic activity. The reasons for this and the structures of the resulting surface organometallic centers are not well understood. We have addressed this problem using actinide and early transition metal complexes as model adsorbates. Characterization tools include catalytic and stoichiometric reaction chemistry, reaction kinetics and isotopic labeling, quantitative poisoning studies, model solution chemistry, and a wide array of surface-sensitive spectroscopies such as CPMAS NMR, EPR, and UV-VIS as well as titration calorimetry. These chemical and physical experiments are closely coupled to model solution chemistry to provide maximum information yield. 4 refs., 2 figs.

  11. Determining the geochemical structure of the mantle from surface isotope distribution patterns? Insights from Ne and He isotopes and abundance ratios

    NASA Astrophysics Data System (ADS)

    Stroncik, N.; Niedermann, S.; Schnabel, E.; Erzinger, J.

    2011-12-01

    It is a common procedure among geochemists to use surface distribution patterns of e.g. Sr, Nd, Pb or He isotopes of lavas erupted at oceanic islands to map the geochemical structure of the Earth's mantle. Advances in noble gas mass spectrometry within the last decade resulting in an increasing availability of Ne isotope data sets allow us to test the strength of this approach. 4He and 21Ne are coupled through the same parent nuclides and therefore should show analogous isotope distribution patterns. Here we present He and Ne fusion data of fresh olivines derived from Big Island, Hawaii, together with He and Ne fusion data of fresh glasses from the Easter Seamount Chain (ESC), indicating that the observed isotope distribution patterns are mainly controlled by melting and shallow mixing processes. He isotopic ratios of the investigated olivines vary from MORB-like (8 ± 1 RA) to ratios more typical for a primitive mantle source (up to 20 and 26 RA for Hawaii and the ESC, respectively; RA = atmospheric 3He/4He ratio of 1.39 x 10-6). In contrast, all Ne isotope data plot within error limits along the Loihi-Kilauea line in a Ne three-isotope diagram. The Loihi-Kilauea line is regarded to be typical for a primitive mantle source. Thus, the Ne isotope data are inconsistent with any kind of zoned plume model or even a heterogeneous mantle source. The combined He and Ne data show that these He and Ne isotope systematics are produced by a pre-degassing fractionation process and subsequent melt mixing. Basically, this process causes a He deficit in melts generated by the plume, as shown by 3He/22NeS below current estimates of solar or planetary composition and 4He/21Ne* lower than the production ratio, making the He isotopic composition more susceptible to changes than the Ne isotopic composition. This can best be explained by a model in which He is fractionated from Ne during formation of melts from a plume (or enriched parts of a plume) at low melting degrees, which

  12. 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. PMID:26336844

  13. Geochemical constraints on the evolution of mafic and felsic rocks in the Bathani volcanic and volcano-sedimentary sequence of Chotanagpur Granite Gneiss Complex

    NASA Astrophysics Data System (ADS)

    Saikia, Ashima; Gogoi, Bibhuti; Ahmad, Mansoor; Ahmad, Talat

    2014-06-01

    The Bathani volcanic and volcano-sedimentary (BVS) sequence is a volcanic and volcano-sedimentary sequence, best exposed near Bathani village in Gaya district of Bihar. It is located in the northern fringe of the Chotanagpur Granite Gneiss Complex (CGGC). The volcano-sedimentary unit comprises of garnet-mica schist, rhyolite, tuff, banded iron formation (BIF) and chert bands with carbonate rocks as enclaves within the rhyolite and the differentiated volcanic sequence comprises of rhyolite, andesite, pillow basalt, massive basalt, tuff and mafic pyroclasts. Emplacement of diverse felsic and mafic rocks together testifies for a multi-stage and multi-source magmatism for the area. The presence of pillow basalt marks the eruption of these rocks in a subaqueous environment. Intermittent eruption of mafic and felsic magmas resulted in the formation of rhyolite, mafic pyroclasts, and tuff. Mixing and mingling of the felsic and mafic magmas resulted in the hybrid rock andesite. Granites are emplaced later, cross-cutting the volcanic sequence and are probably products of fractional crystallization of basaltic magma. The present work characterizes the geochemical characteristics of the magmatic rocks comprising of basalt, andesite, rhyolite, tuff, and granite of the area. Tholeiitic trend for basalt and calc-alkaline affinities of andesite, rhyolite and granite is consistent with their generation in an island arc, subduction related setting. The rocks of the BVS sequence probably mark the collision of the northern and southern Indian blocks during Proterozoic period. The explosive submarine volcanism may be related to culmination of the collision of the aforementioned blocks during the Neoproterozoic (1.0 Ga) as the Grenvillian metamorphism is well established in various parts of CGGC.

  14. 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. PMID:26507725

  15. 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

  16. 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.

  17. Geochemical constraints on the origin of mafic and silicic magmas at Cordón El Guadal, Tatara-San Pedro Complex, central Chile

    NASA Astrophysics Data System (ADS)

    Feeley, T. C.; Dungan, M. A.; Frey, F. A.

    The aim of this study is to quantify the crustal differentiation processes and sources responsible for the origin of basaltic to dacitic volcanic rocks present on Cordón El Guadal in the Tatara-San Pedro Complex (TSPC). This suite is important for understanding the origin of evolved magmas in the southern Andes because it exhibits the widest compositional range of any unconformity-bound sequence of lavas in the TSPC. Major element, trace element, and Sr-isotopic data for the Guadal volcanic rocks provide evidence for complex crustal magmatic histories involving up to six differentiation mechanisms. The petrogenetic processes for andesitic and dacitic lavas containing undercooled inclusions of basaltic andesitic and andesitic magma include: (1) assimilation of garnet-bearing, possibly mafic lower continental crust by primary mantle-derived basaltic magmas; (2) fractionation of olivine + clinopyroxene + Ca-rich plagioclase + Fe-oxides in present non-modal proportions from basaltic magmas at 4-8kbar to produce high-Al basalt and basaltic andesitic magmas; (3) vapor-undersaturated (i.e., PH2Ogeochemical and petrographic features of the Guadal volcanic rocks are interpreted to reflect the development of shallow silicic reservoirs within a region characterized by high crustal temperatures due to focused basaltic activity and high magma supply rates. On the periphery of

  18. A complex plasma device of large surface area

    SciTech Connect

    Nakamura, Y.; Ishihara, O.

    2008-03-15

    A novel complex plasma device (YCOPEX) to create two-dimensional monolayer plasma crystals of a large surface area of 15x90 cm{sup 2} is described. The YCOPEX, in which a plasma is produced by a rf discharge of argon gas, is designed to utilize gravitational force to study fundamental physics of complex plasmas. The device may be used for observation of spatial change of a phase state, propagation of waves, and collisions of flowing dust particles with an obstacle. As an example of experiments, neutral drag forces on microspheres are measured using the gravitational force on those particles. The obtained neutral drag force agrees reasonably with the values estimated from Epstein's formula.

  19. 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 ...

  20. Electromagnetic scattering by harmonically expanding surfaces and related complex resonances

    NASA Astrophysics Data System (ADS)

    Censor, D.

    1985-02-01

    A relativistically exact iterative method is developed for scattering of electromagnetic waves by expanding surfaces. In particular, the problems of the expanding cylinder and sphere are computed. It is shown that expanding scatterers respond to harmonic excitation by radiating nonharmonic waves. These waves involve complex frequencies, which are computed here. The method involves secular terms in t; therefore its validity for harmonic excitation is limited to early times. However, in the case of impulse excitation and transient scattering this problem is automatically resolved by the fact that the signal is exponentially decaying and the secular terms have no large-time effect.

  1. 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.

  2. Complexity of Arsenic Biogeochemistry in Surface Water Systems as Influenced by a Hydrologic Event

    NASA Astrophysics Data System (ADS)

    Markley, C. T.; Herbert, B. E.

    2006-12-01

    The arsenic cycle in oxic, surface water environments is often controlled by oxy-hydroxide minerals through sorption/desorption and precipitation/dissolution reactions. However, there are numerous instances where these minerals are found in low concentrations and/or are minimally reactive with respect to aqueous arsenic species. The presence of other anions may competitively inhibit arsenic sorption to oxy-hydroxide surfaces, thus increasing the bioavailability of arsenic and the potential toxic impacts. Microbe-mediated reactions can further impact arsenic fate and transport through accumulation and biotransformation. Arsenic biotransformation via reduction and/or methylation may result in an increased proportion of thermodynamically unfavorable arsenic species such as arsenite and methylated arsenicals in oxic surface waters. The reduced arsenic species, arsenite, is considered more mobile and toxic than the oxic species, arsenate while methylated arsenicals are often considered less toxic species. The complexity of these biogeochemical characteristics highlights the importance of studying arsenic in surface water environments. Particulate and aqueous phase metals (Fe, Mn, Al) and anions (As, P, S) were measured in surface water samples collected from the outflow creek of an arsenic-contaminated lake at high and low flow rates. Arsenic speciation, quantified via HPLC-ICP-MS, was dominated by methylated arsenicals at concentrations up to 82.7 μg/l. The common oxide-forming elements, Fe, Mn and Al were measured via ICP-AES at concentrations up to 2.4 mg/l, 0.88 mg/l and 3.3 mg/l, respectively. However, arsenic was not associated with the particulate phase mineralogy, being approximately 100% in the aqueous (< 0.2 μm ) phase, indicating high arsenic bioavailability. High alkalinity, phosphorous and sulfur concentrations up to 516 mgHCO3/meq, 2.0mg/l and 50 mg/l, respectively, likely out-competed arsenic for sorption to these oxide mineral surfaces. Geochemical

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. The Proximity Effect on Semiconducting Mineral Surfaces: A new aspect of Mineral Surface Reactivity and Surface Complexation Theory?

    SciTech Connect

    Becker, Udo; Rosso, Kevin M.; Hochella, Michael F.

    2001-07-01

    The observation and description of surface proximity effects, whereby the chemical reaction of one surface site influences the electronic structure and reactivity of neighboring or nearby sites, is presented in this study for semiconducting minerals pyrite (FeS2) and galena (PbS) using ab initio molecular orbital calculations as well as scanning tunneling microscopy and spectroscopy. Surface complexation theory, an important model for attachment/detachment reactions at mineral-water interfaces, will eventually need to be modified to include the influence of proximity effects.

  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. 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.

  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. 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

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. A Non-Electrostatic Surface Complexation Approach to Modeling Radionuclide Migration at the Nevada Test Site: II. Aluminosilicates

    SciTech Connect

    Zavarin, M; Bruton, C J

    2004-12-16

    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) program, radionuclide transport away from selected 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 Kd approach, surface complexation 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. In a companion report (Zavarin and Bruton, 2004), a database of radionuclide surface complexation reactions for calcite and iron oxide minerals was developed. In this report, a second set of reactions is developed: surface complexation (SC) and ion exchange (IE) to aluminosilicate minerals. The most simplified surface complexation model, the one-site non-electrostatic model (NEM), and the Vanselow IE model were used to fit a large number of published sorption data and a reaction constant database was developed. Surface complexation of Am(III), Eu(III), Np(V), Pu(IV), Pu(V), and U(VI) to aluminum oxide, silica, and aluminosilicate minerals was modeled using a generalized approach in which surface complexation to aluminosilicate >SiOH or >AlOH reactive sites was considered equivalent to the reactivity of aluminum oxide and silica reactive sites. Ion exchange was allowed to be mineral-dependent. The generalized NEM approach, in conjunction with Vanselow IE, was able to fit most published sorption data well. Fitting results indicate that surface complexation will dominate over ion exchange at pH >7 for the

  1. Geochemical methods of prospecting for hydrocarbons

    SciTech Connect

    Duchscherer, W. Jr.

    1980-12-01

    Because the commonly used reflection-seismograph exploration technique misses many marginal low-relief structural prospects and regardless of its electronic computer sophistication, overlooks almost all stratigraphic traps, the hydrocarbon exploration industry should take a look at geochemical prospecting methods, which detect geochemical anomalies in the near-surface soils by measuring the thermal dissociation of the soil carbonates that are found overlying hydrocarbon accumulations. To promote understanding of such prospecting techniques, Geochemical Surveys reviews the methods used, the soil-alteration patterns, the lateral and vertical migration of hydrocarbon gases, the halo phenomenon (a ring or annual anomaly), the geochemical modification of sediments, and the data-interpretation and exploration procedures involved in a carbonate ..delta.. C analysis, which measures the residual, stable, cumulative effect of hydrocarbon migration.

  2. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1990-02-01

    The goal of our program is to define those modes of interaction that take place between organometallic molecules and inorganic surfaces and, ultimately, to correlate various molecule-surface structures with catalytic properties.

  3. Interplay between fluid flow and fault-fracture mesh generation within underthrust sediments: Geochemical evidence from the Chrystalls Beach Complex, New Zealand

    NASA Astrophysics Data System (ADS)

    Fagereng, Å.; Harris, C.

    2014-02-01

    The Chrystalls Beach Complex, in the Otago Schist on the South Island of New Zealand, is a mélange comprising sheared trench-fill sediments and fragments of oceanic crust. It represents an exhumed analogue for underthrust sediments actively deforming along modern subduction thrust interfaces. The mélange is cross-cut by a fault-fracture mesh, comprising subvertical extension veins and subhorizontal slickenfibre-coated shear surfaces. Both shear and extension veins have a ‘crack-seal’ microstructure indicating episodic growth. Shear veins are associated with pressure solution selvages along the shear surface, whereas wall rock alteration is not observed adjacent to extension veins. Electron microprobe analyses of selvage seams indicate dissolution of silica from the immediate surroundings of slickenfibre shear veins, and therefore these slickenfibres probably grew by local dissolution-precipitation of silica. On the contrary, no depletion or addition of silica is detected around extension veins, indicating these veins grew by precipitation from advecting fluids. Oxygen isotope ratios measured in vein quartz show that shear and extension veins both precipitated from an aqueous fluid with 7 %° < δ18O < 10 %°, consistent with a fluid derived from low-grade metamorphic dehydration reactions. Fluid pressure therefore probably increased as fluids were introduced to a relatively impermeable mélange with increasing metamorphic grade and decreasing porosity. Fault-fracture mesh generation therefore involved localized shear assisted by dissolution-precipitation creep and concomitant extension fracturing. This led in turn to transient permeability associated with a fluid pressure drop, allowing episodic vein growth. This process may be analogous to geophysically observed episodic tremor and slow slip, which also involves a mixture of deformation styles that, put together, achieve shear slip along the subduction thrust interface.

  4. 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

  5. Complex surfaces plated by thin-film deposition in one operation

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.; Przybyszewski, J. S.; Spalvins, T.

    1967-01-01

    Ion plating deposits thin film on complex surface in one operation. The ionized materials follow electric lines of force to all points on the objects, uniformly plating the surface from all sides simultaneously.

  6. Investigation of the relationship between CO2 reservoir rock property change and the surface roughness change originating from the supercritical CO2-sandstone-groundwater geochemical reaction at CO2 sequestration condition

    NASA Astrophysics Data System (ADS)

    Lee, Minhee; Wang, Sookyun; Kim, Seyoon; Park, Jinyoung

    2015-04-01

    Lab scale experiments were performed to investigate the property changes of sandstone slabs and cores, resulting from the scCO2-rock-groundwater reaction for 180 days under CO2 sequestration conditions (100 bar and 50 °C). The geochemical reactions, including the surface roughness change of minerals in the slab, resulted from the dissolution and the secondary mineral precipitation for the sandstone reservoir of the Gyeongsang basin, Korea were reproduced in laboratory scale experiments and the relationship between the geochemical reaction and the physical rock property change was derived, for the consideration of successful subsurface CO2 sequestration. The use of the surface roughness value (SRrms) change rate and the physical property change rate to quantify scCO2-rock-groundwater reaction is the novel approach on the study area for CO2 sequestration in the subsurface. From the results of SPM (Scanning Probe Microscope) analyses, the SRrms for each sandstone slab was calculated at different reaction time. The average SRrms increased more than 3.5 times during early 90 days reaction and it continued to be steady after 90 days, suggesting that the surface weathering process of sandstone occurred in the early reaction time after CO2 injection into the subsurface reservoir. The average porosity of sandstone cores increased by 8.8 % and the average density decreased by 0.5 % during 90 days reaction and these values slightly changed after 90 days. The average P and S wave velocities of sandstone cores also decreased by 10 % during 90 days reaction. The trend of physical rock property change during the geochemical reaction showed in a logarithmic manner and it was also correlated to the logarithmic increase in SRrms, suggesting that the physical property change of reservoir rocks originated from scCO2 injection directly comes from the geochemical reaction process. Results suggested that the long-term estimation of the physical property change for reservoir rocks in CO2

  7. Formation of host-guest complexes on gold surface investigated by surface-enhanced IR absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Inokuchi, Yoshiya; Mizuuchi, Takahiro; Ebata, Takayuki; Ikeda, Toshiaki; Haino, Takeharu; Kimura, Tetsunari; Guo, Hao; Furutani, Yuji

    2014-01-01

    We apply surface-enhanced infrared absorption (SEIRA) spectroscopy to host-guest complexes in liquid phase to examine the structural change in the complex formation. Two thiol derivatives of 18-crown-6 (18C6) are chemisorbed on a gold surface, and aqueous solutions of MCl salts (M = Li, Na, K, Rb, and Cs) are put to form M+·18C6 complexes. Infrared spectra of these complexes in the 900-2000 cm-1 region are obtained by SEIRA spectroscopy. The observed IR spectra show noticeable peaks due to the complex formation, demonstrating that SEIRA spectroscopy will be a powerful method to investigate the structure of host-guest complexes in supramolecular chemistry.

  8. 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

  9. 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.

  10. 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

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

    SciTech Connect

    Hyun, S. P.; Fox, Patricia M.; Davis, James A.; Campbell, Kate M.; Hayes, Kim F.; Long, Philip E.

    2009-12-15

    U(VI) adsorption by two aquifer sediment samples was studied under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Background-A (BKG-A) sediment was collected upstream of a former uranium mill-tailings site at Rifle, Colorado, and Little Rusty Composite (LRC) was collected on site but with low U contamination. Batch adsorption experiments were performed using artificial groundwater solutions prepared to simulate the field groundwater composition in equilibrium with specific partial pressures of carbon dioxide. 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. The sediment was extracted with a dilute bicarbonate/carbonate solution to determine the background labile U(VI) already present in the sediment. A semi-empirical surface complexation model was developed to describe U(VI) adsorption using FITEQL4. The non-electrostatic, generalized composite surface complexation model successfully simulated U(VI) adsorption over the range of groundwater conditions at the Old Rifle site, using a two-site, two-reaction fitting scheme. The sensitivity of model parameters to background U(VI) concentration on the two samples was evaluated. U(VI) adsorption experiments were also performed using a sand fraction of BKG-A separated through repeated sonication and wet-sieving. Surface area normalized Kd for the bulk and sand fraction indicated similar reactivity for both. The surface complexation model developed in this work is expected to contribute to the prediction of fate and transport of U(VI) in the alluvial aquifer at the Old Rifle site, and to assist in the simulation of biostimulation field experiments performed at the site.

  12. 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

  13. 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.

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

    NASA Astrophysics Data System (ADS)

    Schaefer, M. W.; Leidecker, H.

    1992-12-01

    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.

  15. Supported organometallic complexes: Surface chemistry, spectroscopy, and catalysis

    SciTech Connect

    Marks, T.J.

    1992-02-01

    The long-range goal of this project is to elucidate and understand the surface chemistry and catalytic properties of well-defined, highly-reactive organometallic molecules (principally based upon abundant actinide, lanthanide, and early transition elements) adsorbed on metal oxides and halides. The nature of the adsorbed species is probed by a battery of chemical and physicochemical techniques, to understand the nature of the molecular-surface coordination chemistry and how this can give rise to extremely high catalytic activity. A complementary objective is to delineate the scope and mechanisms of the heterogeneous catalytic reactions, as well as to relate them both conceptually and functionally to model systems generated in solution.

  16. 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.

  17. Dynamical Theory of Charge Transfer Between Complex Atoms and Surfaces

    NASA Astrophysics Data System (ADS)

    Chaudhuri, Basudev; Marston, Brad

    2000-03-01

    An existing dynamical quantum many-body theory of charge transfer(A. V. Onufriev and J. B. Marston, Phys. Rev. B 53), 13340 (1996); J. Merino and J. B. Marston, Phys. Rev. B 58, 6982 (1998). describes atoms with simple s-orbitals, such as alkalis and alkaline-earths, interacting with metal surfaces. The many-body equations of motion (EOM) are developed systematically as an expansion in the number of surface particle-hole excitations. Here we generalize this theory to describe atoms with richer orbital structures, such as atomic oxygen. In the simplest version of the model, only the single-particle p_z-orbitals of the atom, the ones oriented perpendicular to the surface, participate directly in resonant charge transfer as they have the largest overlap with the metallic wavefunctions. However, as the several-electron Russell-Saunders eigenstates, labeled by total angular momenta quantum numbers J, L, and S, are built out of products of single-particle orbitals, non-trivial matrix elements must be incorporated into the many-body EOM's. Comparison to recent experimental results(A. C. Lavery, C. E. Sosolik, and B. H. Cooper, Nucl. Instrum. Meth. B 157), 42 (1999); A. C. Lavery et al. to appear in Phys. Rev. B. on the scattering of low-energy oxygen ions off Cu(001) surfaces is made.

  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. PMID:26574398

  19. 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

  20. Efficient modelling of droplet dynamics on complex surfaces

    NASA Astrophysics Data System (ADS)

    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.

  1. 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.

  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. 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.

  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. Turbulence spectra in the noise source regions of the flow around complex surfaces

    NASA Technical Reports Server (NTRS)

    Olsen, W. A.; Boldman, D. R.

    1983-01-01

    The complex turbulent flow around three complex surfaces was measured in detail with a hot wire. The measured data include extensive spatial surveys of the mean velocity and turbulence intensity and measurements of the turbulence spectra and scale length at many locations. The publication of the turbulence data is completed by reporting a summary of the turbulence spectra that were measured within the noise source locations of the flow. The results suggest some useful simplifications in modeling the very complex turbulent flow around complex surfaces for aeroacoustic predictive models. The turbulence spectra also show that noise data from scale models of moderate size can be accurately scaled up to full size.

  7. 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

  8. Surface polyethylene glycol enhances substrate-mediated gene delivery by nonspecifically immobilized complexes

    PubMed Central

    Pannier, Angela K.; Wieland, Julie A.; Shea, Lonnie D.

    2007-01-01

    Substrate-mediated gene delivery describes the immobilization of gene therapy vectors to a biomaterial, which enhances gene transfer by exposing adhered cells to elevated DNA concentrations within the local microenvironment. Surface chemistry has been shown to affect transfection by nonspecifically immobilized complexes using self-assembled monolayers (SAMs) of alkanethiols on gold. In this report, SAMs were again used to provide a controlled surface to investigate whether the presence of oligo(ethylene glycol) (EG) groups in a SAM could affect complex morphology and enhance transfection. EG groups were included at percentages that did not affect cell adhesion. Nonspecific complex immobilization to SAMs containing combinations of EG- and carboxylic acid-terminated alkanethiols resulted in substantially greater transfection than surfaces containing no EG groups or SAMs composed of EG groups combined with other functional groups. Enhancement in transfection levels could not be attributed to complex binding densities or release profiles. Atomic force microscopy imaging of immobilized complexes revealed that EG groups within SAMs affected complex size and appearance and could indicate the ability of these surfaces to preserve complex morphology upon binding. The ability to control the morphology of the immobilized complexes and influence transfection levels through surface chemistry could be translated to scaffolds for gene delivery in tissue engineering and diagnostic applications. PMID:17920004

  9. Surface complexation of U(VI) on goethite (α-FeOOH)

    NASA Astrophysics Data System (ADS)

    Sherman, David M.; Peacock, Caroline L.; Hubbard, Christopher G.

    2008-01-01

    Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation UO22+, sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)2UO2(H2O)n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO2-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)2UO2(H2O)3 which can form on the dominant {101} surface. However, in the presence of CO2, we find an enhancement of UO2 sorption at low pH and attribute this to a (>FeO)CO2UO2 ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)2UO2CO3. The three proposed surface complexes, (>FeOH)2UO2(H2O)3, >FeOCO2UO2, and (>FeOH)2UO2CO3 are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO2-OH-CO3 aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO2 environments at surface loadings of 0.02-2.0 wt% U.

  10. 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.

  11. 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.

  12. Process for using surface strain measurements to obtain operational loads for complex structures

    NASA Technical Reports Server (NTRS)

    Richards, William Lance (Inventor); Ko, William L. (Inventor)

    2010-01-01

    The invention is an improved process for using surface strain data to obtain real-time, operational loads data for complex structures that significantly reduces the time and cost versus current methods.

  13. Complex ridgelets for shift invariant characterization of surface topography with line singularities [rapid communication

    NASA Astrophysics Data System (ADS)

    Ma, Jianwei; Jiang, Xiangqian; Scott, Paul

    2005-09-01

    A complex ridgelet transform, which provides shift invariance and good performance for line singularities, is proposed to solve the problems with existing wavelet-based methods in surface metrology by taking a dual-tree complex wavelet transform on the projections of the finite Radon transform. Numerical experiments show the efficiency of this methodology in approximation, denoising, and characterization of engineering and bioengineering surfaces with straight scratches.

  14. 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.

  15. 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.

  16. Geochemical and Sr-Nd-Hf-O-C isotopic constraints on the origin of the Neoproterozoic Qieganbulake ultramafic-carbonatite complex from the Tarim Block, Northwest China

    NASA Astrophysics Data System (ADS)

    Ye, Hai-Min; Li, Xian-Hua; Lan, Zhong-Wu

    2013-12-01

    The Qieganbulake ultramafic-carbonatite complex located within the northeastern margin of the Tarim Block of Northwest China hosts the world's second largest vermiculite deposit. Field observations, radiometric dating results and Sr-Nd-Hf isotopes reveal that the parental magmas of the carbonatite and ultramafic rocks are cogenetic and formed synchronously at ~ 810 Ma. They are characterized by unusually enriched Sr-Nd-Hf isotopic compositions (ISr = 0.70570-0.70762, εNd(t) = - 7.7 to - 12.5, and εHf(t) = - 6.7 to - 12.9), indicating that the parent magmas were derived mainly from a subcontinental mantle source that had been metasomatised by subduction processes. Higher δ13C (- 3.65 to - 4.11‰) values compared to primary magmatic carbonate (- 8 to - 4‰) argue for incorporation of recycled inorganic carbon derived from subducted oceanic crusts. The carbonatites and clinopyroxenties define two distinct differentiation trends, which suggest that liquid immiscibility rather than crystal fractionation controlled the petrogenetic process. Pyroxenities have clearly higher apatite ISr and δ18O values than coexisting carbonatites, indicating involvement of crustal components during their emplacement. The Qieganbulake complex is closely associated in time and space with the mid-Neoproterozoic Rodinia breakup event triggered by mantle plume activities in the Tarim Block. Therefore, the mantle plume likely induced partial malting of, and likely mixed with, the metasomatized subcontinental lithospheric mantle, to form the Qieganbulake ultramafic-carbonatite complex.

  17. 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...

  18. 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.

  19. 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

  20. 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

  1. 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

  2. Surface complexation modeling of Cr(VI) adsorption at the goethite-water interface.

    PubMed

    Xie, Jinyu; Gu, Xueyuan; Tong, Fei; Zhao, Yanping; Tan, Yinyue

    2015-10-01

    In this study, a charge distribution multisite surface complexation model (CD-MUSIC) for adsorption of chromate onto goethite was carefully developed. The adsorption of Cr(VI) on goethite was firstly investigated as a function of pH, ionic strength and Cr(VI) concentration. Results showed that an inner-sphere complexation mechanism was involved because the retention of Cr(VI) was little influenced by ionic strength. Then two surface species: a bidentate complex (≡Fe2O2CrOOH) and a monodentate complex (≡FeOCrO3(-3/2)), which is constrained by prior spectroscopic evidence were proposed to fit the macroscopic adsorption data. Modeling results showed that the bidentate complex was found to be the dominant species at low pH, whereas, with increasing pH, monodentate species became more pronounced. The model was then verified by prediction of competitive adsorption of chromate and phosphate at various ratios and ionic strengths. The model successfully predicted the inhibition of chromate with the presence of phosphate, suggesting phosphate has higher affinity to goethite surface than Cr(VI). Results showed that the model developed in this study for Cr(VI) onto goethite was applicable for various conditions. It is a useful supplement for the surface complexation model database for oxyanions onto goethite surfaces. PMID:26057103

  3. Surface enhanced Raman scattering in electrochemical systems: The complex roles of surface roughness

    NASA Astrophysics Data System (ADS)

    Pemberton, Jeanne E.; Guy, Anita L.; Sobocinski, Raymond L.; Tuschel, David D.; Cross, Nathan A.

    1988-06-01

    A series of experiments designed to elucidate the presence and properties of large-scale and atomic-scale roughness produced on Ag electrodes with electrochemical oxidation-reduction cycle (ORC) pretreatments are presented. This report reviews surface enhanced Raman scattering (SERS) and scanning electron microscopic (SEM) characterization of Ag electrodes roughened with controlled-rate ORCs, and presents new results for the laser-induced thermal decay of SERS as a probe of Ag surface active sites and differential reflectance spectroscopy of electrochemically roughened Ag electrodes. These results are interpreted in terms of the presence and properties of both large-scale and atomic-scale roughness on these surfaces.

  4. 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.

  5. 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.

  6. Geochemical, zircon U-Pb dating and Sr-Nd-Hf isotopic constraints on the age and petrogenesis of an Early Cretaceous volcanic-intrusive complex at Xiangshan, Southeast China

    NASA Astrophysics Data System (ADS)

    Yang, Shui-Yuan; Jiang, Shao-Yong; Jiang, Yao-Hui; Zhao, Kui-Dong; Fan, Hong-Hai

    2011-01-01

    The Late Mesozoic geology of Southeast China is characterized by extensive Jurassic to Cretaceous magmatism consisting predominantly of granites and rhyolites and subordinate mafic rocks, forming a belt of volcanic-intrusive complexes. The Xiangshan volcanic-intrusive complex is located in the NW region of the belt and mainly contains the following lithologies: rhyodacite and rhyodacitic porphyry, porphyritic lava, granite porphyry with mafic microgranular enclaves, quartz monzonitic porphyry, and lamprophyre dyke. Major and trace-element compositions, zircon U-Pb dating, and Sr-Nd-Hf isotopic compositions have been investigated for these rocks. The precise SHRIMP and LA-ICP-MS zircon U-Pb dating shows that the emplacement of various magmatic units at Xiangshan took place within a short time period of less than 2 Myrs. The stratigraphically oldest rhyodacite yielded a zircon U-Pb age of 135 ± 1 Ma and the overlying rhyodacitic porphyry has an age of 135 ± 1 Ma. Three porphyritic lava samples yielded zircon U-Pb ages of 136 ± 1 Ma, 132 ± 1 Ma, and 135 ± 1 Ma, respectively. Two subvolcanic rocks (granite porphyry) yielded zircon U-Pb ages of 137 ± 1 Ma and 137 ± 1 Ma. A quartz monzonitic porphyry dyke, which represented the final stage of magmatism at Xiangshan, also yielded a zircon U-Pb age of 136 ± 1 Ma. All these newly obtained precise U-Pb ages demonstrate that the entire magmatic activity at Xiangshan was rapid and possibly took place at the peak of extensional tectonics in SE China. The geochemical data indicate that all these samples from the volcanic-intrusive complex have an A-type affinity. Sr-Nd-Hf isotopic data suggest that the Xiangshan volcanic-intrusive complex derived mainly from remelting of Paleo-Mesoproterozoic crust without significant additions of mantle-derived magma. However, the quartz monzonitic porphyry, which has zircon Hf model ages older than the whole-rock Nd model ages, and which has ɛNd(T) value higher than the other rocks

  7. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    DOE PAGESBeta

    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

  8. 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.

  9. Geochemical and isotopic constraints on the petrogenesis of the Puesto La Peña undersaturated potassic complex, Mendoza province, Argentina: Geodynamic implications

    NASA Astrophysics Data System (ADS)

    Zappettini, Eduardo O.; Villar, Luisa M.; Hernández, Laura B.; Santos, João O.

    2013-03-01

    Major and trace element and radiogenic and stable isotope data are reported for the Miocene Puesto La Peña undersaturated potassic complex, located in the Argentine Precordillera. The complex is composed of a pyroxenite core surrounded by a malignite-borolanite association, followed by radial and ring dikes composed of alkaline lamprophyres, tephrite to phonolite and intermediate varieties, porphyritic microledmorite, benmoreite, alkaline trachyte and a swarm of ultrabasic ouachitite dikes. Late trachytic to phonolitic volcanic necks and associated dikes crop out surrounding the malignitic-borolanitic massif. Major and trace element data are consistent with their derivation by partial melting from an enriched, probably lithospheric, metasomatized heterogeneous mantle involving spinel- and garnet-facies mantle sources. The trace element and isotope data indicate that all rock types are derived from a common parental magma and are thus cogenetic. Sr, Nd and Pb variations in the different studied lithologies are restricted, except for the evidence of Sr decoupling in the ouachitite samples. Their Sr-Nd isotope compositions follow the "mantle array" defined by oceanic basalts, within the OIB field, consistent with an intraplate depleted source. The genesis of the ouachitite is interpreted to be related to mixing between asthenospheric magma and melts from the lower lithosphere consisting of K-rich metasomatic layers. The Dupal like Pb isotopes signature suggests a mantle modification by introduction of continental crust material in the upper mantle; this is consistent with the Sr-Nd isotope data from the late silica-undersaturated felsic dikes and volcanic necks. Multistage mantle extraction would have occurred by the end of Neoproterozoic to lower Paleozoic times as indicated by the isotopic data. Partial melting was initiated by mantle upwelling decompression during lithosphere extension. Back-arc extensional conditions during the latest Early Miocene (19 Ma

  10. 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.

  11. Kinetics of uranium(VI) desorption from contaminated sediments: effect of geochemical conditions and model evaluation.

    PubMed

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

    2009-09-01

    Stirred-flow cell experiments were performed to investigate the kinetics of uranyl [U(VI)] desorption from a contaminated sedimentcollected from the Hanford 300 Area at the U.S. Department of Energy Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(Vl) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the solutions and sediment The solution chemical composition that led to a larger disequilibrium between adsorbed U(VI) and equilibrium adsorption state yielded a faster desorption rate. The experimental results were used to evaluate a multirate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sedimentthat contained complex adsorbed U(VI) in mass transfer limited domains (Lui et al. Water Resour. Res. 2008, 44, W08413). The model was modified and supplemented by including multirate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment With the same setof model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multirate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments. PMID:19764217

  12. 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.

  13. 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.

  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; 0.65-1032mg/L) and SO4 (405-39124mg/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 (0.002-6mg/L) and SO4 (302-2179mg/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 (0-0.8mg/L) and SO4 (10-315mg/L) concentrations, high pH (7.0-8.4) and Cl contents (10-2119mg/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. Geochemical Evidence from the Kohistan Complex for Differentiation of Garnet Granulitic lower Crust in Island Arcs by Dehydration Melting of Amphibole-bearing Plutonics: Implications for the Andesite Model of Continental Crustal Growth

    NASA Astrophysics Data System (ADS)

    Garrido, C. J.; Bodinier, J.; Burg, J.; Zeilinger, G.; Hussain, S. S.; Dawood, H.; Gervilla, F.

    2005-12-01

    We report a geochemical study of the Jijal and Sarangar complexes constituting the lower crust of the Mesozoic Kohistan paleo-island arc (N. Pakistan). The Jijal complex is composed of basal peridotites topped by a gabbroic section made up of mafic garnet granulite-with minor lenses of garnet hornblendite and granite-grading up section to hornblende gabbronorite. The Sarangar complex is constituted by metagabbro. Sarangar gabbro and Jijal hornblende gabbronorite have melt-like, LREE-enriched REE patterns similar to those of island arc basalts. These rocks and Jijal garnet granulite define altogether negative covariations of LaN, YbN and (La/Sm)N with Eu* (=2xEuN/SmN+GdN; N= chondrite normalized), and positive covariations of (Yb/Gd)N with Eu*. REE modeling indicates that these covariations cannot be accounted for by high-pressure crystal fractionation of hydrous primitive or derivative andesites. They are consistent with formation of garnet granulites as plagioclase-garnet assemblages with variable trapped melt fractions via either high-pressure crystallization of primitive island arc basalts or dehydration melting of hornblende gabbronorite, providing that the amount of segregated or restitic garnet was low (< 5 wt.%). Field, petrographic, geochemical and experimental evidence is more consistent with formation of Jijal garnet granulite by dehydration melting of Jijal hornblende gabbronorite. Similarly, Jijal garnet-bearing hornblendite lenses were most likely generated by coeval dehydration melting of hornblendites. Furthermore, melting models and geochronological data point to intrusive leucogranites in the overlying Metaplutonic complex as the melts generated by dehydration melting of the plutonic protoliths of Jijal garnet-bearing restites. Consistently with the metamorphic evolution of the Kohistan lower arc crust, dehydration melting occurred at the mature stage of this island arc when shallower hornblende-bearing plutonics were buried to depth exceeding 25

  16. 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.

  17. 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

  18. 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

  19. 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

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

    DOE PAGESBeta

    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

  1. Charge Localization in Cation-Sulfate Complexes: Implications for Thermodynamic Surface Complexation Models of the Mineral/Water Interface

    SciTech Connect

    Boily, Jean F

    2007-01-25

    The applicability of separating charges of oxyanions across inner- and outer-Helmholtz planes according to the Charge Distribution model was tested by investigating the theoretical charge distribution in a range of metal-sulphate complexes using the methods of Atoms In Molecules and of the Electron Localisation Function. Density Functional Theory gas-phase geometry optimisation calculations revealed that unbound oxygens of the sulphate molecules contracted to relatively constant S-O bond lengths of 1.432 ± 0.019 (3) Å irrespective of the bond strength with the metal ions. The populations of the valence basins of the unbound oxygens also remained relatively constant, showing that even the strongest complexation induces very little charge distribution across the sulphate molecule. Maps of the Laplacian of the electron density and of the Electron Localisation Function revealed that although charge is relatively localised at oxygen centers there is not necessarily a clear charge separation between the inner- and outer-Helmholtz planes. The Proximity and Smit models are presented as alternative surface complexation schemes to provide a molecularly and electronically consistent depiction of the mineral/solution interface. These models are also presented in their capability in accounting for results from large-scale molecular models. It should nonetheless be emphasized that the Charge Distribution model remains a valuable approach and should have the best applicability at low surface loadings and with molecules with sizes similar to those of the compact layer.

  2. 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.

  3. 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.

  4. Surface complexation modeling of uranium(VI) sorbed onto lanthanum monophosphate.

    PubMed

    Ordoñez-Regil, E; Drot, R; Simoni, E

    2003-07-15

    Sorption/desorption are basic processes in the field of contaminant transport. In order to develop mechanistically accurate thermodynamic sorption models, the simulation of retention data has to take into account molecular scale informations provided by structural investigations. In this way, the uranyl sorption constants onto lanthanum monophosphate (LaPO(4)) were determined on the basis of a previously published structural investigation. The surface complexation modeling of U(VI) retention onto LaPO(4) has been performed using the constant capacitance model included in the FITEQLv3.2 program. The electrical behavior of the solid surface was investigated using electrophoretic measurements and potentiometric titration experiments. The point of zero charge was found to be 3.5 and surface complexation modeling has made it possible to calculate the surface acidity constants. The fitting procedure was done with respect to the spectroscopic results, which have shown that LaPO(4) presents two kinds of reactive surface sites (lanthanum atoms and phosphate groups). The uranyl sorption edges were determined for two surface coverages: 40 and 20% of the surface sites that are occupied, assuming complete sorption. The modeling of these experimental data was realized by considering two uranyl species ("free" uranyl and uranyl nitrate complex) sorbed only onto phosphate surface groups according to the previously published structural investigation. The obtained sorption constants present similar values for both surface complexes and make it possible to fit both sorption edges: logK(U)=9.4 for z.tbnd;P(OH)(2)+UO(2)(2+)<-->z.tbnd;P(OH)(2)UO(2)(2+) and logK(UN)=9.7 for z.tbnd;P(OH)(2)+UO(2)NO(3)(+)<-->z.tbnd;P(OH)(2)UO(2)NO(3)(+). PMID:12909028

  5. Adsorption and viscoelastic analysis of polyelectrolyte-surfactant complexes on charged hydrophilic surfaces.

    PubMed

    Dhopatkar, Nishad; Park, Jung Hyun; Chari, Krishnan; Dhinojwala, Ali

    2015-01-27

    The aggregation of surfactants around oppositely charged polyelectrolytes brings about a peculiar bulk phase behavior of the complex, known as coacervation, and can control the extent of adsorption of the polyelectrolyte at an aqueous-solid interface. Adsorption kinetics from turbid premixed polyelectrolyte-surfactant mixtures have been difficult to measure using optical techniques such as ellipsometry and reflectometry, thus limiting the correlation between bulk phases and interfacial adsorption. Here, we investigated the adsorption from premixed solutions of a cationic polysaccharide (PQ10) and the anionic surfactant sodium dodecyl sulfate (SDS) on an amphoteric alumina surface using quartz crystal microbalance with dissipation (QCMD). The surface charge on the alumina was tuned by changing the pH of the premixed solutions, allowing us to assess the role of electrostatic interactions by studying the adsorption on both negatively and positively charged surfaces. We observed a maximum extent of adsorption on both negatively and positively charged surfaces from a solution corresponding to the maximum turbidity. Enhanced adsorption upon diluting the redissolved complexes at a high SDS concentration was seen only on the negatively charged surface, and not on the positively charged one, confirming the importance of electrostatic interactions in controlling the adsorption on a hydrophilic charged surface. Using the Voight based viscoelastic model, QCMD also provided information on the effective viscosity, effective shear modulus, and thickness of the adsorbed polymeric complex. The findings of viscoelastic analysis, corroborated by atomic force microscopy measurements, suggest that PQ10 by itself forms a flat, uniform layer, rigidly attached to the surface. The PQ10-SDS complex shows a heterogeneous surface structure, where the underlayer is relatively compact and tightly attached and the top is a loosely bound diffused overlayer, accounting for most of the adsorbate

  6. 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.

  7. Surface complexation reaction for phase transfer of hydrophobic quantum dot from nonpolar to polar medium.

    PubMed

    Bhandari, Satyapriya; Roy, Shilaj; Pramanik, Sabyasachi; Chattopadhyay, Arun

    2014-09-01

    Chemical reaction between oleate-capped Zn(x)Cd(1-x)S quantum dots (Qdots) and 8-hydroxyquinoline (HQ) led to formation of a surface complex, which was accompanied by transfer of hydrophobic Qdots from nonpolar (hexane) to polar (water) medium with high efficiency. The stability of the complex on the surface was achieved via involvement of dangling sulfide bonds. Moreover, the transferred hydrophilic Qdots--herein called as quantum dot complex (QDC)--exhibited new and superior optical properties in comparison to bare inorganic complexes with retention of the dimension and core structure of the Qdots. Finally, the new and superior optical properties of water-soluble QDC make them potentially useful for biological--in addition to light emitting device (LED)--applications. PMID:25133937

  8. Surface-enhanced resonance Raman scattering spectroscopy of photosystem II pigment-protein complexes

    SciTech Connect

    Picorel, R. Estacion Experimental Aula Dei, Zaragoza ); Chumanov, G.; Cotton, T.M. ); Montoya, G. ); Toon, S.; Seibert, M. )

    1994-06-09

    Three different photosystem II (PSII) pigment-protein complexes (D1-D2-Cyt b[sub 559]-CP47, D1-D2-Cyt b[sub 559], and CP47) isolated from spinach were studied by surface-enhanced resonance Raman scattering (SERRS) spectroscopy. Surface-enhanced Raman scattering (SERS) is a distance sensitive (on a 5-10-[angstrom] scale) spectroscopic tool that can be used to examine structural properties of large biological molecules. It is demonstrated here that SERS can also be used to determine organizational relationships between different pigment-protein complexes. Strong SERRS spectra from the above PSII complexes before and after treatment with sodium dithionite were obtained on roughened Ag electrodes and in citrate-reduced Ag colloids. The D1-D2-Cyt b[sub 559] complex adsorbs with the Cyt b[sub 559] heme close to the surface in the colloid, whereas the complex adsorbs differently on the Ag electrode due to the differing surface properties of the two types of substrates. An analysis of the SERRS spectra led to the following conclusions: CP47 binds next to Cyt b[sub 559] in the D1-D2-Cyt b[sub 559]-CP47 complex and covers the heme, the Cyt b[sub 559] heme is located closer to one side of the complex (the stromal side in the intact thylakoid membrane), and both Chl and [beta]-carotene molecules are located closer to the opposite side of the complex. 37 refs., 7 figs.

  9. 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

  10. 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.

  11. 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.

  12. 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

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

    NASA Astrophysics Data System (ADS)

    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.

  14. 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

  15. 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...

  16. 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.

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

    DOE PAGESBeta

    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

  18. 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

  19. Interactive visual analysis of complex scientific data as families of data surfaces.

    PubMed

    Matković, Kresimir; Gracanin, Denis; Klarin, Borislav; Hauser, Helwig

    2009-01-01

    The widespread use of computational simulation in science and engineering provides challenging research opportunities. Multiple independent variables are considered and large and complex data are computed, especially in the case of multi-run simulation. Classical visualization techniques deal well with 2D or 3D data and also with time-dependent data. Additional independent dimensions, however, provide interesting new challenges. We present an advanced visual analysis approach that enables a thorough investigation of families of data surfaces, i.e., datasets, with respect to pairs of independent dimensions. While it is almost trivial to visualize one such data surface, the visual exploration and analysis of many such data surfaces is a grand challenge, stressing the users' perception and cognition. We propose an approach that integrates projections and aggregations of the data surfaces at different levels (one scalar aggregate per surface, a 1D profile per surface, or the surface as such). We demonstrate the necessity for a flexible visual analysis system that integrates many different (linked) views for making sense of this highly complex data. To demonstrate its usefulness, we exemplify our approach in the context of a meteorological multi-run simulation data case and in the context of the engineering domain, where our collaborators are working with the simulation of elastohydrodynamic (EHD) lubrication bearing in the automotive industry. PMID:19834208

  20. 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.

  1. 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).

  2. Impact of a complex fluid droplet on wettable and non wettable surfaces

    NASA Astrophysics Data System (ADS)

    Bolleddula, Daniel; Aliseda, Alberto

    2008-11-01

    The impact of liquid droplets is a phenomenon prevalent in many natural and industrial processes. Such events include rain drops, fuel injection, and ink-jet printing. To date, research in atomization and droplet impact has been focused on Newtonian fluids. In the coating of pharmaceutical tablets, the coating solutions contain polymers, surfactants, and large concentrations of insoluble solids in suspension which inherently exhibit non-Newtonian behavior. In this work, we will present ongoing droplet impact experiments using complex rheology fluids under a wide range of Weber and Ohnesorge numbers. Both hydrophilic and hydrophobic surfaces are been studied, and the effect of surface roughness has also been considered. We will describe the limits of bouncing, spreading, and splashing for these complex fluids. We will also discuss quantitative information such as spreading rates and contact angle measurements on wettable and non-wettable surfaces obtained from high speed images.

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

    PubMed

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

    2002-01-01

    Two experiments were conducted to study how scene complexity and cues to depth affect human color constancy. Specifically, two levels of scene complexity were compared. The low-complexity scene contained two walls with the same surface reflectance and a test patch which provided no information about the illuminant. In addition to the surfaces visible in the low-complexity scene, the high-complexity scene contained two rectangular solid objects and 24 paper samples with diverse surface reflectances. Observers viewed illuminated objects in an experimental chamber and adjusted the test patch until it appeared achromatic. Achromatic settings made tinder two different illuminants were used to compute an index that quantified the degree of constancy. Two experiments were conducted: one in which observers viewed the stimuli directly, and one in which they viewed the scenes through an optical system that reduced cues to depth. In each experiment, constancy was assessed for two conditions. In the valid-cue condition, many cues provided valid information about the illuminant change. In the invalid-cue condition, some image cues provided invalid information. Four broad conclusions are drawn from the data: (a) constancy is generally better in the valid-cue condition than in the invalid-cue condition: (b) for the stimulus configuration used, increasing image complexity has little effect in the valid-cue condition but leads to increased constancy in the invalid-cue condition; (c) for the stimulus configuration used, reducing cues to depth has little effect for either constancy condition: and (d) there is moderate individual variation in the degree of constancy exhibited, particularly in the degree to which the complexity manipulation affects performance. PMID:11922136

  4. 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.

  5. The geochemical geometry of mantle plumes

    NASA Astrophysics Data System (ADS)

    Jackson, Matthew

    2015-04-01

    Lavas erupted at oceanic hotspot volcanoes exhibit tremendous isotopic variability, which indicates that the mantle sources of the hotspots are highly heterogeneous geochemically. A key question is how the surface expression of hotspot lavas relates to the spatial distribution of the geochemical components within upwelling mantle plumes. Significant progress has been made in recent years relating the geographic distribution of geochemical heterogeneities in hotspot lavas to parallel volcanic lineaments that define the traces of oceanic hotspot tracks. For example, a well known geographic separation of parallel volcanic lineaments at Hawaii - the Loa and Kea trends - are also isotopically resolved. In addition to the Hawaiian example, clear patterns relating the geographic distribution of geochemical components along hotspot tracks are emerging from a suite of global hotspots, and these patterns suggest that geochemical heterogeneities are highly organized within upwelling mantle plume conduits. At the Samoan hotspot, the Pb-isotopic compositions measured in lavas reveal several geochemical groups, and each group corresponds to a different geographic lineament of volcanoes. Each group has a geochemical signature that relates to each of the canonical low 3He/4He mantle endmembers: EMII (enriched mantle 2), EMI (enriched mantle 1), HIMU (high U/Pb) and DM (depleted mantle). In Pb-isotopic space, the four geochemical groups each form an array that trends toward a common component (thus forming an "X-shape" in Pb-isotopic space). The region of isotope space where the 4 Pb-isotopic array intersect is defined by the highest 3He/4He (up to 34 Ra, or ratio to atmosphere) in the Samoan hotspot. In Pb-isotopic space, 3He/4He decreases monotonically along each of the Pb-isotopic groups away from the common region of convergence. In order to quantify the relationship between He and Pb isotopes, 3He/4He is plotted versus distance from the common component in Pb-isotopic space

  6. Assembly and function of a quaternary signal transduction complex monitored by surface plasmon resonance

    NASA Astrophysics Data System (ADS)

    Schuster, Stephan C.; Swanson, Ronald V.; Alex, Lisa A.; Bourret, Robert B.; Simon, Melvin I.

    1993-09-01

    WE have used surface plasmon resonance biosensor technology to monitor the assembly and dynamics of a signal transduction complex which controls chemotaxis in Escherichia coli A quaternary complex formed which consisted of the response regulator CheY, the histidine protein kinase CheA, a coupling protein CheW and a membrane-bound chemoreceptor Tar. Using various experimental conditions and mutant proteins, we have shown that the complex dissociates under conditions that favour phosphorylation of CheY. Direct physical analysis of interactions among proteins in this signal transduction pathway provides evidence for a previously unrecognized binding interaction between the kinase and its substrate. This interaction may be important for enhancing substrate specificity and preventing 'crosstalk' with other systems. The approach is generally applicable to furthering our understanding of how signalling complexes transduce intracellular messages.

  7. 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

  8. 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.

  9. Geochemical Speciation Mass Transfer

    SciTech Connect

    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 mineral 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.

  10. Geochemical Speciation Mass Transfer

    Energy Science and Technology Software Center (ESTSC)

    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

  11. 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.

  12. 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.

  13. 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

  14. 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

  15. Surface-Bound Ruthenium Diimine Organometallic Complexes: Excited-State Properties

    PubMed Central

    2015-01-01

    Ruthenium complexes of the general formula [Ru(CO)(H)(L2)(L′2)][PF6] (L2 = trans-2PPh3, L′ = η2-4,4′-dicarboxybipyridine (1); L2 =trans-2Ph2PCH2CH2COOH, L′2 = bipyridine (2); L2 = Ph2PCHCHPPh2, L′ = η2-5-amino-1,10-phenanthroline (3); L2 = trans-2PPh3, L′2 = η2-4-carboxaldehyde-4′-methylbipyridine (4)) have been shown to have longer emission lifetimes and higher quantum yields in solution compared with more symmetrical molecules such as [Ru(bpy)3][Cl]2. Compound 4 is obtained as a mixture with the corresponding acetal, 4′. These less symmetrical complexes have been covalently immobilized on the surface of silica polyamine composites, and their photophysical properties have been studied. The surface-bound complexes have been characterized by solid-state CPMAS 13C, 31P, and 29Si NMR, UV–vis, and FT-IR spectroscopies. Excited-state lifetime studies revealed that, in general, the lifetimes of the immobilized complexes are 1.4 to 8 times longer than in solution and are dependent on particle size (300–500 μm versus 10–20 nm average diameter silica gels), polymer structure (linear poly(allylamine) versus branched poly(ethylenimine)), and the type of surface tether. One exception to this trend is the previously reported complex [Ru(bpy)2(5-amino-1,10-phenanthroline)][PF6]2 (5), where only a slight increase in lifetime is observed. Only minor changes in emission wavelength are observed for all the complexes. This opens up the possibility for enhanced heterogeneous electron transfer in photocatalytic reactions. PMID:24891753

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. Spectroscopic study on uranyl carboxylate complexes formed at the surface layer of Sulfolobus acidocaldarius.

    PubMed

    Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Steudtner, Robin; Selenska-Pobell, Sonja; Merroun, Mohamed L

    2015-02-14

    The complexation of U(vi) at the proteinaceous surface layer (S-layer) of the archaeal strain Sulfolobus acidocaldarius was investigated over a pH range from pH 1.5 to 6 at the molecular scale using time-resolved laser-induced fluorescence spectroscopy (TRLFS) and U L(III)-edge extended X-ray absorption fine structure (EXAFS). The S-layer, which represents the interface between the cell and its environment, is very stable against high temperatures, proteases, and detergents. This allowed the isolation and purification of S-layer ghosts (= empty cells) that maintain the size and shape of the cells. In contrast to many other microbial cell envelope compounds the studied S-layer is not phosphorylated, enabling the investigation of uranyl carboxylate complexes formed at microbial surfaces. The latter are usually masked by preferentially formed uranyl phosphate complexes. We demonstrated that at highly acidic conditions (pH 1.5 to 3) no uranium was bound by the S-layer. In contrast to that, at moderate acidic pH conditions (pH 4.5 and 6) a complexation of U(vi) at the S-layer via deprotonated carboxylic groups was stimulated. Titration studies revealed dissociation constants for the carboxylic groups of glutamic and aspartic acid residues of pK(a) = 4.78 and 6.31. The uranyl carboxylate complexes formed at the S-layer did not show luminescence properties at room temperature, but only under cryogenic conditions. The obtained luminescence maxima are similar to those of uranyl acetate. EXAFS spectroscopy demonstrated that U(vi) in these complexes is mainly coordinated to carboxylate groups in a bidentate binding mode. The elucidation of the molecular structure of these complexes was facilitated by the absence of phosphate groups in the studied S-layer protein. PMID:25387060

  4. 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.

  5. 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.

  6. 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.

  7. 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. PMID:24219402

  8. Seasonal evolution of ecohydrological controls on land surface temperature over complex terrain

    NASA Astrophysics Data System (ADS)

    Xiang, Tiantian; Vivoni, Enrique R.; Gochis, David J.

    2014-05-01

    The spatiotemporal distribution of Land Surface Temperature (LST) is linked to the partitioning of the coupled surface water and energy budgets. In watersheds with a strong seasonality in precipitation and vegetation cover, the temporal evolution of LST patterns are a signature of the interactions between the land surface and atmosphere. Nevertheless, few studies have sought to understand the topographical and ecohydrological controls on LST in regions of complex terrain. Numerical watershed models, tested against spatially distributed field and remote sensing data, can aid in linking the seasonal evolution of LST to meteorology, terrain, soil, and vegetation. In this study, we use a distributed hydrologic model to explore LST patterns in a semiarid mountain basin during the transition from a dry spring to the wetter North American monsoon (NAM). By accounting for vegetation greening through remotely sensed parameters, the model reproduces LST and surface soil moisture observations derived from ground, aircraft, and satellite platforms with good accuracy at individual sites and as spatial basin patterns. Distributed simulations reveal how LST varies with elevation, slope, and aspect and the role played by the seasonal vegetation canopy in cooling the land surface and increasing the spatial variability in LST. As a result, LST is shown to track well with ecosystem-specific changes in vegetation cover, evapotranspiration, and soil moisture during the NAM. Furthermore, vegetation greening is shown to modulate the spatial heterogeneity of LST during the NAM that should be considered in subsequent atmospheric studies in regions of complex terrain.

  9. 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. PMID:16488660

  10. 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.

  11. EMI of large power systems: magnetic field calculation by substituting surface quantities for complex sources

    NASA Astrophysics Data System (ADS)

    Napieralska, E.; Roger, D.; Komeza, K.; Schulz, C. A.

    2007-08-01

    The aim of this research is the elaboration of a method allowing simple simulation of electromagnetic interferences (EMI) of complex electric systems. The method presented in this paper allows the replacement of the electromagnetic active objects by simple closed surfaces that surround each source. The flux density components are calculated on these surfaces using standard 3D finite element software separately for each object. The magnetic flux density in every point of the free space around the system is calculated with an analytical formula. The main topic of the paper is the definition of the limits of the discussed method.

  12. 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.

  13. A study of molecular adsorption of a cationic surfactant on complex surfaces with atomic force microscopy.

    PubMed

    Sokolov, I; Zorn, G; Nichols, J M

    2016-02-01

    The study of molecular adsorption on solid surfaces is of broad interest. However, so far the study has been restricted to idealized flat smooth rigid surfaces which are rarely the case in real world applications. Here we describe a study of molecular adsorption on a complex surface of the submicron fibers of a fibrous membrane of regenerated cellulose in aqueous media. We use a cationic surfactant, cetyltrimethylammonium chloride (CTAC), as the adsorbing molecule. We study the equilibrium adsorption of CTAC molecules on the same area of the fibers by sequentially immersing the membrane in pure water, 1 mM and then a 20 mM solution of CTAC. Atomic force microscopy (AFM) is applied to study the adsorption. The force-volume mode is used to record the force-deformation curves of the adsorbed molecules on the fiber surface. We suggest a model to separate the forces due to the adsorbed molecules from the elastic deformation of the fiber. Interestingly, knowledge of the surface geometry is not required in this model provided the surface is made of elastically homogeneous material. Different models are investigated to estimate the amount of the adsorbed molecules based on the obtained force curves. The exponential steric repulsion model fits the force data the best. The amount of the adsorbed surfactant molecules and its dependence on the concentration are found to be reasonable compared to the data previously measured by means of Raman scattering done on a flat surface of silica. PMID:26730682

  14. 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.

  15. Complexes of fulvic acid on the surface of hematite, goethite, and akaganeite: FTIR observation.

    PubMed

    Fu, Hongbo; Quan, Xie

    2006-04-01

    The present work extended our knowledge on the binding and complexation of a fulvic acid (FA) derived from leonardite and the iron oxides (hematite, goethite and akaganeite) by Fourier transform infrared spectroscopy (FTIR). As a prerequisite, the iron oxides were firstly prepared and characterized by transmission electron micrograph (TEM). All iron phases were single and well-described crystalloid. The FTIR data obtained by two different sampling preparation methods gave the consisting evidences that under our experimental conditions the interaction mechanism was to the ligand-exchange involving carboxylic functional groups of the FA and the surfaces sites of both hematite and goethite, while no complexation can be evidenced in the case of akaganeite, only surface adsorption. In general, the binding affinities of the iron oxides with the FA was in the order of hematite>goethite>akaganeite. The present method, although associated with some uncertainties, provided an opportunity to increase the knowledge in the field of the humic chemistry. PMID:16293289

  16. 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

  17. Environmental Applications of Geochemical Modeling

    NASA Astrophysics Data System (ADS)

    Zhu, Chen; Anderson, Greg

    2002-05-01

    This book discusses the application of geochemical models to environmental practice and studies, through the use of numerous case studies of real-world environmental problems, such as acid mine drainage, pit lake chemistry, nuclear waste disposal, and landfill leachates. In each example the authors clearly define the environmental threat in question; explain how geochemical modeling may help solve the problem posed; and advise the reader how to prepare input files for geochemical modeling codes and interpret the results in terms of meeting regulatory requirements.

  18. 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

  19. Assembly, organization and regulation of cell-surface receptors by lectin-glycan complexes.

    PubMed

    Elola, María T; Blidner, Ada G; Ferragut, Fátima; Bracalente, Candelaria; Rabinovich, Gabriel A

    2015-07-01

    Galectins are a family of β-galactoside-binding lectins carrying at least one consensus sequence in the carbohydrate-recognition domain. Properties of glycosylated ligands, such as N- and O-glycan branching, LacNAc (N-acetyl-lactosamine) content and the balance of α2,3- and α2,6-linked sialic acid dramatically influence galectin binding to a preferential set of counter-receptors. The presentation of specific glycans in galectin-binding partners is also critical, as proper orientation and clustering of oligosaccharide ligands on multiple carbohydrate side chains increase the binding avidity of galectins for particular glycosylated receptors. When galectins are released from the cells, they typically concentrate on the cell surface and the local matrix, raising their local concentration. Thus galectins can form their own multimers in the extracellular milieu, which in turn cross-link glycoconjugates on the cell surface generating galectin-glycan complexes that modulate intracellular signalling pathways, thus regulating cellular processes such as apoptosis, proliferation, migration and angiogenesis. Subtle changes in receptor expression, rates of protein synthesis, activities of Golgi enzymes, metabolite concentrations supporting glycan biosynthesis, density of glycans, strength of protein-protein interactions at the plasma membrane and stoichiometry may modify galectin-glycan complexes. Although galectins are key contributors to the formation of these extended glycan complexes leading to promotion of receptor segregation/clustering, and inhibition of receptor internalization by surface retention, when these complexes are disrupted, some galectins, particularly galectin-3 and -4, showed the ability to drive clathrin-independent mechanisms of endocytosis. In the present review, we summarize the data available on the assembly, hierarchical organization and regulation of conspicuous galectin-glycan complexes, and their implications in health and disease. PMID:26173257

  20. Acidic Plutonism in the Izu-Ogasawara (Bonin)-Mariana (IBM) Arc and Growth of Arc Crust: Petrological and Geochemical Characteristics of the Tonalite at the Komahashi-Daini Seamount and Difference From the Tanzawa Plutonic Complex

    NASA Astrophysics Data System (ADS)

    Haraguchi, S.; Ishii, T.

    2003-12-01

    Recent seismic refraction and reflection data suggest that the continents are underlain by mafic lower crust and felsic middle crust. Petrogenesis of granitic middle crust layers is important for understanding the formation and evolution of continental crust. In modern tectonic regimes, tonalitic rocks and chemically equivalent volcanic rocks occur in island arcs and active continental margins. Thus, the petrogenesis of tonalite and related rocks in intra-oceanic arc settings is of great importance in understanding the processes of both recent island arc and continental crust formation. The Komahashi-Daini Seamount, in the northern Kyushu-Palau Ridge in the northern Philippine Sea plate, was investigated by the Japanese Geodynamics Project (GDP) cruises in the 1970's, and by the R/V Tansei-maru (Ocean Research Institute, University of Tokyo) in the 1990's. Plutonic rocks were dredged from the seamount, and have great importance for understanding the processes of island arc and continental crust formation. The petrographical and geochemical characteristics of the Komahashi-Daini Seamount tonalite are summarized as follows: (1) These tonalites are classified into biotite-hornblende tonalite and hornblende tonalite. Phenocrysts, especially plagioclase, show common lamellar twins and oscillatory zoning patterns; (2) This tonalite show low content of bulk LILE, and classified into low-K calc-alkaline, 1 to 8 wt.% MgO with 55 to 75 wt.% SiO2; (3) This tonalite shows roughly parallel and increasing total REE content with increasing SiO2 content, except for increasingly strong negative Eu anomaly at higher SiO2. These factors indicate that the Komahashi-Daini Seamount tonalite was produced by fractional crystallization. The parent magma of this tonalite is considered lower than 56 wt.% SiO2. Based on this relationship, we concluded that the source for the parental magma was arc mantle peridotite. We compared these tonalites with typical tonalite, i.e., Tanzawa Complex

  1. Effects of electric field on a copper-dioxolene complex adsorbed on a gold surface

    NASA Astrophysics Data System (ADS)

    Kostyrko, T.; Ślusarski, T.

    2016-06-01

    A model of a copper-dioxolene complex linked to Au(1 1 1) surface with butanethiol linker is investigated using first-principles methods. It is shown that the complex adsorbed at the surface may appear in various locally stable structural forms differing in electron charge and spin density distribution, the symmetric high spin (HS) one and the twisted low spin (LS) structure. The electric field directed perpendicular to the surface controls the amount of the charge transfer between the complex and the substrate, starting from the zero-field value of Q = +0.18 |e| up to the value of Q = +0.94 |e| for the field strength of E = 0.5 V/Å. The field modifies also the mutual stability of the two structural forms, reducing the energy gap between the more energetically stable LS twisted form and the symmetrical HS one, from a value of Δ ∼ 0.29 eV in absence of the field to Δ ∼ 0.11 eV for the field strength of E = 0.35 V/Å.

  2. 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.

  3. 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

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

    PubMed

    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 [Co(II)(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

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

    PubMed

    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. PMID:27147706

  6. 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.

  7. 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

  8. 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.

  9. Estimating aerodynamic roughness over complex salt pan and sandur dust emitting surfaces

    NASA Astrophysics Data System (ADS)

    Nield, Joanna; King, James; Wiggs, Giles; Leyland, Julian; Bryant, Robert; Chiverrell, Richard; Darby, Stephen; Eckardt, Frank; Thomas, David; Vircavs, Larisa; Washington, Richard

    2014-05-01

    Salt pan and sandur surfaces typically consist of complex patterns of small-scale roughness which differ to more commonly studied larger roughness elements. It is important to understand how these surfaces interact with the wind as both sandar and salt pans (or playas) are potential dust emitters, and so improving our understanding of surface-atmosphere interactions over surfaces in these areas is vital. These complexly patterned surfaces are also relative flat, lack vegetation and typically have a large fetch which makes them the ideal experimental surfaces to develop empirical estimations of aerodynamic roughness from terrestrial laser scanner (TLS) datasets. We investigated 20 surfaces with element heights ranging from 1 to 199mm during four field campaigns. Co-located anemometer towers at each location measured actual aerodynamic roughness to compare to a myriad of surface metrics derived from TLS datasets. Using cluster analysis height, shape, spacing and variability metric groups were compared to decipher which best estimated aerodynamic roughness. When height metrics were employed, it was found that over 90% of the variability was explained and height is a better predictor than both shape and spacing. This finding is in juxtaposition to wind erosion models that assume the spacing of larger-scale isolated roughness elements is most important in determining aerodynamic roughness. The study recognizes that when small-scale surface roughness is accurately quantified (with millimetre accuracy using TLS), height is most significance for estimating aerodynamic roughness, irrespective of comparator metric choice. This has very significant implications for the development of aerodynamic roughness predictors which are fundamental to the efficiency of wind erosion models, and, particularly, dust emission schemes in climate models.

  10. 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.

  11. Control of the axial coordination of a surface-confined manganese(III) porphyrin complex

    NASA Astrophysics Data System (ADS)

    Beggan, J. P.; Krasnikov, S. A.; Sergeeva, N. N.; Senge, M. O.; Cafolla, A. A.

    2012-06-01

    The organization and thermal lability of chloro(5,10,15,20-tetraphenylporphyrinato)manganese(III) (Cl-MnTPP) molecules on the Ag(111) surface have been investigated under ultra-high vacuum conditions, using scanning tunnelling microscopy, low energy electron diffraction and x-ray photoelectron spectroscopy. The findings reveal the epitaxial nature of the molecule-substrate interface, and moreover, offer a valuable insight into the latent coordination properties of surface-confined metalloporphyrins. The Cl-MnTPP molecules are found to self-assemble on the Ag(111) surface at room temperature, forming an ordered molecular overlayer described by a square unit cell. In accordance with the threefold symmetry of the Ag(111) surface, three rotationally equivalent domains of the molecular overlayer are observed. The primitive lattice vectors of the Cl-MnTPP overlayer show an azimuthal rotation of ±15° relative to those of the Ag(111) surface, while the principal molecular axes of the individual molecules are found to be aligned with the substrate \\langle 0\\bar {1}1\\rangle and \\langle \\bar {2}1 1\\rangle crystallographic directions. The axial chloride (Cl) ligand is found to be orientated away from the Ag(111) surface, whereby the average plane of the porphyrin macrocycle lies parallel to that of the substrate. When adsorbed on the Ag(111) surface, the Cl-MnTPP molecules display a latent thermal lability resulting in the dissociation of the axial Cl ligand at ˜423 K. The thermally induced dissociation of the Cl ligand leaves the porphyrin complex otherwise intact, giving rise to the coordinatively unsaturated Mn(III) derivative. Consistent with the surface conformation of the Cl-MnTPP precursor, the resulting (5,10,15,20-tetraphenylporphyrinato)manganese(III) (MnTPP) molecules display the same lattice structure and registry with the Ag(111) surface.

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

    NASA Astrophysics Data System (ADS)

    Bain, J. G.; Mayer, K. U.; Blowes, D. W.; Frind, E. O.; Molson, J. W. H.; 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.

  13. 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. PMID:11695738

  14. 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.

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

    PubMed

    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. PMID:25841151

  16. 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.

  17. 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.

  18. Testing limits on matte surface color perception in three-dimensional scenes with complex light fields.

    PubMed

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

    2007-12-01

    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, R., Jacobs, D. (2001). Lambertian reflectance and linear subspaces. In: International Conference on Computer Vision II, pp. 383-390; Ramamoorthi, R., Hanrahan, P., (2001). An efficient representation for irradiance environment maps. SIGGRAPH 01. New York: ACM Press, pp. 497-500] 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

  19. Elaboration of antibiofilm surfaces functionalized with antifungal-cyclodextrin inclusion complexes.

    PubMed

    Gharbi, Aïcha; Humblot, Vincent; Turpin, Frédéric; Pradier, Claire-Marie; Imbert, Christine; Berjeaud, Jean-Marc

    2012-07-01

    To tackle the loss of activity of surfaces functionalized by coating and covalently bound molecules to materials, an intermediate system implying the noncovalent immobilization of active molecules in the inner cavity of grafted cyclodextrins (CDs) was investigated. The antifungal and antibiofilm activities of the most stable complexes of Anidulafungin (ANF; echinocandin) and thymol (THY; terpen) in various CDs were demonstrated to be almost the same as the free molecules. The selected CD was covalently bond to self-assembled monolayers on gold surfaces. The immobilized antifungal agents reduced the number of culturable Candida albicans ATCC 3153 attached to the surface by 64 ± 8% for ANF and 75 ± 15% for THY. The inhibitory activity was persistent for THY-loaded samples, whereas it was completely lost for ANF-loaded surfaces after one use. However, reloading of the echinocandin restored the activity. Using fluorescent dying and confocal microscopy, it was proposed that the ANF-loaded surfaces inhibited the adherence of the yeasts, whereas the activity of immobilized THY was found fungicidal. This kind of tailored approach for functionalizing surfaces that could allow a progressive release of ANF or THY gave promising results but still needs to be improved to display a full activity. PMID:22268719

  20. Complex frequencies and field distributions of localized surface plasmon modes in graphene-coated subwavelength wires

    NASA Astrophysics Data System (ADS)

    Cuevas, Mauro; Riso, Máximo A.; Depine, Ricardo A.

    2016-04-01

    In this work we study the modal characteristics of localized surface plasmons in graphene-coated, circular cross-section wires. Localized surface plasmons are represented in terms of cylindrical multipole partial waves characterized by discrete, complex frequencies that depend on the size of the wire and can be dynamically tuned via a gate voltage. We consider both intrinsically nonplasmonic wires and intrinsically plasmonic wires. In the first case the localized surface plasmons are introduced by the graphene coating, whereas in the second case the localized eigenmodes of the graphene coating are expected to hybridize those already existing in the bare wire. We show that the approach presented here, valid for particle sizes where the retardation effects can be significant, is in good agreement with analytical expressions obtained in the limit when particle size is very small compared to the wavelength of the eigenmode and with results indirectly determined from scattering cross-section spectra.

  1. Application of surface complexation modeling to the understanding of transportation cask weeping

    SciTech Connect

    Granstaff, V.E.; Chambers, W.B.

    1993-11-01

    A new application for surface complexation modeling is described. These models, which describe chemical equilibria among aqueous and adsorbed species, have typically been used for predicting groundwater transport of contaminants by modeling the natural adsorbents as various metal oxides. We have shown that this type of modeling can also be used to explain stainless steel surface contamination and decontamination mechanisms. Stainless steel transportation casks that are submerged in a spent fuel storage pool at nuclear power stations, can become contaminated with radionuclides such as {sup 137}CS, {sup 134}Cs, and {sup 60}Co. Subsequent release or desorption of these contaminants under varying environmental conditions occasionally results in the phenomenon known as ``cask weeping.`` We have postulated that contaminants in the storage pool adsorb onto the hydrous metal oxide surface of the passivated stainless steel and are subsequently released during transportation, due to varying environmental factors, such as humidity, road salt, dirt, and acid rain. It is well known that 304 stainless steel has a chromium enriched passive surface layer; thus its adsorption behavior should be similar to that of chromium oxide. Presented here are adsorption data for Co{sup +2} on Cr{sup 2}O{sup 3} which simulate the stainless steel surface contamination. These data are interpreted using electrostatic surface complexation models. The FITEQL computer program was used to obtain the electrostatic model constants from the experimental data. Because the concentrations of contaminants in the storage pool are too low to be measured accurately by conventional chemical analysis techniques, MINTEQA2 can be used, with the fitted constants, to extrapolate the equilibria to the low concentrations representative of storage pool water.

  2. 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.

  3. 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.

  4. Adjustment of geochemical background by robust multivariate statistics

    USGS Publications Warehouse

    Zhou, D.

    1985-01-01

    Conventional analyses of exploration geochemical data assume that the background is a constant or slowly changing value, equivalent to a plane or a smoothly curved surface. However, it is better to regard the geochemical background as a rugged surface, varying with changes in geology and environment. This rugged surface can be estimated from observed geological, geochemical and environmental properties by using multivariate statistics. A method of background adjustment was developed and applied to groundwater and stream sediment reconnaissance data collected from the Hot Springs Quadrangle, South Dakota, as part of the National Uranium Resource Evaluation (NURE) program. Source-rock lithology appears to be a dominant factor controlling the chemical composition of groundwater or stream sediments. The most efficacious adjustment procedure is to regress uranium concentration on selected geochemical and environmental variables for each lithologic unit, and then to delineate anomalies by a common threshold set as a multiple of the standard deviation of the combined residuals. Robust versions of regression and RQ-mode principal components analysis techniques were used rather than ordinary techniques to guard against distortion caused by outliers Anomalies delineated by this background adjustment procedure correspond with uranium prospects much better than do anomalies delineated by conventional procedures. The procedure should be applicable to geochemical exploration at different scales for other metals. ?? 1985.

  5. 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

  6. 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.

  7. 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

  8. 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.

  9. Development of an electrospray approach to deposit complex molecules on plasma modified surfaces

    NASA Astrophysics Data System (ADS)

    Kitching, K. J.; Lee, H.-N.; Elam, W. T.; Johnston, E. E.; MacGregor, H.; Miller, R. J.; Turecek, F.; Ratner, B. D.

    2003-11-01

    Two established techniques have been coupled to allow surfaces to be precision engineered. Electrospray ionization to bring large, complex, intact molecular ions into the gas phase has been interfaced with a radio frequency (rf) plasma reactor to treat surfaces making them receptive to the deposition of active biomolecules. The new instrument has been designed and used successfully to deposit a number of high molecular weight molecules including the polysaccharide, sodium hyaluronan (HA), that has an important role in a number of physiological functions. Substrate material is treated using a rf glow discharge plasma chamber, to clean and activate the surface in a controlled manner, then exposed to a beam of multiply charged ions in the gas phase that have been generated using electrospray techniques. The ions are deposited gently onto the substrate and become covalently bound. The molecular integrity and stability of HA surfaces prepared in this way was established using x-ray photoelectron spectroscopy, changes in the observed contact angle, time-of-flight secondary ion mass spectrometry, scanning electron microscopy, and a biological assay-platelet adhesion to the surface.

  10. 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.

  11. 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.

  12. 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

  13. A consistent model for surface complexation on birnessite (-MnO2) and its application to a column experiment

    NASA Astrophysics Data System (ADS)

    Appelo, C. A. J.; Postma, D.

    1999-10-01

    Available surface complexation models for birnessite required the inclusion of bidentate bonds or the adsorption of cation-hydroxy complexes to account for experimentally observed H+/Mm+ exchange. These models contain inconsistencies and therefore the surface complexation on birnessite was re-examined. Structural data on birnessite indicate that sorption sites are located on three oxygens around a vacancy in the octahedral layer. The three oxygens together carry a charge of -2, i.e., constitute a doubly charged sorption site. Therefore a new surface complexation model was formulated using a doubly charged, diprotic, sorption site where divalent cations adsorbing via inner-sphere complexes bind to the three oxygens. Using the diprotic site concept we have remodeled the experimental data for sorption on birnessite by Murray (1975) using the surface complexation model of Dzombak and Morel (1990). Intrinsic constants for the surface complexation model were obtained with the non-linear optimization program PEST in combination with a modified version of PHREEQC (Parkhurst, 1995). The optimized model was subsequently tested against independent data sets for synthetic birnessite by Balistrieri and Murray (1982) and Wang et al. (1996). It was found to describe the experimental data well. Finally the model was tested against the results of column experiments where cations adsorbed on natural MnO2 coated sand. In this case as well, the diprotic surface complexation model gave an excellent description of the experimental results.

  14. 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.

  15. 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.

  16. 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.

  17. Nondispersive X-ray emission analysis for geochemical exploration

    NASA Technical Reports Server (NTRS)

    Adler, I.; Lamothe, R.; Schmadebeck, R.; Trombka, J. I.

    1969-01-01

    Nondispersive X-ray emission technique uses lightweight, and rugged X-ray fluorescence units. The X-ray pulse-height spectra is excited by radioactive isotope sources. The technique is applicable for quantitative and qualitative analyses on complex chemical systems, and satisfies the goals for a lunar geochemical exploration device.

  18. 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.

  19. Factor Xa dimerization competes with prothrombinase complex formation on platelet-like membrane surfaces.

    PubMed

    Koklic, Tilen; Chattopadhyay, Rima; Majumder, Rinku; Lentz, Barry R

    2015-04-01

    Exposure of phosphatidylserine (PS) molecules on activated platelet membrane surface is a crucial event in blood coagulation. Binding of PS to specific sites on factor Xa (fXa) and factor Va (fVa) promotes their assembly into a complex that enhances proteolysis of prothrombin by approximately 10⁵. Recent studies demonstrate that both soluble PS and PS-containing model membranes promote formation of inactive fXa dimers at 5 mM Ca²⁺. In the present study, we show how competition between fXa dimerization and prothrombinase formation depends on Ca²⁺ and lipid membrane concentrations. We used homo-FRET measurements between fluorescein-E-G-R-chloromethylketone (CK)-Xa [fXa irreversibly inactivated by alkylation of the active site histidine residue with FEGR (FEGR-fXa)] and prothrombinase activity measurements to reveal the balance between fXa dimer formation and fXa-fVa complex formation. Changes in FEGR-fXa dimer homo-FRET with addition of fVa to model-membrane-bound FEGR-fXa unambiguously demonstrated that formation of the FEGR-fXa-fVa complex dissociated the dimer. Quantitative global analysis according to a model for protein interaction equilibria on a surface provided an estimate of a surface constant for fXa dimer dissociation (K(fXa×fXa)(d, σ)) approximately 10-fold lower than K(fXa×fVa)(d,σ) for fXa-fVa complex. Experiments performed using activated platelet-derived microparticles (MPs) showed that competition between fXa dimerization and fXa-fVa complex formation was even more prominent on MPs. In summary, at Ca²⁺ concentrations found in the maturing platelet plug (2-5 mM), fVa can compete fXa off of inactive fXa dimers to significantly amplify thrombin production, both because it releases dimer inhibition and because of its well-known cofactor activity. This suggests a hitherto unanticipated mechanism by which PS-exposing platelet membranes can regulate amplification and propagation of blood coagulation. PMID:25572019

  20. 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. PMID:25494745

  1. 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

  2. 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.

  3. 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. PMID:18397010

  4. 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

  5. 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

  6. 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

  7. 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.

  8. Investigating the thermodynamic stability of Bacillus subtilis spore-uranium(VI) adsorption though surface complexation modeling

    NASA Astrophysics Data System (ADS)

    Harrold, Z.; Hertel, M.; Gorman-Lewis, D.

    2012-12-01

    Dissolved uranium speciation, mobility, and remediation are increasingly important topics given continued and potential uranium (U) release from mining operations and nuclear waste. Vegetative bacterial cell surfaces are known to adsorb uranium and may influence uranium speciation in the environment. Previous investigations regarding U(VI) adsorption to bacterial spores, a differentiated and dormant cell type with a tough proteinaceous coat, include U adsorption affinity and XAFS data. We investigated the thermodynamic stability of aerobic, pH dependent uranium adsorption to bacterial spore surfaces using purified Bacillus subtilis spores in solution with 5ppm uranium. Adsorption reversibility and kinetic experiments indicate that uranium does not precipitate over the duration of the experiments and equilibrium is reached within 20 minutes. Uranium-spore adsorption edges exhibited adsorption at all pH measured between 2 and 10. Maximum adsorption was achieved around pH 7 and decreased as pH increased above 7. We used surface complexation modeling (SCM) to quantify uranium adsorption based on balanced chemical equations and derive thermodynamic stability constants for discrete uranium-spore adsorption reactions. Site specific thermodynamic stability constants provide insight on interactions occurring between aqueous uranium species and spore surface ligands. The uranium adsorption data and SCM parameters described herein, also provide a basis for predicting the influence of bacterial spores on uranium speciation in natural systems and investigating their potential as biosorption agents in engineered systems.

  9. 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

  10. 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.

  11. 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

  12. 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

  13. 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

  14. 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

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

    PubMed

    Bertics, Victoria J; Ziebis, Wiebke

    2009-11-01

    We used a combination of field and laboratory approaches to address how the bioturbation activity of two crustaceans, the ghost shrimp Neotrypaea californiensis and the fiddler crab Uca crenulata, affects the microbial diversity in the seabed of a coastal lagoon (Catalina Harbor, Santa Catalina Island, CA, USA). Detailed geochemical analyses, including oxygen microsensor measurements, were performed to characterize environmental parameters. We used a whole-assemblage fingerprinting approach (ARISA: amplified ribosomal intergenic spacer analysis) to compare bacterial diversity along geochemical gradients and in relation to subsurface microniches. The two crustaceans have different burrowing behaviors. The ghost shrimp maintains complex, deep-reaching burrows and permanently lives subterranean, supplying its burrow with oxygen-rich water. In contrast, the fiddler crab constructs simpler, J-shaped burrows, which it does not inhabit permanently and does not actively ventilate. Our goal was to address how varying environmental parameters affect benthic microbial communities. An important question in benthic microbial ecology has been whether burrows support similar or unique communities compared with the sediment surface. Our results showed that sediment surface microbial communities are distinct from subsurface assemblages and that different burrow types support diverse bacterial taxa. Statistical comparisons by canonical correspondence analysis indicated that the availability of oxidants (oxygen, nitrate, ferric iron) play a key role in determining the presence and abundance of different taxa. When geochemical parameters were alike, microbial communities associated with burrows showed significant similarity to sediment surface communities. Our study provides implications on the community structure of microbial communities in marine sediments and the factors controlling their distribution. PMID:19458658

  16. Ground surface temperature scenarios in complex high-mountain topography based on regional climate model results

    NASA Astrophysics Data System (ADS)

    Salzmann, Nadine; NöTzli, Jeannette; Hauck, Christian; Gruber, Stephan; Hoelzle, Martin; Haeberli, Wilfried

    2007-06-01

    Climate change can have severe impacts on the high-mountain cryosphere, such as instabilities in rock walls induced by thawing permafrost. Relating climate change scenarios produced from global climate models (GCMs) and regional climate models (RCMs) to complex high-mountain environments is a challenging task. The qualitative and quantitative impact of changes in climatic conditions on local to microscale ground surface temperature (GST) and the ground thermal regime is not readily apparent. This study assesses a possible range of changes in the GST (ΔGST) in complex mountain topography. To account for uncertainties associated with RCM output, a set of 12 different scenario climate time series (including 10 RCM-based and 2 incremental scenarios) was applied to the topography and energy balance (TEBAL) model to simulate average ΔGST for 36 different topographic situations. Variability of the simulated ΔGST is related primarily to the emission scenarios, the RCM, and the approach used to apply RCM results to the impact model. In terms of topography, significant influence on GST simulation was shown by aspect because it modifies the received amount of solar radiation at the surface. North faces showed higher sensitivity to the applied climate scenarios, while uncertainties are higher for south faces. On the basis of the results of this study, use of RCM-based scenarios is recommended for mountain permafrost impact studies, as opposed to incremental scenarios.

  17. Synthesis, Crystal structure, and Hirshfeld Surface Analysis of a New Mixed Ligand Copper(II) Complex.

    PubMed

    Shit, Shyamapada; Marschner, Christoph; Mitra, Samiran

    2016-01-01

    A new mixed ligand copper(II) complex, [Cu(2,4-pydc)(pic)(H(2)O)]∙H(2)O (1) (where 2,4-pydc = pyridine-2,4-dicarboxylate, pic = 2-picolylamine) has been synthesized and characterized by elemental analysis, FT-IR and UV-Vis spectroscopic and thermogravimetric methods. Single crystal X-ray diffraction analysis reveals that copper(II) atom in the title complex adopts distorted square pyramidal geometry. Structural characterization also reveals that interplay of O-H···O, N-H···O, C-H···O, and C-H···π interactions between lattice and coordinated water and ligands significantly contribute to the crystal packing leading to the formation and strengthening of three dimensional supramolecular assembly. Hirshfeld surface analysis employing 3D molecular surface contours and 2D fingerprint plots have been used to analyze intermolecular interactions present in the solid state of the crystal. PMID:26970797

  18. 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

  19. 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.

  20. Highly Variable Holocene Antarctic Climate: A High-Resolution Marine Geochemical Record of Surface and Export Production, Terrigenous Provenance, and Terrigenous Accumulation from the Palmer Deep, West Antarctic Peninsula.

    NASA Astrophysics Data System (ADS)

    Kryc, K. A.; Murray, R. W.; Dunbar, R. B.

    2001-12-01

    The Antarctic Peninsula is an ideal region to investigate climate change at decadal to millennial timescales due to its location in one of the earth's most dynamic climate systems. We have targeted the geochemical sedimentary record of ODP Site 1098 in the Palmer Deep to investigate changes in Holocene glacial evolution and oscillations in the Circumpolar Deep Water as traced by terrigenous provenance, terrigenous accumulation, nutrient utilization, and surface and export production. More than 50 meters of laminated diatomaceous muds, oozes, and muddy diamictons were recovered from the Palmer Deep, comprising the first, high-resolution, continuous Holocene sediment record from the Antarctic continental margin. We report on a synthesis of trace and major element, stable isotope, and C/N geochemistry on samples collected at a temporal resolution ranging from ~8 to ~50 years. We analyzed Si, Al, Ti, P, Ba, biogenic opal, organic C and N, and organic 13C/12C and 15N/14N isotopic ratios every 2.5 to 10 cm downcore. A series of sequential extractions were completed on a subset of samples to better constrain the elemental distribution within the different components of the sediment. Our chronology is based on 36 AMS radiocarbon dates. Biogenic opal, Corg, and P accumulation rates all increase ~2,000 years B.P., reaching a maximum ~5,500 to 7,000 years B.P. Opal concentrations are less variable, yet indicate that biosiliceous production increased during the mid-Holocene. 13C/12C in bulk organic matter are high (with values similar to ice-edge bloom products) ~4500 to 7000 years B.P., signifying stronger diatom bloom events during the mid-Holocene. Prior to ~3000 years B.P., delta15N was lower for ~2,000 years, resulting from less complete utilization of photic zone nitrate. The Al/Ti ratio indicates a change in terrigenous composition ~3500 years B.P. indicating a change in source, weathering style, and/or intensity. All tracers of productivity and terrigenous provenance

  1. 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...

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

    DOE PAGESBeta

    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

  3. 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. PMID:26917140

  4. 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. PMID:22356544

  5. 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

  6. 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

  7. 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.

  8. 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...

  9. Geochemical characteristics of Cretaceous carbonatites from Angola

    NASA Astrophysics Data System (ADS)

    Alberti, A.; Castorina, F.; Censi, P.; Comin-Chiaramonti, P.; Gomes, C. B.

    1999-12-01

    The Early Cretaceous (138-130 Ma) carbonatites and associated alkaline rocks of Angola belong to the Paraná-Angola-Etendeka Province and occur as ring complexes and other central-type intrusions along northeast trending tectonic lineaments, parallel to the trend of coeval Namibian alkaline complexes. Most of the Angolan carbonatite-alkaline bodies are located along the apical part of the Moçamedes Arch, a structure representing the African counterpart of the Ponta Grossa Arch in southern Brazil, where several alkaline-carbonatite complexes were also emplaced in the Early Cretaceous. Geochemical and isotopic (C, 0, Sr and Nd) characteristics determined for five carbonatitic occurrences indicate that: (1) the overall geochemical composition, including the OC isotopes, is within the range of the Early and Late Cretaceous Brazilian occurrences from the Paraná Basin; (2) the La versus {La}/{Yb} relationships are consistent with the exsolution of CO i2-rich melts from trachyphonolitic magmas; and (3) the {143Nd}/{144Nd} and {87Sr}/{86Sr} initial ratios are similar to the initial isotopic ratios (129 Ma) of alkaline complexes in northwest Namibia. In contrast, the Lupongola carbonatites have a distinctly different {143Nd}/{144Nd} initial ratio, suggesting a different source. The Angolan carbonatites have SrNd isotopic compositions ranging from bulk earth to time-integrated depleted sources. Since those from eastern Paraguay (at the western fringe of the Paraná-Angola-Etendeka Province) and Brazil appear to be related to mantle-derived melts with time-integrated enriched or B.E. isotopic characteristics, it is concluded that the carbonatites of the Paraná-Angola-Etendeka Province have compositionally distinct mantle sources. Such mantle heterogeneity is attributed to 'metasomatic processes', which would have occurred at ca 0.6-0.7 Ga (Angola, northwest Namibia and Brazil) and ca 1.8 Ga (eastern Paraguay), as suggested by Nd-model ages.

  10. 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.

  11. 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.

  12. Preliminary study of the effect of the turbulent flow field around complex surfaces on their acoustic characteristics

    NASA Technical Reports Server (NTRS)

    Olsen, W. A.; Boldman, D.

    1978-01-01

    Fundamental theories for noise generated by flow over surfaces exist for only a few simple configurations. The role of turbulence in noise generation by complex surfaces should be essentially the same as for simple configurations. Examination of simple-surface theories indicates that the spatial distributions of the mean velocity and turbulence properties are sufficient to define the noise emission. Measurements of these flow properties were made for a number of simple and complex surfaces. The configurations were selected because of their acoustic characteristics are quite different. The spatial distribution of the turbulent flow properties around the complex surfaces and approximate theory are used to locate and describe the noise sources, and to qualitatively explain the varied acoustic characteristics.

  13. Particles as probes for complex plasmas in front of biased surfaces

    NASA Astrophysics Data System (ADS)

    Basner, R.; Sigeneger, F.; Loffhagen, D.; Schubert, G.; Fehske, H.; Kersten, H.

    2009-01-01

    An interesting aspect in the research of complex (dusty) plasmas is the experimental study of the interaction of micro-particles with the surrounding plasma for diagnostic purposes. Local electric fields can be determined from the behaviour of particles in the plasma, e.g. particles may serve as electrostatic probes. Since in many cases of applications in plasma technology it is of great interest to describe the electric field conditions in front of floating or biased surfaces, the confinement and behaviour of test particles is studied in front of floating walls inserted into a plasma as well as in front of additionally biased surfaces. For the latter case, the behaviour of particles in front of an adaptive electrode, which allows for an efficient confinement and manipulation of the grains, has been experimentally studied in terms of the dependence on the discharge parameters and on different bias conditions of the electrode. The effect of the partially biased surface (dc and rf) on the charged micro-particles has been investigated by particle falling experiments. In addition to the experiments, we also investigate the particle behaviour numerically by molecular dynamics, in combination with a fluid and particle-in-cell description of the plasma.

  14. 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. PMID:26609930

  15. 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.

  16. Kinetic Fractionation Of Heavy Stable Isotopes At Earth Surface Temperatures: Complexity And Systematics

    NASA Astrophysics Data System (ADS)

    Johnson, T.

    2003-04-01

    Many applications of heavy stable isotopes are aimed at the oceans, ground water and surface water. In these environments, Cr, Fe, Cu, Zn, Se, and Mo isotope variations have been observed, and in most cases are generated by kinetic isotope effects (KIE's). Whereas equilibrium isotope effects are thermodynamic quantities that are insensitive to reaction mechanisms, KIE's depend strongly on reaction mechanisms and conditions. For example, the rates of reactions, the speciation of dissolved elements, and transient effects can all greatly affect the sizes of KIE's. Accurate interpretations of measured heavy stable isotope variations thus depend on sufficient understanding of variability in KIE's. Complexity in KIE's arises when they are induced by reactions consisting of multiple reaction steps arranged in series and possibly with branches. Paradoxically, a reaction can have a small KIE even though a single step within it has a large KIE. The key to understanding this, as explained in the carbon and sulfur isotope literature, is to consider the sizes and isotopic compositions of the intermediate species between steps. Intermediates consumed by relatively fast steps have low concentrations and short residence times, and tend to become strongly enriched in heavier isotopes. This reduces the size of the overall KIE. However, this situation takes some time to be established, and in the very early stages of reactions, "start-up effects" may be observed, with anomalously large KIE's. In the face of such complexity, laboratory and field experiments are both needed to develop understanding of KIE systematics. Simple laboratory experiments provide insight into the likely dependence of KIE's on reaction mechanisms and conditions. More complex laboratory experiments (e.g., sediment microcosms) can mimic natural conditions somewhat and provide estimates of naturally relevant KIE's. Finally, in-situ measurement of KIE's in natural settings are needed to determine naturally relevant

  17. 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

  18. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2000-01-01

    The surface reactivity and sorption of Nd and Eu onto K +-saturated Marblehead illite at 25°C, measured in aqueous 0.01, 0.1, and 1.0 M KCl solutions, were interpreted with a multi-site-surface complexation model. Model potentiometric titration and sorption curves (computed using the Gibbs free energy minimization code, Selektor-A) resolve into reactions on variable-charge amphoteric sites on edge surfaces and on permanent-charge siloxane surfaces (φ x). Standard partial molal Gibbs free energy of formation from elements (g 2980) for surface complexes were derived from oxide (SiO 2,am and γ-Al 2O 3) surface deprotonation KA10, KA20 and electrolyte adsorption constants KCl0, KNa0. Because surface complexation reactions on siloxane basal surfaces are negligible in 1 M KCl, models of surface charge and adsorption edges of Nd and Eu presumed that C 1 is equal to 1.6 Fm -2 for amphoteric site types, and a maximum site density of 1.2 ± 0.2 sites nm -2 for the outer-sphere species, (Al>OH 2+Cl -). To obtain values of g 2980 for exchangeable cations and charged X ˜REE complexes, ion exchange sites were assumed to be fully deprotonated in 1.0 M KCl solutions (pH > 2.7). Proton release and REE 3+ uptake on ion exchange sites were then simulated (pH < 5 and I ≤ 0.1 M KCl) using a nonelectrostatic model and assuming a 50% contribution to the total surface area at Γ max,X of 3.0 sites nm -2 whereas the contributions of the silanol (φ Sil = 30%) and aluminol (φ Alu = 20%) surface types were described using a TLM. At pH < 4.5 and I ≤ 0.1 M KCl, "frayed edges" of interlayer site (Y ˜ sites, Γ max,Y = 3.0 sites nm -2) play a dominant role in controlling surface reactions on ion exchange sites; the contribution to total surface area of "frayed edges" (φ Y) decay exponentially (φ Y ≤ 0.1% at pH > 4.0) from initial values of 20 to 48%. The application of Gibbs free energy minimization to sorption processes is innovative in that simultaneous treatment of surface

  20. Acid-base surface chemistry and sorption of some lanthanides on K{sup +}-saturated Marblehead illite: 2. A multisite-surface complexation modeling

    SciTech Connect

    Kulik, D.A.; Aja, S.U.; Sinitsyn, V.A.; Wood, S.A.

    2000-01-01

    The surface reactivity and sorption of Nd and Eu onto K{sup +}-saturated Marblehead illite at 25 C, measured in aqueous 0.01, 0.1, and 1.0 M KCl solutions, were interpreted with a multi-site-surface complexation model. Model potentiometric titration and sorption curves (computed using the Gibbs free energy minimization code, Selektor-A) resolve into reactions on variable-charge amphoteric sites on edge surfaces and on permanent-charge siloxane surfaces ({phi}{sub x}). Standard partial molal Gibbs free energy of formation from elements (g{sub 298}{sup 0}) for surface complexes were derived from oxide surface deprotonation K{sub A1}{sup 0}, K{sub A2}{sup 0} and electrolyte adsorption constants K{sub Cl}{sup 0}, K{sub Na}{sup 0}. Because surface complexation reactions on siloxane basal surfaces are negligible in 1 M KCl, models of surface charge and adsorption edges of Nd and Eu presumed that C{sub 1} is equal to 1.6 Fm{sup {minus}2} for amphoteric site types, and a maximum site density of 1.2 {+-} 0.2 sites nm{sup {minus}2} for the outer-sphere species. To obtain values of g{sub 298}{sup 0} for exchangeable cations and charged X{sup {approximately}}REE complexes, ion exchange sites were assumed to be fully deprotonated in 1.0 M KCl solutions (pH > 2.7). Proton release and REE{sup 3+} uptake on ion exchange sites were then simulated using a nonelectrostatic model and assuming a 50% contribution to the total surface area at {Gamma}{sub max.X} of 3.0 sites nm{sup {minus}2} whereas the contributions of the silanol and aluminol surface types were described using a TLM. At pH < 4.5 and I {le} 0.1 M KCl, frayed edges of interlayer site play a dominant role in controlling surface reactions on ion exchange sites; the contribution to total surface area of frayed edges decay exponentially from initial values of 20 to 48%. The application of Gibbs free energy minimization to sorption processes is innovative in that simultaneous treatment of surface complexation reactions and

  1. 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

  2. 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

  3. 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

  4. 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

  5. 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

  6. 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.

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

    PubMed

    Nagata, Takahiro; Fukushi, Keisuke; Takahashi, Yoshio

    2009-04-15

    A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength. PMID:19176225

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. Bayesian Inference aided analog downscaling for near-surface winds in complex terrain

    NASA Astrophysics Data System (ADS)

    Manor, Alon; Berkovic, Sigalit

    2015-10-01

    Assessing atmospheric boundary layer flows in complex terrain for short-range real-time applications demands fast and reliable downscaling from coarser-resolution meteorological data to the relevant scale. An ideal statistical downscaling numerical experiment was performed for surface winds above complex terrain in Israel's northern Negev desert region. Dynamical downscaling have been performed by the WRF model to create a historical database by the following two sets. The first set used 5 nested domains from 40.5 km to 0.5 km. The second set used 3 nested domains ranging from 40.5 km to 4.5 km. The 4.5 km data (stage 2) was defined as predictors while data on 0.5 km (stage 1) served as predictands for statistical downscaling. Two statistical downscaling algorithms: minimal distance analog and a Bayesian inference aided analog (hereafter Bayesian algorithm) were tested by the above data. Unlike most analog algorithms, the Bayesian algorithm refers to the probability to get the best analog instead of the minimal differences between predictands. The comparison of the two algorithms shows that the Bayesian approach yields improved results. The Bayesian algorithm reproduces the 0.5 km resolution dynamically downscaled surface winds with an average absolute direction difference of 43 and 20 for calm winds and moderate/strong winds respectively. Its average wind speed error is ~ 1.1 ms- 1. ~ 40 days are sufficient to create a representative database. Given the database, the procedure is extremely fast (a few seconds) and easy to operate, which makes it suitable for real-time non-expert fast-response applications.

  15. 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

  16. Potential energy surface of the CO2-N2 van der Waals complex.

    PubMed

    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. PMID:25956094

  17. 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.

  18. 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.

  19. Cortical surface complexity in frontal and temporal areas varies across subgroups of schizophrenia.

    PubMed

    Nenadic, Igor; Yotter, Rachel A; Sauer, Heinrich; Gaser, Christian

    2014-04-01

    Schizophrenia is assumed to be a neurodevelopmental disorder, which might involve disturbed development of the cerebral cortex, especially in frontal and medial temporal areas. Based on a novel spherical harmonics approach to measuring complexity of cortical folding, we applied a measure based on fractal dimension (FD) to investigate the heterogeneity of regional cortical surface abnormalities across subgroups of schizophrenia defined by symptom profiles. A sample of 87 patients with DSM-IV schizophrenia was divided into three subgroups (based on symptom profiles) with predominantly negative (n = 31), disorganized (n = 23), and paranoid (n = 33) symptoms and each compared to 108 matched healthy controls. While global FD measures were reduced in the right hemisphere of the negative and paranoid subgroups, regional analysis revealed marked heterogeneity of regional FD alterations. The negative subgroup showed most prominent reductions in left anterior cingulate, superior frontal, frontopolar, as well as right superior frontal and superior parietal cortices. The disorganized subgroup showed reductions in bilateral ventrolateral/orbitofrontal cortices, and several increases in the left hemisphere, including inferior parietal, middle temporal, and midcingulate areas. The paranoid subgroup showed only few changes, including decreases in the right superior parietal and left fusiform region, and increase in the left posterior cingulate cortex. Our findings suggest regional heterogeneity of cortical folding complexity, which might be related to biological subgroups of schizophrenia with differing degrees of altered cortical developmental pathology. PMID:23813686

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. Adsorption of radium and barium on goethite and ferrihydrite: A kinetic and surface complexation modelling study

    NASA Astrophysics Data System (ADS)

    Sajih, M.; Bryan, N. D.; Livens, F. R.; Vaughan, D. J.; Descostes, M.; Phrommavanh, V.; Nos, J.; Morris, K.

    2014-12-01

    Radium and barium uptake onto ferrihydrite and goethite have been studied in the concentration range 1 nM to 5 mM and from pH 4 to 10, to develop a model to predict radium behaviour in legacy uranium mining wastes. For ferrihydrite, uptake of Ra2+ at nM concentrations was strong at pH >7. At higher concentrations, Ba2+ sorption to ferrihydrite was slightly weaker than that of Ra2+. Experiments with goethite showed weaker binding for both metal ions in all systems. The interactions of radium with both ferrihydrite and goethite are fully reversible. The behaviour of radium during transformation of ferrihydrite to goethite has been studied, and no evidence for irreversible incorporation within the goethite lattice was found; radium uptake to goethite was the same, whether or not it was present during its formation. Calcium competed with radium for ferrihydrite sorption only at high calcium concentrations (>10 mM). Barium is a more effective competitor, and a concentration of 1 mM reduced radium sorption. Sediment samples from a legacy uranium mining site have been analysed, and the in situ Rd values are consistent with radium uptake by surface coatings of ferrihydrite or goethite like phases. Surface complexation models have been developed for radium sorption to ferrihydrite and goethite which simulate the experimental data successfully. In both cases, approaches based on a single surface functional group and tetradentate binding sites simulated the data successfully. These data could be used in underpinning the safety case for legacy mining sites.

  9. Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

    NASA Astrophysics Data System (ADS)

    Johnson, Timothy L.; Fish, William; Gorby, Yuri A.; Tratnyek, Paul G.

    1998-03-01

    Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe 0) is mediated by the thin film of iron (hydr)oxides found on Fe 0 under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl 4) degradation by Fe 0 was studied under the influence of various anions, ligands, and initial CCl 4 concentrations ([ P] o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl 4 disappearance ( kCCl 4), and zero order for the appearance of dissolved Fe 2+ ( kFe 2+). The rate of dechlorination exhibits saturation kinetics with respect to [ P] o, suggesting that CCl 4 is transformed at a limited number of reactive surface sites. Because oxidation of Fe 0 by CCl 4 is the major corrosion reaction in these systems, kFe 2+ also approaches a limiting value at high CCl 4 concentrations. The adsorption of borate strongly inhibited reduction of CCl 4, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased kCCl 4 (and kFe 2+). Thus, it appears that the relatively strong complexation of these ligands at the oxide-electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.

  10. Surface complexation modeling of Fe3O4-H+ and Mg(II) sorption onto maghemite and magnetite.

    PubMed

    Jolsterå, Rickard; Gunneriusson, Lars; Holmgren, Allan

    2012-11-15

    The surface acid/base properties of magnetite (Fe(3)O(4)) particles and the sorption of Mg(2+) onto magnetite and maghemite (γ-Fe(2)O(3)) have been studied using high precision potentiometric titrations, batch experiments, and zeta potential measurements. The acid/base properties of magnetite were found to be very similar to maghemite except for the difference in surface site density, N(s) (sites nm(-2)), 1.50±0.08 for magnetite, and 0.99±0.05 for maghemite. The experimental proton exchange of the magnetite surface increased from pH 10 and above, indicating dissolution/transformation reactions of magnetite at alkaline conditions. Thus, magnetite with its Fe(II) content proved to be less stable toward dissolution in comparison with pure Fe(III) oxides also at high pH values. Three different ratios between surface sites and added Mg(2+) were used in the sorption experiments viz. 0.5, 1, and 2Mg(2+)site(-1). Surface complexation modeling of the Mg(2+) sorption onto maghemite and magnetite was restricted to pH conditions where the interference from Mg(OH)(2)(s) precipitation could be ruled out. The model calculations showed that Mg(2+) sorb onto the magnetite and maghemite surfaces as a mixture of mono- or bidentate surface complexes at 0.5Mg(2+)site(-1) and as monodentate complexes at 1 and 2Mg(2+)site(-1) conditions. Mg(2+) was also found to adsorb more readily at the maghemite surfaces in comparison with magnetite surfaces. For experiments with excess Mg(2+) relative to the number of surface sites, the calculations suggested the formation of polynuclear surface complexes on maghemite. PMID:22889624

  11. 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

  12. 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

  13. 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

  14. Microbiological and Geochemical Characterization of Fluvially Deposited Sulfidic Mine Tailings

    PubMed Central

    Wielinga, Bruce; Lucy, Juliette K.; Moore, Johnnie N.; Seastone, October F.; Gannon, James E.

    1999-01-01

    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. PMID:10103249

  15. Microbiological and geochemical characterization of fluvially deposited sulfidic mine tailings

    SciTech Connect

    Wielinga, B.; Lucy, J.K.; Moore, J.N.; Seastone, O.F.; Gannon, J.E.

    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.

  16. 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

  17. 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

  18. Three-dimensional surface topography of the needle stomatal complexes of Pinus rigida and its hybrid species by complementary microscopy.

    PubMed

    Kim, Ki Woo; Kim, Du-Hyun; Han, Sim-Hee; Lee, Jae-Cheon; Kim, Pan-Gi

    2010-08-01

    Three-dimensional surface topography of needle stomatal complexes was investigated in Pinus rigida, Pinus taeda, and their interspecific hybrid Pinus rigitaeda. The stomatal complexes of P. rigida appeared to be sunken and ca. 15 microm deep by white light scanning interferometry. Stomatal grooves were evident in P. taeda along the stomata and amounted to ca. 5 microm deep. The centers of stomata maintained the similar height to the stomatal apertures. Meanwhile, the stomatal complexes of P. rigitaeda (ca. 15 microm deep) were characterized by distinct stomatal grooves and sunken stomatal chambers. In addition, field emission scanning electron microscopy revealed the stomatal complexes of P. rigida partially filled with epicuticular waxes. It was common to observe distinct stomatal grooves and chamber-filled stomata on P. taeda needles. The stomatal complexes of P. rigitaeda had the distinct stomatal grooves and were partially filled with wax tubules and rodlets. Surface roughness measurements of stomatal complexes showed higher levels of roughness from P. rigida and P. rigitaeda than that from P. taeda. These results indicate that the hybrid species P. rigitaeda showed intermediacy in surface characteristics between the parent species, suggesting the genetic control of needle stomatal complexes in the hybrid species. PMID:20452778

  19. 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. PMID:25074930

  20. 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

  1. Combined Gamma-Ray Spectrometer and Pulsed Neutron Generator System for In-Situ Planetary Geochemical Analysis

    SciTech Connect

    Starr, R. D.; Evans, L. G.; Parsons, A. M.; Akkurt, Hatice; Floyd, H.; Wraight, P.; Ziegler, W.; Schweitzer, J.

    2007-01-01

    A combined pulsed neutron/gamma-ray system can be used on planetary surfaces to provide valuable geochemical analysis of surface materials to depths of {approx}1 m. We describe experimental results that demonstrate the capabilities of such a system.

  2. 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.

  3. Water oxidation surface mechanisms replicated by a totally inorganic tetraruthenium–oxo molecular complex

    PubMed Central

    Piccinin, Simone; Sartorel, Andrea; Aquilanti, Giuliana; Goldoni, Andrea; Bonchio, Marcella; Fabris, Stefano

    2013-01-01

    Solar-to-fuel energy conversion relies on the invention of efficient catalysts enabling water oxidation through low-energy pathways. Our aerobic life is based on this strategy, mastered by the natural Photosystem II enzyme, using a tetranuclear Mn–oxo complex as oxygen evolving center. Within artificial devices, water can be oxidized efficiently on tailored metal-oxide surfaces such as RuO2. The quest for catalyst optimization in vitro is plagued by the elusive description of the active sites on bulk oxides. Although molecular mimics of the natural catalyst have been proposed, they generally suffer from oxidative degradation under multiturnover regime. Here we investigate a nano-sized Ru4–polyoxometalate standing as an efficient artificial catalyst featuring a totally inorganic molecular structure with enhanced stability. Experimental and computational evidence reported herein indicates that this is a unique molecular species mimicking oxygenic RuO2 surfaces. Ru4–polyoxometalate bridges the gap between homogeneous and heterogeneous water oxidation catalysis, leading to a breakthrough system. Density functional theory calculations show that the catalytic efficiency stems from the optimal distribution of the free energy cost to form reaction intermediates, in analogy with metal-oxide catalysts, thus providing a unifying picture for the two realms of water oxidation catalysis. These correlations among the mechanism of reaction, thermodynamic efficiency, and local structure of the active sites provide the key guidelines for the rational design of superior molecular catalysts and composite materials designed with a bottom–up approach and atomic control. PMID:23479603

  4. 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.

  5. The astrocyte surface NAAG receptor and NAAG peptidase signaling complex as a therapeutic target.

    PubMed

    Baslow, Morris H

    2008-06-01

    There is evidence that schizophrenia and other neuropathies may involve malfunction of a unique N-acetylaspartylglutamate (NAAG) receptor and its associated NAAG peptidase, a receptor and enzyme found together on the astrocyte surface. NAAG is a peptide neurotransmitter released by stimulated neurons and specifically targeted to the group II metabotropic glutamate receptor 3 (mGlu(3)), activation of which initiates astrocyte Ca(2+) waves responsible for astrocyte-astrocyte and astrocyte-vascular system signaling and induction of vascular hyperemic responses that increase energy supplies to stimulated neurons. In this review, it is hypothesized that the receptor and enzyme exist as a cytostructural unit on the astrocyte surface, and the nature of this proposed mGlu(3)-NAAG peptidase complex is considered in terms of its physiological signaling role, and of the effect of drugs on this role. The mGlu(3) receptor has been the target of extrinsic antagonists and agonists that mimic NAAG structure and compete with natural NAAG for the receptor site. NAAG metabolism has also been the target of extrinsic NAAG-like substances that inhibit NAAG peptidase, competing with NAAG for the enzyme active site. Several drugs that affect the mGlu(3) receptor or NAAG peptidase have reached a stage of human testing. Two are agonists of the mGlu(3) receptor, and another is an NAAG peptidase inhibitor. These substances appear to have potential for treating schizophrenia and other cognitive neuropathies by interfering with a homeostatic NAAG activated neuron-astrocyte-vascular energy supply system. PMID:18596989

  6. Method for reconstruction of complex surface shapes from a reflection-based non-null interferometric measurement

    NASA Astrophysics Data System (ADS)

    Micali, Jason D.; Greivenkamp, John E.

    2016-03-01

    Complex surface forms are becoming increasingly prevalent in optical designs, requiring advances in manufacturing and surface metrology to maintain the state of the art. Non-null interferometry extends the range of standard interferometers to test complex shapes without the need for complicated and expensive compensating elements. However, non-null measurements will accumulate significant retrace errors, or interferometer-induced errors, which can be difficult to isolate from surface figure errors. Methods discussed in the literature to correct for retrace errors in a reflection-based interferometer are computationally intensive and limited in spatial resolution. A method is presented for reconstructing complex surface shapes in a reflection-based non-null interferometer configuration, which is computationally efficient, easy to implement, and can produce high spatial resolution surface reconstructions. The method is verified against simulated surfaces that contain more than 200 μm of surface departure from a null configuration. Examples are provided to demonstrate the effects of measurement noise and interferometer model uncertainties, as well as an experimental validation of the method.

  7. Precipitation and surface adsorption of metal complexes during electropolishing. Theory and characterization with X-ray nanotomography and surface tension isotherms.

    PubMed

    Nave, Maryana I; Chen-Wiegart, Yu-chen Karen; Wang, Jun; Kornev, Konstantin G

    2015-09-21

    Electropolishing of metals often leads to supersaturation conditions resulting in precipitation of complex compounds. The solubility diagrams and Gibbs adsorption isotherms of the electropolishing products are thus very important to understand the thermodynamic mechanism of precipitation of reaction products. Electropolishing of tungsten wires in aqueous solutions of potassium hydroxide is used as an example illustrating the different thermodynamic scenarios of electropolishing. Electropolishing products are able to form highly viscous films immiscible with the surrounding electrolyte or porous shells adhered to the wire surface. Using X-ray nanotomography, we discovered a gel-like phase formed at the tungsten surface during electropolishing. The results of these studies suggest that the electropolishing products can form a rich library of compounds. The surface tension of the electrolyte depends on the metal oxide ions and alkali-metal complexes. PMID:26279498

  8. Geochemical modeling of cyanide in tailing dam gold processing plant

    NASA Astrophysics Data System (ADS)

    Khodadadi, Ahmad; Monjezi, M.; Mehrpouya, H.; Dehghani, H.

    2009-09-01

    This research is aimed at investigating possible neutralization of cyanide in tailing dam of Muteh gold processing plant in Isfahan, Iran at various conditions such as pH and temperature using USEPA Visual MINTEQ geochemical model simulation. The model is based on geochemical equilibrium which uses the simultaneous solution of the non-linear mass action expressions and linear mass balance relationships to formulate and solve the multiple-component chemical equilibrium problems. In this study the concentration of aqueous species in tailing dam as an aqueous, solid and gaseous were used as input in the model. Temperature and pH variation were simulated. The results of the model indicated that cyanide may be complexes in 10 < pH < 5. In other pH values complexation is not important. The results also indicated that cyanide reduction mechanism in acidic pH and temperature above 30°C is due to cyanide acid formation which is vaporized.

  9. Complex potential surface for the {sup 2}B{sub 1} metastable state of the water anion

    SciTech Connect

    Haxton, Daniel J.; Zhang, Zhiyong; McCurdy, C. William; Rescigno, Thomas N.

    2004-04-23

    The potential energy surface corresponding the complex resonance energy of the 2B1 Feshbach resonance state of the water anion is constructed in its full dimensionality. Complex Kohn variational scattering calculations are used to compute the resonance width, while large-scale Configuration Interaction calculations are used to compute the resonance energy. Near the equilibrium geometry, an accompanying ground state potential surface is constructed from Configuration Interaction calculations that treat correlation at a level similar to that used in the calculations on the anion.

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

    PubMed

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

    2011-07-15

    The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (<0.053 mm). For each size fraction and their composite (sediment), batch and flow-cell experiments were performed to determine uranium adsorption isotherms and kinetic 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. 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. PMID:21648458

  11. 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.

  12. Complex Contact-Based Dynamics of Microsphere Monolayers Revealed by Resonant Attenuation of Surface Acoustic Waves.

    PubMed

    Hiraiwa, M; Abi Ghanem, M; Wallen, S P; Khanolkar, A; Maznev, A A; Boechler, N

    2016-05-13

    Contact-based vibrations play an essential role in the dynamics of granular materials. Significant insights into vibrational granular dynamics have previously been obtained with reduced-dimensional systems containing macroscale particles. We study contact-based vibrations of a two-dimensional monolayer of micron-sized spheres on a solid substrate that forms a microscale granular crystal. Measurements of the resonant attenuation of laser-generated surface acoustic waves reveal three collective vibrational modes that involve displacements and rotations of the microspheres, as well as interparticle and particle-substrate interactions. To identify the modes, we tune the interparticle stiffness, which shifts the frequency of the horizontal-rotational resonances while leaving the vertical resonance unaffected. From the measured contact resonance frequencies we determine both particle-substrate and interparticle contact stiffnesses and find that the former is an order of magnitude larger than the latter. This study paves the way for investigating complex contact-based dynamics of microscale granular crystals and yields a new approach to studying micro- to nanoscale contact mechanics in multiparticle networks. PMID:27232047

  13. 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.

  14. 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. PMID:20809628

  15. Complex Contact-Based Dynamics of Microsphere Monolayers Revealed by Resonant Attenuation of Surface Acoustic Waves

    NASA Astrophysics Data System (ADS)

    Hiraiwa, M.; Abi Ghanem, M.; Wallen, S. P.; Khanolkar, A.; Maznev, A. A.; Boechler, N.

    2016-05-01

    Contact-based vibrations play an essential role in the dynamics of granular materials. Significant insights into vibrational granular dynamics have previously been obtained with reduced-dimensional systems containing macroscale particles. We study contact-based vibrations of a two-dimensional monolayer of micron-sized spheres on a solid substrate that forms a microscale granular crystal. Measurements of the resonant attenuation of laser-generated surface acoustic waves reveal three collective vibrational modes that involve displacements and rotations of the microspheres, as well as interparticle and particle-substrate interactions. To identify the modes, we tune the interparticle stiffness, which shifts the frequency of the horizontal-rotational resonances while leaving the vertical resonance unaffected. From the measured contact resonance frequencies we determine both particle-substrate and interparticle contact stiffnesses and find that the former is an order of magnitude larger than the latter. This study paves the way for investigating complex contact-based dynamics of microscale granular crystals and yields a new approach to studying micro- to nanoscale contact mechanics in multiparticle networks.

  16. Explicit validation of a surface shortwave radiation balance model over snow-covered complex terrain

    NASA Astrophysics Data System (ADS)

    Helbig, N.; Löwe, H.; Mayer, B.; Lehning, M.

    2010-09-01

    A model that computes the surface radiation balance for all sky conditions in complex terrain is presented. The spatial distribution of direct and diffuse sky radiation is determined from observations of incident global radiation, air temperature, and relative humidity at a single measurement location. Incident radiation under cloudless sky is spatially derived from a parameterization of the atmospheric transmittance. Direct and diffuse sky radiation for all sky conditions are obtained by decomposing the measured global radiation value. Spatial incident radiation values under all atmospheric conditions are computed by adjusting the spatial radiation values obtained from the parametric model with the radiation components obtained from the decomposition model at the measurement site. Topographic influences such as shading are accounted for. The radiosity approach is used to compute anisotropic terrain reflected radiation. Validations of the shortwave radiation balance model are presented in detail for a day with cloudless sky. For a day with overcast sky a first validation is presented. Validation of a section of the horizon line as well as of individual radiation components is performed with high-quality measurements. A new measurement setup was designed to determine terrain reflected radiation. There is good agreement between the measurements and the modeled terrain reflected radiation values as well as with incident radiation values. A comparison of the model with a fully three-dimensional radiative transfer Monte Carlo model is presented. That validation reveals a good agreement between modeled radiation values.

  17. Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

    PubMed

    Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

    2013-01-15

    The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination. PMID:23227949

  18. Recognition of geochemical anomalies using a deep autoencoder network

    NASA Astrophysics Data System (ADS)

    Xiong, Yihui; Zuo, Renguang

    2016-01-01

    In this paper, we train an autoencoder network to encode and reconstruct a geochemical sample population with unknown complex multivariate probability distributions. During the training, small probability samples contribute little to the autoencoder network. These samples can be recognized by the trained model as anomalous samples due to their comparatively higher reconstructed errors. The southwestern Fujian district (China) is chosen as a case study area. A variety of learning rates, iterations, and the size of each hidden layer are constructing and training the deep autoencoder networks on all the geochemical samples. The reconstruction error (or, anomaly score) of each training sample is used to recognize multivariate geochemical anomalies associated with Fe polymetallic mineralization. By comparing the results obtained with a continuous restricted Boltzmann machine, we conclude that the autoencoder network can be trained to recognize multivariate geochemical anomalies. Most of the known skarn-type Fe deposits are located in areas with high reconstruction errors or anomaly scores in the anomaly map, indicating that these anomalies may be related to Fe mineralization.

  19. 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.

  20. 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

  1. 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

  2. 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

  3. Fabrication of a photocontrolled surface with switchable wettability based on host-guest inclusion complexation and protein resistance.

    PubMed

    Shen, Qiongxia; Liu, Lichao; Zhang, Weian

    2014-08-12

    A novel surface-modification strategy has been developed for the construction of a photocontrolled silicon wafer surface with switchable wettability based on host-guest inclusion complexation. The silicon wafer was first modified by guest molecule azobenzene (Azo) via a silanization reaction. Subsequently, a series of polymers with different polarities were attached to host molecule β-cyclodextrin (β-CD) to prepare β-CD-containing hemitelechelic polymers via click chemistry. Finally, a photocontrolled silicon wafer surface modified with polymers was fabricated by inclusion complexation between β-CD and Azo, and the surface properties of the substrate are dependent on the polymers we used. The elemental composition, surface morphology, and hydrophilic/hydrophobic property of the modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscope, and contact angle measurements, respectively. The antifouling property of the PEG-functionalized surface was evaluated by a protein adsorption assay using bovine serum albumin, which was also characterized by XPS. The results demonstrate that the surface modified with PEG possesses good protein-resistant properties. PMID:25053175

  4. 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

  5. Photoexpulsion of Surface-Grafted Ruthenium Complexes and Subsequent Release of Cytotoxic Cargos to Cancer Cells from Mesoporous Silica Nanoparticles

    PubMed Central

    Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W.; Chen, Xinqi; Botros, Youssry Y.; Cryns, Vincent L.; Sauvage, Jean-Pierre; Stoddart, J. Fraser

    2014-01-01

    Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions. PMID:23815127

  6. 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

  7. 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

    NASA Astrophysics Data System (ADS)

    Glynn, Pierre D.

    2003-04-01

    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 Kd 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 Kd (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the simulation

  8. 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

    NASA Astrophysics Data System (ADS)

    Glynn, P. D.

    2002-12-01

    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) findings documenting the spatial and temporal variability of 90Sr partitioning are reexamined and found partially caused by his assumption of a kinetically-limited reaction. In the present simulations, sorption is assumed the only retardation process controlling Pu and Np transport, and is modeled using a diffuse-double-layer-surface-complexation model. Transport simulations consider the inflow 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, i.e. the same total number of sorption sites, but with different variances and spatial correlation structures). A case with a spatially uniform distribution of sorption capacities was also simulated. 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 Kd advection-dispersion transport model and compared to each other. Functional differences are often great enough that they prevent a meaningful fit of the simulation results with

  9. 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

  10. Assignment of the complex vibrational spectra of the hydrogenated ZnO polar surfaces using QM/MM embedding

    NASA Astrophysics Data System (ADS)

    French, S. A.; Sokol, A. A.; Bromley, S. T.; Catlow, C. R. A.; Rogers, S. C.; Sherwood, P.

    2003-01-01

    Hydrogenated zinc oxide gives rise to complex vibrational spectra with many prominent features that remain unexplained. Our calculations have unambiguously shown that the presence of vacant oxygen and zinc interstitial surface sites is the only way to rationalize the observed spectra, notably the 1710 cm-1 zinc hydride stretching mode. The large number of such sites, which expose low-coordinated surface ions, are inherent at ionically reconstructed polar surfaces. The thermal stability of the sorbed hydrogen and the infrared activity of the resulting species are correlated with site coordination and coverage.

  11. 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

  12. Precipitation of heavy metals from acid mine drainage and their geochemical modeling

    NASA Astrophysics Data System (ADS)

    Petrilakova, Aneta; Balintova, Magdalena; Holub, Marian

    2014-06-01

    Geochemical modeling plays an increasingly vital role in a number of areas of geoscience, ranging from groundwater and surface water hydrology to environmental preservation and remediation. Geochemical modeling is also used to model the interaction processes at the water - sediment interface in acid mine drainage (AMD). AMD contains high concentrations of sulfate and dissolved metals and it is a serious environmental problem in eastern Slovakia. The paper is focused on comparing the results of laboratory precipitation of metal ions from AMD (the Smolnik creek, Slovakia) with the results obtained by geochemical modeling software Visual Minteq 3.0.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  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. PMID:24846443

  2. The oceanic islands - Azores. [geological, geophysical and geochemical features

    NASA Technical Reports Server (NTRS)

    Ridley, W. I.; Watkins, N. D.; Macfarlane, D. J.

    1974-01-01

    A presentation is made of the known geological, geophysical, and geochemical data on the Azores. The regional setting of the islands is described; under the geological heading, surface geology and petrochemistry are discussed; and paleomagnetism, marine magnetic surveys, gravity, seismology, and heat flow are treated in the geophysics category. A model for the origin of the Azores is constructed on the basis of these observations.

  3. Venus: Geochemical conclusions from the Magellan data

    NASA Astrophysics Data System (ADS)

    Wood, J. A.

    1992-12-01

    Though the Magellan mission was not designed to collect geochemical or petrological information, it has done so nonetheless. Since the time of the Pioneer Venus mission it has been known that high-altitude (greater than 2.5-5 km) mountainous areas on Venus exhibit anomalously low radiothermal emissivity (e less than 0.6). Magellan has greatly refined and extended these observations. The low emissivity requires surface material in the uplands to have a mineralogical composition that gives it a high bulk dielectric constant, greater than 20. The dielectric constant of dry terrestrial volcanic rocks seldom exceeds 7. The high-dielectric character of high-altitude surface material cannot be a primary property of the local volcanic rock, because there is no reason why rock having the required special mineralogy would erupt only at high altitudes. Therefore it is a secondary property; the primary Venus rock has reacted with the atmosphere to form a mineralogically different surface layer, and the secondary minerals formed are controlled by the ambient temperature, which decreases with altitude on Venus. A further investigation of venusian mineralogy is presented.

  4. 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.

  5. Optimal parameter and uncertainty estimation of a land surface model: Sensitivity to parameter ranges and model complexities

    NASA Astrophysics Data System (ADS)

    Xia, Youlong; Yang, Zong-Liang; Stoffa, Paul L.; Sen, Mrinal K.

    2005-01-01

    Most previous land-surface model calibration studies have defined global ranges for their parameters to search for optimal parameter sets. Little work has been conducted to study the impacts of realistic versus global ranges as well as model complexities on the calibration and uncertainty estimates. The primary purpose of this paper is to investigate these impacts by employing Bayesian Stochastic Inversion (BSI) to the Chameleon Surface Model (CHASM). The CHASM was designed to explore the general aspects of land-surface energy balance representation within a common modeling framework that can be run from a simple energy balance formulation to a complex mosaic type structure. The BSI is an uncertainty estimation technique based on Bayes theorem, importance sampling, and very fast simulated annealing. The model forcing data and surface flux data were collected at seven sites representing a wide range of climate and vegetation conditions. For each site, four experiments were performed with simple and complex CHASM formulations as well as realistic and global parameter ranges. Twenty eight experiments were conducted and 50 000 parameter sets were used for each run. The results show that the use of global and realistic ranges gives similar simulations for both modes for most sites, but the global ranges tend to produce some unreasonable optimal parameter values. Comparison of simple and complex modes shows that the simple mode has more parameters with unreasonable optimal values. Use of parameter ranges and model complexities have significant impacts on frequency distribution of parameters, marginal posterior probability density functions, and estimates of uncertainty of simulated sensible and latent heat fluxes. Comparison between model complexity and parameter ranges shows that the former has more significant impacts on parameter and uncertainty estimations.

  6. Molecular statics calculations of proton binding to goethite surfaces: A new approach to estimation of stability constants for multisite surface complexation models

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Felmy, Andrew R.; Hay, Benjamin P.

    1996-05-01

    A new approach to estimating stability constants for proton binding in multisite surface complexation models is presented. The method is based on molecular statics computation of energies for the formation of proton vacancies and interstitials in ideal periodic slabs representing the (100), (110), (010), (001), and (021) surfaces of goethite. Gas-phase energies of clusters representing the hydrolysis products of ferric iron are calculated using the same potential energy functions used for the surface. These energies are linearly related to the hydrolysis constants for ferric iron in aqueous solution. Stability constants for proton binding at goethite surfaces are estimated by assuming the same log K- Δ E relationship for goethite surface protonation reactions. These stability constants predict a pH of zero charge of 8.9, in adequate agreement with measurements on CO 2-free goethite. The estimated stability constants differ significantly from previous estimations based on Pauling bond strength. We find that nearly all the surface oxide ions are reactive; nineteen of the twenty-six surface sites investigated have log Kint between 7.7 and 9.4. This implies a site density between fifteen and sixteen reactive sites/nm for crystals dominated by (110) and (021) crystal faces.

  7. Molecular statics calculations of proton binding to goethite surfaces: A new approach to estimation of stability constants for multisite surface complexation models

    SciTech Connect

    Rustad, J.R.; Felmy, A.R.; Hay, B.P.

    1996-05-01

    A new approach to estimating stability constants for proton binding in multisite surface complexation models is presented. The method is based on molecular statics computation of energies for the formation of proton vacancies and interstitials in ideal periodic slabs representing the (100), (110), (010), (001), and (021) surfaces of goethite. Gas-phase energies of clusters representing the hydrolysis products of ferric iron are calculated using the same potential energy functions used for the