Geochemical typification of kimberlite and related rocks of the North Anabar region, Yakutia

NASA Astrophysics Data System (ADS)

Kargin, A. V.; Golubeva, Yu. Yu.

2017-11-01

The results of geochemical typification of kimberlites and related rocks (alneites and carbonatites) of the North Anabar region are presented with consideration of the geochemical specification of their source and estimation of their potential for diamonds. The content of representative trace elements indicates the predominant contribution of an asthenospheric component (kimberlites and carbonatites) in their source, with a subordinate contribution of vein metasomatic formations containing Cr-diopside and ilmenite. A significant contribution of water-bearing potassium metasomatic parageneses is not recognized. According to the complex of geochemical data, the studied rocks are not industrially diamondiferous.

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...

An archean suture zone in the Tobacco Root Mountains? (1984) Evolution of Archean Continental Crust, SW Montana (1985)

NASA Technical Reports Server (NTRS)

Mogk, D. W.; Kain, L.

1985-01-01

The Lake Plateau area of the Beartooth Mountains, Montana were mapped and geochemically sampled. The allochthonous nature of the Stillwater Complex was interpreted as a Cordilleran-style continental margin. The metamorphic and tectonic history of the Beartooth Mountains was addressed. The Archean geology of the Spanish Peaks area, northern Madison Range was addressed. A voluminous granulite terrain of supracrustal origin was identified, as well as a heretofore unknown Archean batholithic complex. Mapping, petrologic, and geochemical investigations of the Blacktail Mountains, on the western margin of the Wyoming Province, are completed. Mapping at a scale of 1:24000 in the Archean rocks of the Gravelly Range is near completion. This sequence is dominantly of stable-platform origin. Samples were collected for geothermometric/barometric analysis and for U-Pb zircon age dating. The analyses provide the basis for additional geochemical and geochronologic studies. A model for the tectonic and geochemical evolution of the Archean basement of SW Montana is presented.

Baseline studies to select the most sound and sensitive sites to install continuous monitoring per sismo-geochemical networks. The case history of the Norcia-Amatrice-Spoleto seismic sequences (2016-2017)

NASA Astrophysics Data System (ADS)

Quattrocchi, F.; Gallo, F.

2017-12-01

The paper review methodologically and historically - in the frame of seismo-geochemical studies in Italy and abroad to select the most "sensitive" sites along active faults, mostly where structural geology is not able to discover "blind" faults or complex fault crossing systems, with maximum fluids-faults interaction. The paper is highlighting the "site specific" case histories and processes helping in networks design, gathered in occasion of strong-moderate earthquakes, gas-burst or groundwater evolution in geothermal-hydrocarbons field during EU projects (i.e., Geochemical Seismic Zonation, 3F-Faults-Fractures-Fluids Corinth). Some concepts are highlighted based on gather experimental data in 25 years: - if the network is in soil gas is necessary a preliminary study on groundwater too, to understand the sectors of shallow aquifers, as "buffer" bodies, more prone to be oversaturated by geogas from depth; a preliminary grid should consider both the CO2-CH4-Rn fluxes, all gas concentrations and isotopes analyses (TDIC, CH4 CO2 , rare gas) case by case described here, mostly where the regional faults are crossing each other and where a carrier gas is acting i.e., CO2. It is very un-correct to install mono-parametric stations, i.e. only Radon to understand the real WRI processes. - if the network is in groundwater is very important a preliminary study before, during and after seismic sequences, to realize where the maximum anomalies (i.e., anomalous animal behavior, temperature increasing, geochemical anomalies, new gas relase) are and will be envisaged, as found for the Umbria-Marche border (the Colfiorito 1997-1998 and the 2016-2017 Norcia-Amatrice seismic sequences), where a deep pore-pressure dominated situation could be constrained by seismo-geochemistry, along "still silent" close fault segments too. if the network is in groundwater is very important a geochemical multidisciplinary approach to constrain the segment length and relative maximum magnitude.

Archean crust-mantle geochemical differentiation

NASA Astrophysics Data System (ADS)

Tilton, G. R.

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.

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.

Simulating adsorption of U(VI) under transient groundwater flow and hydrochemistry: Physical versus chemical nonequilibrium model

USGS Publications Warehouse

Greskowiak, J.; Hay, M.B.; Prommer, H.; Liu, C.; Post, V.E.A.; Ma, R.; Davis, J.A.; Zheng, C.; Zachara, J.M.

2011-01-01

Coupled intragrain diffusional mass transfer and nonlinear surface complexation processes play an important role in the transport behavior of U(VI) in contaminated aquifers. Two alternative model approaches for simulating these coupled processes were analyzed and compared: (1) the physical nonequilibrium approach that explicitly accounts for aqueous speciation and instantaneous surface complexation reactions in the intragrain regions and approximates the diffusive mass exchange between the immobile intragrain pore water and the advective pore water as multirate first-order mass transfer and (2) the chemical nonequilibrium approach that approximates the diffusion-limited intragrain surface complexation reactions by a set of multiple first-order surface complexation reaction kinetics, thereby eliminating the explicit treatment of aqueous speciation in the intragrain pore water. A model comparison has been carried out for column and field scale scenarios, representing the highly transient hydrological and geochemical conditions in the U(VI)-contaminated aquifer at the Hanford 300A site, Washington, USA. It was found that the response of U(VI) mass transfer behavior to hydrogeochemically induced changes in U(VI) adsorption strength was more pronounced in the physical than in the chemical nonequilibrium model. The magnitude of the differences in model behavior depended particularly on the degree of disequilibrium between the advective and immobile phase U(VI) concentrations. While a clear difference in U(VI) transport behavior between the two models was noticeable for the column-scale scenarios, only minor differences were found for the Hanford 300A field scale scenarios, where the model-generated disequilibrium conditions were less pronounced as a result of frequent groundwater flow reversals. Copyright 2011 by the American Geophysical Union.

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

PubMed

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

2016-01-01

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

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Current State of an Intelligent System to Aid in Tephra Layer Correlation

NASA Astrophysics Data System (ADS)

Hanson-Hedgecock, S.; Bursik, M.; Rogova, G.

2007-12-01

We are developing a computer based intelligent system to correlate tephra layers by using the lithologic, mineralogic, and geochemical characteristics of field samples, to aid geologists in interpreting eruption patterns of volcanic chains and fields. The intelligent system is used to define groups of tephra source vents by utilizing geochemical data, and to correlate tephra layers based on lithostratigraphic characteristics. Understanding the eruption history of a volcano from stratigraphic studies is important for forecasting future eruptive behavior and hazards. In volcanic chains and fields with a complex eruptive history and no central vent, determining the spatio- temporal eruption patterns is difficult. Sedimentologic and chemical variability, and sparse sampling often result in relatively large variances and imprecision in the dataset. Lithostratigraphic and geochemical interpretation also depends on ones' level of expertise and can be subjective. The processing of lithostratigraphic features is conducted by a hybrid classifier, composed of supervised artificial neural networks (ANNs) combined within the framework of the Dempster-Shafer theory of evidence. Since lithostratigraphic features vary with distance from source, hypothetical vent locations are determined by using expert domain knowledge and geostatistical methods. Geochemical data are processed by a suit of fuzzy k- means classifiers. Each fuzzy k-means classifier assigns observations to multiple clusters with various degrees, called membership coefficients. The assignment minimizes a function of the total distance between the centers of clusters and the individual geochemical data patterns weighed by the membership coefficients. Improved clustering results of geochemical data are achieved by the fusion of individual clustering results with an evidential combination method. Lithostratigraphic data from individual tephra beds of the North Mono eruption sequence are used to test the effectiveness of the intelligent system for tephra layer correlation. Geochemical data from tephra bedsets of the Mono and Inyo Craters, CA, are used to test the effectiveness of the intelligent system for eruption sequence correlation. The intelligent system aids correlation by showing matches and disparities between data patterns from different outcrops that may have been overlooked in initial interpretations. Initial results show that the lithostratigraphic classifier is able to accurately differentiate known layers 76% of the time. Output from the lithostratigraphic classifier can furthermore be plotted directly as isopleth maps that can aid in rapid recognition of tephra layers as well as determination of eruption characteristics, e.g. eruption volume, plume height, etc. The intelligent system produces a useful recognition result, while dealing with the uncertainty from sparse data and the imprecise description of layer characteristics.

Geochemistry of subduction zone serpentinites: A review

NASA Astrophysics Data System (ADS)

Deschamps, Fabien; Godard, Marguerite; Guillot, Stéphane; Hattori, Kéiko

2013-09-01

Over the last decades, numerous studies have emphasized the role of serpentinites in the subduction zone geodynamics. Their presence and role in subduction environments are recognized through geophysical, geochemical and field observations of modern and ancient subduction zones and large amounts of geochemical database of serpentinites have been created. Here, we present a review of the geochemistry of serpentinites, based on the compilation of ~ 900 geochemical data of abyssal, mantle wedge and exhumed serpentinites after subduction. The aim was to better understand the geochemical evolution of these rocks during their subduction as well as their impact in the global geochemical cycle. When studying serpentinites, it is essential to determine their protoliths and their geological history before serpentinization. The geochemical data of serpentinites shows little mobility of compatible and rare earth elements (REE) at the scale of hand-specimen during their serpentinization. Thus, REE abundance can be used to identify the protolith for serpentinites, as well as magmatic processes such as melt/rock interactions before serpentinization. In the case of subducted serpentinites, the interpretation of trace element data is difficult due to the enrichments of light REE, independent of the nature of the protolith. We propose that enrichments are probably not related to serpentinization itself, but mostly due to (sedimentary-derived) fluid/rock interactions within the subduction channel after the serpentinization. It is also possible that the enrichment reflects the geochemical signature of the mantle protolith itself which could derive from the less refractory continental lithosphere exhumed at the ocean-continent transition. Additionally, during the last ten years, numerous analyses have been carried out, notably using in situ approaches, to better constrain the behavior of fluid-mobile elements (FME; e.g. B, Li, Cl, As, Sb, U, Th, Sr) incorporated in serpentine phases. The abundance of these elements provides information related to the fluid/rock interactions during serpentinization and the behavior of FME, from their incorporation to their gradual release during subduction. Serpentinites are considered as a reservoir of the FME in subduction zones and their role, notably on arc magma composition, is underestimated presently in the global geochemical cycle.

Biogeochemical Barriers: Redox Behavior of Metals and Metalloids

EPA Science Inventory

Redox conditions and pH are arguably the most important geochemical parameters that control contaminant transport and fate in groundwater systems. Oxidation-reduction (redox) reactions mediate the chemical behavior of both inorganic and organic chemical constituents by affecting...

The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

NASA Astrophysics Data System (ADS)

Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

2013-06-01

The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering capacity to previously studied non-halophilic bacteria. The titration data were used to determine the number of types, concentrations, and associated deprotonation constants of functional groups on the bacterial surface; the neptunium adsorption measurements were used to constrain binding constant values for the important neptunium (V)-bacterial surface species. Together, these results can be incorporated into geochemical speciation models to aid in the prediction of neptunium (V) mobility in complex bacteria-bearing geochemical systems.

Contaminant source identification using semi-supervised machine learning

NASA Astrophysics Data System (ADS)

Vesselinov, Velimir V.; Alexandrov, Boian S.; O'Malley, Daniel

2018-05-01

Identification of the original groundwater types present in geochemical mixtures observed in an aquifer is a challenging but very important task. Frequently, some of the groundwater types are related to different infiltration and/or contamination sources associated with various geochemical signatures and origins. The characterization of groundwater mixing processes typically requires solving complex inverse models representing groundwater flow and geochemical transport in the aquifer, where the inverse analysis accounts for available site data. Usually, the model is calibrated against the available data characterizing the spatial and temporal distribution of the observed geochemical types. Numerous different geochemical constituents and processes may need to be simulated in these models which further complicates the analyses. In this paper, we propose a new contaminant source identification approach that performs decomposition of the observation mixtures based on Non-negative Matrix Factorization (NMF) method for Blind Source Separation (BSS), coupled with a custom semi-supervised clustering algorithm. Our methodology, called NMFk, is capable of identifying (a) the unknown number of groundwater types and (b) the original geochemical concentration of the contaminant sources from measured geochemical mixtures with unknown mixing ratios without any additional site information. NMFk is tested on synthetic and real-world site data. The NMFk algorithm works with geochemical data represented in the form of concentrations, ratios (of two constituents; for example, isotope ratios), and delta notations (standard normalized stable isotope ratios).

Contaminant source identification using semi-supervised machine learning

DOE PAGES

Vesselinov, Velimir Valentinov; Alexandrov, Boian S.; O’Malley, Dan

2017-11-08

Identification of the original groundwater types present in geochemical mixtures observed in an aquifer is a challenging but very important task. Frequently, some of the groundwater types are related to different infiltration and/or contamination sources associated with various geochemical signatures and origins. The characterization of groundwater mixing processes typically requires solving complex inverse models representing groundwater flow and geochemical transport in the aquifer, where the inverse analysis accounts for available site data. Usually, the model is calibrated against the available data characterizing the spatial and temporal distribution of the observed geochemical types. Numerous different geochemical constituents and processes may needmore » to be simulated in these models which further complicates the analyses. In this paper, we propose a new contaminant source identification approach that performs decomposition of the observation mixtures based on Non-negative Matrix Factorization (NMF) method for Blind Source Separation (BSS), coupled with a custom semi-supervised clustering algorithm. Our methodology, called NMFk, is capable of identifying (a) the unknown number of groundwater types and (b) the original geochemical concentration of the contaminant sources from measured geochemical mixtures with unknown mixing ratios without any additional site information. NMFk is tested on synthetic and real-world site data. Finally, the NMFk algorithm works with geochemical data represented in the form of concentrations, ratios (of two constituents; for example, isotope ratios), and delta notations (standard normalized stable isotope ratios).« less

Contaminant source identification using semi-supervised machine learning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vesselinov, Velimir Valentinov; Alexandrov, Boian S.; O’Malley, Dan

Identification of the original groundwater types present in geochemical mixtures observed in an aquifer is a challenging but very important task. Frequently, some of the groundwater types are related to different infiltration and/or contamination sources associated with various geochemical signatures and origins. The characterization of groundwater mixing processes typically requires solving complex inverse models representing groundwater flow and geochemical transport in the aquifer, where the inverse analysis accounts for available site data. Usually, the model is calibrated against the available data characterizing the spatial and temporal distribution of the observed geochemical types. Numerous different geochemical constituents and processes may needmore » to be simulated in these models which further complicates the analyses. In this paper, we propose a new contaminant source identification approach that performs decomposition of the observation mixtures based on Non-negative Matrix Factorization (NMF) method for Blind Source Separation (BSS), coupled with a custom semi-supervised clustering algorithm. Our methodology, called NMFk, is capable of identifying (a) the unknown number of groundwater types and (b) the original geochemical concentration of the contaminant sources from measured geochemical mixtures with unknown mixing ratios without any additional site information. NMFk is tested on synthetic and real-world site data. Finally, the NMFk algorithm works with geochemical data represented in the form of concentrations, ratios (of two constituents; for example, isotope ratios), and delta notations (standard normalized stable isotope ratios).« less

Hydrologic functioning of the deep Critical Zone and contributions to streamflow in a high elevation catchment: testing of multiple conceptual models

NASA Astrophysics Data System (ADS)

Dwivedi, R.; Meixner, T.; McIntosh, J. C.; Ferre, T. P. A.; Eastoe, C. J.; Minor, R. L.; Barron-Gafford, G.; Chorover, J.

2017-12-01

The composition of natural mountainous waters maintains important control over the water quality available to downstream users. Furthermore, the geochemical constituents of stream water in the mountainous catchments represent the result of the spatial and temporal evolution of critical zone structure and processes. A key problem is that high elevation catchments involve rugged terrain and are subject to extreme climate and landscape gradients; therefore, high density or high spatial resolution hydro-geochemical observations are rare. Despite such difficulties, the Santa Catalina Mountains Critical Zone Observatory (SCM-CZO), Tucson, AZ, generates long-term hydrogeochemical data for understanding not only hydrological processes and their seasonal characters, but also the geochemical impacts of such processes on streamflow chemical composition. Using existing instrumentation and hydrogeochemical observations from the last 9+ years (2009 through 2016 and an initial part of 2017), we employed a multi-tracer approach along with principal component analysis to identify water sources and their seasonal character. We used our results to inform hydrological process understanding (flow paths, residence times, and water sources) for our study site. Our results indicate that soil water is the largest contributor to streamflow, which is ephemeral in nature. Although a 3-dimensional mixing space involving precipitation, soil water, interflow, and deep groundwater end-members could explain most of the streamflow chemistry, geochemical complexity was observed to grow with catchment storage. In terms of processes and their seasonal character, we found soil water and interflow were the primary end-member contributors to streamflow in all seasons. Deep groundwater only contributes to streamflow at high catchment storage conditions, but it provides major ions such as Na, Mg, and Ca that are lacking in other water types. In this way, our results indicate that any future efforts aimed at explaining concentration-discharge behavior of our field site should consider at least three-dimensional mixing space or 4 end-members.

Geochemistry of glacial sediments in the area of the Bend massive sulfide deposit, north-central Wisconsin

USGS Publications Warehouse

Woodruff, L.G.; Attig, J.W.; Cannon, W.F.

2004-01-01

Geochemical exploration in northern Wisconsin has been problematic because of thick glacial overburden and complex stratigraphic record of glacial history. To assess till geochemical exploration in an area of thick glacial cover and complex stratigraphy samples of glacial materials were collected from cores from five rotasonic boreholes near a known massive sulfide deposit, the Bend deposit in north-central Wisconsin. Diamond drilling in the Bend area has defined a long, thin zone of mineralization at least partly intersected at the bedrock surface beneath 30-40 m of unconsolidated glacial sediments. The bedrock surface has remnant regolith and saprolite resulting from pre-Pleistocene weathering. Massive sulfide and mineralized rock collected from diamond drill core from the deposit contain high (10s to 10,000s ppm) concentrations of Ag, As, Au, Bi, Cu, Hg, Se, Te, and Tl. Geochemical properties of the glacial stratigraphic units helped clarify the sequence and source areas of several glacial ice advances preserved in the section. At least two till sheets are recognized. Over the zone of mineralization, saprolite and preglacial alluvial and lacustrine samples are preserved on the bedrock surface in a paleoriver valley. The overlying till sheet is a gray, silty carbonate till with a source hundreds of kilometers to the northwest of the study area. This gray till is overlain by red, sandy till with a source to the north in Proterozoic rocks of the Lake Superior area. The complex glacial stratigraphy confounds down-ice geochemical till exploration. The presence of remnant saprolite, preglacial sediment, and far-traveled carbonate till minimized glacial erosion of mineralized material. As a result, little evidence of down-ice glacial dispersion of lithologic or mineralogic indicators of Bend massive sulfide mineralization was found in the samples from the rotasonic cores. This study points out the importance of determining glacial stratigraphy and history, and identifying favorable lithologies required for geochemical exploration. Drift prospecting in Wisconsin and other areas near the outer limits of the Pleistocene ice sheets may not be unsuccessful, in part, because of complex stratigraphic sequences of multiple glaciations where deposition dominates over erosion. ?? 2004 Elsevier B.V. All rights reserved.

Analysis of a Complex Faulted CO 2 Reservoir Using a Three-dimensional Hydro-geochemical-Mechanical Approach

DOE PAGES

Nguyen, Ba Nghiep; Hou, Zhangshuan; Bacon, Diana H.; ...

2017-08-18

This work applies a three-dimensional (3D) multiscale approach recently developed to analyze a complex CO 2 faulted reservoir that includes some key geological features of the San Andreas and nearby faults. The approach couples the STOMP-CO2-R code for flow and reactive transport modeling to the ABAQUS ® finite element package for geomechanical analysis. The objective is to examine the coupled hydro-geochemical-mechanical impact on the risk of hydraulic fracture and fault slip in a complex and representative CO 2 reservoir that contains two nearly parallel faults. STOMP-CO2-R/ABAQUS ® coupled analyses of this reservoir are performed assuming extensional and compressional stress regimesmore » to predict evolutions of fluid pressure, stress and strain distributions as well as potential fault failure and leakage of CO 2 along the fault damage zones. The tendency for the faults to slip and pressure margin to fracture are examined in terms of stress regime, mineral composition, crack distributions in the fault damage zones and geomechanical properties. Here, this model in combination with a detailed description of the faults helps assess the coupled hydro-geochemical-mechanical effect.« less

Analysis of a Complex Faulted CO 2 Reservoir Using a Three-dimensional Hydro-geochemical-Mechanical Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ba Nghiep; Hou, Zhangshuan; Bacon, Diana H.

This work applies a three-dimensional (3D) multiscale approach recently developed to analyze a complex CO 2 faulted reservoir that includes some key geological features of the San Andreas and nearby faults. The approach couples the STOMP-CO2-R code for flow and reactive transport modeling to the ABAQUS ® finite element package for geomechanical analysis. The objective is to examine the coupled hydro-geochemical-mechanical impact on the risk of hydraulic fracture and fault slip in a complex and representative CO 2 reservoir that contains two nearly parallel faults. STOMP-CO2-R/ABAQUS ® coupled analyses of this reservoir are performed assuming extensional and compressional stress regimesmore » to predict evolutions of fluid pressure, stress and strain distributions as well as potential fault failure and leakage of CO 2 along the fault damage zones. The tendency for the faults to slip and pressure margin to fracture are examined in terms of stress regime, mineral composition, crack distributions in the fault damage zones and geomechanical properties. Here, this model in combination with a detailed description of the faults helps assess the coupled hydro-geochemical-mechanical effect.« less

Reactive Fluid Flow and Applications to Diagenesis, Mineral Deposits, and Crustal Rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rye, Danny M.; Bolton, Edward W.

2002-11-04

The objective is to initiate new: modeling of coupled fluid flow and chemical reactions of geologic environments; experimental and theoretical studies of water-rock reactions; collection and interpretation of stable isotopic and geochemical field data at many spatial scales of systems involving fluid flow and reaction in environments ranging from soils to metamorphic rocks. Theoretical modeling of coupled fluid flow and chemical reactions, involving kinetics, has been employed to understand the differences between equilibrium, steady-state, and non-steady-state behavior of the chemical evolution of open fluid-rock systems. The numerical codes developed in this project treat multi-component, finite-rate reactions combined with advective andmore » dispersive transport in multi-dimensions. The codes incorporate heat, mass, and isotopic transfer in both porous and fractured media. Experimental work has obtained the kinetic rate laws of pertinent silicate-water reactions and the rates of Sr release during chemical weathering. Ab-initio quantum mechanical techniques have been applied to obtain the kinetics and mechanisms of silicate surface reactions and isotopic exchange between water and dissolved species. Geochemical field-based studies were carried out on the Wepawaug metamorphic schist, on the Irish base-metal sediment-hosted ore system, in the Dalradian metamorphic complex in Scotland, and on weathering in the Columbia River flood basalts. The geochemical and isotopic field data, and the experimental and theoretical rate data, were used as constraints on the numerical models and to determine the length and time scales relevant to each of the field areas.« less

Analytical techniques for identification and study of organic matter in returned lunar samples

NASA Technical Reports Server (NTRS)

Burlingame, A. L.

1974-01-01

The results of geochemical research are reviewed. Emphasis is placed on the contribution of mass spectrometric data to the solution of specific structural problems. Information on the mass spectrometric behavior of compounds of geochemical interest is reviewed and currently available techniques of particular importance to geochemistry, such as gas chromatograph-mass spectrometer coupling, modern sample introduction methods, and computer application in high resolution mass spectrometry, receive particular attention.

Development of the Next Generation of Biogeochemistry Simulations Using EMSL's NWChem Molecular Modeling Software

NASA Astrophysics Data System (ADS)

Bylaska, E. J.; Kowalski, K.; Apra, E.; Govind, N.; Valiev, M.

2017-12-01

Methods of directly simulating the behavior of complex strongly interacting atomic systems (molecular dynamics, Monte Carlo) have provided important insight into the behavior of nanoparticles, biogeochemical systems, mineral/fluid systems, nanoparticles, actinide systems and geofluids. The limitation of these methods to even wider applications is the difficulty of developing accurate potential interactions in these systems at the molecular level that capture their complex chemistry. The well-developed tools of quantum chemistry and physics have been shown to approach the accuracy required. However, despite the continuous effort being put into improving their accuracy and efficiency, these tools will be of little value to condensed matter problems without continued improvements in techniques to traverse and sample the high-dimensional phase space needed to span the ˜10^12 time scale differences between molecular simulation and chemical events. In recent years, we have made considerable progress in developing electronic structure and AIMD methods tailored to treat biochemical and geochemical problems, including very efficient implementations of many-body methods, fast exact exchange methods, electron-transfer methods, excited state methods, QM/MM, and new parallel algorithms that scale to +100,000 cores. The poster will focus on the fundamentals of these methods and the realities in terms of system size, computational requirements and simulation times that are required for their application to complex biogeochemical systems.

CONTRIBUTION TO THE GEOCHEMISTRY OF TANTALUM AND NIOBIUM IN THE HYDROTHERMAL-PNEUMATHOLYTIC PROCESS (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beus, A.A.; Sitnin, A.A.

1961-01-01

S>Data obtained as a result of geochemical investigations show that tantalum and niobium are typical elements of high-temperature postmagmatic processes (early albitization, greysening) connected with granites. The separation of tantalum and niobium in the hydrothermal-pneumatholytic process (greysening stage), which leads to the concentration of tantalum in albitized and greysenized granites (40 to 100 times compared to the average content in granites) is connected with the different mobility and stability of their acido- complex compounds (in particular fluor- and oxyfluorcomplexes), the existence of which in greysening solutions is suggested. A natural analogy in the behavior of both elements in the processesmore » of postmagmatic metasomatose in granites and granitic pegmatites is suggested. (tr-auth)« less

Landscape and bio- geochemical strategy for monitoring transformation and reclamation of the soil mining sites

NASA Astrophysics Data System (ADS)

Korobova, Elena

2010-05-01

Sites of active or abandoned mining represent areas of considerable technogenic impact and need scientifically ground organization of their monitoring and reclamation. The strategy of monitoring and reclamation depends on the scale and character of the physical, chemical and biological consequences of the disturbances. The geochemical studies for monitoring and rehabilitation of the career-dump complexes should methodically account of formation of the particular new landforms and the changes in circulation of the remobilized elements of the soil cover. However, the general strategy should account of both the initial and transformed landscape geochemical structure of the area with due regard to the natural and new content of chemical elements in the environmental components. For example the tailings and waste rocks present new geochemical fields with specifically different concentration of chemical elements that cause formation of new geochemical barriers and landscapes. The way of colonization of the newly formed landscapes depends upon the new geochemical features of the technogenic environment and the adaptive ability of local and intrusive flora. The newly formed biogeochemical anomalies need organization of permanent monitoring not only within the anomaly itself but also of its impact zones. Spatial landscape geochemical monitoring combined with bio-geochemical criteria of threshold concentrations seems to be a helpful tool for decision making on reclamation and operation of the soil mining sites to provide a long-term ecologically sustainable development of the impact zone as a whole.

The Lowest δ7Li Yet Recorded in MORB Glasses: The Connection with Oceanic Core Complex Formation, Refractory Rutile-bearing Eclogitic Mantle Sources and Melt Supply

NASA Astrophysics Data System (ADS)

Casey, J. F.; Gao, Y.; Benavidez, R.; Dragoi, C.

2010-12-01

The region between 12°N and 16°N along the Mid-Atlantic Ridge is known for its prolific development of oceanic core complexes and for a geochemical anomaly centered at ~14°N. We examine the correlation of the geochemical anomaly with a region characterized by low magma supply. Basalt glasses over the geochemical anomaly are unusual in exhibiting E-MORB to T-MORB HIMU-DMM isotopic gradients. The most enriched MORBs exhibit positive Ta and Nb anomalies and negative Th and Pb anomalies that are similar to some OIB basalts. Some more primitive basalts exhibit positive Ti, Sr and Eu anomalies. The center of the geochemical anomaly is characterized by elevated La/Sm ratios that are strongly correlated with Nb/La, Nb/Nb*, Ta/Ta* and Sr, Nd, Pb isotopic anomalies. In addition, we have recently documented a regional anomaly in δ7Li, with the lowest values ever recorded in MORB glasses near the center of the anomaly. We interpret this data to indicate that the mantle source in the 12-16°N region of the Mid-Atlantic Ridge involves subducted slab components including a refractory rutile-bearing eclogitic source that has suffered significant dehydration and a previously depleted mantle source that has undergone an ancient depletion event that results in little melt supply being contributed to the ridge axis. We examine melt supply implications in the context of core complex development and these unusual mantle source characteristics.

Modeling Low-temperature Geochemical Processes

NASA Astrophysics Data System (ADS)

Nordstrom, D. K.

2003-12-01

Geochemical modeling has become a popular and useful tool for a wide number of applications from research on the fundamental processes of water-rock interactions to regulatory requirements and decisions regarding permits for industrial and hazardous wastes. In low-temperature environments, generally thought of as those in the temperature range of 0-100 °C and close to atmospheric pressure (1 atm=1.01325 bar=101,325 Pa), complex hydrobiogeochemical reactions participate in an array of interconnected processes that affect us, and that, in turn, we affect. Understanding these complex processes often requires tools that are sufficiently sophisticated to portray multicomponent, multiphase chemical reactions yet transparent enough to reveal the main driving forces. Geochemical models are such tools. The major processes that they are required to model include mineral dissolution and precipitation; aqueous inorganic speciation and complexation; solute adsorption and desorption; ion exchange; oxidation-reduction; or redox; transformations; gas uptake or production; organic matter speciation and complexation; evaporation; dilution; water mixing; reaction during fluid flow; reaction involving biotic interactions; and photoreaction. These processes occur in rain, snow, fog, dry atmosphere, soils, bedrock weathering, streams, rivers, lakes, groundwaters, estuaries, brines, and diagenetic environments. Geochemical modeling attempts to understand the redistribution of elements and compounds, through anthropogenic and natural means, for a large range of scale from nanometer to global. "Aqueous geochemistry" and "environmental geochemistry" are often used interchangeably with "low-temperature geochemistry" to emphasize hydrologic or environmental objectives.Recognition of the strategy or philosophy behind the use of geochemical modeling is not often discussed or explicitly described. Plummer (1984, 1992) and Parkhurst and Plummer (1993) compare and contrast two approaches for modeling groundwater chemistry: (i) "forward modeling," which predicts water compositions from hypothesized reactions and user assumptions and (ii) "inverse modeling," which uses water, mineral, and isotopic compositions to constrain hypothesized reactions. These approaches simply reflect the amount of information one has to work with. With minimal information on a site, a modeler is forced to rely on forward modeling. Optimal information would include detailed mineralogy on drill cores or well cuttings combined with detailed water analyses at varying depths and sufficient spatial distribution to follow geochemical reactions and mixing of waters along defined flow paths. With optimal information, a modeler will depend on inverse modeling.This chapter outlines the main concepts and key developments in the field of geochemical modeling for low-temperature environments and illustrates their use with examples. It proceeds with a short discussion of what modeling is, continues with concepts and definitions commonly used, and follows with a short history of geochemical models, a discussion of databases, the codes that embody models, and recent examples of how these codes have been used in water-rock interactions. An important new stage of development seems to have been reached in this field with questions of reliability and validity of models. Future work will be obligated to document ranges of certainty and sources of uncertainty, sensitivity of models and codes to parameter errors and assumptions, propagation of errors, and delineation of the range of applicability.

Distribution of chemical elements in calc-alkaline igneous rocks, soils, sediments and tailings deposits in northern central Chile

NASA Astrophysics Data System (ADS)

Oyarzún, Jorge; Oyarzun, Roberto; Lillo, Javier; Higueras, Pablo; Maturana, Hugo; Oyarzún, Ricardo

2016-08-01

This study follows the paths of 32 chemical elements in the arid to semi-arid realm of the western Andes, between 27° and 33° S, a region hosting important ore deposits and mining operations. The study encompasses igneous rocks, soils, river and stream sediments, and tailings deposits. The chemical elements have been grouped according to the Goldschmidt classification, and their concentrations in each compartment are confronted with their expected contents for different rock types based on geochemical affinities and the geologic and metallogenic setting. Also, the element behavior during rock weathering and fluvial transport is here interpreted in terms of the ionic potentials and solubility products. The results highlight the similarity between the chemical composition of the andesites and that of the average Continental Crust, except for the higher V and Mn contents of the former, and their depletion in Mg, Ni, and Cr. The geochemical behavior of the elements in the different compartments (rocks, soils, sediments and tailings) is highly consistent with the mobility expected from their ionic potentials, their sulfates and carbonates solubility products, and their affinities for Fe and Mn hydroxides. From an environmental perspective, the low solubility of Cu, Zn, and Pb due to climatic, chemical, and mineralogical factors reduces the pollution risks related to their high to extremely high contents in source materials (e.g., rocks, altered zones, tailings). Besides, the complex oxyanions of arsenic get bound by colloidal particles of Fe-hydroxides and oxyhydroxides (e.g., goethite), thus becoming incorporated to the fine sediment fraction in the stream sediments.

A graphical method to evaluate predominant geochemical processes occurring in groundwater systems for radiocarbon dating

USGS Publications Warehouse

Han, Liang-Feng; Plummer, Niel; Aggarwal, Pradeep

2012-01-01

A graphical method is described for identifying geochemical reactions needed in the interpretation of radiocarbon age in groundwater systems. Graphs are constructed by plotting the measured 14C, δ13C, and concentration of dissolved inorganic carbon and are interpreted according to specific criteria to recognize water samples that are consistent with a wide range of processes, including geochemical reactions, carbon isotopic exchange, 14C decay, and mixing of waters. The graphs are used to provide a qualitative estimate of radiocarbon age, to deduce the hydrochemical complexity of a groundwater system, and to compare samples from different groundwater systems. Graphs of chemical and isotopic data from a series of previously-published groundwater studies are used to demonstrate the utility of the approach. Ultimately, the information derived from the graphs is used to improve geochemical models for adjustment of radiocarbon ages in groundwater systems.

Merging metagenomics and geochemistry reveals environmental controls on biological diversity and evolution.

PubMed

Alsop, Eric B; Boyd, Eric S; Raymond, Jason

2014-05-28

The metabolic strategies employed by microbes inhabiting natural systems are, in large part, dictated by the physical and geochemical properties of the environment. This study sheds light onto the complex relationship between biology and environmental geochemistry using forty-three metagenomes collected from geochemically diverse and globally distributed natural systems. It is widely hypothesized that many uncommonly measured geochemical parameters affect community dynamics and this study leverages the development and application of multidimensional biogeochemical metrics to study correlations between geochemistry and microbial ecology. Analysis techniques such as a Markov cluster-based measure of the evolutionary distance between whole communities and a principal component analysis (PCA) of the geochemical gradients between environments allows for the determination of correlations between microbial community dynamics and environmental geochemistry and provides insight into which geochemical parameters most strongly influence microbial biodiversity. By progressively building from samples taken along well defined geochemical gradients to samples widely dispersed in geochemical space this study reveals strong links between the extent of taxonomic and functional diversification of resident communities and environmental geochemistry and reveals temperature and pH as the primary factors that have shaped the evolution of these communities. Moreover, the inclusion of extensive geochemical data into analyses reveals new links between geochemical parameters (e.g. oxygen and trace element availability) and the distribution and taxonomic diversification of communities at the functional level. Further, an overall geochemical gradient (from multivariate analyses) between natural systems provides one of the most complete predictions of microbial taxonomic and functional composition. Clustering based on the frequency in which orthologous proteins occur among metagenomes facilitated accurate prediction of the ordering of community functional composition along geochemical gradients, despite a lack of geochemical input. The consistency in the results obtained from the application of Markov clustering and multivariate methods to distinct natural systems underscore their utility in predicting the functional potential of microbial communities within a natural system based on system geochemistry alone, allowing geochemical measurements to be used to predict purely biological metrics such as microbial community composition and metabolism.

Spatial variation of volcanic rock geochemistry in the Virunga Volcanic Province: Statistical analysis of an integrated database

NASA Astrophysics Data System (ADS)

Barette, Florian; Poppe, Sam; Smets, Benoît; Benbakkar, Mhammed; Kervyn, Matthieu

2017-10-01

We present an integrated, spatially-explicit database of existing geochemical major-element analyses available from (post-) colonial scientific reports, PhD Theses and international publications for the Virunga Volcanic Province, located in the western branch of the East African Rift System. This volcanic province is characterised by alkaline volcanism, including silica-undersaturated, alkaline and potassic lavas. The database contains a total of 908 geochemical analyses of eruptive rocks for the entire volcanic province with a localisation for most samples. A preliminary analysis of the overall consistency of the database, using statistical techniques on sets of geochemical analyses with contrasted analytical methods or dates, demonstrates that the database is consistent. We applied a principal component analysis and cluster analysis on whole-rock major element compositions included in the database to study the spatial variation of the chemical composition of eruptive products in the Virunga Volcanic Province. These statistical analyses identify spatially distributed clusters of eruptive products. The known geochemical contrasts are highlighted by the spatial analysis, such as the unique geochemical signature of Nyiragongo lavas compared to other Virunga lavas, the geochemical heterogeneity of the Bulengo area, and the trachyte flows of Karisimbi volcano. Most importantly, we identified separate clusters of eruptive products which originate from primitive magmatic sources. These lavas of primitive composition are preferentially located along NE-SW inherited rift structures, often at distance from the central Virunga volcanoes. Our results illustrate the relevance of a spatial analysis on integrated geochemical data for a volcanic province, as a complement to classical petrological investigations. This approach indeed helps to characterise geochemical variations within a complex of magmatic systems and to identify specific petrologic and geochemical investigations that should be tackled within a study area.

Effects of pH and anions on the sorption of selenium ions onto magnetite.

PubMed

Kim, Seung Soo; Min, Je Ho; Lee, Jae Kwang; Baik, Min Hoon; Choi, Jong-Won; Shin, Hyung Seon

2012-02-01

This study analyzes the influence of carbonate and silicate, which are generally abundant in granitic groundwater, on the sorption of selenium ions onto magnetite in order to understand the behaviors of selenium in a radioactive waste repository. Selenite was sorbed onto magnetite very well below pH 10, but silicate and carbonate hindered the sorption of selenite onto magnetite. On the other hand, little selenate was sorbed onto magnetite in neutral and weak alkaline solutions of 0.02 M NaNO(3) or NaClO(4), matching the ionic strength in a granitic groundwater, even though silicate or carbonate was not contained in the solutions. The surface complexation constants between selenite and magnetite were obtained by using a geochemical program, FITEQL 4.0, from the experimental data, and the formation of an inner-sphere surface complex such as =FeOSeO(2)(-) was suggested for the sorption of selenite onto magnetite from the diffuse double layer model calculation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

PubMed

Nie, Zhe; Finck, Nicolas; Heberling, Frank; Pruessmann, Tim; Liu, Chunli; Lützenkirchen, Johannes

2017-04-04

Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

The evolution of a calc-alkaline basic to silicic magma system: Geochemical and Rb-Sr, Sm-Nd, and 18O /16O isotopic evidence from the Late Hercynian Atesina-Cima d'Asta volcano-plutonic complex, northern Italy

NASA Astrophysics Data System (ADS)

Barth, Susanne; Oberli, Felix; Meier, Martin; Blattner, Peter; Bargossi, Giuseppe M.; Di Battistini, Gianfranco

1993-09-01

Geochemical and Sr-Nd-O isotopic data presented for basaltic andesitic to rhyolitic and for quartz noritic to monzogranitic rock suites from the Late Hercynian calc-alkaline Atesina volcanic complex (AVC) and the Cima d'Asta pluton (CAP), Southern Alps (northern Italy), provide information on both the primary magmatic processes and the effects of (mainly Triassic) hydrothermal overprint. Fluid infiltration led to mobilization of major and trace elements (K 2O, Na 2O, CaO, Rb, Sr, and Ba), opensystem behavior in total-rock Rb-Sr, and shift in δ18O to elevated values (total rock up to 16.6%. and volcanic matrix up to 17.8%.). Oxygen isotopic disequilibrium between quartz-feldspar pairs suggests water-rock interaction at medium/low temperatures. The δ18O values of quartz, the REE characterized by regular LREE enrichment/HREE depletion, and the Sm-Nd isotopic signatures, however, remained virtually unaffected by secondary processes. The initial ɛNd values (at 270 Ma) of the AVC and CAP magmatites are restricted to overlapping ranges of -3.6 to -6.5 and of -2.7 to -6.5, respectively, indicating significant crustal contribution; these values and associated T DM model ages of 1.1-1.6 Ga agree well with those of typical South Alpine lower crustal magmatites. The AVC and CAP rocks do not follow the "normal" trend of increasingly crustal Nd isotopic signatures with progressive degree of magma evolution expected for a single-stage AFC-type process, but instead display an inversion of this relationship. Geochemical and isotopic constraints favor a model of a large-scale MASH-type melting and mixing zone at or near the base of the continental crust. Distinct elemental enrichment/depletion and REE crossover patterns displayed by high-silica as compared to less silicic AVC rhyolites suggest subsequent magma evolution within a shallow-level compositionally zoned chamber.

Sorption and transport of iodine species in sediments from the Savannah River and Hanford Sites.

PubMed

Hu, Qinhong; Zhao, Pihong; Moran, Jean E; Seaman, John C

2005-07-01

Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at the Savannah River and Hanford Sites, where anthropogenic (129)I from prior nuclear fuel processing activities poses an environmental risk. We conducted integrated column and batch experiments to investigate the interconversion, sorption and transport of iodine species, and the sediments we examined exhibit a wide range in organic matter, clay mineralogy, soil pH, and texture. The results of our experiments illustrate complex behavior with various processes occurring, including iodate reduction, irreversible retention or mass loss of iodide, and rate-limited and nonlinear sorption. There was an appreciable iodate reduction to iodide, presumably mediated by the structural Fe(II) in some clay minerals; therefore, careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. The different iodine species exhibited dramatically different sorption and transport behavior in three sediment samples, possessing different physico-chemical properties, collected from different depths at the Savannah River Site. Our study yielded additional insight into processes and mechanisms affecting the geochemical cycling of iodine in the environment, and provided quantitative estimates of key parameters (e.g., extent and rate of sorption) for risk assessment at these sites.

Numerical simulation of in-situ chemical oxidation (ISCO) and biodegradation of petroleum hydrocarbons using a coupled model for bio-geochemical reactive transport

NASA Astrophysics Data System (ADS)

Marin, I. S.; Molson, J. W.

2013-05-01

Petroleum hydrocarbons (PHCs) are a major source of groundwater contamination, being a worldwide and well-known problem. Formed by a complex mixture of hundreds of organic compounds (including BTEX - benzene, toluene, ethylbenzene and xylenes), many of which are toxic and persistent in the subsurface and are capable of creating a serious risk to human health. Several remediation technologies can be used to clean-up PHC contamination. In-situ chemical oxidation (ISCO) and intrinsic bioremediation (IBR) are two promising techniques that can be applied in this case. However, the interaction of these processes with the background aquifer geochemistry and the design of an efficient treatment presents a challenge. Here we show the development and application of BIONAPL/Phreeqc, a modeling tool capable of simulating groundwater flow, contaminant transport with coupled biological and geochemical processes in porous or fractured porous media. BIONAPL/Phreeqc is based on the well-tested BIONAPL/3D model, using a powerful finite element simulation engine, capable of simulating non-aqueous phase liquid (NAPL) dissolution, density-dependent advective-dispersive transport, and solving the geochemical and kinetic processes with the library Phreeqc. To validate the model, we compared BIONAPL/Phreeqc with results from the literature for different biodegradation processes and different geometries, with good agreement. We then used the model to simulate the behavior of sodium persulfate (NaS2O8) as an oxidant for BTEX degradation, coupled with sequential biodegradation in a 2D case and to evaluate the effect of inorganic geochemistry reactions. The results show the advantages of a treatment train remediation scheme based on ISCO and IBR. The numerical performance and stability of the integrated BIONAPL/Phreeqc model was also verified.

Application of a flexible lattice Boltzmann method based simulation tool for modelling physico-chemical processes at different scales

NASA Astrophysics Data System (ADS)

Patel, Ravi A.; Perko, Janez; Jacques, Diederik

2017-04-01

Often, especially in the disciplines related to natural porous media, such as for example vadoze zone or aquifer hydrology or contaminant transport, the relevant spatial and temporal scales on which we need to provide information is larger than the scale where the processes actually occur. Usual techniques used to deal with these problems assume the existence of a REV. However, in order to understand the behavior on larger scales it is important to downscale the problem onto the relevant scale of the processes. Due to the limitations of resources (time, memory) the downscaling can only be made up to the certain lower scale. At this lower scale still several scales may co-exist - the scale which can be explicitly described and a scale which needs to be conceptualized by effective properties. Hence, models which are supposed to provide effective properties on relevant scales should therefor be flexible enough to represent complex pore-structure by explicit geometry on one side, and differently defined processes (e.g. by the effective properties) which emerge on lower scale. In this work we present the state-of-the-art lattice Boltzmann method based simulation tool applicable to advection-diffusion equation coupled to geochemical processes. The lattice Boltzmann transport solver can be coupled with an external geochemical solver which allows to account for a wide range of geochemical reaction networks through thermodynamic databases. The applicability to multiphase systems is ongoing. We provide several examples related to the calculation of an effective diffusion properties, permeability and effective reaction rate based on a continuum scale based on the pore scale geometry.

Biokinetics of yttrium and comparison with its geochemical twin holmium

DOE PAGES

Leggett, Rich

2017-06-01

The transition metal yttrium (Y, atomic number 39) is chemically similar to elements in the lanthanide family (atomic numbers 57-71, lanthanum through lutetium) and is always present with the lanthanides in rare earth ores. Yttrium and the lanthanide holmium are particularly close chemical and physical analogues and are referred to as geochemical twins because they typically show little fractionation in geological material. Extensive measurements on rocks, soils, and meteorites indicate that the Y/Ho mass concentration ratio rarely falls far from the “chondritic” or “solar system” ratio of ~26. Our paper presents a new biokinetic model for yttrium in adult humansmore » and examines whether yttrium and holmium may be biological as well as geochemical twins. Collected data on yttrium and holmium in plants and human tissues do not allow precise derivations of Y/Ho concentration ratios but with occasional exceptions yield ratios that are reasonably consistent with chondritic values. Predictions of the time-dependent behavior of yttrium in adult humans based on the yttrium model presented here closely approximate predictions of the behavior of holmium based on a previously developed model for holmium. We know that yttrium and holmium are close biological analogues, but the available comparative data are too limited and imprecise to reveal whether there are any significant differences in their biological behavior.« less

Cambrian ophiolite complexes in the Beishan area, China, southern margin of the Central Asian Orogenic Belt

NASA Astrophysics Data System (ADS)

Shi, Yuruo; Zhang, Wei; Kröner, Alfred; Li, Linlin; Jian, Ping

2018-03-01

We present zircon ages and geochemical data for Cambrian ophiolite complexes exposed in the Beishan area at the southern margin of the Central Asian Orogenic Belt (CAOB). The complexes consist of the Xichangjing-Xiaohuangshan and Hongliuhe-Yushishan ophiolites, which both exhibit complete ophiolite stratigraphy: chert, basalt, sheeted dikes, gabbro, mafic and ultramafic cumulates and serpentinized mantle peridotites. Zircon grains of gabbro samples yielded 206Pb/238U ages of 516 ± 8, 521 ± 4, 528 ± 3 and 535 ± 6 Ma that reflect the timing of gabbro emplacement. The geochemical data of the basaltic rocks show enrichment in large-ion lithophile elements and depletion in the high field strength elements relative to normal mid-oceanic ridge basalt (NMORB) in response to aqueous fluids or melts expelled from the subducting slab. The gabbro samples have higher whole-rock initial 87Sr/86Sr ratios and lower positive εNd(t) values than NMORB. These geochemical signatures resulted from processes or conditions that are unique to subduction zones, and the ophiolites are therefore likely to have formed within a supra-subduction zone (SSZ) environment. We suggest that the Cambrian ophiolite complexes in the Beishan area formed within a SSZ setting, reflecting an early Paleozoic subduction of components of the Paleo-Central Asian Ocean and recording an early Paleozoic southward subduction event in the southern CAOB along the northern margin of the Tarim and North China Cratons.

Late-paleozoic granitoid complexes of the southwest Primorye: geochemistry, age and typification

NASA Astrophysics Data System (ADS)

Veldemar, A. A.; Vovna, G. M.

2017-12-01

The article presents the first data of geochemical studies of the Late Permian granitoids of the Gamov Complex located in the southwestern part of the Voznesenskiy terrane. The purpose of the study was to identify the main geochemical features of the Late Paleozoic granitoids of the southwestern Primorye, which in the future will allow us to draw conclusions about the petrogenesis of these granitoids. Elemental analysis of 20 samples was carried out, conducted statistical and mathematical processing of the data, have been constructed representative diagrams and graphs for this group of rocks. Elemental analysis was performed by atomic emission (ICP-AES) and inductively-coupled-plasma (ICP-MS) mass spectrometry, at the Analytical Center FEGI FEB RAS.

Chemical mixing model studies of lunar orbital geochemical data - Apollo 16 and 17 highlands compositions

NASA Technical Reports Server (NTRS)

Spudis, P. D.; Hawke, B. R.

1982-01-01

Chemical mixing model studies of lunar geochemical data for the central and Taurus-Littrow lunar highlands were performed utilizing pristine highland rock types as end member compositions. The central highlands show considerable diversity in composition; anorthosite is the principal rock type in the Apollo 16/Descartes region, while norite predominates in the highlands west of the landing site. This change in crustal composition is coincident with a major color boundary seen in earth-based multispectral data and probably represents the presence of distinct geochemical provinces within the central highlands. The Taurus-Littrow highlands are dominated by norite; anorthosite is far less abundant than in the central highlands. This suggests that the impact target for the Serenitatis basin was different than that of the Nectaris basin and further strengthens the hypothesis that the lunar highlands are petrologically heterogeneous on a regional basis. It is suggested that the lunar highlands should be viewed in terms of geochemical provinces that have undergone distinct and complex igneous and impact histories.

Uncertainty quantification and experimental design based on unsupervised machine learning identification of contaminant sources and groundwater types using hydrogeochemical data

NASA Astrophysics Data System (ADS)

Vesselinov, V. V.

2017-12-01

Identification of the original groundwater types present in geochemical mixtures observed in an aquifer is a challenging but very important task. Frequently, some of the groundwater types are related to different infiltration and/or contamination sources associated with various geochemical signatures and origins. The characterization of groundwater mixing processes typically requires solving complex inverse models representing groundwater flow and geochemical transport in the aquifer, where the inverse analysis accounts for available site data. Usually, the model is calibrated against the available data characterizing the spatial and temporal distribution of the observed geochemical species. Numerous geochemical constituents and processes may need to be simulated in these models which further complicates the analyses. As a result, these types of model analyses are typically extremely challenging. Here, we demonstrate a new contaminant source identification approach that performs decomposition of the observation mixtures based on Nonnegative Matrix Factorization (NMF) method for Blind Source Separation (BSS), coupled with a custom semi-supervised clustering algorithm. Our methodology, called NMFk, is capable of identifying (a) the number of groundwater types and (b) the original geochemical concentration of the contaminant sources from measured geochemical mixtures with unknown mixing ratios without any additional site information. We also demonstrate how NMFk can be extended to perform uncertainty quantification and experimental design related to real-world site characterization. The NMFk algorithm works with geochemical data represented in the form of concentrations, ratios (of two constituents; for example, isotope ratios), and delta notations (standard normalized stable isotope ratios). The NMFk algorithm has been extensively tested on synthetic datasets; NMFk analyses have been actively performed on real-world data collected at the Los Alamos National Laboratory (LANL) groundwater sites related to Chromium and RDX contamination.

GIS Methodic and New Database for Magmatic Rocks. Application for Atlantic Oceanic Magmatism.

NASA Astrophysics Data System (ADS)

Asavin, A. M.

2001-12-01

There are several geochemical Databases in INTERNET available now. There one of the main peculiarities of stored geochemical information is geographical coordinates of each samples in those Databases. As rule the software of this Database use spatial information only for users interface search procedures. In the other side, GIS-software (Geographical Information System software),for example ARC/INFO software which using for creation and analyzing special geological, geochemical and geophysical e-map, have been deeply involved with geographical coordinates for of samples. We join peculiarities GIS systems and relational geochemical Database from special software. Our geochemical information system created in Vernadsky Geological State Museum and institute of Geochemistry and Analytical Chemistry from Moscow. Now we tested system with data of geochemistry oceanic rock from Atlantic and Pacific oceans, about 10000 chemical analysis. GIS information content consist from e-map covers Wold Globes. Parts of these maps are Atlantic ocean covers gravica map (with grid 2''), oceanic bottom hot stream, altimeteric maps, seismic activity, tectonic map and geological map. Combination of this information content makes possible created new geochemical maps and combination of spatial analysis and numerical geochemical modeling of volcanic process in ocean segment. Now we tested information system on thick client technology. Interface between GIS system Arc/View and Database resides in special multiply SQL-queries sequence. The result of the above gueries were simple DBF-file with geographical coordinates. This file act at the instant of creation geochemical and other special e-map from oceanic region. We used more complex method for geophysical data. From ARC\\View we created grid cover for polygon spatial geophysical information.

The Guaymas Basin Hiking Guide to Hydrothermal Mounds, Chimneys, and Microbial Mats: Complex Seafloor Expressions of Subsurface Hydrothermal Circulation

PubMed Central

Teske, Andreas; de Beer, Dirk; McKay, Luke J.; Tivey, Margaret K.; Biddle, Jennifer F.; Hoer, Daniel; Lloyd, Karen G.; Lever, Mark A.; Røy, Hans; Albert, Daniel B.; Mendlovitz, Howard P.; MacGregor, Barbara J.

2016-01-01

The hydrothermal mats, mounds, and chimneys of the southern Guaymas Basin are the surface expression of complex subsurface hydrothermal circulation patterns. In this overview, we document the most frequently visited features of this hydrothermal area with photographs, temperature measurements, and selected geochemical data; many of these distinct habitats await characterization of their microbial communities and activities. Microprofiler deployments on microbial mats and hydrothermal sediments show their steep geochemical and thermal gradients at millimeter-scale vertical resolution. Mapping these hydrothermal features and sampling locations within the southern Guaymas Basin suggest linkages to underlying shallow sills and heat flow gradients. Recognizing the inherent spatial limitations of much current Guaymas Basin sampling calls for comprehensive surveys of the wider spreading region. PMID:26925032

The use of multifractal modelling for targeting resources from soil and stream geochemistry data: the case of the Variscan basement of the Iberian Peninsula

NASA Astrophysics Data System (ADS)

Gonçalves, Mario; Mateus, Antonio

2016-04-01

The safeguarding of access/use of many critical raw materials for Society requires that much of previously dismissed areas for exploration must be re-evaluated with new criteria in which the significance of "anomaly" should not be treated independently of the geochemical signals of the ore-forming processes and how the different chemical elements are interrelated. For much of the previous decade, several multifractal methods were methodically being refined as automatic tools to analyze and detect geochemical anomalies. These included the early concentration-area method (Cheng et al., 1994), singularity mapping (Cheng, 2007), and spectrum-area (Cheng et al., 2000), which has been recently combined with the bi-dimensional empirical mode decomposition (Xu et al., 2016) as a tool to separate different contributing sources of an otherwise complex geochemical pattern. We propose yet another approach, the use of geochemical indexes, which links to the geological and ore-forming processes known to define a given region in order to assess much of these numerical approaches. Therefore, we picked several areas from the Variscan basement in Portugal, with different geologic and metallogentic contexts, some of them previously analyzed with multifractal methods (Gonçalves et al., 2001; Jesus et al., 2013) and a multi-element geochemical campaign on which to test the different multifractal methods combined with the geochemical indexes, as an advantageous alternative to principal component mapping, for example. Some preliminary essays with stochastic models similar to those reported in Gonçalves (2001) and Agterberg (2007), with different overprinted pulses are presented as well. Acknowledgments: This is a contribution from UID/GEO/50019/2013 - Instituto Dom Luiz, supported by FCT. Agterberg, 2007, Math. Geol., 39, 1. Cheng et al, 1994, J. Geochem. Explor., 51, 109. Cheng et al., 2000, Nat. Resour. Res, 9, 43. Cheng, 2007, Ore Geol. Rev., 32, 314. Gonçalves, 2001, Math. Geol., 33, 41. Gonçalves et al., 2001, J. Geochem. Explor., 72, 91. Jesus et al., 2013, J. Geochem. Explor., 126-127, 23. Xu et al., 2016, J. Geochem. Explor., in press

A Uranium Bioremediation Reactive Transport Benchmark

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yabusaki, Steven B.; Sengor, Sevinc; Fang, Yilin

A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailings site in Rifle, Colorado, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, microbially-mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introducesmore » acetate and bromide through the upgradient boundary in 14-day and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions, as well as aqueous and surface complexation reactions for UO2++, Fe++, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC.« less

A reworked Lake Zone margin: Chronological and geochemical constraints from the Ordovician arc-related basement of the Hovd Zone (western Mongolia)

NASA Astrophysics Data System (ADS)

Soejono, Igor; Buriánek, David; Janoušek, Vojtěch; Svojtka, Martin; Čáp, Pavel; Erban, Vojtěch; Ganpurev, Nyamtsetseg

2017-12-01

The primary relationships and character of the boundaries between principal lithotectonic domains in the Mongolian tract of the Central Asian Orogenic Belt (CAOB) are still poorly constrained. This brings much uncertainty in understanding of the orogeny configuration and the complete accretionary history. The plutonic Khuurai Tsenkher Gol Complex and the mainly metasedimentary Bij Group represent associated medium- to high-grade basement complexes exposed in the Hovd Zone close to its boundary with the Lake Zone in western Mongolia. The Khuurai Tsenkher Gol Complex is composed of variously deformed acid to basic magmatic rocks intimately associated with the metamorphosed sedimentary and volcanic rocks of the Bij Group. Results of our field work, new U-Pb zircon ages and whole-rock geochemical data suggest an existence of two separate magmatic events within the evolution of the Khuurai Tsenkher Gol Complex. Early to Mid-Ordovician (476 ± 5 Ma and 467 ± 4 Ma protoliths) normal- to high-K calc-alkaline orthogneisses, metadiorites and metagabbros predominate over Mid-Silurian (430 ± 3 Ma) tholeiitic-mildly alkaline quartz monzodiorites. Whereas the geochemical signature of the former suite unequivocally demonstrates its magmatic-arc origin, that of the latter quartz monzodiorite suggests an intra-plate setting. As shown by Sr-Nd isotopic data, the older arc-related magmas were derived from depleted mantle and/or were generated by partial melting of juvenile metabasic crust. Detrital zircon age populations of the metasedimentary rocks together with geochemical signatures of the associated amphibolites imply that the Bij Group was a volcano-sedimentary sequence, formed probably in the associated fore-arc wedge basin. Moreover, our data argue for an identical provenance of the Altai and Hovd domains, overall westward sediment transport during the Early Palaeozoic and the east-dipping subduction polarity. The obvious similarities of the Khuurai Tsenkher Gol Complex (Hovd Zone) with the neighbouring Togtokhinshil Complex (Lake Zone) suggest that both magmatic complexes originally belonged to the same magmatic arc, related to the Palaeo-Asian subduction system. The geodynamic cause of the later, within-plate magmatic pulse is unclear, but was probably still related to the effects of retreating subduction (slab window/ocean ridge subduction or back-arc lithosphere thinning). The Khuurai Tsenkher Gol Complex was subsequently separated from the western margin of the Lake Zone and imbricated into the Hovd Zone mélange. It is proposed that the Lake/Hovd zones boundary in the study area represents a younger deformation zone rather than a true terrane boundary/suture. This could be a general feature of the suture zones within this part of the CAOB.

A COMSOL-GEMS interface for modeling coupled reactive-transport geochemical processes

NASA Astrophysics Data System (ADS)

Azad, Vahid Jafari; Li, Chang; Verba, Circe; Ideker, Jason H.; Isgor, O. Burkan

2016-07-01

An interface was developed between COMSOL MultiphysicsTM finite element analysis software and (geo)chemical modeling platform, GEMS, for the reactive-transport modeling of (geo)chemical processes in variably saturated porous media. The two standalone software packages are managed from the interface that uses a non-iterative operator splitting technique to couple the transport (COMSOL) and reaction (GEMS) processes. The interface allows modeling media with complex chemistry (e.g. cement) using GEMS thermodynamic database formats. Benchmark comparisons show that the developed interface can be used to predict a variety of reactive-transport processes accurately. The full functionality of the interface was demonstrated to model transport processes, governed by extended Nernst-Plank equation, in Class H Portland cement samples in high pressure and temperature autoclaves simulating systems that are used to store captured carbon dioxide (CO2) in geological reservoirs.

K, U, and Th behavior in Martian environmental conditions

NASA Technical Reports Server (NTRS)

Zolotov, M. YU.; Krot, T. V.; Moroz, L. V.

1993-01-01

The possibility of K, U, and Th content determination from orbit and in situ allows consideration of those elements as geochemical indicators in the planetary studies. In the case of Mars the unambiguous interpretations of such data in terms of igneous rocks are remarkably constrained by the widespread rock alteration and the existence of exogenic deposits. Besides, the terrestrial experience indicates that K, U, and Th contents could be used as indicators of environmental geochemical processes. Thus the determination of K, U, and Th contents in the Martian surface materials could provide the indirect data on the conditions of some exogenic geological processes. The speculations on the K, U, and Th behavior in the Martian environments show that aeolian and aqueous processes leads to the preferential accumulation of K, U, and Th in fine dust material. The separation of K, U, and Th on Mars is smaller in scale to that on Earth.

Metal-organic complexes in geochemical processes: Estimation of standard partial molal thermodynamic properties of aqueous complexes between metal cations and monovalent organic acid ligands at high pressures and temperatures

NASA Astrophysics Data System (ADS)

Shock, Everetr L.; Koretsky, Carla M.

1995-04-01

Regression of standard state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state allows evaluation of standard partial molal entropies ( overlineSo) of aqueous metal-organic complexes involving monovalent organic acid ligands. These values of overlineSo provide the basis for correlations that can be used, together with correlation algorithms among standard partial molal properties of aqueous complexes and equation-of-state parameters, to estimate thermodynamic properties including equilibrium constants for complexes between aqueous metals and several monovalent organic acid ligands at the elevated pressures and temperatures of many geochemical processes which involve aqueous solutions. Data, parameters, and estimates are given for 270 formate, propanoate, n-butanoate, n-pentanoate, glycolate, lactate, glycinate, and alanate complexes, and a consistent algorithm is provided for making other estimates. Standard partial molal entropies of association ( Δ -Sro) for metal-monovalent organic acid ligand complexes fall into at least two groups dependent upon the type of functional groups present in the ligand. It is shown that isothermal correlations among equilibrium constants for complex formation are consistent with one another and with similar correlations for inorganic metal-ligand complexes. Additional correlations allow estimates of standard partial molal Gibbs free energies of association at 25°C and 1 bar which can be used in cases where no experimentally derived values are available.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pilgrim, Corey D.; Zavarin, Mavrik; Casey, William H.

Here, the rates of ligand exchange into the geochemically important [NpO 2(CO 3) 3] 4– aqueous complex are measured as a function of pressure in order to complement existing data on the isostructural [UO 2(CO 3) 3] 4– complex. Experiments are conducted at pH conditions where the rate of exchange is independent of the proton concentration. Unexpectedly, the experiments show a distinct difference in the pressure dependencies of rates of exchange for the uranyl and neptunyl complexes.

Critical Safe Disposal of Spent Fuel: Behavior of Neutron Poisons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kienzler, Bernhard; Gmal, Bernhard

2007-07-01

In contrast to Yucca Mountain, European repository concepts rely on deep underground conditions which guarantee permanently a reducing geochemical environment. As long as no water comes into contact with the disposed nuclear fuel, criticality is excluded by compliance with the disposal conditions (limitation of U/Pu in the canisters). Penetration of water into the canister may also be considered as a scenario. However, water in a disposal results in geochemical reactions proceeding over very long periods of time: (1) Presence of water allows the corrosion of the steel of the canister material forming hydrogen and iron corrosion products. (2) Hydrogen pressuresmore » affect the zircaloy cladding even at low temperatures. Failure of fuel cladding and spacers leads to changes in the geometrical configuration. (3) UO{sub 2} matrix corrosion results in geochemically controlled reformation of secondary phase. (4) Even if the dissolution rate of UO{sub 2} is low, elements accounting for burnup credit do not behave similar as uranium. Geochemical reactions are analyzed in detail and compositions are presented which have a high probability to be formed in the long-term needing to be analyzed with respect to K{sub eff}. (authors)« less

Geochemical prospecting for copper and nickel in the Wulgai and Tor Tangi areas southeast of Hindubagh, Quetta Division, Pakistan

USGS Publications Warehouse

Stanin, S. Anthony; Wahid, M.A.; Khan, Shamsher

1975-01-01

Showings of magnetite, copper, and possible nickel mineralization in the Hindubagh chromite mining district are near Wulgai and Tor Tangi. Several hundred samples of clastic material from dry streambeds in these areas were sieved for the minus-80-mesh fraction and analyzed for copper using 2, 2'-biquinoline and for nickel using alpha-furildioxime. The copper threshold is 75 ppm, and the nickel threshold is 400 ppm. A geochemical map has been prepared that shows nine areas of anomalously high copper and six areas of high nickel. The nickel anomalies may represent secondary dispersion patterns derived from the erosion of nickeliferous ultramafic rocks of the Hindubagh intrusive complex. Copper showings in and near four of the anomalous copper areas indicate that detailed geological investigation and detailed geochemical sampling of rocks, soil, and unconsolidated clastic material are required to determine the source of the anomalies.

An alternative to fully coupled reactive transport simulations for long-term prediction of chemical reactions in complex geological systems

NASA Astrophysics Data System (ADS)

De Lucia, Marco; Kempka, Thomas; Kühn, Michael

2014-05-01

Fully-coupled reactive transport simulations involving multiphase hydrodynamics and chemical reactions in heterogeneous settings are extremely challenging from a computational point of view. This often leads to oversimplification of the investigated system: coarse spatial discretization, to keep the number of elements in the order of few thousands; simplified chemistry, disregarding many potentially important reactions. A novel approach for coupling non-reactive hydrodynamic simulations with the outcome of single batch geochemical simulations was therefore introduced to assess the potential long-term mineral trapping at the Ketzin pilot site for underground CO2 storage in Germany [1],[2]. The advantage of the coupling is the ability to use multi-million grid non-reactive hydrodynamics simulations on one side and few batch 0D geochemical simulations on the other, so that the complexity of both systems does not need to be reduced. This contribution shows the approach which was taken to validate this simplified coupling scheme. The procedure involved batch simulations of the reference geochemical model, then performing both non-reactive and fully coupled 1D and 3D reactive transport simulations and finally applying the simplified coupling scheme based on the non-reactive and geochemical batch model. The TOUGHREACT/ECO2N [3] simulator was adopted for the validation. The degree of refinement of the spatial grid and the complexity and velocity of the mineral reactions, along with a cut-off value for the minimum concentration of dissolved CO2 allowed to originate precipitates in the simplified approach were found out to be the governing parameters for the convergence of the two schemes. Systematic discrepancies between the approaches are not reducible, simply because there is no feedback between chemistry and hydrodynamics, and can reach 20 % - 30 % in unfavourable cases. However, even such discrepancy is completely acceptable, in our opinion, given the amount of uncertainty underlying the geochemical models. References [1] Klein, E., De Lucia, M., Kempka, T. Kühn, M. 2013. Evaluation of longterm mineral trapping at the Ketzin pilot site for CO2 storage: an integrative approach using geochemical modelling and reservoir simulation. International Journal of Greenhouse Gas Control 19: 720-730, doi:10.1016/j.ijggc.2013.05.014 [2] Kempka, T., Klein, E., De Lucia, M., Tillner, E. Kühn, M. 2013. Assessment of Long-term CO2 Trapping Mechanisms at the Ketzin Pilot Site (Germany) by Coupled Numerical Modelling. Energy Procedia 37: 5419-5426, doi:10.1016/j.egypro.2013.06.460 [3] Xu, T., Spycher, N., Sonnenthal, E., Zhang, G., Zheng, L., Pruess, K. 2010. TOUGHREACT Version 2.0: A simulator for subsurface reactive transport under non-isothermal multiphase flow conditions, Computers & Geosciences 37(6), doi:10.1016/j.cageo.2010.10.007

A geochemical and geophysical reappraisal to the significance of the recent unrest at Campi Flegrei caldera (Southern Italy)

NASA Astrophysics Data System (ADS)

Moretti, Roberto; De Natale, Giuseppe; Troise, Claudia

2017-04-01

Volcanic unrest at calderas involve complex interaction between magma, hydrothermal fluids and crustal stress and strain. Campi Flegrei caldera (CFc), located in the Naples (Italy) area and characterised by the highest volcanic risk on Earth for the extreme urbanisation, undergoes unrest phenomena involving several meters of uplift and intense shallow micro-seismicity since several decades. Despite unrest episodes display in the last decade only moderate ground deformation and seismicity, current interpretations of geochemical data point to a highly pressurized hydrothermal system. We show that at CFc, the usual assumption of vapour-liquid coexistence in the fumarole plumes leads to largely overestimated hydrothermal pressures and, accordingly, interpretations of elevated unrest. By relaxing unconstrained geochemical assumptions, we infer an alternative model yielding better agreement between geophysical and geochemical observations. The model reconciles discrepancies between what observed 1) for two decades since the 1982-84 large unrest, when shallow magma was supplying heat and fluids to the hydrothermal system, and 2) in the last decade. Compared to the 1980's unrest, the post-2005 phenomena are characterized by much lower aquifers overpressure and magmatic involvement, as indicated by geophysical data and despite large changes in geochemical indicators. Our interpretation points out a model in which shallow sills, intruded during 1969-1984, have completely cooled, so that fumarole emissions are affected now by deeper, CO2-richer, magmatic gases producing a relatively modest heating and overpressure of the hydrothermal system. Our results do have important implications on the short-term eruption hazard assessment and on the best strategies for monitoring and interpreting geochemical data.

Using geochemistry as a tool for correlating proximal andesitic tephra: Case studies from Mt Rainier (USA) and Mt Ruapehu (New Zealand)

USGS Publications Warehouse

Donoghue, S.L.; Vallance, J.; Smith, I.E.M.; Stewart, R.B.

2007-01-01

Volcanic hazards assessments at andesite stratovolcanoes rely on the assessment of frequency and magnitude of past events. The identification and correlation of proximal and distal andesitic tephra, which record the explosive eruptive history, are integral to such assessments. These tephra are potentially valuable stratigraphic marker beds useful to the temporal correlation and age dating of Quaternary volcanic, volcaniclastic and epiclastic sedimentary deposits with which they are interbedded. At Mt Ruapehu (New Zealand) and Mt Rainier (USA), much of the detail of the recent volcanic record remains unresolved because of the difficulty in identifying proximal tephra. This study investigates the value of geochemical methods in discriminating andesitic tephra. Our dataset comprises petrological and geochemical analyses of tephra that span the late Quaternary eruptive record of each volcano. Our data illustrate that andesitic tephra are remarkably heterogeneous in composition. Tephra compositions fluctuate widely over short time intervals, and there are no simple or systematic temporal trends in geochemistry within either eruptive record. This complexity in tephra geochemistry limits the application of geochemical approaches to tephrostratigraphic studies, beyond a general characterisation useful to provenance assignation. Petrological and geochemical data suggest that the products of andesite systems are inherently variable and therefore intractable to discrimination by simple geochemical methods alone. Copyright ?? 2006 John Wiley & Sons, Ltd.

Geochemical characteristics of charnockite and high grade gneisses from Southern Peninsular Shield and their significance in crustal evolution

NASA Technical Reports Server (NTRS)

Sugavanam, E. B.; Vidyadharan, K. T.

1988-01-01

Presented here are the results of detailed investigations encompassing externsive structural mapping in the charnockite-high grade gneiss terrain of North Arcot district and the type area in Pallavaram in Tamil Nadu supported by petrography, mineral chemistry, major, minor and REE distribution patterns in various lithounits. This has helped in understanding the evolutionary history of the southern peninsular shield. A possible tectonic model is also suggested. The results of these studies are compared with similar rock types from parts of Andhra Pradesh, Kerala, Sri Lanka, Lapland and Nigeria which has brought about a well defined correlation in geochemical characteristics. The area investigated has an interbanded sequence of thick pile of charnockite and a supracrustal succession of shelf type sediments, layered igneous complex, basic and ultrabasic rocks involved in a complex structural, tectonic, igneous and metamorphic events.

Petrographic and geochemical characterization of the granitic rocks of the Araguainha impact crater, Brazil

NASA Astrophysics Data System (ADS)

Silva, Dailto; Lana, Cristiano; Souza Filho, Carlos Roberto

2016-03-01

Petrographic and geochemical data obtained on the Araguainha impact crater (Goiás/Mato Grosso States, Brazil) indicate the existence of several molten products that originated during impact-induced congruent melting of an alkali-granite exposed in the inner part of the central uplift of the structure. Although previous studies have described these melts to some extent, there is no detailed discussion on the petrographic and geochemical variability in the granite and its impactogenic derivatives, and therefore, little is known about the geochemical behavior and mobility of trace elements during its fusion in the central part of the Araguainha crater. This paper demonstrates that the preserved granitoid exposed in the core of the structure is a magnesium-rich granite, similar to postcollisional, A-type granites, also found in terrains outside the Araguainha crater, in the Brasília orogenic belt. The molten products are texturally distinct and different from the original rock, but have very similar geochemical composition, making it difficult to separate these lithotypes based on concentrations of major and minor elements. This also applies for trace and rare earth elements (REE), thus indicating a high degree of homogenization during impact-induced congruent melting under high pressure and postshock temperature conditions. Petrographic observations, along with geochemical data, indicate that melting occurs selectively, where some of the elements are transported with the melt. Simultaneously, there is an effective dissolution of the rock (granite), which leads to entrainment of the most resistant solid phases (intact or partially molten minerals) into the melt. Minerals more resistant to melting, such as quartz and oxides, contribute substantially to a chemical balance between the preserved granite and the fusion products generated during the meteoritic impact.

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.

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.

Quantifying reactive transport processes governing arsenic mobility in a Bengal Delta aquifer

NASA Astrophysics Data System (ADS)

Rawson, Joey; Neidhardt, Harald; Siade, Adam; Berg, Michael; Prommer, Henning

2017-04-01

Over the last few decades significant progress has been made to characterize the extent and severity of groundwater arsenic pollution in S/SE Asia, and to understand the underlying geochemical processes. However, comparably little effort has been made to merge the findings from this research into quantitative frameworks that allow for a process-based quantitative analysis of observed arsenic behavior and predictions of its future fate. Therefore, this study developed and tested field-scale numerical modelling approaches to represent the primary and secondary geochemical processes associated with the reductive dissolution of Fe-oxy(hydr)oxides and the concomitant release of sorbed arsenic. We employed data from an in situ field experiment in the Bengal Delta Plain, which investigated the influence of labile organic matter (sucrose) on the mobility of Fe, Mn, and As. The data collected during the field experiment were used to guide our model development and to constrain the model parameterisation. Our results show that sucrose oxidation coupled to the reductive dissolution of Fe-oxy(hydr)oxides was accompanied by multiple secondary geochemical reactions that are not easily and uniquely identifiable and quantifiable. Those secondary reactions can explain the disparity between the observed Fe and As behavior. Our modelling results suggest that a significant fraction of the released As is scavenged through (co-)precipitation with newly formed Fe-minerals, specifically magnetite, rather than through sorption to pre-existing and freshly precipitated iron minerals.

Mineralogical and geochemical anomalous data of the K-T boundary samples

NASA Technical Reports Server (NTRS)

Miura, Y.; Shibya, G.; Imai, M.; Takaoka, N.; Saito, S.

1988-01-01

Cretaceous-Tertiary boundary problem has been discussed previously from the geological research, mainly by fossil changes. Although geochemical bulk data of Ir anomaly suggest the extraterrestrial origin of the K-T boundary, the exact formation process discussed mainly by mineralogical and geochemical study has been started recently, together with noble gas contents. The K-T boundary sample at Kawaruppu River, Hokkaido was collected, in order to compare with the typical K-T boundary samples of Bubbio, Italy, Stevns Klint, Denmark, and El Kef, Tunisia. The experimental data of the silicas and calcites in these K-T boundary samples were obtained from the X-ray unit-cell dimension (i.e., density), ESR signal and total linear absorption coefficient, as well as He and Ne contents. The K-T boundary samples are usually complex mixture of the terrestrial activities after the K-T boundary event. The mineralogical and geochemical anomalous data indicate special terrestrial atmosphere at the K-T boundary formation probably induced by asteroid impact, followed the many various terrestrial activities (especially the strong role of sea-water mixture, compared with terrestrial highland impact and impact craters in the other earth-type planetary bodies).

Haemorrhagic diarrhoea and reproductive failure in Bonsmara cattle resulting from anomalous heavy metal concentrations in soils, forages and drinking water associated with geochemical anomalies of toxic elements on the farm Puntlyf, South Africa

NASA Astrophysics Data System (ADS)

Elsenbroek, J. H.; Meyer, J.; Myburgh, J.

2003-05-01

Poor livestock health conditions are associated with geochemical Pb anomalies on a farm approximately 40km east of Pretoria, South Africa. A generic risk assessment of drinking water for Bonsmara cattle obtained from three separate subterranean water sources on the farm, revealed the presence of several potentially hazardous constituents suspected for the development of adverse health effects in the herd. The two main symptoms of the herd, namely, severe haemorrhagic diarrhoea in calves and reproductive failure in cows, have been investigated. A selenium-induced copper deficiency was proposed as the main cause to the calf diarrhoea, due to complexing between high concentrations of Se, Mo, Hg and Pb in drinking water. It was also anticipated that such Cu deficiencies would lead to low systemic Se inducing hypothyroidism in the cows due to inadequate iodine activation required for thyroid hormone formation and consequently adversely affect reproduction. The anomalous Pb in borehole drinking water on the southem part of the farm, suggests a clear genetic link with the underlying geochemical Pb anomalies detected by means of an ongoing regional geochemical survey.

HANDBOOK: GROUNDWATER - METHODOLOGY - VOL. 2

EPA Science Inventory

The subsurface environment of ground water is characterized by a complex interplay of physical, geochemical and biological forces that govern the release, transport and fate of a variety of chemical substances. There are literally as many varied hydrogeologic settings as there ar...

Simultaneous leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary rocks: II. Kinetic and reactive transport modeling.

PubMed

Tabelin, Carlito Baltazar; Sasaki, Ryosuke; Igarashi, Toshifumi; Park, Ilhwan; Tamoto, Shuichi; Arima, Takahiko; Ito, Mayumi; Hiroyoshi, Naoki

2017-12-01

Predicting the fates of arsenic (As) and selenium (Se) in natural geologic media like rocks and soils necessitates the understanding of how their various oxyanionic species behave and migrate under dynamic conditions. In this study, geochemical factors and processes crucial in the leaching and transport of arsenite (As III ), arsenate (As V ), selenite (Se IV ) and selenate (Se VI ) in tunnel-excavated rocks of marine origin were investigated using microscopic/extraction techniques, column experiments, dissolution-precipitation kinetics and one-dimensional reactive transport modeling. The results showed that evaporite salts were important because aside from containing As and Se, they played crucial roles in the evolution of pH and concentrations of coexisting ions, both of which had strong effects on adsorption-desorption reactions of As and Se species with iron oxyhydroxide minerals/phases. The observed leaching trends of As V , As III , Se IV and Se VI were satisfactorily simulated by one-dimensional reactive transport models, which predict that preferential adsorptions of As V and Se IV were magnified by geochemical changes in the columns due to water flow. Moreover, our results showed that migrations of As III , Se IV and Se VI could be predicted adequately by 1D solute transport with simple activity-K' d approach, but surface complexation was more reliable to simulate adsorption-desorption behavior of As V . Copyright © 2017 Elsevier Ltd. All rights reserved.

Ore-forming adakitic porphyry produced by fractional crystallization of oxidized basaltic magmas in a subcrustal chamber (Jiamate, East Junggar, NW China)

NASA Astrophysics Data System (ADS)

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen G.; Zhang, Di; Jielili, Reyaniguli; Xiang, Peng; Li, Hao; Wu, Chu; You, Jun; Liu, Jie; Ke, Qiang

2018-01-01

Adakitic intrusions are supposed to have a close genetic and spatial relationship to porphyry Cu deposits. However, the genesis of adakitic intrusions is still under dispute. Here, we describe newly discovered intrusive complex rocks, which are composed of ore-bearing, layered magnetite-bearing gabbroic and adakitic rocks in Jiamate, East Junggar, NW China. These Jiamate Complex intrusions have diagnostic petrologic, geochronologic and geochemical signatures that indicate they were all generated from the same oxidized precursor magma source. Additionally, these layered rocks underwent the same fractional crystallization process as the ore-bearing adakitic rocks in the adjacent Kalaxiangar Porphyry Cu Belt (KPCB) in an oceanic island arc (OIA) setting. The rocks studied for this paper include layered magnetite-bearing gabbroic intrusive rocks that contain: (1) gradual contact changes between lithological units of mafic and intermediate rocks, (2) geochemical signatures that are the same as those found in oceanic island arc (OIA) rocks, (3) typical adakitic geochemistry, and (4) similar characteristics and apparent fractional crystallization relationships of ultra-basic to basic rocks to those in the nearby Beitashan Formation and to ore-bearing adakitic rocks in the KPCB. They also display similar zircon U-Pb and zircon Hf model ages. The Jiamate Complex intrusions contain intergrowths of magnetite and layered gabbro, and the intermediate-acidic intrusions of the Complex display typical adakitic affinities. Moreover, in conjunction with previously published geochronological and geochemistry data of the mafic rocks in the Beitashan Formation and in the KPCB area, additional data generated for the Jiamate Complex intrusions rocks indicate that they were formed from fractional crystallization processes. The Jiamate Complex intrusions most likely were derived from a metasomatized mantle wedge that was underplated at the root of the Saur oceanic island arc (Saur OIA). The ore-bearing adakitic intrusions in the KPCB and the adakitic Jiamate Complex intrusions were both probably generated from the same basaltic parental magmas through fractional crystallization. In addition, characteristics of the layered, magnetite-bearing, oxidized, basaltic Jiamate Complex intrusive rocks indicate that they are likely to be the parental arc magmas for the nearby porphyry Cu deposits. This conclusion is based on new interpretations of the regional and local geology, on interpretation of new geochemical analysis, new stable isotope analysis, new geothermobarometry, and new zircon age dating as well as other techniques and interpretations.

Ore-forming adakitic porphyry produced by fractional crystallization of oxidized basaltic magmas in a subcrustal chamber (Jiamate, East Junggar, NW China)

USGS Publications Warehouse

Hong, Tao; Xu, Xing-Wang; Gao, Jun; Peters, Stephen; Zhang, Di; Jielili, Reyaniguli; Xiang, Peng; Li, Hao; Wu, Chu; You, Jun; Liu, Jie; Ke, Qiang

2018-01-01

Adakitic intrusions are supposed to have a close genetic and spatial relationship to porphyry Cu deposits. However, the genesis of adakitic intrusions is still under dispute. Here, we describe newly discovered intrusive complex rocks, which are composed of ore-bearing, layered magnetite-bearing gabbroic and adakitic rocks in Jiamate, East Junggar, NW China. These Jiamate Complex intrusions have diagnostic petrologic, geochronologic and geochemical signatures that indicate they were all generated from the same oxidized precursor magma source. Additionally, these layered rocks underwent the same fractional crystallization process as the ore-bearing adakitic rocks in the adjacent Kalaxiangar Porphyry Cu Belt (KPCB) in an oceanic island arc (OIA) setting. The rocks studied for this paper include layered magnetite-bearing gabbroic intrusive rocks that contain: (1) gradual contact changes between lithological units of mafic and intermediate rocks, (2) geochemical signatures that are the same as those found in oceanic island arc (OIA) rocks, (3) typical adakitic geochemistry, and (4) similar characteristics and apparent fractional crystallization relationships of ultra-basic to basic rocks to those in the nearby Beitashan Formation and to ore-bearing adakitic rocks in the KPCB. They also display similar zircon U-Pb and zircon Hf model ages.The Jiamate Complex intrusions contain intergrowths of magnetite and layered gabbro, and the intermediate-acidic intrusions of the Complex display typical adakitic affinities. Moreover, in conjunction with previously published geochronological and geochemistry data of the mafic rocks in the Beitashan Formation and in the KPCB area, additional data generated for the Jiamate Complex intrusions rocks indicate that they were formed from fractional crystallization processes. The Jiamate Complex intrusions most likely were derived from a metasomatized mantle wedge that was underplated at the root of the Saur oceanic island arc (Saur OIA). The ore-bearing adakitic intrusions in the KPCB and the adakitic Jiamate Complex intrusions were both probably generated from the same basaltic parental magmas through fractional crystallization. In addition, characteristics of the layered, magnetite-bearing, oxidized, basaltic Jiamate Complex intrusive rocks indicate that they are likely to be the parental arc magmas for the nearby porphyry Cu deposits. This conclusion is based on new interpretations of the regional and local geology, on interpretation of new geochemical analysis, new stable isotope analysis, new geothermobarometry, and new zircon age dating as well as other techniques and interpretations.

Compositional Heterogeneity and Spatial Segmentation of Suprasubduction (ssz-type) Ophiolites: Evidence From The Kamchatka Arc

NASA Astrophysics Data System (ADS)

Osipenko, A.; Krylov, K.

In ophiolite complexes from the Eastern Asian accretion belts the spatial heterogeneity of geochemical parameters for different components of an ophiolite sequence is estab- lished: restite mantle-derived peridotites, cumulative layered complex and volcanics. This heterogeneity is displayed as at a regional level (tens - hundred km), and at a level of local structures (hundred i - first tens km). As a rule, distinction is observed on a complex of geochemical parameters (concentration and form of REE spectra, EPG distribution, isotope characteristics, Cr-spinel and pyroxene composition etc.). Revealed at once in several suprasubduction-type ophiolite belts (Kamuikotan, Philip- pines New Guinea etc.), the spatial variations of geochemical parameters have not gradual, and discrete character. For an explanation of the reasons of ophiolite com- positional heterogeneity several mechanisms are offered: (1) tectonical overlapping of various fragments of lithosphere; (2) different specify of deep processes, resulting to compositional heterogeneity of rocks from the same lithosphere level; 3) hetero- geneity of the upper mantle and/or mantle metasomatism; 4) evolution of ophiolites (Shervais, 2001) and/or center of magma generation (mixture of continuous series of melt portions, separated during different stages of progressive mantle source melting (Bazylev et al., 2001)); 5) preservations of relict blocks of low lithosphere and upper mantle from the previous stage in suprasubduction conditions. The authors consider regional geochemical heterogeneity and segmentation of suprasubduction ophiolites (SSZ-type) on an example of peridotites from the Eastern Kamchatka ophiolite belt (EKOB), where sublongitude zones, crossed the basic geological structures of a penin- sula (including EROB) were allocated earlier. For each of zones the complex of geo- chemical attributes, steady is established within the limits of a zone, but distinct from of the characteristics of other zones. Among the factors causing an unequal degree of partial melting of peridotites, a main role play a geothermal regime and composition of fluid phase (first of all, the role of water fluid is great). These parameters, in turn, are supervised by a geodynamic regime of magma generation (such characteristics as speed of subduction and geometry of a subducted plate) and finally determine speed of uplift from the diapir in mantle, depth of the termination of partial melting, amount of 1 extracted melt, form and capacity of the magma chamber etc. The local heterogeneity in SSZ-ophiolites is considered on an example of a complex of the Kamchatka Cape Peninsula - the largest ophiolite complex in EKOB. Isotope, geochemical and miner- alogical study have shown, that a part, prevailing on volume, of this complex consist suprasubduction-type magmatic rocks (restite high-depleted harzburgites and related layered cumulative complex), whereas peridotites of harzburgite-lherzolite series and high-grade metabasites (retrograde eclogites and garnet amphibolites) composition- ally correspond to series of N-MORB and Ò-MORB-type. The presence in ophiolite of the Kamchatka Cape Peninsula alongside with high-depleted harzburgites as well moderately- and low-depleted peridotites of harzburgite-lherzolite series allows to as- sume, that Late Mesozoic suprasubduction ophiolites were formed on peridotitic basis of abyssal type. Thus the transformation of "oceanic" substrate was not complete, that has allowed to be kept relict peridotites of lherzolitic type and high-pressure metamor- phics. Probably it reflects pulsing character of geodynamics of suprasubduction-type ophiolite formation, it is possible is connected with "jumping" of spreading axes in suprasubduction conditions. During followed multistage napping in a northeast direc- tion in the Upper Cretaceous time disintegrated fragments of both mantle complexes were tectonically concurrent. In the report the alternative versions of tectonic models of development are also discussed for the Eastern Kamchatka ophiolites. 2

A Record of Uranium-Series Transport in Fractured, Unsaturated Tuff at Nopal I, Sierra Peña Blanca, Chihuahua, Mexico

NASA Astrophysics Data System (ADS)

Denton, J.; Goldstein, S. J.; Paviet, P.; Nunn, A. J.; Amato, R. S.; Hinrichs, K. A.

2015-12-01

In this study we utilize U-series disequilibria measurements to investigate mineral fluid interactions and the role fractures play in the geochemical evolution of an analogue for a high level nuclear waste repository, the Nopal I uranium ore deposit. Samples of fracture-fill materials have been collected from a vertical drill core and surface fractures. High uranium concentrations in these materials (12-7700 ppm) indicate U mobility and transport from the deposit in the past. U concentrations generally decrease with horizontal distance away from the ore deposit but show no trend with depth. Isotopic activity ratios indicate a complicated geochemical evolution in terms of the timing and extent of actinide mobility, possibly due to changing environmental (redox) conditions over the history of the deposit. 234U/238U activity ratios are generally distinct from secular equilibrium and indicate some degree of open system U behavior during the past 1.2 Ma. However, calculated closed system 238U-234U-230Th model ages are generally >313 ka and >183 ka for the surface fracture and drill core samples respectively, suggesting closed system behavior for U and Th over this most recent time period. Whole rock isochrons drawn for the drill core samples show that at two of three depths fractures have remained closed with respect to U and Th mobility for >200 ka. However, open system behavior for U in the last 350 ka is suggested at 67 m depth. 231Pa/235U activity ratios within error of unity suggest closed system behavior for U and Pa for at least the past 185 ka. 226Ra/230Th activity ratios are typically <1 (0.7-1.2), suggesting recent (<8 ka) radium loss and mobility due to ongoing fluid flow in the fractures. Overall, the mainly closed system behavior of U-Th-Pa over the past ~200 ka provides one indicator of the geochemical immobility of these actinides over long time-scales for potential nuclear waste repositories sited in fractured, unsaturated tuff.

UNDERSTANDING VARIATION IN PARTITION COEFFICIENT KD, VALUES, VOLUME III: AMERICIUM, ARSENIC, CURIUM, IODINE, NEPTUNIUM, RADIUM, AND TECHNETIUM

EPA Science Inventory

This report describes the conceptualization, measurement, and use of the partition (or distribution) coefficient, Kd, parameter, and the geochemical aqueous solution and sorbent properties that are most important in controlling adsorption/retardation behavior of selected contamin...

New results of microfaunal and geochemical investigations in the Permian-Triassic boundary interval from the Jadar Block (NW Serbia)

NASA Astrophysics Data System (ADS)

Sudar, Milan N.; Kolar-Jurkovšek, Tea; Nestell, Galina P.; Jovanović, Divna; Jurkovšek, Bogdan; Williams, Jeremy; Brookfield, Michael; Stebbins, Alan

2018-04-01

Detail results of microfaunal, sedimentological and geochemical investigations are documented from a newly discovered section of the Permian-Triassic boundary (PTB) interval in the area of the town of Valjevo (northwestern Serbia). The presence of various and abundant microfossils (conodonts, foraminifers, and ostracodes) found in the Upper Permian "Bituminous limestone" Formation enabled a determination of the Changhsingian Hindeodus praeparvus conodont Zone. This paper is the first report of latest Permian strata from the region, as well as from all of Serbia, where the PTB interval sediments have been part of a complex/integrated study by means of biostratigraphy and geochemistry.

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.

Investigating Processes of Materials Formation via Liquid Phase and Cryogenic TEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Yoreo, James J.; Sommerdijk, Nico

2016-06-14

The formation of materials in solutions is a widespread phenomenon in synthetic, biological and geochemical systems, occurring through dynamic processes of nucleation, self-assembly, crystal growth, and coarsening. The recent advent of liquid phase TEM and advances in cryogenic TEM are transforming our understanding of these phenomena by providing new insights into the underlying physical and chemical mechanisms. The techniques have been applied to metallic and semiconductor nanoparticles, geochemical and biological minerals, electrochemical systems, macromolecular complexes, and selfassembling systems, both organic and inorganic. New instrumentation and methodologies currently on the horizon promise new opportunities for advancing the science of materials synthesis.

Geochemical behavior of heavy metals in a Zn-Pb-Cu mining area in the State of Mexico (central Mexico).

PubMed

Lizárraga-Mendiola, L; González-Sandoval, M R; Durán-Domínguez, M C; Márquez-Herrera, C

2009-08-01

The geochemical behavior of zinc, lead and copper from sulfidic tailings in a mine site with potential to generate acidic drainage (pyrite (55%) and sphalerite (2%)) is reported in this paper. The mining area is divided in two zones, considering the topographic location of sampling points with respect to the tailings pile: (a) outer zone, out of the probable influence of acid mine drainage (AMD) pollution, and (b) inner zone, probably influenced by AMD pollution. Maximum total ions concentrations (mg/L) measured in superficial waters found were, in the outer zone: As (0.2), Cd (0.9), Fe (19), Mn (39), Pb (5.02), SO4(2-) (4650), Zn (107.67), and in the inner zone are As (0.1), Cd (0.2), Fe (88), Mn (13), Pb (6), SO4(2-) (4,880), Zn (46). The presence of these ions that exceeding the permissible maximum limits for human consume, could be associated to tailings mineralogy and acid leachates generated in tailings pile.

Geochemical Fate and Transport of Diphenhydramine and Cetirizine in Soil

NASA Astrophysics Data System (ADS)

Wireman, R.; Rutherford, C. J.; Vulava, V. M.; Cory, W. C.

2015-12-01

Pharmaceuticals compounds presence in natural soils and water around the world has become a growing concern. These compounds are being discharged into the environment through treated wastewater or municipal sludge applications. The main goal of this study is determine their geochemical fate in natural soils. In this study we investigated sorption and transport behavior of diphenhydramine (DPH) and cetirizine (CTZ) in natural soils. These two commonly-used antihistamines are complex aromatic hydrocarbons with polar functional groups. Two clean acidic soils (pH~4.5) were used for these studies - an A-horizon soil that had higher organic matter content (OM, 7.6%) and a B-horizon soil that had lower OM (1.6%), but higher clay content (5.1%). Sorption isotherms were measured using batch reactor experiments. Data indicated that sorption was nonlinear and that it was stronger in clay-rich soils. The pKa's of DPH and CTZ are 8.98 and 8.27 respectively, i.e., these compounds are predominantly in cationic form at soil pH. In these forms, they preferentially sorb to negatively charged mineral surfaces (e.g., clay) present in the soils. Soil clay mineral characterization indicated that kaolinite was the dominant clay mineral present along with small amount of montmorillonite. The nonlinear sorption isotherms were fitted with Freundlich model. Transport behavior of both compounds was measured using glass chromatography columns. As expected both DPH and CTZ were strongly retained in the clay-rich soil as compared with OM-rich soil. The asymmetrical shape of the breakthrough curves indicated that there were likely two separate sorption sites in the soil, each with different reaction rates with each compound. A two-region advection-dispersion transport code was used to model the transport breakthrough curves. There was no evidence of transformation or degradation of the compounds during our sorption and transport studies.

Geochemical Fate and Transport of Sildenafil and Vardenafil

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Integrative molecular and microanalytical studies of syntrophic partnerships linking C, S, and N cycles in anoxic environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orphan, Victoria

2016-07-15

Syntrophy and other forms of symbiotic associations between microorganisms are central to carbon and nutrient cycling in the environment. However, the inherent interdependence of these interactions, dynamic behavior, and frequent existence at thermodynamic limits has hindered our ability to both recognize syntrophic partnerships in nature and effectively study their behavior in the laboratory. To characterize and understand the underlying factors influencing syntrophic associations within complex communities requires a suite of tools that extend beyond basic molecular identification and cultivation. This specifically includes methods that preserve the natural spatial relationships between metabolically interdependent microorganisms while allowing downstream geochemical and/or molecular analysis.more » With support from this award, we have developed and applied new combinations of molecular, microscopy, and stable isotope-based methodologies that enable the characterization of fundamental links between phylogenetically-identified microorganisms and their specific metabolic activities and interactions in the environment. Through the coupling of fluorescence in situ hybridization (FISH) with cell capture and targeted metagenomics (Magneto-FISH), and FISH + secondary ion mass spectrometry (i.e. FISH-SIMS or FISH-nanoSIMS), we have defined new microbial interactions and the ecophysiology of anaerobic microorganisms involved in environmental methane cycling.« less

A Sr-Nd isotopic study of sand-sized sediment provenance and transport for the San Francisco Bay coastal system

USGS Publications Warehouse

Rosenbauer, Robert J.; Foxgrover, Amy C.; Hein, James R.; Swarzenski, Peter W.; Barnard, P.L.; Jaffee, B.E.; Schoellhamer, D.H.

2013-01-01

A diverse suite of geochemical tracers, including 87Sr/86Sr and 143Nd/144Nd isotope ratios, the rare earth elements (REEs), and select trace elements were used to determine sand-sized sediment provenance and transport pathways within the San Francisco Bay coastal system. This study complements a large interdisciplinary effort (Barnard et al., 2012) that seeks to better understand recent geomorphic change in a highly urbanized and dynamic estuarine-coastal setting. Sand-sized sediment provenance in this geologically complex system is important to estuarine resource managers and was assessed by examining the geographic distribution of this suite of geochemical tracers from the primary sources (fluvial and rock) throughout the bay, adjacent coast, and beaches. Due to their intrinsic geochemical nature, 143Nd/144Nd isotopic ratios provide the most resolved picture of where sediment in this system is likely sourced and how it moves through this estuarine system into the Pacific Ocean. For example, Nd isotopes confirm that the predominant source of sand-sized sediment to Suisun Bay, San Pablo Bay, and Central Bay is the Sierra Nevada Batholith via the Sacramento River, with lesser contributions from the Napa and San Joaquin Rivers. Isotopic ratios also reveal hot-spots of local sediment accumulation, such as the basalt and chert deposits around the Golden Gate Bridge and the high magnetite deposits of Ocean Beach. Sand-sized sediment that exits San Francisco Bay accumulates on the ebb-tidal delta and is in part conveyed southward by long-shore currents. Broadly, the geochemical tracers reveal a complex story of multiple sediment sources, dynamic intra-bay sediment mixing and reworking, and eventual dilution and transport by energetic marine processes. Combined geochemical results provide information on sediment movement into and through San Francisco Bay and further our understanding of how sustained anthropogenic activities which limit sediment inputs to the system (e.g., dike and dam construction) as well as those which directly remove sediments from within the Bay, such as aggregate mining and dredging, can have long-lasting effects

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

PubMed Central

2011-01-01

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4+ production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface. PMID:21943229

Modeling the Hydrogeochemical Transport of Radionuclides through Engineered Barriers System in the Proposed LLW Disposal Site of Taiwan - 12082

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Wen-Sheng; Liu, Chen-Wuing; Tsao, Jui-Hsuan

2012-07-01

A proposed site for final disposal of low-level radioactive waste located in Daren Township of Taitung County along the southeastern coast has been on the selected list in Taiwan. The geology of the Daren site consists of argillite and meta-sedimentary rocks. A mined cavern design with a tunnel system of 500 m below the surface is proposed. Concrete is used as the main confinement material for the engineered barrier. To investigate the hydrogeochemical transport of radionuclides through engineered barriers system, HYDROGEOCHEM5.0 model was applied to simulate the complex chemical interactions among radionuclides, the cement minerals of the concrete, groundwater flow,more » and transport in the proposed site. The simulation results showed that the engineered barriers system with the side ditch efficiently drained the ground water and lowered the concentration of the concrete degradation induced species (e.g., hydrogen ion, sulfate, and chloride). The velocity of groundwater observed at side ditch gradually decreased with time due to the fouling of pore space by the mineral formation of ettringite and thaumasite. The short half-life of Co-60, Sr-90 and Cs-137 significantly reduced the concentrations, whereas the long half-life of I-129(1.57x10{sup 7} years) and Am-241(432 years) remain stable concentrations at the interface of waste canister and concrete barrier after 300 years. The mineral saturation index (SI) was much less than zero due to the low aqueous concentration of radionuclide, so that the precipitation formation of Co-60, Sr-90, I-129, Cs-137 and Am-241 related minerals were not found. The effect of adsorption/desorption (i.e., surface complexation model) could be a crucial geochemical mechanism for the modeling of liquid-solid phase behavior of radionuclide in geochemically dynamic environments. Moreover, the development of advanced numerical models that are coupled with hydrogeochemical transport and dose assessment of radionuclide is required in the future. (authors)« less

The effect of diagenesis and fluid migration on rare earth element distribution in pore fluids of the northern Cascadia accretionary margin

USGS Publications Warehouse

Kim, Ji-Hoon; Torres, Marta E.; Haley, Brian A.; Kastner, Miriam; Pohlman, John W.; Riedel, Michael; Lee, Young-Joo

2012-01-01

Analytical challenges in obtaining high quality measurements of rare earth elements (REEs) from small pore fluid volumes have limited the application of REEs as deep fluid geochemical tracers. Using a recently developed analytical technique, we analyzed REEs from pore fluids collected from Sites U1325 and U1329, drilled on the northern Cascadia margin during the Integrated Ocean Drilling Program (IODP) Expedition 311, to investigate the REE behavior during diagenesis and their utility as tracers of deep fluid migration. These sites were selected because they represent contrasting settings on an accretionary margin: a ponded basin at the toe of the margin, and the landward Tofino Basin near the shelf's edge. REE concentrations of pore fluid in the methanogenic zone at Sites U1325 and U1329 correlate positively with concentrations of dissolved organic carbon (DOC) and alkalinity. Fractionations across the REE series are driven by preferential complexation of the heavy REEs. Simultaneous enrichment of diagenetic indicators (DOC and alkalinity) and of REEs (in particular the heavy elements Ho to Lu), suggests that the heavy REEs are released during particulate organic carbon (POC) degradation and are subsequently chelated by DOC. REE concentrations are greater at Site U1325, a site where shorter residence times of POC in sulfate-bearing redox zones may enhance REE burial efficiency within sulfidic and methanogenic sediment zones where REE release ensues. Cross-plots of La concentrations versus Cl, Li and Sr delineate a distinct field for the deep fluids (z > 75 mbsf) at Site U1329, and indicate the presence of a fluid not observed at the other sites drilled on the Cascadia margin. Changes in REE patterns, the presence of a positive Eu anomaly, and other available geochemical data for this site suggest a complex hydrology and possible interaction with the igneous Crescent Terrane, located east of the drilled transect.

Re-evaluating across-axis geochemical variations at the East Pacific Rise and Juan de Fuca Ridge: on- and off-axis melt delivery

NASA Astrophysics Data System (ADS)

Perfit, M. R.; Walters, R. L.

2014-12-01

High spatial density geochemical data sets from the N-EPR and S-JdFR are used to re-evaluate the across-axis geochemical variations in major and trace elements at mid-ocean ridges (MORs). At two axial melt lens (AML) segments, north and south, at the 9-10°N EPR, N-MORB MgO varies across-axis from the most primitive above the AML to more evolved away from the axis. This trend is distinct at the northern (magmatically more robust) segment with an axial MgO range of 8-9 wt% and off-axis (>2km) range of 6.5-8 wt%. This decrease is also reflected in E-MORB MgO variation. There is more variability at the southern segment but, off-axis progression to more evolved MgO is still evident. Interestingly, the Cleft segment, JdFR, displays similar geochemical behavior to the EPR with an axial MgO range of 7-8.5 wt% and off-axis (>2km) range of 6-7.5 wt%. EPR geochemical studies over the past 30 years have described models of upper crustal accumulation ranging from eruptions limited to the axis, to temporal variation in the composition of magma in the AML, to multiple eruption sites across the ridge crest and flanks (<5km). Eruptions limited to the axis, with topographically controlled flow off-axis, cannot reproduce the observed off-axis change to more evolved N-MORB. Time-dependence could explain one instance of evolved lavas off-axis but, similar geochemical behavior is observed at two separate AML segments. Multiple instances of consistent compositional variability at multiple AML segments, and at different ridges, point to a common process of crustal accretion at MORs. In light of recent geophysical discoveries of Off-axis AMLs (OAMLs) at the EPR and JdFR, we propose that the trend of more evolved lavas for the majority of N-MORB lavas with distance from the axis is controlled by thermal distribution in the underlying crystal mush zone (CMZ). Higher magma flux beneath the axis facilitates higher temperatures and high porosity melt pathways, reducing crustal residence times, and erupting more primitive lava compositions. OAMLs at the edges of the CMZ, where it is cooler, feed more evolved off-axis eruptions. Lower magma flux at the edges increases crustal residence time and the extent to which magmas crystallize. OAMLs outside of the CMZ host magmas that may escaped any central mixing and erupt a greater range of compositions.

Origin and evolution of the Ilmeny-Vishnevogorsky carbonatites (Urals, Russia): insights from trace-element compositions, and Rb-Sr, Sm-Nd, U-Pb, Lu-Hf isotope data

NASA Astrophysics Data System (ADS)

Nedosekova, I. L.; Belousova, E. A.; Sharygin, V. V.; Belyatsky, B. V.; Bayanova, T. B.

2013-02-01

The carbonatites of the Ilmeny-Vishnevogorsky Alkaline Complex (IVAC) are specific in geological and geochemical aspects and differ by some characteristics from classic carbonatites of the zoned alkaline-ultramafic complexes. Geological, geochemical and isotopic data and comparison with relevant experimental systems show that the IVAC carbonatites are genetically related to miaskites, and seem to be formed as a result of separation of carbonatite liquid from a miaskitic magma. Appreciable role of a carbonate fluid is established at the later stages of carbonatite formation. The trace element contents in the IVAC carbonatites are similar to carbonatites of the ultramafic-alkaline complexes. The characteristic signatures of the IVAC carbonatites are a high Sr content, a slight depletion in Ba, Nb, Та, Ti, Zr, and Hf, and enrichment in HREE in comparison with carbonatites of ultramafic-alkaline complexes. This testifies a specific nature of the IVAC carbonatites related to the fractionation of a miaskitic magma and to further Late Paleozoic metamorphism. Isotope data suggest a mantle source for IVAC carbonatites and indicate that moderately depleted mantle and enriched EMI-type components participated in magma generation. The lower crust could have been involved in the generation of the IVAC magma.

Modelling radionuclide transport in fractured media with a dynamic update of K d values

DOE PAGES

Trinchero, Paolo; Painter, Scott L.; Ebrahimi, Hedieh; ...

2015-10-13

Radionuclide transport in fractured crystalline rocks is a process of interest in evaluating long term safety of potential disposal systems for radioactive wastes. Given their numerical efficiency and the absence of numerical dispersion, Lagrangian methods (e.g. particle tracking algorithms) are appealing approaches that are often used in safety assessment (SA) analyses. In these approaches, many complex geochemical retention processes are typically lumped into a single parameter: the distribution coefficient (Kd). Usually, the distribution coefficient is assumed to be constant over the time frame of interest. However, this assumption could be critical under long-term geochemical changes as it is demonstrated thatmore » the distribution coefficient depends on the background chemical conditions (e.g. pH, Eh, and major chemistry). In this study, we provide a computational framework that combines the efficiency of Lagrangian methods with a sound and explicit description of the geochemical changes of the site and their influence on the radionuclide retention properties.« less

Establishing geochemical background levels of selected trace elements in areas having geochemical anomalies: The case study of the Orbetello lagoon (Tuscany, Italy).

PubMed

Romano, Elena; Bergamin, Luisa; Croudace, Ian W; Ausili, Antonella; Maggi, Chiara; Gabellini, Massimo

2015-07-01

The determination of background concentration values (BGVs) in areas, characterised by the presence of natural geochemical anomalies and anthropogenic impact, appears essential for a correct pollution assessment. For this purpose, it is necessary to establish a reliable method for determination of local BGVs. The case of the Orbetello lagoon, a geologically complex area characterized by Tertiary volcanism, is illustrated. The vertical concentration profiles of As, Cd, Cr, Cu, Hg, Ni, Pb and Zn were studied in four sediment cores. Local BGVs were determined considering exclusively samples not affected by anthropogenic influence, recognized by means of multivariate statistics and radiochronological dating ((137)Cs and (210)Pb). Results showed BGVs well-comparable with mean crustal or shale values for most of the considered elements except for Hg (0.87 mg/kg d.w.) and As (16.87 mg/kg d.w.), due to mineralization present in the catchment basin draining into the lagoon. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tracing water and suspended matter in Raritan and Lower New York Bays using dissolved and particulate elemental concentrations

USGS Publications Warehouse

Paulson, A.J.

2005-01-01

The concentrations of 22 elements also were measured in the suspended matter of Raritan and Lower New York Bays and brackish water sources. The elemental composition of the suspended matter in surface and bottom waters was correlated with Fe concentrations, which ranged between 50 and 900 μmol g− 1. Statistical differences among the geographical regions were detected in the relationships of Ti, Ni, Co, As, and U with Fe, with particulate As being an especially strong geochemical indicator of Raritan River particles. The geochemical signatures of Lower New York Bay particles were similar to those of Upper New York Bay. The geochemical signatures of Raritan River particles were distinctly different than those of the Upper New York Bay, but the influence of Raritan River particles appeared to be limited to only inner Raritan Bay. This study illustrates the utility of trace elements for characterization of physical processes in complex estuaries.

Continuum-based DFN-consistent numerical framework for the simulation of oxygen infiltration into fractured crystalline rocks

NASA Astrophysics Data System (ADS)

Trinchero, Paolo; Puigdomenech, Ignasi; Molinero, Jorge; Ebrahimi, Hedieh; Gylling, Björn; Svensson, Urban; Bosbach, Dirk; Deissmann, Guido

2017-05-01

We present an enhanced continuum-based approach for the modelling of groundwater flow coupled with reactive transport in crystalline fractured rocks. In the proposed formulation, flow, transport and geochemical parameters are represented onto a numerical grid using Discrete Fracture Network (DFN) derived parameters. The geochemical reactions are further constrained by field observations of mineral distribution. To illustrate how the approach can be used to include physical and geochemical complexities into reactive transport calculations, we have analysed the potential ingress of oxygenated glacial-meltwater in a heterogeneous fractured rock using the Forsmark site (Sweden) as an example. The results of high-performance reactive transport calculations show that, after a quick oxygen penetration, steady state conditions are attained where abiotic reactions (i.e. the dissolution of chlorite and the homogeneous oxidation of aqueous iron(II) ions) counterbalance advective oxygen fluxes. The results show that most of the chlorite becomes depleted in the highly conductive deformation zones where higher mineral surface areas are available for reactions.

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.

A Mesozoic orogenic cycle from post-collision to subduction in the southwestern Korean Peninsula: New structural, geochemical, and chronological evidence

NASA Astrophysics Data System (ADS)

Park, Seung-Ik; Kwon, Sanghoon; Kim, Sung Won; Hong, Paul S.; Santosh, M.

2018-05-01

The Early to Middle Mesozoic basins, distributed sporadically over the Korean Peninsula, preserve important records of the tectonic history of some of the major orogenic belts in East Asia. Here we present a comprehensive study of the structural, geochemical, geochronological, and paleontological features of a volcano-sedimentary package, belonging to the Oseosan Volcanic Complex of the Early to Middle Mesozoic Chungnam Basin, within the Mesozoic subduction-collision orogen in the southwestern Korean Peninsula. The zircon U-Pb data from rhyolitic volcanic rocks of the complex suggest Early to Middle Jurassic emplacement age of ca. 178-172 Ma, harmonious with plant fossil taxa found from the overlying tuffaceous sedimentary rock. The geochemical data for the rhyolitic volcanic rocks are indicative of volcanic arc setting, implying that the Chungnam Basin has experienced an intra-arc subsidence during the basin-expanding stage by subduction of the Paleo-Pacific (Izanagi) Plate. The Jurassic arc-related Oseosan Volcanic Complex was structurally stacked by the older Late Triassic to Early Jurassic post-collisional basin-fill of the Nampo Group by the Jangsan fault during basin inversion. The Late Jurassic to Early Cretaceous K-feldspar and illite K-Ar ages marked the timing of inversion tectonics, contemporaneous with the magmatic quiescence in the southern Korean Peninsula, likely due to flat-lying or low-angle subduction. The basin evolution history preserved in the Mesozoic Chungnam Basin reflects a Mesozoic orogenic cycle from post-collision to subduction in the southwestern Korean Peninsula. This, in turn, provides a better understanding of the spatial and temporal changes in Mesozoic tectonic environments along the East Asian continental margin.

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.

Parameter Sensitivity and Laboratory Benchmarking of a Biogeochemical Process Model for Enhanced Anaerobic Dechlorination

NASA Astrophysics Data System (ADS)

Kouznetsova, I.; Gerhard, J. I.; Mao, X.; Barry, D. A.; Robinson, C.; Brovelli, A.; Harkness, M.; Fisher, A.; Mack, E. E.; Payne, J. A.; Dworatzek, S.; Roberts, J.

2008-12-01

A detailed model to simulate trichloroethene (TCE) dechlorination in anaerobic groundwater systems has been developed and implemented through PHAST, a robust and flexible geochemical modeling platform. The approach is comprehensive but retains flexibility such that models of varying complexity can be used to simulate TCE biodegradation in the vicinity of nonaqueous phase liquid (NAPL) source zones. The complete model considers a full suite of biological (e.g., dechlorination, fermentation, sulfate and iron reduction, electron donor competition, toxic inhibition, pH inhibition), physical (e.g., flow and mass transfer) and geochemical processes (e.g., pH modulation, gas formation, mineral interactions). Example simulations with the model demonstrated that the feedback between biological, physical, and geochemical processes is critical. Successful simulation of a thirty-two-month column experiment with site soil, complex groundwater chemistry, and exhibiting both anaerobic dechlorination and endogenous respiration, provided confidence in the modeling approach. A comprehensive suite of batch simulations was then conducted to estimate the sensitivity of predicted TCE degradation to the 36 model input parameters. A local sensitivity analysis was first employed to rank the importance of parameters, revealing that 5 parameters consistently dominated model predictions across a range of performance metrics. A global sensitivity analysis was then performed to evaluate the influence of a variety of full parameter data sets available in the literature. The modeling study was performed as part of the SABRE (Source Area BioREmediation) project, a public/private consortium whose charter is to determine if enhanced anaerobic bioremediation can result in effective and quantifiable treatment of chlorinated solvent DNAPL source areas. The modelling conducted has provided valuable insight into the complex interactions between processes in the evolving biogeochemical systems, particularly at the laboratory scale.

A comparison study on detection of key geochemical variables and factors through three different types of factor analysis

NASA Astrophysics Data System (ADS)

Hoseinzade, Zohre; Mokhtari, Ahmad Reza

2017-10-01

Large numbers of variables have been measured to explain different phenomena. Factor analysis has widely been used in order to reduce the dimension of datasets. Additionally, the technique has been employed to highlight underlying factors hidden in a complex system. As geochemical studies benefit from multivariate assays, application of this method is widespread in geochemistry. However, the conventional protocols in implementing factor analysis have some drawbacks in spite of their advantages. In the present study, a geochemical dataset including 804 soil samples collected from a mining area in central Iran in order to search for MVT type Pb-Zn deposits was considered to outline geochemical analysis through various fractal methods. Routine factor analysis, sequential factor analysis, and staged factor analysis were applied to the dataset after opening the data with (additive logratio) alr-transformation to extract mineralization factor in the dataset. A comparison between these methods indicated that sequential factor analysis has more clearly revealed MVT paragenesis elements in surface samples with nearly 50% variation in F1. In addition, staged factor analysis has given acceptable results while it is easy to practice. It could detect mineralization related elements while larger factor loadings are given to these elements resulting in better pronunciation of mineralization.

Cryptotephras: the revolution in correlation and precision dating1

PubMed Central

DAVIES, SIWAN M

2015-01-01

From its Icelandic origins in the study of visible tephra horizons, tephrochronology took a remarkable step in the late 1980 s with the discovery of a ca. 4300-year-old microscopic ash layer in a Scottish peat bog. Since then, the search for these cryptotephra deposits in distal areas has gone from strength to strength. Indeed, a recent discovery demonstrates how a few fine-grained glass shards from an Alaskan eruption have been dispersed more than 7000 km to northern Europe. Instantaneous deposition of geochemically distinct volcanic ash over such large geographical areas gives rise to a powerful correlation tool with considerable potential for addressing a range of scientific questions. A prerequisite of this work is the establishment of regional tephrochronological frameworks that include well-constrained age estimates and robust geochemical signatures for each deposit. With distal sites revealing a complex record of previously unknown volcanic events, frameworks are regularly revised, and it has become apparent that some closely timed eruptions have similar geochemical signatures. The search for unique and robust geochemical fingerprints thus hinges on rigorous analysis by electron microprobe and laser ablation-inductively coupled plasma-mass spectrometry. Historical developments and significant breakthroughs are presented to chart the revolution in correlation and precision dating over the last 50 years using tephrochronology and cryptotephrochronology. PMID:27512240

Advances in the hydrogeochemistry and microbiology of acid mine waters

USGS Publications Warehouse

Nordstrom, D. Kirk

2000-01-01

The last decade has witnessed a plethora of research related to the hydrogeochemistry and microbiology of acid mine waters and associated tailings and waste-rock waters. Numerous books, reviews, technical papers, and proceedings have been published that examine the complex bio-geochemical process of sulfide mineral oxidation, develop and apply geochemical models to site characterization, and characterize the microbial ecology of these environments. This review summarizes many of these recent works, and provides references for those investigating this field. Comparisons of measured versus calculated Eh and measured versus calculated pH for water samples from several field sites demonstrate the reliability of some current geochemical models for aqueous speciation and mass balances. Geochemical models are not, however, used to predict accurately time-dependent processes but to improve our understanding of these systems and to constrain possible processes that contribute to actual or potential water quality issues. Microbiological studies are demonstrating that there is much we have yet to learn about the types of different microorganisms and their function and ecology in mine-waste environments. A broad diversity of green algae, bacteria, archaea, yeasts, and fungi are encountered in acid mine waters, and a better understanding of their ecology and function may potentially enhance remediation possibilities as well as our understanding of the evolution of life.

Mineralogical and Geochemical Trends in a Fluviolacustrine Sequence in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Rampe, E.; Ming, D.; Morris, R.; Blake, D.; Vaniman, D.; Bristow, T.; Chipera, S.; Yen, A.; Grotzinger, J.; DesMarais, D.

2016-01-01

The Mars Science Laboratory rover, Curiosity, landed at Gale crater in August 2012 and has been investigating a sequence of dominantly fluviolacustrine sediments deposited 3.6-3.2 billion years ago. Curiosity collects quantitative mineralogical data with the CheMin XRD/XRF instrument and quantitative chemical data with the APXS and ChemCam instruments. These datasets show stratigraphic mineralogical and geochemical variability that suggest a complex aqueous history. The Murray Formation, primarily composed of fine-laminated mudstone, has been studied in detail since the arrival at the Pahrump Hills in September 2014. CheMin data from four samples show variable amounts of iron oxides, phyllosilicates, sulfates, amorphous and crystalline silica, and mafic silicate minerals. Geochemical data throughout the section show that there is significant variability in Zn, Ni, and Mn concentrations. Mineralogical and geochemical trends with stratigraphy suggest one of possibly several aqueous episodes involved alteration in an open system under acidic pH, though other working hypotheses may explain these and other trends. Data from the Murray Formation contrast with those collected from the Sheepbed mudstone located approximately 60 meters below the base of the Murray Formation, which showed evidence for diagenesis in a closed system at circumneutral pH. Ca-sulfates filled late-stage veins in both mudstones.

Preliminary study of a potential CO2 reservoir area in Hungary

NASA Astrophysics Data System (ADS)

Sendula, Eszter; Király, Csilla; Szabó, Zsuzsanna; Falus, György; Szabó, Csaba; Kovács, István; Füri, Judit; Kónya, Péter; Páles, Mariann; Forray, Viktória

2014-05-01

Since the first international agreement in 1997 (the Kyoto Protocol) the reduction of greenhouse gas emission has a key role in the European Union's energy and climate change policy. Following the Directive 2009/31/EC we are experiencing a significant change in the Hungarian national activity. Since the harmonization procedure, which was completed in May 2012, the national regulation obligates the competent authority to collect and regularly update all geological complexes that are potential for CO2 geological storage. In Hungary the most abundant potential storage formations are mostly saline aquifers of the Great Hungarian Plain (SE-Hungary), with sandstone reservoir and clayey caprock. The Neogene basin of the Great Hungarian Plain was subsided and then filled by a prograding delta system from NW and NE during the Late Miocene, mostly in the Pannonian time. The most potential storage rock was formed as a fine-grained sandy turbidite interlayered by thin argillaceous beds in the deepest part of the basin. It has relatively high porosity, depth and more than 1000 m thickness. Providing a regional coverage for the sandy turbidite, a 400-500 m thick argillaceous succession was formed in the slope environment. The composition, thickness and low permeability is expected to make it a suitable, leakage-safe caprock of the storage system. This succession is underlain by argillaceous rocks that were formed in the basin, far from sediment input and overlain by interfingering siltstone, sandstone and claystone succession formed in delta and shoreline environments and in the alluvial plain. Core samples have been collected from the potential reservoir rock and its cap rock in the Great Hungarian Plain's succession. The water compositions of the studied depth were known from well-log database. Using the information, acquired from these archive documents, we have constructed input data for geochemical modeling in order to to study the effect of pCO2 injection in the potential CO2 storage environment. From the potential reservoir rock samples (sandstone) thin sections were prepared to determine the mineral composition, pore distribution, pore geometry and grain size. The volume ratio of the minerals was calculated using pixel counter. To have more accurate mineral composition, petrographic observation and SEM analyzes have been carried out. The caprock samples involved in the study can be divided into mudstone and aleurolite samples. To determine the mineral composition of these samples, XRD, DTA, FTIR, SEM analysis has been carried out. To obtain a picture about the geochemical behavior of the potential CO2 storage system, geochemical models were made for the reservoir rocks. For the equilibrium geochemical model, PHREEQC 3.0 was used applying LLNL database. The data used in the model are real pore water compositions from the studied area and an average mineral composition based on petrographic microscope and SEM images. In the model we considered the cation-anion ratio (<10%) and the partial pressure of CO2. First of all, we were interested in the direction of the geochemical reactions during an injection process. Present work is focused on the mineralogy of the most potential storage rock and its caprock, and their expectable geochemical reactions for the effect of scCO2.

ARSENIC GEOCHEMICAL BEHAVIOR DURING GROUND WATER-SURFACE WATER INTERACTIONS AT A CONTAMINATED SITE

EPA Science Inventory

Research results will be presented that address arsenic mobilization and cycling mechanisms at a Superfund site in eastern Massachusetts. The site is located in the headwaters of the Aberjona Watershed. In order to support assessments of the risk posed by off-site migration of ar...

Geochemical Evidence for a Terrestrial Magma Ocean

NASA Technical Reports Server (NTRS)

Agee, Carl B.

1999-01-01

The aftermath of phase separation and crystal-liquid fractionation in a magma ocean should leave a planet geochemically differentiated. Subsequent convective and other mixing processes may operate over time to obscure geochemical evidence of magma ocean differentiation. On the other hand, core formation is probably the most permanent, irreversible part of planetary differentiation. Hence the geochemical traces of core separation should be the most distinct remnants left behind in the mantle and crust, In the case of the Earth, core formation apparently coincided with a magma ocean that extended to a depth of approximately 1000 km. Evidence for this is found in high pressure element partitioning behavior of Ni and Co between liquid silicate and liquid iron alloy, and with the Ni-Co ratio and the abundance of Ni and Co in the Earth's upper mantle. A terrestrial magma ocean with a depth of 1000 km will solidify from the bottom up and first crystallize in the perovskite stability field. The largest effect of perovskite fractionation on major element distribution is to decrease the Si-Mg ratio in the silicate liquid and increase the Si-Mg ratio in the crystalline cumulate. Therefore, if a magma ocean with perovskite fractionation existed, then one could expect to observe an upper mantle with a lower than chondritic Si-Mg ratio. This is indeed observed in modern upper mantle peridotites. Although more experimental work is needed to fully understand the high-pressure behavior of trace element partitioning, it is likely that Hf is more compatible than Lu in perovskite-silicate liquid pairs. Thus, perovskite fractionation produces a molten mantle with a higher than chondritic Lu-Hf ratio. Arndt and Blichert-Toft measured Hf isotope compositions of Barberton komatiites that seem to require a source region with a long-lived, high Lu-Hf ratio. It is plausible that that these Barberton komatiites were generated within the majorite stability field by remelting a perovskite-depleted part of the upper mantle transition zone.

Mathematical simulation of water and salt transfer in geosystems of solonetzic soils in the Northern Caspian region

NASA Astrophysics Data System (ADS)

Golovanov, A. I.; Sotneva, N. I.

2009-03-01

The Dzhanybek two-dimensional radial-axial mathematical model was developed for water and salt transfer in geosystems of solonetzic complexes of the Northern Caspian region; the model is capable of considering the geochemical links and revealing the features of migration processes between the conjugated elements of the microcatena. The simulation results suggested that the stabilization of salinization-desalinization processes occurs under stable weather conditions within approximately 100 years. When the weather conditions changed (the total moisture pool of the area increased from 1978), the simulation results indicated a tendency toward salinization of dark-colored soils in microdepressions and removal of salts in the upper 1-m thick soil layer on microhighs and microslopes. Predictions for 2040 showed that a deep accumulation of salts in microdepressions and desalinization of soils of microhighs and microslopes will occur under the current weather conditions. Thus, the changes in the halogeochemical capacity of geosystems of solonetzic complexes primarily depend on the climatic conditions, although the capacity value remains almost constant with increasing total water reserves; the changes occur only between the conjugated soils of solonetzic complexes, which is of great importance for predicting the soil-geochemical status of the entire landscape.

Numerical investigation of coupled density-driven flow and hydrogeochemical processes below playas

NASA Astrophysics Data System (ADS)

Hamann, Enrico; Post, Vincent; Kohfahl, Claus; Prommer, Henning; Simmons, Craig T.

2015-11-01

Numerical modeling approaches with varying complexity were explored to investigate coupled groundwater flow and geochemical processes in saline basins. Long-term model simulations of a playa system gain insights into the complex feedback mechanisms between density-driven flow and the spatiotemporal patterns of precipitating evaporites and evolving brines. Using a reactive multicomponent transport model approach, the simulations reproduced, for the first time in a numerical study, the evaporite precipitation sequences frequently observed in saline basins ("bull's eyes"). Playa-specific flow, evapoconcentration, and chemical divides were found to be the primary controls for the location of evaporites formed, and the resulting brine chemistry. Comparative simulations with the computationally far less demanding surrogate single-species transport models showed that these were still able to replicate the major flow patterns obtained by the more complex reactive transport simulations. However, the simulated degree of salinization was clearly lower than in reactive multicomponent transport simulations. For example, in the late stages of the simulations, when the brine becomes halite-saturated, the nonreactive simulation overestimated the solute mass by almost 20%. The simulations highlight the importance of the consideration of reactive transport processes for understanding and quantifying geochemical patterns, concentrations of individual dissolved solutes, and evaporite evolution.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-10-01

Surface complexation modeling (SCM) has emerged as a powerful tool for simulating heavy metal adsorption processes on the surface of soil solid components under different geochemical conditions. The component additivity (CA) approach is one of the strategies that have been widely used in multicomponent systems. In this study, potentiometric titration, isothermal adsorption, zeta potential measurement, and extended X-ray absorption fine-structure (EXAFS) spectra analysis were conducted to investigate Cd adsorption on 2 : 1 clay mineral montmorillonite, on Gram-positive bacteria Bacillus subtilis, and their mineral-organic composite. We developed constant capacitance models of Cd adsorption on montmorillonite, bacterial cells, and mineral-organic composite. The adsorption behavior of Cd on the surface of the composite was well explained by CA-SCM. Some deviations were observed from the model simulations at pH < 5, where the values predicted by the model were lower than the experimental results. The Cd complexes of X2Cd, SOCd+, R-COOCd+, and R-POCd+ were the predominant species on the composite surface over the pH range of 3 to 8. The distribution ratio of the adsorbed Cd between montmorillonite and bacterial fractions in the composite as predicted by CA-SCM closely coincided with the estimated value of EXAFS at pH 6. The model could be useful for the prediction of heavy metal distribution at the interface of multicomponents and their risk evaluation in soils and associated environments.

Alkanes as Components of Soil Hydrocarbon Status: Behavior and Indication Significance

NASA Astrophysics Data System (ADS)

Gennadiev, A. N.; Zavgorodnyaya, Yu. A.; Pikovskii, Yu. I.; Smirnova, M. A.

2018-01-01

Studies of soils on three key plots with different climatic conditions and technogenic impacts in Volgograd, Moscow, and Arkhangelsk oblasts have showed that alkanes in the soil exchange complex have some indication potential for the identification of soil processes. The following combinations of soil-forming factors and processes have been studied: (a) self-purification of soil after oil pollution; (b) accumulation of hydrocarbons coming from the atmosphere to soils of different land use patterns; and (c) changes in the soil hydrocarbon complex beyond the zone of technogenic impact due to the input of free hydrocarbon-containing gases. At the injection input of hydrocarbon pollutants, changes in the composition and proportions of alkanes allow tracing the degradation trend of pollutants in the soil from their initial content to the final stage of soil self-purification, when the background concentrations of hydrocarbons are reached. Upon atmospheric deposition of hydrocarbons onto the soil, from the composition and mass distribution of alkanes, conclusions can be drawn about the effect of toxicants on biogeochemical processes in the soil, including their manifestation under different land uses. Composition analysis of soil alkanes in natural landscapes can reveal signs of hydrocarbon emanation fluxes in soils. The indication potentials of alkanes in combination with polycyclic aromatic hydrocarbons and other components of soil hydrocarbon complex can also be used for the solution of other soil-geochemical problems.

Changes in sediment-associated trace element concentrations in the Seine river basin (1994-2001)

USGS Publications Warehouse

Meybeck, Michel; Horowitz, A.J.; Grosbois, C.; Gueguen, Y.; ,

2003-01-01

In the 1980's, based on the concentrations of particulate-associated Hg, Cd, Pb, Cu and Zn relative to very low natural background levels, the Seine River Basin was one of the most impacted in the world. Over the past 20 years, there has been a general decline in these elevated concentrations that parallels declines in Paris sewage sludge trace element levels. Within the basin, marked differences in spatial and temporal geochemical patterns have been observed: (1) between major tributaries, (2) between trace elements, and (3) with stream order and population density, all of which illustrate the complexity of the geochemical processes ongoing in the basin.

Pressure dependence of carbonate exchange with [NpO 2(CO 3) 3] 4– in aqueous solutions

DOE PAGES

Pilgrim, Corey D.; Zavarin, Mavrik; Casey, William H.

2016-12-13

Here, the rates of ligand exchange into the geochemically important [NpO 2(CO 3) 3] 4– aqueous complex are measured as a function of pressure in order to complement existing data on the isostructural [UO 2(CO 3) 3] 4– complex. Experiments are conducted at pH conditions where the rate of exchange is independent of the proton concentration. Unexpectedly, the experiments show a distinct difference in the pressure dependencies of rates of exchange for the uranyl and neptunyl complexes.

The Middlesex Fells Volcanic Complex: A Revised Tectonic Model based on Geochronology, Geochemistry, and Field Data

NASA Astrophysics Data System (ADS)

Hampton, R.

2017-12-01

The Boston Bay area is composed of several terranes originating on the paleocontinent of Avalonia, an arc terrane that accreted onto the continent of Laurentia during the Devonian. Included in these terranes is the Middlesex Fells Volcanic Complex, a bimodal complex composed of both intrusive and extrusive igneous rocks. Initial studies suggested that this volcanic complex formed during a rift event as the Avalonian continent separated from its parent continent 700-900 Ma. New geochemical and geochronological data and field relationships observed in this study establishes a new tectonic model. U-Pb laser ablation zircon data on four samples from different units within the complex reveal that the complex erupted 600 Ma. ICP-MS geochemical analysis of the metabasalt member of the complex yield a trace element signature enriched in Rb, Pb, and Sr and depleted in Th, indicating a subduction component to the melt and interpreted as an eruption into a back-arc basin. The felsic units similarly have an arc related signature when plotted on trace element spider diagrams and tectonic discrimination diagrams. Combined with the field relationships, including an erosional unconformity, stratigraphic and intrusional relationships and large faults from episodic extension events, this data suggests that the Middlesex Fells Volcanic Complex was erupted as part of the arc-sequence of Avalonia and as part of the formation of a back-arc basin well after Avalonia separated from its parent continent. This model presents a significantly younger eruption scenario for the Middlesex Fells Volcanics than previously hypothesized and may be used to study and compare to other volcanics from Avalon terranes in localities such as Newfoundland and the greater Boston area.

GEOCHEMICAL AND BIOLOGICAL ASPECTS OF SULFIDE MINERAL DISSOLUTION: LESSONS FROM IRON MOUNTAIN, CALIFORNIA. (R826189)

EPA Science Inventory

Abstract

The oxidative dissolution of sulfide minerals leading to acid mine drainage (AMD) involves a complex interplay between microorganisms, solutions, and mineral surfaces. Consequently, models that link molecular level reactions and the microbial communities that ...

Merging Hydrologic, Geochemical, and Geophysical Approaches to Understand the Regolith Architecture of a Deeply Weathered Piedmont Critical Zone

NASA Astrophysics Data System (ADS)

Cosans, C.; Moore, J.; Harman, C. J.

2017-12-01

Located in the deeply weathered Piedmont in Maryland, Pond Branch has a rich legacy of hydrological and geochemical research dating back to the first geochemical mass balance study published in 1970. More recently, geophysical investigations including seismic and electrical resistivity tomography have characterized the subsurface at Pond Branch and contributed to new hypotheses about critical zone evolution. Heterogeneity in electrical resistivity in the shallow subsurface may suggest disparate flow paths for recharge, with some regions with low hydraulic conductivity generating perched flow, while other hillslope sections recharge to the much deeper regolith boundary. These shallow and deep flow paths are hypothesized to be somewhat hydrologically and chemically connected, with the spatially and temporally discontinuous connections resulting in different hydraulic responses to recharge and different concentrations of weathering solutes. To test this hypothesis, we combined modeling and field approaches. We modeled weathering solutes along the hypothesized flow paths using PFLOTRAN. We measured hydrologic gradients in the hillslopes and riparian zone using piezometer water levels. We collected geochemical data including major ions and silica. Weathering solute concentrations were measured directly in the precipitation, hillslope springs, and the riparian zone for comparison to modeled concentration values. End member mixing methods were used to determine contributions of precipitation, hillslopes, and riparian zone to the stream. Combining geophysical, geochemical, and hydrological methods may offer insights into the source of stream water and controls on chemical weathering. Previous hypotheses that Piedmont critical zone architecture results from a balance of erosion, soil, and weathering front advance rates cannot account for the inverted regolith structure observed through seismic investigations at Pond Branch. Recent alternative hypotheses including weathering along tectonically-induced fractures and weathering front advance have been proposed, but additional data are needed to test them. Developing a thorough, nuanced understanding of the geochemical and hydrological behavior of Pond Branch may help test and refine hypotheses for Piedmont critical zone evolution.

The impact of biostimulation on the fate of sulfate and associated sulfur dynamics in groundwater

NASA Astrophysics Data System (ADS)

Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

2014-08-01

The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides within the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction.

THE IMPACT OF BIOSTIMULATION ON THE FATE OF SULFATE AND ASSOCIATED SULFUR DYNAMICS IN GROUNDWATER

PubMed Central

Miao, Ziheng; Carreón-Diazconti, Concepcion; Carroll, Kenneth C.; Brusseau, Mark L.

2014-01-01

The impact of electron-donor addition on sulfur dynamics for a groundwater system with low levels of metal contaminants was evaluated with a pilot-scale biostimulation test conducted at a former uranium mining site. Geochemical and stable-isotope data collected before, during, and after the test were analyzed to evaluate the sustainability of sulfate reducing conditions induced by the test, the fate of hydrogen sulfide, and the impact on aqueous geochemical conditions. The results of site characterization activities conducted prior to the test indicated the absence of measurable bacterial sulfate reduction. The injection of an electron donor (ethanol) induced bacterial sulfate reduction, as confirmed by an exponential decrease of sulfate concentration in concert with changes in oxidation-reduction potential, redox species, alkalinity, production of hydrogen sulfide, and fractionation of δ34S-sulfate. High, stoichiometrically-equivalent hydrogen sulfide concentrations were not observed until several months after the start of the test. It is hypothesized that hydrogen sulfide produced from sulfate reduction was initially sequestered in the form of iron sulfides until the exhaustion of readily reducible iron oxides associated with the sediment. The fractionation of δ34S for sulfate was atypical, wherein the enrichment declined in the latter half of the experiment. It was conjectured that mixing effects associated with the release of sulfate from sulfate minerals associated with the sediments, along with possible sulfide re-oxidation contributed to this behavior. The results of this study illustrate the biogeochemical complexity that is associated with in-situ biostimulation processes involving bacterial sulfate reduction. PMID:25016586

The Magmatic Structure of Mt. Vesuvius: Isotopic and Thermal Constraints

NASA Astrophysics Data System (ADS)

Civetta, L.; D'Antonio, M.; de Lorenzo, S.; Gasparini, P.

2002-12-01

Mt. Vesuvius is an active volcano famous for the AD 79 eruption that destroyed Pompeii, Herculaneum and Stabiae. Because of the intense urbanization around and on the volcano, the risk today is very high. Therefore, the knowledge of the structure and behavior of the magmatic system is fundamental both for the interpretation of any change in the dynamics of the volcano and for prediction of eruptions. A review of available and new isotopic data on rocks from Mt. Vesuvius, together with mineralogical and geochemical data and recent geophysical results, allow us to constrain a thermal modeling that describes history and present state of Mt. Vesuvius magmatic system. This system is formed by a "deep", complex magmatic reservoir where mantle-derived magmas arrive, stagnate and differentiate. The reservoir extends discontinuously between 10 and 20 km of depth, is hosted in densely fractured crustal rocks, where magmas and crust can interact, and has been fed more than once since 400 ka. The hypothesis of crustal contamination is favored by the high temperatures reached by crustal rocks as a consequence of repetitive intrusions of magma. From the "deep" reservoir magmas of K-basaltic to K-tephritic to K-phonotephritic composition rise to shallow depths where they stagnate at 3-5 km of depth before plinian eruptions, and through crystallization and mixing processes with the residual portion of the feeding systems, generate isotopically and geochemically layered reservoirs. Alternatively, during "open conduit" conditions deep, volatile-rich magma batches rise from the "deep" reservoir to less than 1 km of depth and mix with the crystal-rich, volatile-poor resident magma, triggering eruptions.

Trace elements at the intersection of marine biological and geochemical evolution

USGS Publications Warehouse

Robbins, Leslie J.; Lalonde, Stefan V.; Planavsky, Noah J.; Partin, Camille A.; Reinhard, Christopher T.; Kendall, Brian; Scott, Clinton T.; Hardisty, Dalton S.; Gill, Benjamin C.; Alessi, Daniel S.; Dupont, Christopher L.; Saito, Mak A.; Crowe, Sean A.; Poulton, Simon W.; Bekker, Andrey; Lyons, Timothy W.; Konhauser, Kurt O.

2016-01-01

Life requires a wide variety of bioessential trace elements to act as structural components and reactive centers in metalloenzymes. These requirements differ between organisms and have evolved over geological time, likely guided in some part by environmental conditions. Until recently, most of what was understood regarding trace element concentrations in the Precambrian oceans was inferred by extrapolation, geochemical modeling, and/or genomic studies. However, in the past decade, the increasing availability of trace element and isotopic data for sedimentary rocks of all ages has yielded new, and potentially more direct, insights into secular changes in seawater composition – and ultimately the evolution of the marine biosphere. Compiled records of many bioessential trace elements (including Ni, Mo, P, Zn, Co, Cr, Se, and I) provide new insight into how trace element abundance in Earth's ancient oceans may have been linked to biological evolution. Several of these trace elements display redox-sensitive behavior, while others are redox-sensitive but not bioessential (e.g., Cr, U). Their temporal trends in sedimentary archives provide useful constraints on changes in atmosphere-ocean redox conditions that are linked to biological evolution, for example, the activity of oxygen-producing, photosynthetic cyanobacteria. In this review, we summarize available Precambrian trace element proxy data, and discuss how temporal trends in the seawater concentrations of specific trace elements may be linked to the evolution of both simple and complex life. We also examine several biologically relevant and/or redox-sensitive trace elements that have yet to be fully examined in the sedimentary rock record (e.g., Cu, Cd, W) and suggest several directions for future studies.

Release behavior of uranium in uranium mill tailings under environmental conditions.

PubMed

Liu, Bo; Peng, Tongjiang; Sun, Hongjuan; Yue, Huanjuan

2017-05-01

Uranium contamination is observed in sedimentary geochemical environments, but the geochemical and mineralogical processes that control uranium release from sediment are not fully appreciated. Identification of how sediments and water influence the release and migration of uranium is critical to improve the prevention of uranium contamination in soil and groundwater. To understand the process of uranium release and migration from uranium mill tailings under water chemistry conditions, uranium mill tailing samples from northwest China were investigated with batch leaching experiments. Results showed that water played an important role in uranium release from the tailing minerals. The uranium release was clearly influenced by contact time, liquid-solid ratio, particle size, and pH under water chemistry conditions. Longer contact time, higher liquid content, and extreme pH were all not conducive to the stabilization of uranium and accelerated the uranium release from the tailing mineral to the solution. The values of pH were found to significantly influence the extent and mechanisms of uranium release from minerals to water. Uranium release was monitored by a number of interactive processes, including dissolution of uranium-bearing minerals, uranium desorption from mineral surfaces, and formation of aqueous uranium complexes. Considering the impact of contact time, liquid-solid ratio, particle size, and pH on uranium release from uranium mill tailings, reducing the water content, decreasing the porosity of tailing dumps and controlling the pH of tailings were the key factors for prevention and management of environmental pollution in areas near uranium mines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

USGS Publications Warehouse

Davis, J.A.; Gloor, R.

1981-01-01

Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (Mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the Mr range 1000 < Mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes. surface, the present work will focus on the influence of molecular size and pH on the adsorption behavior of dissolved organic material of a Swiss lake. From a geochemical point of view, it is important to know the molecular-weight distribution of adsorbed organic matter so that we may better assess its reactivity with trace elements. The study also serves as a first step in quantifying the role of adsorption in the geochemical cycle of organic carbon in lacustrine environments. For water-treatment practice, we need to determine whether molecular weight fractionation occurs during adsorption by aluminum oxide. Such a fractionation could be significant in the light of recent reports that chloroform and other organochlorine compounds are preferentially produced by particular molecular-weight fractions (25-27). ?? 1981 American Chemical Society.

Geochemistry of serpentinites in subduction zones: A review

NASA Astrophysics Data System (ADS)

Deschamps, Fabien; Godard, Marguerite; Guillot, Stéphane; Hattori, Kéiko

2013-04-01

Over the last decades, numerous studies have emphasized the role of serpentinites in the subduction zones geodynamics. Their presence and effective role in this environment is acknowledged notably by geophysical, geochemical and field observations of (paleo-) subduction zones. In this context, with the increasing amount of studies concerning serpentinites in subduction environments, a huge geochemical database was created. Here, we present a review of the geochemistry of serpentinites, based on the compilation of ~ 900 geochemical analyses of abyssal, mantle wedge and subducted serpentinites. The aim was to better understand the geochemical evolution of these rocks during their subduction history as well as their impact in the global geochemical cycle. When studying serpentinites, it is often a challenge to determine the nature of the protolith and their geological history before serpentinisation. The present-day (increasing) geochemical database for serpentinites indicates little to no mobility of incompatible elements at the scale of the hand-sample in most serpentinized peridotites. Thus, Rare Earth Elements (REE) distribution can be used to identify the initial protolith for abyssal and mantle wedge serpentinites, as well as magmatic processes such as melt/rock interactions taking place before serpentinisation. In the case of subducted serpentinites, the interpretation of trace element data is more difficult due to secondary enrichments independent of the nature of the protolith, notably in (L)REE. We propose that these enrichments reflect complex interactions probably not related to serpentinisation itself, but mostly to fluid/rock or sediment/rock interactions within the subduction channel, as well as intrinsic feature of the mantle protolith which could derive from the continental lithosphere exhumed at the ocean-continent transition. Additionally, during the last ten years, numerous studies have been carried out, notably using in situ approaches, to better constrain the geochemical budget of fluid-mobile elements (FME; e.g. B, Li, Cl, As, Sb, U, Th, Sr) stored in serpentinites and serpentine phases. These elements are good markers of the fluid/rock interactions taking place during serpentinisation. Today, the control of serpentinites on the behaviour of these elements, from their incorporation to their gradually release during subduction, is better understood. Serpentinites must be considered as a component of the FME budget in subduction zones and their role, notably on arc magmas composition, is undoubtedly underestimated presently in the global geochemical cycle.

Leaching and geochemical behavior of fired bricks containing coal wastes.

PubMed

Taha, Yassine; Benzaazoua, Mostafa; Edahbi, Mohamed; Mansori, Mohammed; Hakkou, Rachid

2018-03-01

High amounts of mine wastes are continuously produced by the mining industry all over the world. Recycling possibility of some wastes in fired brick making has been investigated and showed promising results. However, little attention is given to the leaching behavior of mine wastes based fired bricks. The objective of this paper is to evaluate the geochemical behavior of fired bricks containing different types of coal wastes. The leachates were analyzed for their concentration of As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Zn and sulfates using different leaching tests; namely Tank Leaching tests (NEN 7375), Toxicity Characteristic Leaching Procedure (TCLP) and pH dependence test (EPA, 1313). The results showed that the release of constituents of potential interest was highly reduced after thermal treatment and were immobilized within the glassy matrix of the fired bricks. Moreover, it was also highlighted that the final pH of all fired samples changed and stabilized around 8-8.5 when the initial pH of leaching solution was in the range 2.5-11.5. The release of heavy metals and metalloids (As) tended to decrease with the increase of pH from acidic to alkaline solutions while Mo displayed a different trend. Copyright © 2017 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leggett, Rich

The transition metal yttrium (Y, atomic number 39) is chemically similar to elements in the lanthanide family (atomic numbers 57-71, lanthanum through lutetium) and is always present with the lanthanides in rare earth ores. Yttrium and the lanthanide holmium are particularly close chemical and physical analogues and are referred to as geochemical twins because they typically show little fractionation in geological material. Extensive measurements on rocks, soils, and meteorites indicate that the Y/Ho mass concentration ratio rarely falls far from the “chondritic” or “solar system” ratio of ~26. Our paper presents a new biokinetic model for yttrium in adult humansmore » and examines whether yttrium and holmium may be biological as well as geochemical twins. Collected data on yttrium and holmium in plants and human tissues do not allow precise derivations of Y/Ho concentration ratios but with occasional exceptions yield ratios that are reasonably consistent with chondritic values. Predictions of the time-dependent behavior of yttrium in adult humans based on the yttrium model presented here closely approximate predictions of the behavior of holmium based on a previously developed model for holmium. We know that yttrium and holmium are close biological analogues, but the available comparative data are too limited and imprecise to reveal whether there are any significant differences in their biological behavior.« less

Reactive transport simulation via combination of a multiphase-capable transport code for unstructured meshes with a Gibbs energy minimization solver of geochemical equilibria

NASA Astrophysics Data System (ADS)

Fowler, S. J.; Driesner, T.; Hingerl, F. F.; Kulik, D. A.; Wagner, T.

2011-12-01

We apply a new, C++-based computational model for hydrothermal fluid-rock interaction and scale formation in geothermal reservoirs. The model couples the Complex System Modelling Platform (CSMP++) code for fluid flow in porous and fractured media (Matthai et al., 2007) with the Gibbs energy minimization numerical kernel GEMS3K of the GEM-Selektor (GEMS3) geochemical modelling package (Kulik et al., 2010) in a modular fashion. CSMP++ includes interfaces to commercial file formats, accommodating complex geometry construction using CAD (Rhinoceros) and meshing (ANSYS) software. The CSMP++ approach employs finite element-finite volume spatial discretization, implicit or explicit time discretization, and operator splitting. GEMS3K can calculate complex fluid-mineral equilibria based on a variety of equation of state and activity models. A selection of multi-electrolyte aqueous solution models, such as extended Debye-Huckel, Pitzer (Harvie et al., 1984), EUNIQUAC (Thomsen et al., 1996), and the new ELVIS model (Hingerl et al., this conference), makes it well-suited for application to a wide range of geothermal conditions. An advantage of the GEMS3K solver is simultaneous consideration of complex solid solutions (e.g., clay minerals), gases, fluids, and aqueous solutions. Each coupled simulation results in a thermodynamically-based description of the geochemical and physical state of a hydrothermal system evolving along a complex P-T-X path. The code design allows efficient, flexible incorporation of numerical and thermodynamic database improvements. We demonstrate the coupled code workflow and applicability to compositionally and physically complex natural systems relevant to enhanced geothermal systems, where temporally and spatially varying chemical interactions may take place within diverse lithologies of varying geometry. Engesgaard, P. & Kipp, K. L. (1992). Water Res. Res. 28: 2829-2843. Harvie, C. E.; Møller, N. & Weare, J. H. (1984). Geochim. Cosmochim. Acta 48: 723-751. Kulik, D. A., Wagner, T., Dmytrieva S. V, et al. (2010). GEM-Selektor home page, Paul Scherrer Institut. Available at http://gems.web.psi.ch. Matthäi, S. K., Geiger, S., Roberts, S. G., Paluszny, A., Belayneh, M., Burri, A., Mezentsev, A., Lu, H., Coumou, D., Driesner, T. & Heinrich C. A. (2007). Geol. Soc. London, Spec. Publ. 292: 405-429. Thomsen, K. Rasmussen, P. & Gani, R. (1996). Chem. Eng. Sci. 51: 3675-3683.

Integrating surrogate models into subsurface simulation framework allows computation of complex reactive transport scenarios

NASA Astrophysics Data System (ADS)

De Lucia, Marco; Kempka, Thomas; Jatnieks, Janis; Kühn, Michael

2017-04-01

Reactive transport simulations - where geochemical reactions are coupled with hydrodynamic transport of reactants - are extremely time consuming and suffer from significant numerical issues. Given the high uncertainties inherently associated with the geochemical models, which also constitute the major computational bottleneck, such requirements may seem inappropriate and probably constitute the main limitation for their wide application. A promising way to ease and speed-up such coupled simulations is achievable employing statistical surrogates instead of "full-physics" geochemical models [1]. Data-driven surrogates are reduced models obtained on a set of pre-calculated "full physics" simulations, capturing their principal features while being extremely fast to compute. Model reduction of course comes at price of a precision loss; however, this appears justified in presence of large uncertainties regarding the parametrization of geochemical processes. This contribution illustrates the integration of surrogates into the flexible simulation framework currently being developed by the authors' research group [2]. The high level language of choice for obtaining and dealing with surrogate models is R, which profits from state-of-the-art methods for statistical analysis of large simulations ensembles. A stand-alone advective mass transport module was furthermore developed in order to add such capability to any multiphase finite volume hydrodynamic simulator within the simulation framework. We present 2D and 3D case studies benchmarking the performance of surrogates and "full physics" chemistry in scenarios pertaining the assessment of geological subsurface utilization. [1] Jatnieks, J., De Lucia, M., Dransch, D., Sips, M.: "Data-driven surrogate model approach for improving the performance of reactive transport simulations.", Energy Procedia 97, 2016, p. 447-453. [2] Kempka, T., Nakaten, B., De Lucia, M., Nakaten, N., Otto, C., Pohl, M., Chabab [Tillner], E., Kühn, M.: "Flexible Simulation Framework to Couple Processes in Complex 3D Models for Subsurface Utilization Assessment.", Energy Procedia, 97, 2016 p. 494-501.

Formation of environmentally persistent free radicals as the mechanism for reduced catechol degradation on hematite-silica surface under UV irradiation.

PubMed

Li, Hao; Pan, Bo; Liao, Shaohua; Zhang, Di; Xing, Baoshan

2014-05-01

Iron is rich in soils, and is recently reported to form stable complexes with organic free radicals, generating environmentally persistent free radicals (EPFRs). The observation may challenge the common viewpoint that iron is an effective catalyst to facilitate the degradation of various organic chemicals. But no study was specifically designed to investigate the possible inhibited degradation of organic chemicals because of the formation of EPFRs in dry environment. We observed that catechol degradation under UV irradiation was decreased over 20% in silica particles coated with 1% hematite in comparison to uncoated silica particles. Stabilized semiquinone or quinine and phenol radicals were involved in HMT-silica system. EPFR formation was thus the reason for the reduced catechol degradation on HMT-silica surface under UV irradiation at ambient temperature. EPFRs should be incorporated in the studies of organic contaminants geochemical behavior, and will be a new input in their environmental fate modeling. Copyright © 2014 Elsevier Ltd. All rights reserved.

The late Archean Schreiber Hemlo and White River Dayohessarah greenstone belts, Superior Province: collages of oceanic plateaus, oceanic arcs, and subduction accretion complexes

NASA Astrophysics Data System (ADS)

Polat, A.; Kerrich, R.; Wyman, D. A.

1998-04-01

The late Archean (ca. 2.80-2.68 Ga) Schreiber-Hemlo and White River-Dayohessarah greenstone belts of the Superior Province, Canada, are supracrustal lithotectonic assemblages of ultramafic to tholeiitic basalt ocean plateau sequences, and tholeiitic to calc-alkaline volcanic arc sequences, and siliciclastic turbidites, collectively intruded by arc granitoids. The belts have undergone three major phases of deformation; two probably prior to, and one during the assembly of the southern Superior Province. Imbricated lithotectonic assemblages are often disrupted by syn-accretion strike-slip faults, suggesting that strike-slip faulting was an important aspect of greenstone belt evolution. Field relations, structural characteristics, and high-precision ICP-MS trace-element data obtained for representative lithologies of the Schreiber-Hemlo and White River-Dayohessarah greenstone belts suggest that they represent collages of oceanic plateaus, juvenile oceanic island arcs, in subduction-accretion complexes. Stratigraphic relationships, structural, and geochemical data from these Archean greenstone belts are consistent with a geodynamic evolution commencing with the initiation of a subduction zone at the margins of an oceanic plateau, similar to the modern Caribbean oceanic plateau and surrounding subduction-accretion complexes. All supracrustal assemblages include both ocean plateau and island-arc geochemical characteristics. The structural and geochemical characteristics of vertically and laterally dismembered supracrustal units of the Schreiber-Hemlo and White River-Dayohessarah greenstone belts cannot be explained either by a simple tectonic juxtaposition of lithotectonic assemblages with stratified volcanic and sedimentary units, or cyclic mafic to felsic bimodal volcanism models. A combination of out-of-sequence thrusting, and orogen-parallel strike-slip faulting of accreted ocean plateaus, oceanic arcs, and trench turbidites can account for the geological and geochemical characteristics of these greenstone belts. Following accretion, all supracrustal assemblages were multiply intruded by syn- to post-tectonic high-Al, and high-La/Yb n slab-derived trondhjemite-tonalite-granodiorite (TTG) plutons. The amalgamation processes of these lithotectonic assemblages are comparable to those of Phanerozoic subduction-accretion complexes, such as the Circum-Pacific, the western North American Cordilleran, and the Altaid orogenic belts, suggesting that subduction-accretion processes significantly contributed to the growth of the continental crust in the late Archean. The absence of blueschist and eclogite facies metamorphic rocks in Archean subduction-accretion complexes may be attributed to elevated thermal gradients and shallow-angle subduction. The melting of a hotter Archean mantle at ridges and in plumes would generate relatively small, hot, and hence shallowly subducting oceanic plates, promoting high-temperature metamorphism, migmatization, and slab melting. Larger, colder, Phanerozoic plates typically subduct at a steeper angle, generating high-pressure low-temperature conditions for blueschists and eclogites in the subduction zones, and low-La/Yb n granitoids from slab dehydration, and wedge melting. Metasedimentary subprovinces in the Superior Province, such as the Quetico and English River Subprovinces, have formerly been interpreted as accretionary complexes, outboard of the greenstone belt magmatic arcs. Here the greenstone-granitoid subprovinces are interpreted as collages of subduction-accretion complexes, island arcs and oceanic plateaus amalgamated at convergent plate margins, and the neighbouring metasedimentary subprovinces as foreland basins.

Using multifractal modeling as a standard tool in geochemical exploration for predicting mineralized areas

NASA Astrophysics Data System (ADS)

Gonçalves, Mario A.

2015-04-01

It has been 20 years since the pioneering work of Cheng et al (1994) first proposed a quantitative relationship for the areas enclosing concentration values of an element above given thresholds and their distribution in the field, known as concentration-area (CA) method, which is based in multifractal theory. The method allows the definition of geochemical anomalies in wide set of geological backgrounds but it took nearly 15 years before it became a widely used methodology for mineral exploration. The method was also extended to 1D and 3D data sets. It is worth noting the variety of methods that spanned from the theory of fractals. Building on previous models, including multiplicative cascades and size-grade relationships, increasing evidence points to the powerful tools of fractal theory to describe and model ore deposit distribution and formation. However, while much of these approaches become complex and not easy to use, the CA method is remarkable for its utter simplicity and disarming results obtained when confronted with the geological reality in the field. This is most valued by companies and professionals undertaking geochemical exploration surveys for the characterization or refining of potential ore targets or known mineralized areas. Several approaches have combined the CA method with geostatistic modeling and simulation and other established statistical techniques in order to enhance anomalous threshold identification. Examples are not restricted to geochemical exploration alone, other applications being studies on environmental change. Some of these examples will be addressed as they have been applied to different regions in the world, but particular emphasis will be put on geochemical exploration surveys in different geotectonic units of the Variscan basement in the Iberian Peninsula. These include quartz-vein gold mineralization in Northern Portugal and several surveys for base metals over two wide areas, which served to re-evaluate much of the scattered geochemical data sets that have been accumulating for decades of mining exploration in Southern Portugal. The studied zones include: the tectonic controlled quartz-vein Au-Sb mineralizations, the gabbroic and ultramafic complex of the southern border of the Ossa-Morena Zone, and the rocks belonging to the World-class massive sulfide province, the Iberian Pyrite Belt (IPB). The methodology used the CA method but also variogram analysis and modelling to outline and classify different sets of mineral deposits before confirmation in the field. This diversity of geologic contexts serves to show how effective and powerful the CA method can be, since it not only enhances already known mineralizations, it allowed the screening and identification of several new mineralized spots that have been previously overlooked. This has been of particularly economic importance because a major re-analysis of data and new exploration campaigns are currently under way for the next years in the IPB, with the potential for opening a new paradigm in the exploration for massive sulfide deposits in the region. Cheng et al, 1994, J. Geochem. Explor., 51, 109.

Three Techniques to Help Students Teach Themselves Concepts in Environmental Geochemistry.

ERIC Educational Resources Information Center

Brown, I. Foster

1984-01-01

Describes techniques in which students learn to: (1) create elemental "fairy tales" based on the geochemical behavior of elements and on imagination to integrate concepts; (2) to visually eliminate problems of bias; and (3) to utilize multiple working hypotheses as a basis for testing concepts of classification and distinguishing…

LONG-TERM GEOCHEMICAL BEHAVIOR OF A ZEROVALENT IRON PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM IN GROUNDWATER

EPA Science Inventory

Passive, in-situ reactive barriers have proven to be viable, cost-effective systems for the remediation of Cr-contaminated groundwater at some sites. Permeable reactive barriers (PRBs) are installed in the flow-path of groundwater, most typically as vertical treatment walls. Re...

Geochemical behavior of ultramafic waste rocks with carbon sequestration potential: a case study of the Dumont Nickel Project, Amos, Québec.

PubMed

Kandji, El Hadji Babacar; Plante, Benoit; Bussière, Bruno; Beaudoin, Georges; Dupont, Pierre-Philippe

2017-04-01

The geochemical behavior of ultramafic waste rocks and the effect of carbon sequestration by these waste rocks on the water drainage quality were investigated using laboratory-scale kinetic column tests on samples from the Dumont Nickel Project (RNC Minerals, QC, Canada). The test results demonstrated that atmospheric CO 2 dissolution induced the weathering of serpentine and brucite within the ultramafic rocks, generating high concentrations of Mg and HCO 3 - with pH values ranging between 9 and 10 in the leachates that promote the precipitation of secondary Mg carbonates. These alkaline pH values appear to have prevented the mobilization of many metals; Fe, Ni, Cu, and Zn were found at negligible concentrations in the leachates. Posttesting characterization using chemical analyses, diffuse reflectance infrared Fourier transform (DRIFT), and scanning electron microscope (SEM) observations confirmed the precipitation of secondary hydrated Mg carbonates as predicted by thermodynamic calculations. The formation of secondary Mg carbonates induced cementation of the waste particles, resulting in the development of a hardpan.

The chemical behavior of the transuranic elements and the barrier function in natural aquifer systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jewett, J.R.

1997-09-17

In a geological repository for long-lived radioactive wastes, such as actinides and certain fission products, most of the stored radionuclides remain immobile in the particular geological formation. If any of these could possibly become mobile, only trace concentrations of a few radionuclides would result. Nevertheless, with an inventory in the repository of many tonnes of transuranic elements, the amounts that could disperse cannot be neglected. A critical assessment of the chemical behavior of these nuclides, especially their migration properties in the aquifer system around the repository site, is mandatory for analysis of the long-term safety. The chemistry requited for thismore » includes many geochemical multicomponent reactions that are so far only partially understood and [which] therefore can be quantified only incompletely. A few of these reactions have been discussed in this paper based on present knowledge. If a comprehensive discussion of the subject is impossible because of this [lack of information], then an attempt to emphasize the importance of the predominant geochemical reactions of the transuranic elements in various aquifer systems should be made.« less

The role of the U.S. Geological Survey in the lithium industry

USGS Publications Warehouse

Vine, J.D.

1978-01-01

The U.S. Geological Survey has responsibility in the U.S. Department of the Interior to assess the nation's energy and mineral resources. The evaluation of reserves and resources of a commodity such as lithium should be a continuing process in the light of advancing technology and ever-growing knowledge of its geologic occurrence and geochemical behavior. Although reserves of lithium vary with market demand because of the investment required to find, develop, and appraise an ore body, total resources are a function of the geologic occurrence and geochemical behavior of lithium. By studying known deposits and publishing data on their origin and occurrence, the U.S. Geological Survey can aid in the discovery of new deposits and improve the resource base. Resource data are used both by the government and the private sector. Government funding for research on energy-related technologies such as electric vehicle batteries and fusion power requires assurance that there will be enough lithium available in time for commercialization. Questions of availability for all mineral commodities must be answered by the U.S. Geological Survey so that intelligent decisions can be made. ?? 1978.

Geochemical behavior, environmental availability, and reconstruction of historical trends of Cu, Pb, and Zn in sediment cores of the Cananéia-Iguape coastal system, Southeastern Brazil.

PubMed

Tramonte, Keila Modesto; Figueira, Rubens Cesar Lopes; Majer, Alessandra Pereira; de Lima Ferreira, Paulo Alves; Batista, Miriam Fernanda; Ribeiro, Andreza Portella; de Mahiques, Michel Michaelovitch

2018-02-01

The Cananéia-Iguape system is located in a coastal region of southeastern Brazil, recognized by UNESCO as an Atlantic Forest Biosphere Reserve. This system has suffered substantial environmental impacts due to the opening of an artificial channel and by past intensive mining activities. In this paper was performed the sequential chemical extraction of Cu, Pb, and Zn, on previously described sediment cores, and the statistical treatment of the data, allowing to estimate the remobilization geochemical behavior, the available content and the trend of accumulation between 1926 and 2008. The maximum available level (sum of all mobile fraction) were, in mgkg -1 , 18.74 for Cu, 177.55 for Pb and 123.03 for Zn. Considering its environmental availability, Pb remains a concern in the system. It was possible to recognize the anthropic contribution of Pb, being the mining activities considered the only potential source of this metal in the region. Copyright © 2017 Elsevier Ltd. All rights reserved.

THE INTERPLAY BETWEEN GEOCHEMICAL REACTIONS AND ADVECTION-DISPERSION IN CONTAMINANT TRANSPORT AT A URANIUM MILL TAILINGS SITE

EPA Science Inventory

It is well known that the fate and transport of contaminants in the subsurface are controlled by complex processes including advection, dispersion-diffusion, and chemical reactions. However, the interplay between the physical transport processes and chemical reactions, and their...

The formation and stability of saline minerals at the Martian surface

NASA Astrophysics Data System (ADS)

Tosca, Nicholas James, III

Evaporite minerals have been identified throughout the martian sedimentary record. Because evaporites can record detailed paleo-environmental information and often host fossil biosignatures on Earth, they are priority targets for future exploration. However, understanding processes that control the formation of these minerals on Mars requires an understanding of the behavior of Fe in highly concentrated evaporating fluids. In this study, a model is developed using the Pitzer ion interaction approach that accurately describes thermodynamic properties of the Fe2(SO4)3-H2SO4-H 2O system. Incorporating this model into a multicomponent thermodynamic database enables detailed study of evaporite mineral formation and stability on Mars. From geochemical modeling, the variation in evaporite mineralogy on Mars may be traced to volatile-anion input -- a variable intimately tied to pH. Using the "chemical divide" concept, evaporites at the martian surface can be used as sensitive probes of pH, atmospheric composition, and cation proportion in solution. Applying this approach to saline assemblages in Nakhlite meteorites and in Meridiani Planum sediments reveals two geochemical systems; each characterized by different pH and anion proportion. A complicating factor however is the concomitant oxidation of soluble Fe-bearing minerals. Such a process may have contributed to complex Fe mineralogy observed at Meridiani Planum through diagenesis. Fe-oxidation experiments at high ionic strength show a progression of mineral phases that begins with the formation of schwertmannite and subsequent ageing to jarosite and nano-crystalline goethite; a process strongly controlled by pH. Low water activity and small particle size drive the ageing of goethite to hematite which provides the final step of a mechanism that is consistent with the distribution of Fe-minerals at Meridiani Planum. These results show that the instability of Fe2+-sulfate minerals at the martian surface may lead to the association of Fe-oxide and Fe-hydroxysulfate minerals with evaporite salts. Indeed, such a geologic association has been observed through remote sensing techniques. Thus, as the Fe-sulfates are sensitive to pH, Fe-oxidation and relative humidity, understanding these phase relationships in greater detail will ultimately exploit the presence of these minerals as a unique set of geochemical probes.

Influence of hydrological and geochemical processes on the transport of chelated metals and chromate in fractured shale bedrock

NASA Astrophysics Data System (ADS)

Jardine, P. M.; Mehlhorn, T. L.; Larsen, I. L.; Bailey, W. B.; Brooks, S. C.; Roh, Y.; Gwo, J. P.

2002-03-01

Field-scale processes governing the transport of chelated radionuclides in groundwater remain conceptually unclear for highly structured, heterogeneous environments. The objectives of this research were to provide an improved understanding and predictive capability of the hydrological and geochemical mechanisms that control the transport behavior of chelated radionuclides and metals in anoxic subsurface environments that are complicated by fracture flow and matrix diffusion. Our approach involved a long-term, steady-state natural gradient field experiment where nonreactive Br - and reactive 57Co(II)EDTA 2-, 109CdEDTA 2-, and 51Cr(VI) were injected into a fracture zone of a contaminated fractured shale bedrock. The spatial and temporal distribution of the tracer and solutes was monitored for 500 days using an array of groundwater sampling wells instrumented within the fast-flowing fracture regime and a slower flowing matrix regime. The tracers were preferentially transported along strike-parallel fractures coupled with the slow diffusion of significant tracer mass into the bedrock matrix. The chelated radionuclides and metals were significantly retarded by the solid phase with the mechanisms of retardation largely due to redox reactions and sorption coupled with mineral-induced chelate-radionuclide dissociation. The formation of significant Fe(III)EDTA - byproduct that accompanied the dissociation of the radionuclide-chelate complexes was believed to be the result of surface interactions with biotite which was the only Fe(III)-bearing mineral phase present in these Fe-reducing environments. These results counter current conceptual models that suggest chelated contaminants move conservatively through Fe-reducing environments since they are devoid of Fe-oxyhydroxides that are known to aggressively compete for chelates in oxic regimes. Modeling results further demonstrated that chelate-radionuclide dissociation reactions were most prevalent along fractures where accelerated weathering processes are expected to expose more primary minerals than the surrounding rock matrix. The findings of this study suggest that physical retardation mechanisms (i.e. diffusion) are dominant within the matrix regime, whereas geochemical retardation mechanisms are dominant within the fracture regime.

Constraints on the Amount of deeply subducted Water from numerical Models in comparison with natural Samples

NASA Astrophysics Data System (ADS)

Konrad-Schmolke, M.; Halama, R.

2014-12-01

The subduction of hydrated slab mantle to beyond-arc depths is the most important and yet weakly constrained factor in the quantification of the Earth's deep geologic water cycle. During subduction of hydrated oceanic lithosphere, dehydration reactions in the downgoing plate lead to a partitioning of water between upper and lower plate. Water retained in the slab is recycled into the mantle where it controls its rheology and thus plate tectonic velocities. Hence, quantification of the water partitioning in subduction zones is crucial for the understanding of mass transfer between the Earth's surface and the mantle. Combined thermomechanical and thermodynamic models yield quantitative constraints on the water cycle in subduction zones, but unless model results can be linked to natural observations, the reliability of such models remains speculative. We present combined thermomechanical, thermodynamic and geochemical models of active and paleo-subduction zones, whose results can be tested with independent geochemical features in natural rocks. In active subduction zones, evidence for the validity of our model comes from the agreement between modeled and observed across-arc trends of boron concentrations and isotopic compositions in arc volcanic rocks. In the Kamchatkan subduction zone, for example, the model successfully predicts complex geochemical patterns and the spatial distribution of arc volcanoes. In paleo-subduction zones (e.g. Western Gneiss Region and Western Alps), constraints on the water budget and dehydration behavior of the subducting slab come from trace element zoning patterns in ultra-high pressure (UHP) garnets. Distinct enrichments of Cr, Ni and REE in the UHP zones of the garnets can be reconciled by our models that predict intense rehydration and trace element re-enrichment of the eclogites at UHP conditions by fluids released from the underlying slab mantle. Models of present-day subduction zones indicate the presence of 2.5-6 wt.% of water within the uppermost 15 km of the subducted slab mantle. Depending on hydration depth, between 25 and 90% of this water is recycled into the deeper mantle. The Lower Devonian example from the Western Gneiss Region indicates that subduction of water into the Earth's deeper mantle is an active process at least since the middle Paleozoic.

Estimation of palaeohydrochemical conditions using carbonate minerals

NASA Astrophysics Data System (ADS)

Amamiya, H.; Mizuno, T.; Iwatsuki, T.; Yuguchi, T.; Murakami, H.; Saito-Kokubu, Y.

2014-12-01

The long-term evolution of geochemical environment in deep underground is indispensable research subject for geological disposal of high-level radioactive waste, because the evolution of geochemical environment would impact migration behavior of radionuclides in deep underground. Many researchers have made efforts previously to elucidate the geochemical environment within the groundwater residence time based on the analysis of the actual groundwater. However, it is impossible to estimate the geochemical environment for the longer time scale than the groundwater residence time in this method. In this case, analysis of the chemical properties of secondary minerals are one of useful method to estimate the paleohydrochemical conditions (temperature, salinity, pH and redox potential). In particular, carbonate minerals would be available to infer the long-term evolution of hydrochemical for the following reasons; -it easily reaches chemical equilibrium with groundwater and precipitates in open space of water flowing path -it reflects the chemical and isotopic composition of groundwater at the time of crystallization We reviewed the previous studies on carbonate minerals and geochemical conditions in deep underground and estimated the hydrochemical characteristics of past groundwater by using carbonate minerals. As a result, it was found that temperature and salinity of the groundwater during crystallization of carbonate minerals were evaluated quantitatively. On the other hand, pH and redox potential can only be understood qualitatively. However, it is suggested that the content of heavy metal elements such as manganese, iron and uranium, and rare earth elements in the carbonate minerals are useful indicators for estimating redox potential. This study was carried out under a contract with METI (Ministry of Economy, Trade and Industry) as part of its R&D supporting program for developing geological disposal technology.

Mineral and Geochemical Classification From Spectroscopy/Diffraction Through Neural Networks

NASA Astrophysics Data System (ADS)

Ferralis, N.; Grossman, J.; Summons, R. E.

2017-12-01

Spectroscopy and diffraction techniques are essential for understanding structural, chemical and functional properties of geological materials for Earth and Planetary Sciences. Beyond data collection, quantitative insight relies on experimentally assembled, or computationally derived spectra. Inference on the geochemical or geophysical properties (such as crystallographic order, chemical functionality, elemental composition, etc.) of a particular geological material (mineral, organic matter, etc.) is based on fitting unknown spectra and comparing the fit with consolidated databases. The complexity of fitting highly convoluted spectra, often limits the ability to infer geochemical characteristics, and limits the throughput for extensive datasets. With the emergence of heuristic approaches to pattern recognitions though machine learning, in this work we investigate the possibility and potential of using supervised neural networks trained on available public spectroscopic database to directly infer geochemical parameters from unknown spectra. Using Raman, infrared spectroscopy and powder x-ray diffraction from the publicly available RRUFF database, we train neural network models to classify mineral and organic compounds (pure or mixtures) based on crystallographic structure from diffraction, chemical functionality, elemental composition and bonding from spectroscopy. As expected, the accuracy of the inference is strongly dependent on the quality and extent of the training data. We will identify a series of requirements and guidelines for the training dataset needed to achieve consistent high accuracy inference, along with methods to compensate for limited of data.

Isotope-Geochemical Evidence for the Nature of Protolite Eclogite of the Kokchetav Massif (Kazakhstan)

NASA Astrophysics Data System (ADS)

Shatsky, V. S.; Skuzovatov, S. Yu.; Ragozin, A. L.; Dril, S. I.

2018-03-01

In the present paper, the results of our isotope-geochemical studies on eclogites of the ultrahighpressure metamorphic complex of the Kokchetav massif are reported. The fact that the distribution of nonmobile elements in most of the samples was close to that of E-type MORB basalts is shown by using geochemical multielement diagrams normalized to N-MORB. Six samples were found to have a negative anomaly over niobium that may have resulted from contamination with crustal material. For eclogites of the Kokchetav massif, the 147Sm/144Nd ratio was found to range widely from 0.143 to 0.367. The ɛNd-values calculated for the age of the highly barometric stage of metamorphism (530 million years) varied from-10.3 to +8.1. Eclogites show a dispersion of model ages from 1.95 billion years to 670 million years. On the graphs in the ɛNd( T)-87Sr/86Sr and ɛNd( T)- T coordinates, eclogites were shown to form trends that can be interpreted as a result of contamination of the eclogite protolith by the host rocks. Based on the data obtained, it is proposed that the basalts of rift zones that may have geochemical characteristics of N-MORB basalts and at the same time may be contaminated by the continental crust may have served as proxies for eclogite protoliths of the Kokchetav massif.

Analysis of hydrologic and geochemical time-series data at James Cave, Virginia: Implications for epikarst influence on recharge in Appalachian karst aquifers

USGS Publications Warehouse

Eagle, Sarah D.; Orndorff, William; Schwartz, Benjamin F.; Doctor, Daniel H.; Gerst, Jonathan D.; Schreiber, Madeline E.

2016-01-01

The epikarst, which consists of highly weathered rock in the upper vadose zone of exposed karst systems, plays a critical role in determining the hydrologic and geochemical characteristics of recharge to an underlying karst aquifer. This study utilized time series (2007–2014) of hydrologic and geochemical data of drip water collected within James Cave, Virginia, to examine the influence of epikarst on the quantity and quality of recharge in a mature, doline-dominated karst terrain. Results show a strong seasonality of both hydrology and geochemistry of recharge, which has implications for management of karst aquifers in temperate climatic zones. First, recharge (discharge from the epikarst to the underlying aquifer) reaches a maximum between late winter and early spring, with the onset of the recharge season ranging from as early as December to as late as March during the study period. The timing and duration of the recharge season were found to be a function of precipitation in excess of evapotranspiration on a seasonal time scale. Secondly, seasonally variable residence times for water in the epikarst influence rock-water interaction and, hence, the geochemical characteristics of recharge. Overall, results highlight the strong and complex influence that the epikarst has on karst recharge, which requires long-term and high-resolution data sets to accurately understand and quantify.

Continuum-based DFN-consistent numerical framework for the simulation of oxygen infiltration into fractured crystalline rocks.

PubMed

Trinchero, Paolo; Puigdomenech, Ignasi; Molinero, Jorge; Ebrahimi, Hedieh; Gylling, Björn; Svensson, Urban; Bosbach, Dirk; Deissmann, Guido

2017-05-01

We present an enhanced continuum-based approach for the modelling of groundwater flow coupled with reactive transport in crystalline fractured rocks. In the proposed formulation, flow, transport and geochemical parameters are represented onto a numerical grid using Discrete Fracture Network (DFN) derived parameters. The geochemical reactions are further constrained by field observations of mineral distribution. To illustrate how the approach can be used to include physical and geochemical complexities into reactive transport calculations, we have analysed the potential ingress of oxygenated glacial-meltwater in a heterogeneous fractured rock using the Forsmark site (Sweden) as an example. The results of high-performance reactive transport calculations show that, after a quick oxygen penetration, steady state conditions are attained where abiotic reactions (i.e. the dissolution of chlorite and the homogeneous oxidation of aqueous iron(II) ions) counterbalance advective oxygen fluxes. The results show that most of the chlorite becomes depleted in the highly conductive deformation zones where higher mineral surface areas are available for reactions. Copyright © 2017 Elsevier B.V. All rights reserved.

Geochemical and isotopic constraints on the tectonic setting of Serra dos Carajas belt, eastern Para, Brazil

NASA Technical Reports Server (NTRS)

Olszewski, W. J., Jr.; Gibbs, A. K.; Wirth, K. R.

1986-01-01

The lower part of the Serra dos Carajas belt is the metavolcanic and metasedimentary Grao para Group (GPG). The GPG is thought to unconformably overlie the older (but undated) Xingu Complex, composed of medium and high-grade gneisses and amphibolite and greenstone belts. The geochemical data indicate that the GPG has many features in common with ancient and modern volcanic suites erupted through continental crust. The mafic rocks clearly differ from those of most Archean greenstone belts, and modern MORB, IAB, and hot-spot basalts. The geological, geochemical, and isotopic data are all consistent with deposition on continental crust, presumably in a marine basin formed by crustal extension. The isotopic data also suggest the existence of depleted mantle as a source for the parent magmas of the GPG. The overall results suggest a tectonic environment, igneous sources, and petrogenesis similar to many modern continental extensional basins, in contrast to most Archean greenstone belts. The Hammersley basin in Australia and the circum-Superior belts in Canada may be suitable Archean and Proterozoic analogues, respectively.

Hawai'i and Gale Crater: A Mars Analogue Study of Igneous, Sedimentary, Weathering, and Alteration Trends in Geochemistry

NASA Technical Reports Server (NTRS)

Berger, J. A.; Flemming, R. L.; Schmidt, M. E.; Gellert, R.; Morris, R. V.; Ming, D. W.

2017-01-01

Sedimentary rocks in Gale Crater on Mars indicate a varied provenance with a range of alteration and weathering [1, 2]. Geochemical trends identified in basaltic and alkalic sedimentary rocks by the Alpha Particle X-ray Spectrometer (APXS) on the Mars rover Curiosity represent a complex interplay of igneous, sedimentary, weathering, and alteration processes. Assessing the relative importance of these processes is challenging with unknown compositions for parent sediment sources and with the constraints provided by Curiosity's instruments. We therefore look to Mars analogues on Earth where higher-resolution analyses and geologic context can constrain interpretations of Gale Crater geochemical observations. We selected Maunakea (AKA Mauna Kea) and Kohala volcanoes, Hawai'i, for an analogue study because they are capped by post-shield transitional basalts and alkalic lavas (hawaiites, mugearites) with compositions similar to Gale Crater [1, 3]. Our aim was to characterize Hawaiian geochemical trends associated with igneous processes, sediment transport, weathering, and alteration. Here, we present initial results and discuss implications for selected trends observed by APXS in Gale Crater.

SOME GEOCHEMICAL METHODS OF URANIUM EXPLORATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Illsley, C.T.; Bills, C.W.; Pollock, J.W.

Geochemical research and development projects were carried on to provide basic information which may be applied to exploration or general studies of uranium geology. The applications and limitations of various aspects of geochemistry to uranium geological problems are considerd. Modifications of existing analytical techniques were made and tested in the laboratory and in the field. These include rapid quantitative determination of unranium in water, soil and peat, and of trace amounts of sulfate and phosphate in water. Geochemical anomaly'' has been defined as a significant departure from the average abundance background of an element where the distribution has not beenmore » disturbed by mineralization. The detection and significance of geocthemical anomalies are directly related to the mobility of the element being sought in the zone of weathering. Mobility of uranium is governed by complex physical, chemical, and biological factors. For uranium anomalies in surface materils, the chemicaly factors affecting mobility are the most sigificant. The effects of pH, solubility, coprecipitution, adsorption complexion, or compound formation are discussed in relation to anomalies detected in water, soil, and stream sediments. (auth)« less

Al Kushaymiyah as a target for a Colorado-type molybdenite deposit

USGS Publications Warehouse

Theobald, P.K.

1971-01-01

The granitic complex in the vicinity of Al Kushaymiyah was singled out by Whitlow (19,69, 1969a, 1971), as one of the most promising areas for exploration in the Southern Wajd quadrangle (Jackson and others, 1962). He noted in particular the intensity of shattering and silicification of these potassium-rich granites, and the presence of unusual concentrations of tungsten , molybdenum, and tin in samples from the area. In the light of shield-wide compilations, this area again stands out as the principal geochemical anomaly for the three metals. The similarity of these unusual geologic and geochemical features to those of Colorado-type molybdenite deposits is striking and suggests that the Al Kushaymiyah provides a favorableenvironment to explore for a stockwork molybdenum deposit.

Geological and geochemical record of 3400-million-year-old terrestrial meteorite impacts

NASA Technical Reports Server (NTRS)

Lowe, Donald R.; Byerly, Gary R.; Asaro, Frank; Kyte, Frank T.

1989-01-01

Beds of sand-sized spherules in the 3400-million-year-old Fig Tree Group, Barberton Greenstone belt, South Africa, formed by the fall of quenched liquid silicate droplets into a range of shallow- to deep-water depositional environments. The regional extent of the layers, their compositional complexity, and lack of included volcanic debris suggest that they are not products of volcanic activity. The layers are greatly enriched in iridium and other platinum group elements in roughly chondritic proportions. Geochemical modeling based on immobile element abundances suggests that the original average spherule composition can be approximated by a mixture of fractionated tholeiitic basalt, komatiite, and CI carbonaceous chondrite. The spherules are thought to be the products of large meteorite impacts on the Archean earth.

Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

2016-07-22

Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruentmore » dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.« less

Petrology, geochemistry and zircon U-Pb geochronology of a layered igneous complex from Akarui Point in the Lützow-Holm Complex, East Antarctica: Implications for Antarctica-Sri Lanka correlation

NASA Astrophysics Data System (ADS)

Kazami, Sou; Tsunogae, Toshiaki; Santosh, M.; Tsutsumi, Yukiyasu; Takamura, Yusuke

2016-11-01

The Lützow-Holm Complex (LHC) of East Antarctica forms part of a complex subduction-collision orogen related to the amalgamation of the Neoproterozoic supercontinent Gondwana. Here we report new petrological, geochemical, and geochronological data from a metamorphosed and disrupted layered igneous complex from Akarui Point in the LHC which provide new insights into the evolution of the complex. The complex is composed of mafic orthogneiss (edenite/pargasite + plagioclase ± clinopyroxene ± orthopyroxene ± spinel ± sapphirine ± K-feldspar), meta-ultramafic rock (pargasite + olivine + spinel + orthopyroxene), and felsic orthogneiss (plagioclase + quartz + pargasite + biotite ± garnet). The rocks show obvious compositional layering reflecting the chemical variation possibly through magmatic differentiation. The metamorphic conditions of the rocks were estimated using hornblende-plagioclase geothermometry which yielded temperatures of 720-840 °C. The geochemical data of the orthogneisses indicate fractional crystallization possibly related to differentiation within a magma chamber. Most of the mafic-ultramafic samples show enrichment of LILE, negative Nb, Ta, P and Ti anomalies, and constant HFSE contents in primitive-mantle normalized trace element plots suggesting volcanic arc affinity probably related to subduction. The enrichment of LREE and flat HREE patterns in chondrite-normalized REE plot, with the Nb-Zr-Y, Y-La-Nb, and Th/Yb-Nb/Yb plots also suggest volcanic arc affinity. The felsic orthogneiss plotted on Nb/Zr-Zr diagram (low Nb/Zr ratio) and spider diagrams (enrichment of LILE, negative Nb, Ta, P and Ti anomalies) also show magmatic arc origin. The morphology, internal structure, and high Th/U ratio of zircon grains in felsic orthogneiss are consistent with magmatic origin for most of these grains. Zircon U-Pb analyses suggest Early Neoproterozoic (847.4 ± 8.0 Ma) magmatism and protolith formation. Some older grains (1026-882 Ma) are regarded as xenocrysts from basement entrained in the magma through limited crustal reworking. The younger ages (807-667 Ma) might represent subsequent thermal events. The results of this study suggest that the ca. 850 Ma layered igneous complex in Akarui Point was derived from a magma chamber constructed through arc-related magmatism which included components from ca. 1.0 Ga felsic continental crustal basement. The geochemical characteristics and the timing of protolith emplacement from this complex are broadly identical to those of similar orthogneisses from Kasumi Rock and Tama Point in the LHC and the Kadugannawa Complex in Sri Lanka, which record Early Neoproterozoic (ca. 1.0 Ga) arc magmatism. Although the magmatic event in Akarui Point is slightly younger, the thermal event probably continued from ca. 1.0 Ga to ca. 850 Ma or even to ca. 670 Ma. We therefore correlate the Akarui Point igneous complex with those in the LHC and Kadugannawa Complex formed under similar Early Neoproterozoic arc magmatic events during the convergent margin processes prior to the assembly of the Gondwana supercontinent.

The Toxicological Geochemistry of Dusts, Soils, and Other Earth Materials: Insights From In Vitro Physiologically-based Geochemical Leach Tests

NASA Astrophysics Data System (ADS)

Plumlee, G. S.; Ziegler, T. L.; Lamothe, P.; Meeker, G. P.; Sutley, S.

2003-12-01

Exposure to mineral dusts, soils, and other earth materials results in chemical reactions between the materials and different body fluids that include, depending upon the exposure route, lung fluids, gastrointestinal fluids, and perspiration. In vitro physiologically-based geochemical leach tests provide useful insights into these chemical reactions and their potential toxicological implications. We have conducted such leach tests on a variety of earth materials, including asbestos, volcanic ash, dusts from dry lake beds, mine wastes, wastes left from the roasting of mercury ores, mineral processing wastes, coal dusts and coal fly ash, various soils, and complex dusts generated by the World Trade Center collapse. Size-fractionated samples of earth materials that have been well-characterized mineralogically and chemically are reacted at body temperature (37 C) for periods from 2 hours up to multiple days with various proportions of simulated lung, gastric, intestinal, and/or plasma-based fluids. Results indicate that different earth materials may have quite different solubility and dissolution behavior in vivo, depending upon a) the mineralogic makeup of the material, and b) the exposure route. For example, biodurable minerals such as asbestos and volcanic ash particles, whose health effects result because they dissolve very slowly in vivo, bleed off low levels of trace metals into the simulated lung fluids; these include metals such as Fe and Cr that are suspected by health scientists of contributing to the generation of reactive oxygen species and resulting DNA damage in vivo. In contrast, dry lake bed dusts and concrete-rich dusts are highly alkaline and bioreactive, and cause substantial pH increases and other chemical changes in the simulated body fluids. Many of the earth materials tested contain a variety of metals that can be quite soluble (bioaccessible), depending upon the material and the simulated body fluid composition. For example, due to their acidic pH and high chloride concentrations, simulated gastric fluids are most efficient at solubilizing metals such as Hg, Pb, Zn, and others that form strong chloride complexes; although these metals tend to partially reprecipitate in the near-neutral simulated intestinal fluids, complexes with organic ligands (i.e., amino and carboxylic acids) enhance their solubility. These metals are also quite soluble in near-neutral, protein-rich plasma-based fluids because they form strong complexes with the proteins. In contrast, metalloids that form oxyanion species (such as As, Cr, Mo, W) are commonly more soluble in near-neutral pH simulated lung fluids than in simulated gastric fluids.

INEEL Subregional Conceptual Model Report Volume 2: Summary of Existing Knowledge of Geochemical Influences on the Fate and Transport of Contaminants in the Subsurface at the INEEL

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul L. Wichlacz; Robert C. Starr; Brennon Orr

2003-09-01

This document summarizes previous descriptions of geochemical system conceptual models for the vadose zone and groundwater zone (aquifer) beneath the Idaho National Engineering and Environmental Laboratory (INEEL). The primary focus is on groundwater because contaminants derived from wastes disposed at INEEL are present in groundwater, groundwater provides a pathway for potential migration to receptors, and because geochemical characteristics in and processes in the aquifer can substantially affect the movement, attenuation, and toxicity of contaminants. The secondary emphasis is perched water bodies in the vadose zone. Perched water eventually reaches the regional groundwater system, and thus processes that affect contaminants inmore » the perched water bodies are important relative to the migration of contaminants into groundwater. Similarly, processes that affect solutes during transport from nearsurface disposal facilities downward through the vadose zone to the aquifer are relevant. Sediments in the vadose zone can affect both water and solute transport by restricting the downward migration of water sufficiently that a perched water body forms, and by retarding solute migration via ion exchange. Geochemical conceptual models have been prepared by a variety of researchers for different purposes. They have been published in documents prepared by INEEL contractors, the United States Geological Survey (USGS), academic researchers, and others. The documents themselves are INEEL and USGS reports, and articles in technical journals. The documents reviewed were selected from citation lists generated by searching the INEEL Technical Library, the INEEL Environmental Restoration Optical Imaging System, and the ISI Web of Science databases. The citation lists were generated using the keywords ground water, groundwater, chemistry, geochemistry, contaminant, INEL, INEEL, and Idaho. In addition, a list of USGS documents that pertain to the INEEL was obtained and manually searched. The documents that appeared to be the most pertinent were selected from further review. These documents are tabulated in the citation list. This report summarizes existing geochemical conceptual models, but does not attempt to generate a new conceptual model or select the ''right'' model. This document is organized as follows. Geochemical models are described in general in Section 2. Geochemical processes that control the transport and fate of contaminants introduced into groundwater are described in Section 3. The natural geochemistry of the Eastern Snake River Plain Aquifer (SRPA) is described in Section 4. The effect of waste disposal on the INEEL subsurface is described in Section 5. The geochemical behavior of the major contaminants is described in Section 6. Section 7 describes the site-specific geochemical models developed for various INEEL facilities.« less

Microbial distributions detected by an oligonucleotide microarray across geochemical zones associated with methane in marine sediments from the Ulleung Basin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Briggs, Brandon R; Graw, Michael; Brodie, Eoin L

2013-11-01

The biogeochemical processes that occur in marine sediments on continental margins are complex; however, from one perspective they can be considered with respect to three geochemical zones based on the presence and form of methane: sulfate–methane transition (SMTZ), gas hydrate stability zone (GHSZ), and free gas zone (FGZ). These geochemical zones may harbor distinct microbial communities that are important in biogeochemical carbon cycles. The objective of this study was to describe the microbial communities in sediments from the SMTZ, GHSZ, and FGZ using molecular ecology methods (i.e. PhyloChip microarray analysis and terminal restriction fragment length polymorphism (T-RFLP)) and examining themore » results in the context of non-biological parameters in the sediments. Non-metric multidimensional scaling and multi-response permutation procedures were used to determine whether microbial community compositions were significantly different in the three geochemical zones and to correlate samples with abiotic characteristics of the sediments. This analysis indicated that microbial communities from all three zones were distinct from one another and that variables such as sulfate concentration, hydrate saturation of the nearest gas hydrate layer, and depth (or unmeasured variables associated with depth e.g. temperature, pressure) were correlated to differences between the three zones. The archaeal anaerobic methanotrophs typically attributed to performing anaerobic oxidation of methane were not detected in the SMTZ; however, the marine benthic group-B, which is often found in SMTZ, was detected. Within the GHSZ, samples that were typically closer to layers that contained higher hydrate saturation had indicator sequences related to Vibrio-type taxa. These results suggest that the biogeographic patterns of microbial communities in marine sediments are distinct based on geochemical zones defined by methane.« less

Geochemical and mineralogical fingerprints to distinguish the exploited ferruginous mineralisations of Grotta della Monaca (Calabria, Italy)

NASA Astrophysics Data System (ADS)

Dimuccio, Luca Antonio; Rodrigues, Nelson; Larocca, Felice; Pratas, João; Amado, Ana Margarida; de Carvalho, Luís A. E. Batista

2017-02-01

This study examines the geochemical and mineralogical variations in the ferruginous mineralisations that crop out within Grotta della Monaca, which is considered to be the most striking and best known example of a prehistoric iron mine-cave from the southern Apennines (Calabria, Italy). Previous archaeological research identified three local and distinct ancient exploitation phases of these ferruginous mineralisations: (1) an Upper Palaeolithic phase; (2) a Late Neolithic phase; and (3) a post-Medieval phase. These materials, which have various forms of complex mineralogical admixtures and range in colour from yellow-orange to red and darker brown shades, mainly consist of iron oxides/hydroxides (essentially goethite and lepidocrocite), which are often mixed with subordinate and variable amounts of other matrix components (carbonates, sulphates, arsenates, silicates and organic matter). Such ferruginous mineralisations generally correspond to geochemically heterogeneous massive dyke/vein/mammillary/stratiform facies that are exposed within the local caves along open fractures and inclined bedding planes and that partially cover cave wall niches/notches/pockets and ceiling cupolas/holes. Selected samples/sub-samples are analysed through a multi-technique approach with a handheld portable X-ray Fluorescence, X-ray Diffraction, micro-Raman and Fourier Transform Infrared spectroscope (both conventional and attenuated total reflection), which is combined with subsequent multivariate statistical analysis of the elemental concentration data. The geochemical and mineralogical results are used to individualise similar compositional clusters. As expected, the identified groups, each of which has very specific geochemical-mineralogical ;fingerprints; and spatial distributions, enable us to identify the sampled ferruginous mineralisations. These specific mineral resources can be compared to similar raw materials that are found in other neighbouring archaeological sites, with obvious implications toward understanding local exploitation strategies through time and the exchanges and kinship networks of these materials.

Tree harvest in an experimental sand ecosystem: plant effects on nutrient dynamics and solute generation.

Treesearch

C. K. Keller; R. O' Brien; J. R. Havig; J. L. Smith; B. T. Bormann; D. Wang

2006-01-01

The hydrochemical signatures of forested ecosystems are known to be determined by a time-variant combination of physical-hydrologic, geochemical, and biologic processes. We studied subsurface potassium (K), calcium (Ca), and nitrate (NO3) in an experimental red-pine mesocosm to determine how trees affect the behavior of these nutrients in soil...

Chemical Geology: An Annotated Bibliography. CEGS Programs Publication Number 11.

ERIC Educational Resources Information Center

Billings, Gale K.

The annotated bibliography is intended to aid geologists whose primary background is not in geochemistry. The references thus range from chemistry texts to papers on complex geochemical applications. The emphasis has been on those books and papers concerned with the application of chemical concepts to geology. Citations are arranged topically to…

Lagrangian simulation of mixing and reactions in complex geochemical systems

NASA Astrophysics Data System (ADS)

Engdahl, Nicholas B.; Benson, David A.; Bolster, Diogo

2017-04-01

Simulations of detailed geochemical systems have traditionally been restricted to Eulerian reactive transport algorithms. This note introduces a Lagrangian method for modeling multicomponent reaction systems. The approach uses standard random walk-based methods for the particle motion steps but allows the particles to interact with each other by exchanging mass of their various chemical species. The colocation density of each particle pair is used to calculate the mass transfer rate, which creates a local disequilibrium that is then relaxed back toward equilibrium using the reaction engine PhreeqcRM. The mass exchange is the only step where the particles interact and the remaining transport and reaction steps are entirely independent for each particle. Several validation examples are presented, which reproduce well-known analytical solutions. These are followed by two demonstration examples of a competitive decay chain and an acid-mine drainage system. The source code, entitled Complex Reaction on Particles (CRP), and files needed to run these examples are hosted openly on GitHub (https://github.com/nbengdahl/CRP), so as to enable interested readers to readily apply this approach with minimal modifications.

Cadomian magmatism and metamorphism at the Ossa Morena/Central Iberian zone boundary, Iberian Massif, Central Portugal: Geochemistry and P-T constraints of the Sardoal Complex

NASA Astrophysics Data System (ADS)

Henriques, S. B. A.; Neiva, A. M. R.; Tajčmanová, L.; Dunning, G. R.

2017-01-01

A well preserved Cadomian basement is exposed in the Iberian Massif, Central Portugal, at the Ossa Morena/Central Iberian zone boundary, which allows the determination of reliable geochemical data. A sequence of Cadomian and Variscan magmatic and tectonometamorphic events has been already described for this area and are documented in other areas of the Avalonian-Cadomian orogen. However, the geochemical information concerning the Cadomian basement for this area is still limited. We present whole rock geochemical and oxygen isotopic information to characterize the igneous protoliths of the Sardoal Complex, located within the Tomar-Badajoz-Córdoba Shear Zone, and identify their tectonic setting. We use detailed petrography, mineral chemistry and P-T data to characterize the final Cadomian tectonometamorphic event. The Sardoal Complex contains orthogneiss and amphibolite units. The protoliths of the orthogneiss are calc-alkaline magmas of acid composition and peraluminous character that were generated in an active continental margin in three different stages (ca. 692 Ma, ca. 569 Ma and ca. 548 Ma). The most significant processes in their petrogenesis are the partial melting of old metasedimentary and meta-igneous crust at different crustal levels and the crystal fractionation of plagioclase, alkali feldspars, apatite, zircon and Fe-Ti oxides. The protoliths of the amphibolite, older than ca. 540 Ma, are tholeiitic and calc-alkaline magmas of basic composition that display N-, T- and E-MORB affinities. They were generated in an active continental margin. Crustal contamination and fractional crystallization of hornblende and diopside were involved in their petrogenesis. However, the fractional crystallization was not significant. The magmatic activity recorded in the Sardoal Complex indicates the existence of a long-lived continental arc (ca. 692-540 Ma) with coeval felsic and mafic magmatism. The final stage of the Cadomian metamorphism is usually represented in other areas of the Cadomian basement as a LP-HT metamorphic event. However, the P-T data obtained by thermodynamic modelling indicates medium pressure/high temperature conditions at ca. 540 Ma. These data suggest that the Sardoal Complex represents a deeper level of the exhumed Cadomian basement where the final stage of the Cadomian metamorphism was recorded.

Nature and geodynamic setting of the protoliths of the UHP metamorphic Complex and migmatites in Bixiling area, the Dabie Orogen, China

NASA Astrophysics Data System (ADS)

Li, H.; Jahn, B.; Wang, D.; Yu, H.; Liu, Z.; Hou, G.

2013-12-01

As the largest coesite-bearing mafic-ultramafic body in the Dabie-Sulu orogen, the Bixiling Complex is composed of meta-ultramafic rocks, MgAl-rich eclogites and FeTi-rich eclogites. The FeTi-rich eclogites are further divided into low-Si-high-Fe type (Type I) and high-Si-low-Fe type (Type II) according to their mineral assemblages and bulk chemical composition. Field, petrographic, petrological and geochemical characteristics of these rocks, although suffered an ultra-high pressure metamorphism, still show a magmatic differentiation process among the protoliths of the meta-ultramafic rocks, MgAl-rich eclogites and Type I FeTi-rich eclogites. A small degree of lower crustal contamination occurred during their magma chamber process. Amphibolite is widespread in the periphery of the complex. Non-foliation and fine-grained texture are their obvious characteristics. Geochemical and isotopic affinities suggest that the amphibolites represent a product of complete retrogression from type II FeTi-rich eclogites. The UHP complex is enclosed in granitic gneisses, which variably include two-mica plagioclase gneiss, epidote two-mica plagioclase gneiss, or white-mica plagioclase gneiss. They all show TTG, especially trondjhemitic composition. A migmatite outcrop was found near the northeastern end of the complex. The migmatites consist of dark colored, non-foliated amphibolites and light-colored, fine-grained trondhjemitic gneisses. Field occurrences, microstructures observed under optical microscope and SEM, Sr-Nd isotopic data suggest an origin of partial melting. Chemical composition of two stages of amphiboles occurred in both the amphibolites and the trondhjemitic gneisses also imply a partial melting process occurred. Trace element, Sr-Nd isotope and SHRIMP zircon U-Pb dating of MgAl-rich eclogite, amphibolites and trondhjemite suggest that the migmatites represent a partial melting of crustal materials at about 780Ma, possibly accompanied by the coeval emplacement of a differentiated mafic intrusive body. These rocks were deeply subducted into a mantle depth during the Triassic continental collision between the Yangtze Craton and North China Craton, and thereafter were exhumed to the surface. Their residual geochemical characteristics and spatial / temporal relationship could impose constraints on the tectonic evolution of the Dabieshan UHP terrane.

Evaluating sensitivity of complex electrical methods for monitoring CO2 intrusion into a shallow groundwater system and associated geochemical transformations

NASA Astrophysics Data System (ADS)

Dafflon, B.; Wu, Y.; Hubbard, S. S.; Birkholzer, J. T.; Daley, T. M.; Pugh, J. D.; Peterson, J.; Trautz, R. C.

2011-12-01

A risk factor of CO2 storage in deep geological formations includes its potential to leak into shallow formations and impact groundwater geochemistry and quality. In particular, CO2 decreases groundwater pH, which can potentially mobilize naturally occurring trace metals and ions commonly absorbed to or contained in sediments. Here, geophysical studies (primarily complex electrical method) are being carried out at both laboratory and field scales to evaluate the sensitivity of geophysical methods for monitoring dissolved CO2 distribution and geochemical transformations that may impact water quality. Our research is performed in association with a field test that is exploring the effects of dissolved CO2 intrusion on groundwater geochemistry. Laboratory experiments using site sediments (silica sand and some fraction of clay minerals) and groundwater were initially conducted under field relevant CO2 partial pressures (pCO2). A significant pH drop was observed with inline sensors with concurrent changes in fluid conductivity caused by CO2 dissolution. Electrical resistivity and electrical phase responses correlated well with the CO2 dissolution process at various pCO2. Specifically, resistivity decreased initially at low pCO2 condition resulting from CO2 dissolution followed by a slight rebound because of the transition of bicarbonate into non-dissociated carbonic acid at lower pH slightly reducing the total concentration of dissociated species. Continuous electrical phase decreases were also observed, which are interpreted to be driven by the decrease of surface charge density (due to the decrease of pH, which approaches the PZC of the sediments). In general, laboratory experiments revealed the sensitivity of electrical signals to CO2 intrusion into groundwater formations and can be used to guide field data interpretation. Cross well complex electrical data are currently being collected periodically throughout a field experiment involving the controlled release of dissolved CO2 into groundwater. The objective of the geophysical cross well monitoring effort is to evaluate the sensitivity of complex electrical methods to dissolved CO2 at the field scale. Here, we report on the ability to translate laboratory-based petrophysical information from lab to field scales, and on the potential of field complex electrical methods for remotely monitoring CO2-induced geochemical transformations.

The Stillwater Complex and its anorthosites: an accident of magmatic underplating?

USGS Publications Warehouse

Czamanske, G.K.; Bohlen, S.R.

1990-01-01

The Stillwater Complex, emplaced 2700??40 Ma, is exposed at the edge of a 4000-km2 block of Late Archean rocks that formed 40 to 110 m.y. yearlier. Voluminous plagioclase cumulates (anorthosites) within the Middle Banded series of the complex are difficult to explain either by in situ fractionation of mafic magma or by popular models for mixing of two magma types. Current models for the evolution of the lowermost continental crust by magmatic underplating suggest that a major crust-forming event of about 100 m.y. duration would satisfy geologic and geochemical constraints for the formation of the Stillwater Complex and the related granitoids. -from Authors

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.

Applicability of direct total reflection X-ray fluorescence analysis for selenium determination in solutions related to environmental and geochemical studies

NASA Astrophysics Data System (ADS)

Marguí, E.; Floor, G. H.; Hidalgo, M.; Kregsamer, P.; Roman-Ross, G.; Streli, C.; Queralt, I.

2010-12-01

A significant amount of environmental studies related to selenium determination in different environmental compartments have been published in the last years due to the narrow range between the Se nutritious requirement as essential element and toxic effects upon exposure. However, the direct analysis of complex liquid samples like natural waters and extraction solutions presents significant problems related to the low Se concentrations and the complicated matrix of this type of samples. The goal of the present research was to study the applicability of direct TXRF analysis of different type of solutions commonly used in environmental and geochemical studies, confirm the absence or presence of matrix effects and evaluate the limits of detection and accuracy for Se determination in the different matrices. Good analytical results were obtained for the direct analysis of ground and rain water samples with limits of detection for Se two orders of magnitude lower than the permissible Se concentration in drinking waters ([Se] = 10 μg/L) according to the WHO. However, the Se detection limits for more complex liquid samples such as thermal waters and extraction solutions were in the μg/L range due to the presence of high contents of other elements present in the matrix (i.e., Br, Fe, Zn) or the high background of the TXRF spectrum that hamper the Se determination at trace levels. Our results give insight into the possibilities and drawbacks of direct TXRF analysis and to a certain extent the potential applications in the environmental and geochemical field.

Unraveling the Alteration History of Serpentinites and Associated Ultramafic Rocks from the Kampos HPLT Subduction Complex, Syros, Greece

NASA Astrophysics Data System (ADS)

Cooperdock, E. H. G.; Stockli, D. F.

2016-12-01

Serpentinization, hydration of peridotite, has a profound effect on fundamental tectonic and petrologic processes such as deformation of the lithosphere, bulk rheology, fluid-mobile element cycling and deep earth carbon cycling. Though numerous studies have investigated the petrology, structure and geochemistry of serpentinites, the absolute chronology of serpentinization remains elusive due to a lack of accessory minerals that can be dated using established geochronological techniques. Magnetite forms as a common secondary mineral in serpentinites from the fluid-induced breakdown reaction of primary peridotite minerals. Magnetite (U-Th)/He chronometry provides the potential to directly date the cooling of exhumed ultramafic bodies and the low-temperature fluid alteration of serpentinites. We present the first application of magnetite (U-Th)/He chronometry to date stages of alteration in ultramafic rocks from the Kampos mélange belt, a high-pressure low-temperature (HP-LT) subduction complex that experienced exhumation in the Miocene on the island of Syros, Greece. Two generations of magnetite are distinguishable by grain size, magnetite trace element geochemistry and (U-Th)/He age. Large magnetite grains (mm) from a chlorite schist and a serpentinite schist have distinct geochemical signatures indicative of formation during blackwall-related fluid alteration and record Mid-Miocene exhumation-related cooling ages, similar to zircon (U-Th)/He ages from northern Syros. Smaller grains (µm) from the serpentinite schist lack blackwall-related fluid signatures and record post-exhumation mineral formation associated with widespread high-angle Pliocene normal faulting. These results reveal evidence for multiple episodes of fluid-rock alteration, which has implications for the cooling history and local geochemical exchanges of this HP-LT terrane. Given the fundamental impact of serpentinizaton on a vast array of tectonic, petrological, and geochemical processes, the ability to differentiate and date these alteration events can be used to address significant questions related to serpentinization in exhumed subduction complexes, continental margins, or obducted ophiolites.

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

NASA Astrophysics Data System (ADS)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

The Geochemical Behavior and Transport Characteristics of Xenoestrogens

NASA Astrophysics Data System (ADS)

Wallace, T. C.; Bennett, P. C.

2003-12-01

Xenoestrogens are estrogenic active synthetic chemicals that mimic the actions of female sex hormones. Xenoestrogens can be produced synthetically and naturally, and exposure can occur from a variety of sources- food additives, plastics, pesticides, or pharmaceuticals. These environmental chemicals are also known as endocrine disruptors because exposure to low doses (ng/L) have been linked to adverse effects in the reproductive and developmental stages in aquatic species (i.e. reproductive anomalies, feminization, infertility, alterations in growth during life cycles, and changes in community structures). Determining the exposure risks of these toxicological compounds, however, requires a better understanding of the geochemical behavior and transport of synthetic estrogens it is discharged to. Estrogen and its metabolites are also useful tracers because of their specific medical usage (sources from birth control pills, estrogen replacement therapy, and livestock farming), slow degradation before excretion, and unique physiochemical properties (low volatility, hydrophobicity, and high Kow). Estradiol concentrations analyzed by an enzyme-linked immunoassay (ELISA) show that <2-55 ng/L are discharged to Walnut Creek, a stream that also connects to the Colorado River(TX). The bioavailability of these compounds is affected by sorption processes, where xenoestrogens become associated with solid phases. A series of batch sorption experiments using sediment collected from Walnut Creek downstream of an Austin waste water treatment plant and synthetic estrogen standards (Simga@ Estrone, 17B-Estradiol, and Estriol), examined the distribution of estrogen between solid and aqueous phases. Analysis of the concentrations sorbed to sediment result in Freundlich sorption isotherms using HPLC/UV techniques (High Performance Liquid Chromatography with UV detectors- 220 and 280nm). Sorption occurs rapidly with 98% of 17B-Estradiol sorbed within 30 minutes (Estriol=80%, Estrone=95%), which is compared to photolysis degradation rates under UV and a broader spectrum sun lamp. Ultraviolet/Visible (UV/VIS) spectroscopy of the estrogen standards with dilute fulvic acid may indicate complexing with organic material. The hydrophobic nature of estrogen molecules due to a phenolic group seem to play a large role in the sorption rate. This sorption may alter direct photolysis decay rates, thereby acting as both a `sunscreen' and a carrier by increasing the exposure distance and bioavailability of xenoestrogens in the aquatic environment.

Geochemical and geochronological constraints on the origin and evolution of rocks in the active Woodlark Rift of Papua New Guinea

NASA Astrophysics Data System (ADS)

Zirakparvar, Nasser Alexander

Tectonically active regions provide important natural laboratories to glean information that is applicable to developing a better understanding of the geologic record. One such area of the World is Papua New Guinea, much of which is situated in an active and transient plate boundary zone. The focus of this PhD research is to develop a better understanding of rocks in the active Woodlark Rift, situated in Papua New Guinea's southernmost reaches. In this region, rifting and lithospheric rupture is occurring within a former subduction complex where there is a history of continental subduction and (U)HP metamorphism. The lithostratigraphic units exposed in the Woodlark Rift provide an opportunity to better understand the records of plate boundary processes at many scales from micron-sized domains within individual minerals to regional geological relationships. This thesis is composed of three chapters that are independent of one another but are all related to the overall goal of developing a better understanding of the record of plate boundary processes in the rocks currently exposed in the Woodlark Rift. The first chapter, published in its entirety in Earth and Planetary Science Letters (2011 v. 309, p. 56 - 66), is entitled 'Lu-Hf garnet geochronology applied to plate boundary zones: Insights from the (U)HP terrane exhumed within the Woodlark Rift'. This chapter focuses on the use of the Lu-Hf isotopic system to date garnets in the Woodlark Rift. Major findings of this study are that some of the rocks in the Woodlark Rift preserve a Lu-Hf garnet isotopic record of initial metamorphism and continental subduction occurring in the Late Mesozoic, whereas others only preserve a record of tectonic processes related to lithospheric rupture during the initiation of rifting in the Late Cenozoic. The second chapter is entitled 'Geochemical and geochronological constraints on the origin of rocks in the active Woodlark Rift of Papua New Guinea: Recognizing the dispersed fragments of an active margin'. This chapter uses a panoply of geochronological (U-Pb zircon) and geochemical (Lu-Hf and Sm-Nd isotopes, trace/REEs, and major elements) tools to investigate the origin the major lithostratigraphic units in the Woodlark Rift. Important findings in this chapter include the establishment of a tectonic link between sialic metamorphic rocks in the Woodlark Rift and the remnants of a Late Cretaceous aged bi-modal volcanic province along Australia's northern Queensland coast. This link is important because it identifies another rifted fragment of the former Australian continental margin in Gondwana, and demonstrates the complexity of recognizing the dispersed fragments of active margins. Another important finding of this chapter is that Quaternary aged high silica rhyolites erupted in the western Woodlark Rift have mantle isotopic and geochemical signatures, and are therefore not the extrusive equivalents of partially melted metamorphic rocks found in the lower plates of large metamorphic core complexes. This is important because it signifies that lithospheric rupture has already occurred, despite the fact that mid-ocean ridge basalts are not yet being erupted and there are still topographically prominent metamorphic core complexes in the region. This chapter is not yet published, but is being prepared for submission to Gondwana Research. The third chapter is entitled 'Zircon growth in rapidly evolving plate boundary zones: Evidence from the active Woodlark Rift of Papua New Guinea'. The original purpose of this chapter was simply to use U-Pb dating of zircons from felsic and intermediate gneisses in the Woodlark Rift to understand the history of rocks from (U)HP terranes that don't preserve the (U)HP metamorphic paragenesis. It was soon realized that the types of U-Pb zircon analyses typically performed on a SIMS instrument were going to be insufficient to fully understand the geochemical and geochronological records within zircons from these rocks. Because of this, traditional SIMS analyses for zircons from these rocks are augmented by U-Pb age and elemental depth profiles that elucidate the isotopic and geochemical nature of the sharp boundaries between different aged domains in these polygenetic zircons. The results presented in this chapter demonstrate that zircon U-Pb ages record specific plate boundary events that can be related to the development of the Woodlark Rift, and that traditional assumptions regarding geochemical equilibrium might not hold true in all situations.

Geochemical characterization of elements in Vitis vinifera cv. Negroamaro grape berries grown under different soil managements.

PubMed

Pepi, Salvatore; Coletta, Antonio; Crupi, Pasquale; Leis, Marilena; Russo, Sabrina; Sansone, Luigi; Tassinari, Renzo; Chicca, Milvia; Vaccaro, Carmela

2016-04-01

The present geochemical study concerns the impact of viticultural practices in the chemical composition of the grape cultivar "Negroamaro" in Apulia, a southern Italian region renowned for its quality wine. Three types of soil management (SM), two cover cropping with different mixtures, and a soil tillage were considered. For each SM, the vines were irrigated according to two irrigation levels. Chemical composition of soil and of berries of Vitis vinifera cultivar "Negroamaro" were analyzed by X-ray fluorescence, inductively coupled plasma-mass spectrometry and multivariate statistics (linear discrimination analysis). In detail, we investigated major and trace elements behavior in the soil according to irrigation levels, the related index of bioaccumulation (BA) and the relationship between trace element concentration and soil management in "Negroamaro" grapes. The results indicate that soil management affects the mobility of major and trace elements. A specific assimilation of these elements in grapes from vines grown under different soil management was confirmed by BA. Multivariate statistics allowed to associate the vines to the type of soil management. This geochemical characterization of elements could be useful to develop fingerprints of vines of the cultivar "Negroamaro" according to soil management and geographical origin.

Light is an active contributor to the vital effects of coral skeleton proxies

NASA Astrophysics Data System (ADS)

Juillet-Leclerc, Anne; Reynaud, Stéphanie; Dissard, Delphine; Tisserand, Guillaume; Ferrier-Pagès, Christine

2014-09-01

Symbiotic colonies of the coral Acropora sp. were cultured in a factorial design of three temperatures (21, 25 and 28 °C) and two light intensities (200 and 400 μmol photon m-2 s-1), under constant conditions. A temperature of 25 °C and a light intensity of 200 μmol photon m-2 s-1 was the starting culture condition. Metabolic (photosynthesis, respiration, calcification and surface expansion rate) and geochemical measurements (δ18O, δ13C, Sr/Ca and Mg/Ca) were conducted on 6 colonies for each experimental condition. Metabolic measurements confirmed that respiration, photosynthesis, calcification and surface expansion rate responded to the combined effect of temperature and light. Under each light intensity, mean calcification rate was linearly correlated with mean photosynthetic activity. Geochemical measurements were also influenced by temperature and, to a lesser degree, by light. All geochemical proxies measured on 6 nubbins showed a wide scattering of values, regardless of the environmental condition. Compared to the other proxies, δ18O exhibited a different behavior. It was the only proxy exhibiting temperature tracer behavior. However, while mean values of Sr/Ca, Mg/Ca and δ13C were well correlated, the correlation between the later and mean δ18O differed with light level. This suggests that both skeleton deposition and temperature oxygen fractionation differs according to light intensity. Overall, the effect of light on geochemical values seems to compromise the use of proxy calibrations solely based on temperature influence. Under high light conditions, the great amplitude shown by individual net photosynthesis is directly proportional to the highly variable zooxanthellae density. As light is affecting all of the proxies, we thus assume that the strong geochemical variability observed could be explained by various algae densities, each nubbin responding according to its zooxanthellae amount. Accordingly, we suggest that each symbiosome (the assemblage of few corallites with their symbionts) presents its own vital effect influence over time. Therefore, at a bulk sample scale, light could be considered as one of the major causes of what is commonly referred to as the 'vital effect'. The meaning of δ18O calibration versus temperature established from distinct colonies differs from calibration calculated from samples collected following the growth axis of a single coral head. Finally, in order to quantitatively reconstruct climatic condition, we suggest a new paradigm based on the statistical treatment of the combination of time-series information from several proxies, all measured on the same sample from a continuous symbiosome.

The Cauaburi magmatic arc: Litho-stratigraphic review and evolution of the Imeri Domain, Rio Negro Province, Amazonian Craton

NASA Astrophysics Data System (ADS)

Carneiro, Marcia C. R.; Nascimento, Rielva S. C.; Almeida, Marcelo E.; Salazar, Carlos A.; Trindade, Ivaldo Rodrigues da; Rodrigues, Vanisse de Oliveira; Passos, Marcel S.

2017-08-01

A lithostratigraphic review of the Cauaburi Complex was carried out by means of field, tectono-metamorphic and geochemical data, which were the basis for the sub-division of the Cauaburi Complex orthogneisses into the Santa Izabel do Rio Negro, Cumati and São Jorge facies. These rocks crop out between São Gabriel da Cachoeira and Santa Izabel do Rio Negro, Amazonas, Brazil. The gneisses of the Santa Izabel do Rio Negro and Cumati facies are metaluminous and of calc-alkaline affinity; in turn, the rocks of the São Jorge facies are peraluminous and of alkaline affinity. They vary from (amphibole)-biotite granodiorites/monzogranites (Cumati and Santa Izabel do Rio Negro facies) to spessartite-bearing biotite monzogranites (São Jorge facies). The Cauaburi Complex geochemical signature is compatible with that of granites generated in collisional settings (magmatic arc?) and its evolution is related to three distinct tectono-metamorphic events: D1, causing foliation S1, which developed during the Cauaburi Complex syn-tectonic emplacement in the Cauaburi Orogeny; D2/M2, causing foliation S2, which was generated under amphibolite facies conditions (717.9 °C and 5.84 kbars), and the emplacement of I- and S-type granite during the Içana Orogen, and low-temperature D3, associated with the K'Mudku Event, which caused foliation S3 and reworking via transcurrent shear zones under greenschist facies conditions.

Resolving the Multi-scale Behavior of Geochemical Weathering in the Critical Zone Using High Resolution Hydro-geochemical Models

NASA Astrophysics Data System (ADS)

Pandey, S.; Rajaram, H.

2015-12-01

This work investigates hydrologic and geochemical interactions in the Critical Zone (CZ) using high-resolution reactive transport modeling. Reactive transport models can be used to predict the response of geochemical weathering and solute fluxes in the CZ to changes in a dynamic environment, such as those pertaining to human activities and climate change in recent years. The scales of hydrology and geochemistry in the CZ range from days to eons in time and centimeters to kilometers in space. Here, we present results of a multi-dimensional, multi-scale hydro-geochemical model to investigate the role of subsurface heterogeneity on the formation of mineral weathering fronts in the CZ, which requires consideration of many of these spatio-temporal scales. The model is implemented using the reactive transport code PFLOTRAN, an open source subsurface flow and reactive transport code that utilizes parallelization over multiple processing nodes and provides a strong framework for simulating weathering in the CZ. The model is set up to simulate weathering dynamics in the mountainous catchments representative of the Colorado Front Range. Model parameters were constrained based on hydrologic, geochemical, and geophysical observations from the Boulder Creek Critical Zone Observatory (BcCZO). Simulations were performed in fractured rock systems and compared with systems of heterogeneous and homogeneous permeability fields. Tracer simulations revealed that the mean residence time of solutes was drastically accelerated as fracture density increased. In simulations that include mineral reactions, distinct signatures of transport limitations on weathering arose when discrete flow paths were included. This transport limitation was related to both advective and diffusive processes in the highly heterogeneous systems (i.e. fractured media and correlated random permeability fields with σlnk > 3). The well-known time-dependence of mineral weathering rates was found to be the most pronounced in the fractured systems, with a departure from the maximum system-averaged dissolution rate occurring after ~100 kyr followed by a gradual decrease in the reaction rate with time that persists beyond 104 kyr.

A computer program for geochemical analysis of acid-rain and other low-ionic-strength, acidic waters

USGS Publications Warehouse

Johnsson, P.A.; Lord, D.G.

1987-01-01

ARCHEM, a computer program written in FORTRAN 77, is designed primarily for use in the routine geochemical interpretation of low-ionic-strength, acidic waters. On the basis of chemical analyses of the water, and either laboratory or field determinations of pH, temperature, and dissolved oxygen, the program calculates the equilibrium distribution of major inorganic aqueous species and of inorganic aluminum complexes. The concentration of the organic anion is estimated from the dissolved organic concentration. Ionic ferrous iron is calculated from the dissolved oxygen concentration. Ionic balances and comparisons of computed with measured specific conductances are performed as checks on the analytical accuracy of chemical analyses. ARCHEM may be tailored easily to fit different sampling protocols, and may be run on multiple sample analyses. (Author 's abstract)

Noble gas and hydrocarbon tracers in multiphase unconventional hydrocarbon systems: Toward integrated advanced reservoir simulators

NASA Astrophysics Data System (ADS)

Darrah, T.; Moortgat, J.; Poreda, R. J.; Muehlenbachs, K.; Whyte, C. J.

2015-12-01

Although hydrocarbon production from unconventional energy resources has increased dramatically in the last decade, total unconventional oil and gas recovery from black shales is still less than 25% and 9% of the totals in place, respectively. Further, the majority of increased hydrocarbon production results from increasing the lengths of laterals, the number of hydraulic fracturing stages, and the volume of consumptive water usage. These strategies all reduce the economic efficiency of hydrocarbon extraction. The poor recovery statistics result from an insufficient understanding of some of the key physical processes in complex, organic-rich, low porosity formations (e.g., phase behavior, fluid-rock interactions, and flow mechanisms at nano-scale confinement and the role of natural fractures and faults as conduits for flow). Noble gases and other hydrocarbon tracers are capably of recording subsurface fluid-rock interactions on a variety of geological scales (micro-, meso-, to macro-scale) and provide analogs for the movement of hydrocarbons in the subsurface. As such geochemical data enrich the input for the numerical modeling of multi-phase (e.g., oil, gas, and brine) fluid flow in highly heterogeneous, low permeability formations Herein we will present a combination of noble gas (He, Ne, Ar, Kr, and Xe abundances and isotope ratios) and molecular and isotopic hydrocarbon data from a geographically and geologically diverse set of unconventional hydrocarbon reservoirs in North America. Specifically, we will include data from the Marcellus, Utica, Barnett, Eagle Ford, formations and the Illinois basin. Our presentation will include geochemical and geological interpretation and our perspective on the first steps toward building an advanced reservoir simulator for tracer transport in multicomponent multiphase compositional flow (presented separately, in Moortgat et al., 2015).

Two Centuries of Climate Variability From a Gulf of Papua Coral Confirms a Coherent, Widespread Multidecadal Signal

NASA Astrophysics Data System (ADS)

Cole, J. E.; Lough, J.; Reed, E. V.; Schrag, D. P.

2016-12-01

The Indo-Pacific warm pool is intimately involved with large-scale climate variability on seasonal to secular time scales. The lack of long instrumental observations in this region has motivated paleoclimatic analyses using diverse proxy data sources. We present here new multicentury paleoclimate records from a Gulf of Papua coral that capture past variability with a Pacific-wide signature. We have developed stable isotope, Sr/Ca, skeletal density, and luminescence data from a coral core recovered at Bramble Cay, Australia (9°S, 144°E). The geochemical records span CE 1775-1993 and are dominated by low-frequency (decade-century scale) variability that is consistent with records from other proxies in the same region, and with other coral records from far-flung sites across the southwest Pacific. Unlike in many Pacific coral records, we observe no strong trend towards warmer conditions. Although skeletal density bands are clearly visible, they show inconsistent seasonal phasing with the geochemical tracers of sea surface temperature (SST; Sr/Ca and oxygen isotope content), and skeletal density does not correlate with these tracers on longer time scales. In this coral, density banding must be controlled by a more complex mix of internal and/or external factors. Luminescent banding and reconstructed salinity provide similar histories, suggesting a common hydroclimatic signal with significant variability at periods of decades and longer. The strong low-frequency behavior in these new climate records of SST and hydroclimate, from a remote region of the Indo-Pacific, confirms an important source of internal climate variability, on a poorly documented time scale, from a region with far-reaching climatic importance.

Microfluidic Experiments Studying Pore Scale Interactions of Microbes and Geochemistry

NASA Astrophysics Data System (ADS)

Chen, M.; Kocar, B. D.

2016-12-01

Understanding how physical phenomena, chemical reactions, and microbial behavior interact at the pore-scale is crucial to understanding larger scale trends in groundwater chemistry. Recent studies illustrate the utility of microfluidic devices for illuminating pore-scale physical-biogeochemical processes and their control(s) on the cycling of iron, uranium, and other important elements 1-3. These experimental systems are ideal for examining geochemical reactions mediated by microbes, which include processes governed by complex biological phenomenon (e.g. biofilm formation, etc.)4. We present results of microfluidic experiments using a model metal reducing bacteria and varying pore geometries, exploring the limitations of the microorganisms' ability to access tight pore spaces, and examining coupled biogeochemical-physical controls on the cycling of redox sensitive metals. Experimental results will provide an enhanced understanding of coupled physical-biogeochemical processes transpiring at the pore-scale, and will constrain and compliment continuum models used to predict and describe the subsurface cycling of redox-sensitive elements5. 1. Vrionis, H. A. et al. Microbiological and geochemical heterogeneity in an in situ uranium bioremediation field site. Appl. Environ. Microbiol. 71, 6308-6318 (2005). 2. Pearce, C. I. et al. Pore-scale characterization of biogeochemical controls on iron and uranium speciation under flow conditions. Environ. Sci. Technol. 46, 7992-8000 (2012). 3. Zhang, C., Liu, C. & Shi, Z. Micromodel investigation of transport effect on the kinetics of reductive dissolution of hematite. Environ. Sci. Technol. 47, 4131-4139 (2013). 4. Ginn, T. R. et al. Processes in microbial transport in the natural subsurface. Adv. Water Resour. 25, 1017-1042 (2002). 5. Scheibe, T. D. et al. Coupling a genome-scale metabolic model with a reactive transport model to describe in situ uranium bioremediation. Microb. Biotechnol. 2, 274-286 (2009).

Volcanism and erosion during the past 930 k.y. at the Tatara-San Pedro complex, Chilean Andes

USGS Publications Warehouse

Singer, B.S.; Thompson, R.A.; Dungan, M.A.; Feeley, T.C.; Nelson, S.T.; Pickens, J.C.; Brown, L.L.; Wulff, A.W.; Davidson, J.P.; Metzger, J.

1997-01-01

Geologic mapping, together with 73 new K-Ar and 40Ar/39Ar age determinations of 45 samples from 17 different volcanic units, plus paleomagnetic orientations, geochemical compositions, and terrestrial photogrammetry are used to define the chronostratigraphy of the Tatara-San Pedro complex, an eruptive center at 36??S on the volcanic front of the Andean southern volcanic zone. The Tatara-San Pedro complex preserves ???55 km3 of lavas that erupted from at least three central vent regions. Remnant, unconformity-bound sequences of lavas are separated by lacunae that include significant periods of erosion. Quaternary volcanism commenced ca. 930 ka with eruption of voluminous dacitic magma, followed 100 k.y. later by the only major rhyolitic eruption. From 780 ka onward, more than 80% of the preserved volume is basaltic andesite (52%-57% SiO2), but petrographically and geochemically diverse dacitic magmas (63%-69% SiO2) erupted sporadically throughout this younger, dominantly mafic phase of activity. A few basaltic lavas (49%-52% SiO2) are present, mainly in portions of the complex older than 230 ka. The number of vents, the petrologic and geochemical diversity, and the temporal distribution of mafic and silicic lavas are consistent with emplacement of many separate batches of made magma into the shallow crust beneath the Tatara-San Pedro complex over the past million years. Nearly two-thirds of the preserved volume of the Tatara-San Pedro complex comprises the two youngest volcanoes, which were active between ca. 188-83 ka and 90-19 ka. Repeated advances of mountain glaciers punctuated growth of the complex with major erosional episodes that removed much of the pre-200 ka volcanic record, particularly on the south flank of the complex. Dating the inception of a glaciation on the basis of preserved material is difficult, but the age of the oldest lava above a lacuna may be used to estimate the timing of deglaciation. On this basis, the argon ages of basal lavas of multiple sequences indicate minimum upper limits of lacunae at ca. 830, 790, 610, 400, 330, 230, 110, and 17 ka. These are broadly consistent with global ice-volume peaks predicted by the oxygen isotope-based astronomical time scale and with age brackets on North American glacial advances. Estimated growth rates for the two young volcanoes are 0.2 to 0.3 km3/k.y.; these are three to five times greater than a growth rate estimated from all preserved lavas in the complex (0.06 km3/k.y.). Removal of up to 50%-95% of the material erupted between 930 and 200 ka by repeated glacial advances largely explains this discrepancy, and it raises the possibility that episodic erosion of midlatitude frontal arc complexes may be extensive and common.

Sorption, Photodegradation, and Chemical Transformation of Naproxen and Ibuprofen in Soils and Water

NASA Astrophysics Data System (ADS)

Vulava, V. M.; Cory, W. C.; Murphey, V.; Ulmer, C.

2015-12-01

Trace levels of pharmaceutically active compounds (PhACs) are increasingly being found in municipal drinking water and natural streams around the world. PhACs enter natural water systems after passing through wastewater treatment plants that have proven to be relatively inefficient at removing them. Once they are released into the environment, they can undergo (1) soil sorption, (2) photodegradation, and/or (3) chemical transformation into structurally similar compounds. The overarching goal of this study is to understand the geochemical fate of common PhACs in the environment. Here we report on our studies with naproxen (NAP) and ibuprofen (IBP) in soils and water. Both compounds are complex nonpolar (aromatic) organic molecules with polar (carboxylic acid) functional groups. The carboxylic functional groups are likely to be deprotonated at environmentally relevant pHs (~4-8). Sorption studies of both compounds were conducted in clean and relatively acidic (soil pH ~4.5-6.5) natural soils that contained varying levels of organic matter (OM), clay minerals, and Fe oxides. OM was observed to play an important role in each of the above three processes. Sorption was observed to be stronger and nonlinear in higher OM soils, while weaker but still significant in lower OM, higher clay soils; the amphiphilic nature of NAP and IBP combined with the complex charged and nonpolar surfaces available in the soil was observed to control the sorption behavior. Both NAP and IBP underwent rapid photodegradation in aqueous suspensions when exposed to simulated sunlight. The degradation rates were observed to change in the presence of humic acid or fulvic acid. During sorption and photodegradation experiments, common transformation products were observed for both NAP and IBP. The transformation products produced were indicative of chemical transformation and not biological factors. Concentrations of the transformation products were significantly higher in the photoexposed aqueous suspensions compared to that formed in soil solutions. This study also helped in understanding the important role OM plays in geochemical fate of PhACs. The transformation products identified here are known to have higher ecotoxicity than the parent PhACs.

Geochemistry of the Bela Ophiolite, Pakistan

NASA Astrophysics Data System (ADS)

Khan, M.; Nicholson, K. N.; Mahmood, K.

2008-12-01

The Bela ophiolite complex of Balochistan, Pakistan has been the subject of several geochemical and tectonic studies in the past. However until now there has never been a combined structural, geochemical and tectonic assimilation study which adequately explains the observed geochemistry and structural geology in a global tectonic framework. Here we present the geochemical findings of our work. The Bela ophiolite complex consists of two major units: the basal section or Lower Unit, and the Upper Unit, between the two is a mélange zone. The Lower Unit is relatively homogeneous and consists almost entirely of flow basalts and pillow basalts. The base of the Upper Unit is the metamorphic sole which is overlain by a sequence of massive basalts flows and intrusions of gabbro and granites. The entire Upper Unit is cut by doleritic dykes and sills. Geochemically the Lower Unit is comprised of basaltic lavas with E-MORB affinities. These lavas are tholeiitic, low-K series lavas with trace element signatures of E-type MORB. For example ratios such as V/Ti, Zr/Y, Nb/Th, Th/La and Nb/U all suggest these lavas are E-MORB. Previous workers have suggested these lavas are back-arc basin (BAB) however the samples lack the characteristic signatures of subduction modified MORB. This conclusion is supported by chondrite and N-MORB normalized spider diagrams where the Lower Unit lavas are enriched in the LILE with respect to the HFSE. The Upper Unit of the Bela Ophiolite sequence has a slightly more complex history. The older lavas sequences, the massive basalt flows, gabbros and granites, all formed in an oceanic arc environment. These lavas exhibit classic arc signatures such as a negative Nb and Ti anomalies, are enriched in LILE and LREE relative to HSFE, and plot in the volcanic arc and island arc fields in classic ternary plots such as 2Nb- Zr/4-Y and Y/15-La/10-Nb/8. The younger sequence of intrusions found in the Bela ophiolite appear to have BAB signatures. These lavas have relatively flat MORB normalized plots, are slightly depleted in the LILE relative the HFSE, and have a very small negative Nb anomaly. Source characteristics for both units have been determined using trace element data. This work suggests that the E-MORB lavas are derived from partial melting of enriched mantle. The lavas found in the Upper Unit have all been sourced from depleted or N-MORB mantle which has been modified by subducting fluids. It is possible that the younger BAB samples have a slightly more enriched source than the corresponding arc lavas which might indicate movement of the subduction zone allowing the influx of new mantle material below the wedge. In conclusion, our new geochemical work shows that the Bela ophiolite contains three distinct magmatic sequences: a lower E-MORB sequence over lain by a series of volcanic arc lavas which are cut by BAB-type sills and dykes.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

High radiogenic heat-producing Caenozoic granites: implications for the origin of Quman geothermal field in Taxkorgan, northwestern China

NASA Astrophysics Data System (ADS)

Shuai, W.; Shihua, Q.

2017-12-01

As a new found geothermal field, Quman geothermal field (Taxkorgan, China) holds a wellhead temperature of 144 ° and a shallow buried depth of heat reservoir. The heat source of the geothermal field is thought to be the heat flow from the upper mantle, which is disputable with the average Pamir Moho depth of 70 km. The new geochemical data of Taxkorgan alkaline complex, which is located to the west of the geothermal field and is exposed for 60 km along the western side of the Taxkorgan Valley, shed a light on the origin of Quman geothermal field. Together with the lithological association, the geochemical results present that Taxkorgan alkaline complex are mainly composed of alkaline syenites and subalkaline granitoids. Based on the contents of Th, U and K of 25 rock samples, the average radioactive heat generation of the complex (9.08 μW/m3) is 2 times of the standard of high heat production granites (HHPGs) (5 μW/m3), and 4 times of the average upper continental crust (UCC) heat production (2.7 μW/m3). According to U-Pd dating of zircon in aegirine-augite syenite, the crystallization age of the complex is 11 Ma. The complex has incompatible element abundances higher than generally observed for the continental crust, therefore a mantle source should be considered. The results of apatite fission track ange and track length of the complex indicate a low uplift rate (0.11 mm/a) in 3 5 Ma and a high uplift rate (2 3 mm/a) since ca. 2Ma, which indicates a low exposed age of the complex. Therefore, combined with previous studies, we propose that radioactive heat production of the complex and afterheat of magma cooling are the heat source of Quman geothermal field. With a shallow buried heat source, the geothermal field is potential for EGS development.

Natural geochemical analogues of the near field of high-level nuclear waste repositories

DOE Office of Scientific and Technical Information (OSTI.GOV)

Apps, J.A.

1995-09-01

United States practice has been to design high-level nuclear waste (HLW) geological repositories with waste densities sufficiently high that repository temperatures surrounding the waste will exceed 100{degrees}C and could reach 250{degrees}C. Basalt and devitrified vitroclastic tuff are among the host rocks considered for waste emplacement. Near-field repository thermal behavior and chemical alteration in such rocks is expected to be similar to that observed in many geothermal systems. Therefore, the predictive modeling required for performance assessment studies of the near field could be validated and calibrated using geothermal systems as natural analogues. Examples are given which demonstrate the need for refinementmore » of the thermodynamic databases used in geochemical modeling of near-field natural analogues and the extent to which present models can predict conditions in geothermal fields.« less

Geochemical modeling of low melt-fraction anatexis in a peraluminous system: The Pena Negra complex (central Spain)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bea, F.

1991-07-01

A study was made of the chemical fractionation associated with four cases of anatectic segregation of low melt-fraction cordieritic granites from migmatized meta-greywackes. The aims of the study were to (1) reveal the fractionation patterns of major and trace elements, (2) compare the major element chemistry of leucogranites and the quantitative behavior of source minerals during anatexis - inferred by mass-balance adjustment - with available experimental data for peraluminous systems, and (3) discuss the behavior of trace elements in crustal melting by comparing the chemically determined composition of leucogranites with the results of three fractionation models. Two of these assumemore » a perfect diffusive behavior of trace elements within residual solids, but they use a different set of distribution coefficients. The third assumes a perfect nondiffusive behavior. In relation to their source rocks, the leucogranites are strongly depleted in Li, Transition Elements, and Light Rare Earth Elements, but enriched in K{sub 2}O, SiO{sub 2}, and Ba. Mass balance analysis using the Anatexis Mixing Model shows that the chemistry of cordierite leucogranites is compatible with its having originated by closed-system, water-undersaturated anatexis on previously migmatized meta-greywackes, leaving a residue enriched in cordierite plus biotite and exhausted in K-feldspar. Biotite melts congruently unless important amounts of sillimanite were also present in the source. Compared with experimental metals obtained from sources with the same chemical composition but with a different femic mineralogy (biotite + sillimanite, instead of cordierite + biotite), the Pena Negra leucogranites are richer in K{sub 2}O and MgO with a lower Fe/(Fe + Mg) ratio. The differences in magnesium are believed to result from the changes in the mineral assemblage of the source rocks.« less

Porosity Development in a Coastal Setting: A Reactive Transport Model to Assess the Influence of Heterogeneity of Hydrological, Geochemical and Lithological Conditions

NASA Astrophysics Data System (ADS)

Maqueda, A.; Renard, P.; Cornaton, F. J.

2014-12-01

Coastal karst networks are formed by mineral dissolution, mainly calcite, in the freshwater-saltwater mixing zone. The problem has been approached first by studying the kinetics of calcite dissolution and then coupling ion-pairing software with flow and mass transport models. Porosity development models require high computational power. A workaround to reduce computational complexity is to assume the calcite dissolution reaction is relatively fast, thus equilibrium chemistry can be used to model it (Sanford & Konikow, 1989). Later developments allowed the full coupling of kinetics and transport in a model. However kinetics effects of calcite dissolution were found negligible under the single set of assumed hydrological and geochemical boundary conditions. A model is implemented with the coupling of FeFlow software as the flow & transport module and PHREEQC4FEFLOW (Wissmeier, 2013) ion-pairing module. The model is used to assess the influence of heterogeneities in hydrological, geochemical and lithological boundary conditions on porosity evolution. The hydrologic conditions present in the karst aquifer of Quintana Roo coast in Mexico are used as a guide for generating inputs for simulations.

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.

Sm-Nd isotopic systematics of the ancient Gneiss complex, southern Africa

NASA Technical Reports Server (NTRS)

Carlson, R. W.; Hunter, D. R.; Barker, F.

1983-01-01

In order to shed some new light on the question of the absolute and relative ages of the Ancient Gneiss Complex and Onverwacht Group, a Sm-Nd whole-rock and mineral isochron study of the AGC was begun. At this point, the whole-rock study of samples from the Bimodal Suite selected from those studied for their geochemical characteristics by Hunter et al., is completed. These results and their implications for the chronologic evolution of the Kaapvaal craton and the sources of these ancient rocks are discussed.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

The use of decision tree induction and artificial neural networks for recognizing the geochemical distribution patterns of LREE in the Choghart deposit, Central Iran

NASA Astrophysics Data System (ADS)

Zaremotlagh, S.; Hezarkhani, A.

2017-04-01

Some evidences of rare earth elements (REE) concentrations are found in iron oxide-apatite (IOA) deposits which are located in Central Iranian microcontinent. There are many unsolved problems about the origin and metallogenesis of IOA deposits in this district. Although it is considered that felsic magmatism and mineralization were simultaneous in the district, interaction of multi-stage hydrothermal-magmatic processes within the Early Cambrian volcano-sedimentary sequence probably caused some epigenetic mineralizations. Secondary geological processes (e.g., multi-stage mineralization, alteration, and weathering) have affected on variations of major elements and possible redistribution of REE in IOA deposits. Hence, the geochemical behaviors and distribution patterns of REE are expected to be complicated in different zones of these deposits. The aim of this paper is recognizing LREE distribution patterns based on whole-rock chemical compositions and automatic discovery of their geochemical rules. For this purpose, the pattern recognition techniques including decision tree and neural network were applied on a high-dimensional geochemical dataset from Choghart IOA deposit. Because some data features were irrelevant or redundant in recognizing the distribution patterns of each LREE, a greedy attribute subset selection technique was employed to select the best subset of predictors used in classification tasks. The decision trees (CART algorithm) were pruned optimally to more accurately categorize independent test data than unpruned ones. The most effective classification rules were extracted from the pruned tree to describe the meaningful relationships between the predictors and different concentrations of LREE. A feed-forward artificial neural network was also applied to reliably predict the influence of various rock compositions on the spatial distribution patterns of LREE with a better performance than the decision tree induction. The findings of this study could be effectively used to visualize the LREE distribution patterns as geochemical maps.

Ar-Ar ages, Sr-Nd isotope geochemistry, and implications for the origin of the silicate rocks of the Jacupiranga ultramafic-alkaline complex (Brazil)

NASA Astrophysics Data System (ADS)

Chmyz, Luanna; Arnaud, Nicolas; Biondi, João Carlos; Azzone, Rogério Guitarrari; Bosch, Delphine; Ruberti, Excelso

2017-08-01

The Jacupiranga Complex is one of several Meso-Cenozoic alkaline intrusive complexes along the margins of the intracratonic Paraná Basin in southern Brazil. The complex encompasses a wide range of rock-types, including dunites, wehrlites, clinopyroxenites, melteigites-ijolites, feldspar-bearing rocks (diorites, syenites, and monzonites), lamprophyres and apatite-rich carbonatites. While carbonatites have been extensively investigated over the last decades, little attention has been paid to the silicate rocks. This study presents new geochonological and geochemical data on the Jacupiranga Complex, with particular emphasis on the silicate lithotypes. 40Ar/39Ar ages for different lithotypes range from 133.7 ± 0.5 Ma to 131.4 ± 0.5 Ma, while monzonite zircon analyzed by SHRIMP yields a U-Pb concordia age of 134.9 ± 1.3 Ma. These ages indicate a narrow time frame for the Jacupiranga Complex emplacement, contemporaneous with the Paraná Magmatic Province. Most of the Jacupiranga rocks are SiO2-undersaturated, except for a quartz-normative monzonite. Based on geochemical compositions, the Jacupiranga silicate lithotypes may be separated into two magma-evolution trends: (1) a strongly silica-undersaturated series, comprising part of the clinopyroxenites and the ijolitic rocks, probably related to nephelinite melts and (2) a mildly silica-undersaturated series, related to basanite parental magmas and comprising the feldspar-bearing rocks, phonolites, lamprophyres, and part of the clinopyroxenites. Dunites and wehrlites are characterized by olivine compositionally restricted to the Fo83-84 interval and concentrations of CaO (0.13-0.54 wt%) and NiO (0.19-0.33 wt%) consistent with derivation by fractional crystallization, although it is not clear whether these rocks belong to the nephelinite or basanite series. Lamprophyre dikes within the complex are considered as good representatives of the basanite parental magma. Compositions of calculated melts in equilibrium with diopside cores from clinopyroxenites are quite similar to those of the lamprophyres, suggesting that at least a part of the clinopyroxenites is related to the basanite series. Some feldspar-bearing rocks (i.e. meladiorite and monzonite) show petrographic features and geochemical and isotope compositions indicative of crustal assimilation, although this may be relegated to a local process. Relatively high CaO/Al2O3 and La/Zr and low Ti/Eu ratios from the lamprophyres and calculated melts in equilibrium with cumulus clinopyroxene point to a lithospheric mantle metasomatized by CO2-rich fluids, suggesting vein-plus-wall-rock melting mechanisms. The chemical differences among those liquids are thought to reflect both variable contributions of melting resulting from veins and variable clinopyroxene/garnet proportions of the source.

Reduced order models for prediction of groundwater quality impacts from CO₂ and brine leakage

DOE PAGES

Zheng, Liange; Carroll, Susan; Bianchi, Marco; ...

2014-12-31

A careful assessment of the risk associated with geologic CO₂ storage is critical to the deployment of large-scale storage projects. A potential risk is the deterioration of groundwater quality caused by the leakage of CO₂ and brine leakage from deep subsurface reservoirs. In probabilistic risk assessment studies, numerical modeling is the primary tool employed to assess risk. However, the application of traditional numerical models to fully evaluate the impact of CO₂ leakage on groundwater can be computationally complex, demanding large processing times and resources, and involving large uncertainties. As an alternative, reduced order models (ROMs) can be used as highlymore » efficient surrogates for the complex process-based numerical models. In this study, we represent the complex hydrogeological and geochemical conditions in a heterogeneous aquifer and subsequent risk by developing and using two separate ROMs. The first ROM is derived from a model that accounts for the heterogeneous flow and transport conditions in the presence of complex leakage functions for CO₂ and brine. The second ROM is obtained from models that feature similar, but simplified flow and transport conditions, and allow for a more complex representation of all relevant geochemical reactions. To quantify possible impacts to groundwater aquifers, the basic risk metric is taken as the aquifer volume in which the water quality of the aquifer may be affected by an underlying CO₂ storage project. The integration of the two ROMs provides an estimate of the impacted aquifer volume taking into account uncertainties in flow, transport and chemical conditions. These two ROMs can be linked in a comprehensive system level model for quantitative risk assessment of the deep storage reservoir, wellbore leakage, and shallow aquifer impacts to assess the collective risk of CO₂ storage projects.« less

Geochemistry, petrography, and zircon U-Pb geochronology of Paleozoic metaigneous rocks in the Mount Veta area of east-central Alaska: implications for the evolution of the westernmost part of the Yukon-Tanana terrane

USGS Publications Warehouse

Dusel-Bacon, Cynthia; Day, Warren C.; Aleinikoff, John N.

2013-01-01

We report the results of new mapping, whole-rock major, minor, and trace-element geochemistry, and petrography for metaigneous rocks from the Mount Veta area in the westernmost part of the allochthonous Yukon–Tanana terrane (YTT) in east-central Alaska. These rocks include tonalitic mylonite gneiss and mafic metaigneous rocks from the Chicken metamorphic complex and the Nasina and Fortymile River assemblages. Whole-rock trace-element data from the tonalitic gneiss, whose igneous protolith was dated by SHRIMP U–Pb zircon geochronology at 332.6 ± 5.6 Ma, indicate derivation from tholeiitic arc basalt. Whole-rock analyses of the mafic rocks suggest that greenschist-facies rocks from the Chicken metamorphic complex, a mafic metavolcanic rock from the Nasina assemblage, and an amphibolite from the Fortymile River assemblage formed as island-arc tholeiite in a back-arc setting; another Nasina assemblage greenschist has MORB geochemical characteristics, and another mafic metaigneous rock from the Fortymile River assemblage has geochemical characteristics of calc-alkaline basalt. Our geochemical results imply derivation in an arc and back-arc spreading region within the allochthonous YTT crustal fragment, as previously proposed for correlative units in other parts of the terrane. We also describe the petrography and geochemistry of a newly discovered tectonic lens of Alpine-type metaharzburgite. The metaharzburgite is interpreted to be a sliver of lithospheric mantle from beneath the Seventymile ocean basin or from sub-continental mantle lithosphere of the allochthonous YTT or the western margin of Laurentia that was tectonically emplaced within crustal rocks during closure of the Seventymile ocean basin and subsequently displaced and fragmented by faults.

Porphyry Cu-Au mineralization in the Mirkuh Ali Mirza magmatic complex, NW Iran

NASA Astrophysics Data System (ADS)

Maghsoudi, A.; Yazdi, M.; Mehrpartou, M.; Vosoughi, M.; Younesi, S.

2014-01-01

The Mirkuh Ali Mirza Cu-Au porphyry system in East Azerbaijan Province is located on the western part of the Cenozoic Alborz-Azerbaijan volcanic belt. The belt is also an important Cu-Mo-Au metallogenic province in northwestern Iran. The exposed rocks in the study area consist of a volcaniclastic sequence, subvolcanic rocks and intermediate to mafic lava flows of Neogene age. The volcanic rocks show a typical subduction-related magmatic arc geological and geochemical signature, with low concentration of Nb, Ta, and Ti. Mineralization is hosted by Neogene dacitic tuff and porphyritic dacite situated at the intersections of northeast and northwest faults. Field observations, alteration zonation, geochemical haloes and isotopic data of the Mirkuh Ali Mirza magmatic complex show similarities with typical convergent margin Cu-Au porphyry type deposits. The following features confirm the classic model for Cu-Au porphyry systems: (a) close spatial association with high-K calcalkaline to shoshonitic rock related to post-collision extensional setting (b) low grade Cu (0.57%) (c) stockworks as well as disseminated sulfides (c) zonality of the alteration patterns from intense phyllic at the center to outward weak-phyllic, argillic, and propylitic (d) the presence of a pyritic halo (e) accompanied by sheeted veins and low-sulfidation epithermal gold (f) mineralization spatially associated with intersection of structures, (g) genetically related to diorite porphyry stocks at depth (h) geochemical zonation of (Cu ± Au ± Ag ± Bi) → (Cu + Mo ± Bi ± Au ± Pb ± Zn ± As) → (Au + Mo ± Pb ± Zn) → (As + Ag + Sb + Mn + Ba + Pb + Zn + Hg) → Hg from center to outwards (i) The range of sulfur isotopic values is approximately zero (interpreted to have magmatic source) and similar to other subduction-related porphyry Cu deposits.

Environmental chemistry at vapor/water interfaces: insights from vibrational sum frequency generation spectroscopy.

PubMed

Jubb, Aaron M; Hua, Wei; Allen, Heather C

2012-01-01

The chemistry that occurs at surfaces has been an intense area of study for many years owing to its complexity and importance in describing a wide range of physical phenomena. The vapor/water interface is particularly interesting from an environmental chemistry perspective as this surface plays host to a wide range of chemistries that influence atmospheric and geochemical interactions. The application of vibrational sum frequency generation (VSFG), an inherently surface-specific, even-order nonlinear optical spectroscopy, enables the direct interrogation of various vapor/aqueous interfaces to elucidate the behavior and reaction of chemical species within the surface regime. In this review we discuss the application of VSFG to the study of a variety of atmospherically important systems at the vapor/aqueous interface. Chemical systems presented include inorganic ionic solutions prevalent in aqueous marine aerosols, small molecular solutes, and long-chain fatty acids relevant to fat-coated aerosols. The ability of VSFG to probe both the organization and reactions that may occur for these systems is highlighted. A future perspective toward the application of VSFG to the study of environmental interfaces is also provided.

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

USGS Publications Warehouse

Donato, M.M.

1991-01-01

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

Microstructures imply cataclasis and authigenic mineral formation control geomechanical properties of New Zealand's Alpine Fault

NASA Astrophysics Data System (ADS)

Schuck, B.; Janssen, C.; Schleicher, A. M.; Toy, V. G.; Dresen, G.

2018-05-01

The Alpine Fault is capable of generating large (MW > 8) earthquakes and is the main geohazard on South Island, NZ, and late in its 250-291-year seismic cycle. To minimize its hazard potential, it is indispensable to identify and understand the processes influencing the geomechanical behavior and strength-evolution of the fault. High-resolution microstructural, mineralogical and geochemical analyses of the Alpine Fault's core demonstrate wall rock fragmentation, assisted by mineral dissolution, and cementation resulting in the formation of a fine-grained principal slip zone (PSZ). A complex network of anastomosing and mutually cross-cutting calcite veins implies that faulting occurred during episodes of dilation, slip and sealing. Fluid-assisted dilatancy leads to a significant volume increase accommodated by vein formation in the fault core. Undeformed euhedral chlorite crystals and calcite veins that have cut footwall gravels demonstrate that these processes occurred very close to the Earth's surface. Microstructural evidence indicates that cataclastic processes dominate the deformation and we suggest that powder lubrication and grain rolling, particularly influenced by abundant nanoparticles, play a key role in the fault core's velocity-weakening behavior rather than frictional sliding. This is further supported by the absence of smectite, which is reasonable given recently measured geothermal gradients of more than 120 °C km-1 and the impermeable nature of the PSZ, which both limit the growth of this phase and restrict its stability to shallow depths. Our observations demonstrate that high-temperature fluids can influence authigenic mineral formation and thus control the fault's geomechanical behavior and the cyclic evolution of its strength.

Hydrologic Responses to CO2 Injection in Basalts Based on Flow-through Experiments

NASA Astrophysics Data System (ADS)

Thomas, D.; Hingerl, F.; Garing, C.; Bird, D. K.; Benson, S. M.; Maher, K.

2015-12-01

Experimental studies of basalt-CO2 interactions have increased our ability to predict geochemical responses within a mafic reservoir during geologic CO2 sequestration. However, the lack of flow-through experiments prevents the use of coupled hydrologic-geochemical models to predict evolution of permeability and porosity, critical parameters for assessing storage feasibility. We present here results of three flow-through experiments on an intact basalt core during which we employed X-ray Computed Tomography (CT) to quantify porosity evolution and fluid flow. Using a single core of glassy basaltic tuff from the Snake River Plain (Menan Buttes complex), we performed tracer tests using a solution of NaI (~100,000 ppm) before and after injection of CO2-saturated water at reservoir conditions (90 bar, 50°C) to image porosity and flow path distribution. During the tracer tests, CT scans were taken at 2.5-minute intervals, and outlet fluid was discretely sampled at the same intervals and subsequently measured via ICP-MS, enabling interpretation of the tracer breakthrough curve through both imaging and geochemical analyses. Comparison of the porosity distribution from before and after injection of CO2 shows an overall decrease in core-averaged porosity from 34% to 31.1%. Permeability decreased exponentially from ~4.9x10-12 m2 to 1.18 x10-12 m2. The decrease in porosity and permeability suggests geochemical transformations in the mineral assemblage of the core, which we observe through petrographic analysis of an unaltered sample of the same lithology in contrast with the altered core. There is a significant increase in grain coatings, as well as reduction in the grain size, suggesting dissolution re-precipitation mechanisms. Finally, to develop a framework for the coupled geochemical and hydrologic responses observed experimentally, we have calibrated a reactive transport model at the core scale using the TOUGHREACT simulator [1]. [1] Xu et al. (2011) Comput. Geosci.

Geochemical modeling of mercury speciation in surface water and implications on mercury cycling in the everglades wetland.

PubMed

Jiang, Ping; Liu, Guangliang; Cui, Wenbin; Cai, Yong

2018-06-01

The geochemical model PHREEQC, abbreviated from PH (pH), RE (redox), EQ (equilibrium), and C (program written in C), was employed on the datasets generated by the USEPA Everglades Regional Environmental Monitoring and Assessment Program (R-EMAP) to determine the speciation distribution of inorganic mercury (iHg) in Everglades water and to explore the implications of iHg speciation on mercury cycling. The results suggest that sulfide and DOM were the key factors that regulate inorganic Hg speciation in the Everglades. When sulfide was present at measurable concentrations (>0.02 mg/L), Hg-S complexes dominated iHg species, occurring in the forms of HgS 2 2- , HgHS 2 - , and Hg(HS) 2 that were affected by a variety of environmental factors. When sulfide was assumed nonexistent, Hg-DOM complexes occurred as the predominant Hg species, accounting for almost 100% of iHg species. However, when sulfide was presumably present at a very low, environmentally relevant concentration (3.2 × 10 -7  mg/L), both Hg-DOM and Hg-S complexes were present as the major iHg species. These Hg-S species and Hg-DOM complex could be related to methylmercury (MeHg) in environmental matrices such floc, periphyton, and soil, and the correlations are dependent upon different circumstances (e.g., sulfide concentrations). The implications of the distribution of iHg species on MeHg production and fate in the Everglades were discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Hydrogeological study of the aquifer system of the northern Sahara in the Algero-Tunisian border: A case study of Oued Souf region

NASA Astrophysics Data System (ADS)

Halassa, Younes; Zeddouri, Aziez; Mouhamadou, Ould Babasy; Kechiched, Rabah; Benhamida, Abdeldjebbar Slimane

2018-05-01

The aquifer system in The Algero-Tunisian border and Chotts region is mainly composed of two aquifers: The first is the Complex Terminal (CT) and the second is the Intercalary aquifer (CI). This study aims the identification and spatial evolution of factors that controlling the water quality in the Complex Terminal aquifer (CT) in the Chotts region (Oued Souf region - Southeastern of Algeria). The concentration of major elements, temperature, pH and salinity were monitored during 2015 in 34 wells from the CT aquifer. The geological, geophysical, hydrogeological and hydrochemical methods were applied in order to carried out a model for the investigated aquifer system and to characterize the hydrogeological and the geochemical behavior, as well as the geometrical and the lithological configuration. Multivariate statistical analyses such as Principal Component Analysis (PCA) were also used for the treatment of several data. Results show that the salinity follows the same regional distribution of Chloride, Sodium, Magnesium, Sulfate and Calcium. Note that the salinity shows low contents in the upstream part of investigated region suggesting restricted dissolution of salts. Hydro-chemical study and saturation indexes highlight the dominance of the dissolution and the precipitation of calcite, dolomite, anhydrite, gypsum and halite. The PCA analysis indicates that Na+, Cl-, Ca2+, Mg2+, SO42- and K+ variables that influence the water mineralization.

Controls on the Fate and Speciation of Np(V) During Iron (Oxyhydr)oxide Crystallization.

PubMed

Bots, Pieter; Shaw, Samuel; Law, Gareth T W; Marshall, Timothy A; Mosselmans, J Frederick W; Morris, Katherine

2016-04-05

The speciation and fate of neptunium as Np(V)O2(+) during the crystallization of ferrihydrite to hematite and goethite was explored in a range of systems. Adsorption of NpO2(+) to iron(III) (oxyhydr)oxide phases was reversible and, for ferrihydrite, occurred through the formation of mononuclear bidentate surface complexes. By contrast, chemical extractions and X-ray absorption spectroscopy (XAS) analyses showed the incorporation of Np(V) into the structure of hematite during its crystallization from ferrihydrite (pH 10.5). This occurred through direct replacement of octahedrally coordinated Fe(III) by Np(V) in neptunate-like coordination. Subsequent analyses on mixed goethite and hematite crystallization products (pH 9.5 and 11) showed that Np(V) was incorporated during crystallization. Conversely, there was limited evidence for Np(V) incorporation during goethite crystallization at the extreme pH of 13.3. This is likely due to the formation of a Np(V) hydroxide precipitate preventing incorporation into the goethite particles. Overall these data highlight the complex behavior of Np(V) during the crystallization of iron(III) (oxyhydr)oxides, and demonstrate clear evidence for neptunium incorporation into environmentally important mineral phases. This extends our knowledge of the range of geochemical conditions under which there is potential for long-term immobilization of radiotoxic Np in natural and engineered environments.

Geochemistry of selenium.

PubMed

Kabata-Pendias, A

1998-01-01

Selenium (Se) is one of the most peculiar chemical elements in the geo- and biospheres. It partly resembles sulfur and tellurium; however, its behavior in the geosphere and its functions in the biosphere are very specific. Despite a relatively large database, its cycling in both the natural environment and in that modified by human activities requires further study. Selenium is rather concentrated in the geospheric cycle and is also bioconcentrated. The values of its accumulation ratios are: 5 for soil/sandstone, 2 for animal tissues/sandstone, and 5 for animal tissues/grain. For a specific plant/soil system, the bioconcentration factor for plants always has to be estimated because some plants can absorb extremely high concentrations of Se. Their ability to accumulate and tolerate high Se levels is related to different Se metabolisms. These plants play a significant role in geochemical prospecting and animal nutrition. This paper presents some geochemical observations toward a better understanding of the environmental properties of Se.

Geochemical exploration for copper-nickel deposits in the cool-humid climate of northeastern Minnesota

USGS Publications Warehouse

Miller, W.R.; Ficklin, W.H.; McHugh, J.B.

1992-01-01

Water was used as a medium for geochemical exploration to detect copper-nickel mineralization along the basal zone of the Duluth Complex. Ni2+ is the most important pathfinder for the detection of the mineralized rocks, followed by Cu2+ and SO42- and to a lesser extent Mg2+ and SiO2. A normalized sum plot using these species defines the mineralization more consistently than a single-element plot, mainly because the absence of one variable does not significantly influence the normalized sum value. A hydrogeochemical survey was conducted in an area of known copper-nickel mineralization in the cool-humid climate of northeastern Minnesota. The area is covered with glacial drift, and wetlands are abundant. Modeling of the chemistry of waters indicates that the waters are oxidizing and have a pH of 7 or less. The most important pathfinder species in the waters, Cu2+, Ni2+, and SO42-, are derived from the simple weathering of sulfide minerals and are mobile in the waters in this environment. Plots of Cu and Ni concentrations in soils show that Cu followed by Ni are the most useful indicator elements for delineating copper-nickel mineralization. The ability of soils and water to delineate the mineralization supports the use of both media for geochemical exploration in this cool-humid environment. In the wetlands, abundant water is available and soils are scarce or absent; where soils are abundant, waters are generally scarce or absent. The use of both media is recommended for geochemical exploration in this environment. ?? 1992.

Fluid-rock interactions related to metamorphic reducing fluid flow in meta-sediments: example of the Pic-de-Port-Vieux thrust (Pyrenees, Spain)

NASA Astrophysics Data System (ADS)

Trincal, Vincent; Buatier, Martine; Charpentier, Delphine; Lacroix, Brice; Lanari, Pierre; Labaume, Pierre; Lahfid, Abdeltif; Vennemann, Torsten

2017-09-01

In orogens, shortening is mainly accommodated by thrusts, which constitute preferential zones for fluid-rock interactions. Fluid flow, mass transfer, and mineralogical reactions taking place along thrusts have been intensely investigated, especially in sedimentary basins for petroleum and uranium research. This study combines petrological investigations, mineralogical quantifications, and geochemical characterizations with a wide range of analytical tools with the aim of defining the fluid properties (nature, origin, temperature, and redox) and fluid-host rock interactions (mass transfers, recrystallization mechanisms, and newly formed synkinematic mineralization) in the Pic-de-Port-Vieux thrust fault zone (Pyrenees, Spain). We demonstrate that two geochemically contrasted rocks have been transformed by fluid flow under low-grade metamorphism conditions during thrusting. The hanging-wall Triassic red pelite was locally bleached, while the footwall Cretaceous dolomitic limestone was mylonitized. The results suggest that thrusting was accompanied by a dynamic calcite recrystallization in the dolomitic limestone as well as by leaching of iron via destabilization of iron oxides and phyllosilicate crystallization in the pelite. Geochemical and physical changes highlighted in this study have strong implications on the understanding of the thrust behavior (tectonic and hydraulic), and improve our knowledge of fluid-rock interactions in open fluid systems in the crust.

Hydrochemical analysis to evaluate the seawater ingress in a small coral island of India.

PubMed

Banerjee, Pallavi; Singh, V S; Singh, Ajay; Prasad, R K; Rangarajan, R

2012-06-01

The sustainable development of the limited groundwater resources in the tropical island requires a thorough understanding of detail hydrogeological regime including the hydrochemical behavior of groundwater. Detail analysis of chemical data of groundwater helps in assessing the different groundwater zone affected by formation as well as sea water. Groundwater and saline water interaction is better understood using groundwater major ion chemistry over an island aquifer. Multivariate methods to analyze the geochemical data are used to understand geochemical evolution of groundwater. The methods are successfully used to group the data to evaluate influence of various environs in the study area. Various classification methods such as piper, correlation method, and salinity hazard measurements are also employed to critical study of geochemical characteristics of groundwater to identify vulnerable parts of the aquifer. These approaches have been used to successfully evaluate the aquifer zones of a tiny island off the west coast of India. The most part of island is found to be safe for drinking, however some parts of island are identified that are affected by sea water ingress and dissolution of formation minerals. The analysis has successfully leaded to identification of that part of aquifer on the island which needs immediate attention for restoration and avoids further deterioration.

The southwestern extension of the Jiao-Liao-Ji belt in the North China Craton: Geochronological and geochemical evidence from the Wuhe Group in the Bengbu area

NASA Astrophysics Data System (ADS)

Liu, Chaohui; Zhao, Guochun; Liu, Fulai; Cai, Jia

2018-04-01

The Wuhe complex is located at the southeastern margin of the North China Craton. The complex consists of metamorphosed Paleoproterozoic potassic granitoids and supracrustal rocks, of which the latter include the Fengyang and Wuhe groups. Meta-mafic rocks from the lower Wuhe Group have igneous zircon U-Pb ages of 2126 ± 37 Ma with εHf(t) values of -6.22 to +8.38, and xenocrystic zircons of 2.39-2.36 Ga, 2.55-2.54 Ga and 2.77-2.69 Ga. Geochemically, the meta-mafic rocks can be classified into two groups. Group 1 island arc tholeiites display flat to slightly right declined REE patterns and moderately negative Nb, Ta, Zr, and Ti anomalies. Group 2 mature arc calcalkaline basalts display strongly fractionated chondrite-normalized REE patterns and evidently negative Nb, Ta and Ti anomalies. These meta-mafic rocks formed by partial melting of sub-arc depleted mantle wedge which had been modified by slab-derived melts at an active continental margin. Depositional age of the group can be constrained in the period of 2.16-2.10 Ga based on ages of the youngest detrital zircons and latter intrusions. U-Pb ages of detrital zircons yield major age peaks of 2.69 Ga and 2.52 Ga, with minor peaks at 2.88 Ga, 2.78 Ga, 2.35 Ga and 2.17 Ga, most of which are derived from the late Mesoarchean to early Paleoproterozoic granitoids in the Wuhe complex and the Jiaodong Terrane. Metamorphic zircons in the marbles coexisting with garnet amphibolites or granulites occur as either single grains or overgrowth (or recrystallization) rims surrounding magmatic zircon cores and yield ages of 1882 ± 19 Ma to 1844 ± 15 Ma. The comparable ca. 2.1 Ga potassic granites with A-type granite affinity, the ca. 2.1 Ga meta-mafic rocks with arc-like geochemical features, the 2.1-1.9 Ga meta-sedimentary units and the 1.9-1.8 Ga subduction- and collision-related granulite-facies metamorphism suggest that the Wuhe complex and the Jiao-Liao-Ji Belt share the same late Paleoproterozoic tectonic evolution process and the former is the southwestern extension of the latter.

Alkaline igneous rocks of Magnet Cove, Arkansas: Mineralogy and geochemistry of syenites

USGS Publications Warehouse

Flohr, M.J.K.; Ross, M.

1990-01-01

Syenites from the Magnet Cove alkaline igneous complex form a diverse mineralogical and geochemical suite. Compositional zoning in primary and late-stage minerals indicates complex, multi-stage crystallization and replacement histories. Residual magmatic fluids, rich in F, Cl, CO2 and H2O, reacted with primary minerals to form complex intergrowths of minerals such as rinkite, fluorite, V-bearing magnetite, F-bearing garnet and aegirine. Abundant sodalite and natrolite formed in pegmatitic segregations within nepheline syenite where Cl- and Na-rich fluids were trapped. During autometasomatism compatible elements such as Mn, Ti, V and Zr were redistributed on a local scale and concentrated in late-stage minerals. Early crystallization of apatite and perovskite controlled the compatible behavior of P and Ti, respectively. The formation of melanite garnet also affected the behaviour of Ti, as well as Zr, Hf and the heavy rare-earth elements. Pseudoleucite syenite and garnet-nepheline syenite differentiated along separate trends, but the two groups are related to the same parental magma by early fractionation of leucite, the presumed precursor of intergrowths of K-feldspar and nepheline. The Diamond Jo nepheline syenite group defines a different differentiation trend. Sphene-nepheline syenite, alkali syenite and several miscellaneous nepheline syenites do not consistently plot with the other syenite groups or each other on element and oxide variation diagrams, indicating that they were derived from still other parental syenite magmas. Mineral assemblages indicate that relatively high f{hook};O2, at or above the fayalite-magnetite-quartz buffer, prevailed throughout the crystallization history of the syenites. ?? 1990.

Geochemistry of Rock Samples Collected from the Iron Hill Carbonatite Complex, Gunnison County, Colorado

USGS Publications Warehouse

Van Gosen, Bradley S.

2008-01-01

A study conducted in 2006 by the U.S. Geological Survey collected 57 surface rock samples from nine types of intrusive rock in the Iron Hill carbonatite complex. This intrusive complex, located in Gunnison County of southwestern Colorado, is known for its classic carbonatite-alkaline igneous geology and petrology. The Iron Hill complex is also noteworthy for its diverse mineral resources, including enrichments in titanium, rare earth elements, thorium, niobium (columbium), and vanadium. This study was performed to reexamine the chemistry and metallic content of the major rock units of the Iron Hill complex by using modern analytical techniques, while providing a broader suite of elements than the earlier published studies. The report contains the geochemical analyses of the samples in tabular and digital spreadsheet format, providing the analytical results for 55 major and trace elements.

Geochemical Constraints for Mercury's PCA-Derived Geochemical Terranes

NASA Astrophysics Data System (ADS)

Stockstill-Cahill, K. R.; Peplowski, P. N.

2018-05-01

PCA-derived geochemical terranes provide a robust, analytical means of defining these terranes using strictly geochemical inputs. Using the end members derived in this way, we are able to assess the geochemical implications for Mercury.

Markov Chain Monte Carlo Inversion of Mantle Temperature and Composition, with Application to Iceland

NASA Astrophysics Data System (ADS)

Brown, Eric; Petersen, Kenni; Lesher, Charles

2017-04-01

Basalts are formed by adiabatic decompression melting of the asthenosphere, and thus provide records of the thermal, chemical and dynamical state of the upper mantle. However, uniquely constraining the importance of these factors through the lens of melting is challenging given the inevitability that primary basalts are the product of variable mixing of melts derived from distinct lithologies having different melting behaviors (e.g. peridotite vs. pyroxenite). Forward mantle melting models, such as REEBOX PRO [1], are useful tools in this regard, because they can account for differences in melting behavior and melt pooling processes, and provide estimates of bulk crust composition and volume that can be compared with geochemical and geophysical constraints, respectively. Nevertheless, these models require critical assumptions regarding mantle temperature, and lithologic abundance(s)/composition(s), all of which are poorly constrained. To provide better constraints on these parameters and their uncertainties, we have coupled a Markov Chain Monte Carlo (MCMC) sampling technique with the REEBOX PRO melting model. The MCMC method systematically samples distributions of key REEBOX PRO input parameters (mantle potential temperature, and initial abundances and compositions of the source lithologies) based on a likelihood function that describes the 'fit' of the model outputs (bulk crust composition and volume and end-member peridotite and pyroxenite melts) relative to geochemical and geophysical constraints and their associated uncertainties. As a case study, we have tested and applied the model to magmatism along Reykjanes Peninsula in Iceland, where pyroxenite has been inferred to be present in the mantle source. This locale is ideal because there exist sufficient geochemical and geophysical data to estimate bulk crust compositions and volumes, as well as the range of near-parental melts derived from the mantle. We find that for the case of passive upwelling, the models that best fit the geochemical and geophysical observables require elevated mantle potential temperatures ( 120 °C above ambient mantle), and 5% pyroxenite. The modeled peridotite source has a trace element composition similar to depleted MORB mantle, whereas the trace element composition of the pyroxenite is similar to enriched mid-ocean ridge basalt. These results highlight the promise of this method for efficiently exploring the range of mantle temperatures, lithologic abundances, and mantle source compositions that are most consistent with available observational constraints in individual volcanic systems. 1 Brown and Lesher (2016), G-cubed, 17, 3929-3968

Numerically Simulating Carbonate Mineralization of Basalt with Injection of Carbon Dioxide into Deep Saline Formations

DOE Office of Scientific and Technical Information (OSTI.GOV)

White, Mark D.; McGrail, B. Peter; Schaef, Herbert T.

2006-07-08

The principal mechanisms for the geologic sequestration of carbon dioxide in deep saline formations include geological structural trapping, hydrological entrapment of nonwetting fluids, aqueous phase dissolution and ionization, and geochemical sorption and mineralization. In sedimentary saline formations the dominant mechanisms are structural and dissolution trapping, with moderate to weak contributions from hydrological and geochemical trapping; where, hydrological trapping occurs during the imbibition of aqueous solution into pore spaces occupied by gaseous carbon dioxide, and geochemical trapping is controlled by generally slow reaction kinetics. In addition to being globally abundant and vast, deep basaltic lava formations offer mineralization kinetics that makemore » geochemical trapping a dominate mechanism for trapping carbon dioxide in these formations. For several decades the United States Department of Energy has been investigating Columbia River basalt in the Pacific Northwest as part of its environmental programs and options for natural gas storage. Recently this nonpotable and extensively characterized basalt formation is being reconsidered as a potential reservoir for geologic sequestration of carbon dioxide. The reservoir has an estimated storage capacity of 100 giga tonnes of carbon dioxide and comprises layered basalt flows with sublayering that generally alternates between low permeability massive and high permeability breccia. Chemical analysis of the formation shows 10 wt% Fe, primarily in the +2 valence. The mineralization reaction that makes basalt formations attractive for carbon dioxide sequestration is that of calcium, magnesium, and iron silicates reacting with dissolved carbon dioxide, producing carbonate minerals and amorphous quartz. Preliminary estimates of the kinetics of the silicate-to-carbonate reactions have been determined experimentally and this research is continuing to determine effects of temperature, pressure, rock composition and mineral assemblages on the reaction rates. This study numerically investigates the injection, migration and sequestration of supercritical carbon dioxide in deep Columbia River basalt formations using the multifluid subsurface flow and reactive transport simulator STOMP-CO2 with its ECKEChem module. Simulations are executed on high resolution multiple stochastic realizations of the layered basalt systems and demonstrate the migration behavior through layered basalt formations and the mineralization of dissolved carbon dioxide. Reported results include images of the migration behavior, distribution of carbonate formation, quantities of injected and sequestered carbon dioxide, and percentages of the carbon dioxide sequestered by different mechanisms over time.« less

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 crustal remelts associated with large impact craters. A resetting mechanism involving aggressive hydrothermal alteration of zircon facilitated by halogen-complexing is proposed, inducing rapid, postshock lead loss and subsequent annealing.

Tectonic Origin of Serpentinites on Syros, Greece: Geochemical Signatures of Seafloor Serpentinization Preserved in the HP/LT Subduction Complex

NASA Astrophysics Data System (ADS)

Raia, N. H.; Cooperdock, E. H. G.; Barnes, J.; Stockli, D. F.; Schwarzenbach, E. M.

2016-12-01

Serpentinized ultramafic rocks are commonly found in exhumed HP/LT subduction complexes, but their tectonic origins (i.e., setting of serpentinization) are difficult to decipher due to extensive alteration. Growing literature and geochemical datasets demonstrate that immobile elements (REE, HFSE) in serpentinites can retain magmatic signatures indicative of the tectonic setting of parent peridotite, while fluid-mobile elements and stable isotopic signatures shed light on the fluids causing serpentinization. This study combines whole-rock trace and major element geochemistry, stable isotope (δD and δO) analyses with petrographic observation to determine the tectonic origin of ultramafic rocks in the HP/LT Aegean subduction complex. The best-preserved HP rocks of the Cycladic Blueschist Unit (CBU) are found on Syros, Greece, where serpentinized ultramafic rocks within the CBU are closely associated with metamorphosed remnants of subducted oceanic crust. All samples are completely serpentinized, lacking relict pyroxene or spinel grains, with typical assemblages consisting of serpentine, talc, chlorite, magnetite, and minor carbonate. The serpentinizing fluid was characterized using stable isotopes. δD and δO values of bulk-rock serpentinite powders and chips, respectively, suggest seafloor serpentinites hydrated by seawater at low T, typical of alteration at mid-ocean ridges and hyper-extended margins (δD = -64 to -33‰ and δO = 5.2 to 9.0‰). To fingerprint a tectonic origin, whole rock serpentinite REE patterns are compared to a global database of whole rock serpentinite analyses from fore-arc mantle wedge, mid-ocean ridge, and hyper-extended margin tectonic settings. Whole rock major element, trace element, and REE analyses are consistent with limited melt extraction, flat REE patterns (LaN/SmN = 0.2-2.6, SmN/YbN = 0.3-3.5; N= C1 normalized), and do not show pronounced Eu anomalies. These data are consistent with abyssal peridotites derived from hyper-extended margin settings, although some overlap with mid-ocean ridge serpentinites makes it difficult to rule out. In any case, the geochemical signatures retained in these serpentinites indicate they are unlikely sourced from the mantle wedge, as has been historically speculated.

Elemental mobility in sulfidic mine tailings reclaimed with paper mill by-products as sealing materials.

PubMed

Jia, Yu; Stahre, Nanna; Mäkitalo, Maria; Maurice, Christian; Öhlander, Björn

2017-09-01

Sealing layers made of two alkaline paper mill by-products, fly ash and green liquor dregs, were placed on top of 50-year-old sulfide-containing tailings as a full-scale remediation approach. The performance and effectiveness of the sealing layers with high water content for an oxygen barrier and low hydraulic conductivity for a sealing layer in preventing the formation of acid rock drainage were evaluated 5 years after the remediation. The leaching behavior of the covered tailings was studied using batch leaching tests (L/S ratio 10 L/kg). The leaching results revealed that, in general, the dregs- and ash-covered tailings released relatively lower concentrations of many elements contained in acid rock drainage compared to those from the uncovered tailings. A change in the chemical composition and mineralogical state of the tailings was observed for the tailings beneath the covers. The increase in pH caused by the alkaline materials promoted metal precipitation. Geochemical modeling using PHREEQC confirmed most of the geochemical changes of the covered tailings. Both the ash and dregs showed potential to function as sealing materials in terms of their geochemical properties. However, mobilization of Zn and Ni from the lower part of the dregs-covered tailings was observed. The same phenomenon was observed for the lower part of the ash-covered tailings. Ash showed advantages over dregs as a cover material; based on geochemical studies, the ash immobilized more elements than the dregs did. Lysimeters were installed below the sealing layers, and infiltrating water chemistry and hydrology were studied to monitor the amount and quality of the leachate percolating through.

Using an intelligent system to aid in tephra layer correlation of the tephra beds of the Mono-Inyo Craters, California

NASA Astrophysics Data System (ADS)

Hanson-Hedgecock, S.; Bursik, M.; Rogova, G.

2008-12-01

We are developing an intelligent system to correlate tephra layers by using the lithologic and geochemical characteristics of field samples, to aid geologists in interpreting eruption patterns in volcanic fields. Understanding the eruption history of a volcanic field from stratigraphic studies is important for forecasting future eruptive behavior and hazards. The intelligent system is used to define groups of tephra source vents and to correlate tephra layers based on a combination of geochemical data and lithostratigraphic characteristics. The tephra beds of the Mono-Inyo Craters, California, are used to test the ability of the intelligent system for tephra layer correlation. The data processing is performed by a suite of both unsupervised and supervised classifiers, built and combined within the framework of the Dempster-Shafer theory of evidence. We have developed algorithms to calculate isopleth maps of thickness, lithic and pumice size that are used in the processing of the lithostratigraphic data. This spatial information is important in the determination of eruption patterns and is used by an evidential nearest neighbor classifier to correlate tephra layers. Integrating a better isopleth approximation function and expert knowledge about stratigraphic order of the tephra layers into the classifier improves the lithostratigraphic correlation from 56% to 87% of layers correctly identified. Geochemical data for defining groups of tephra sources are processed by a suit of fuzzy k-means classifiers. Improved clustering results of geochemical data are achieved by the fusion of individual clustering results with an evidential combination method. The intelligent system aids correlation by showing matches and disparities between data patterns from different outcrops that may have been overlooked. The intelligent system produces a useful recognition result, while dealing with the uncertainty from sparse data and the imprecise description of layer characteristics.

Micromechanical Tests and Geochemical Modeling to Evaluate Evolution of Rock Alteration by CO2-Water Mixtures

NASA Astrophysics Data System (ADS)

Aman, M.; Sun, Y.; Ilgen, A.; Espinoza, N.

2015-12-01

Injection of large volumes of CO2 into geologic formations can help reduce the atmospheric CO2 concentration and lower the impact of burning fossil fuels. However, the injection of CO2 into the subsurface shifts the chemical equilibrium between the mineral assemblage and the pore fluid. This shift will situationally facilitate dissolution and reprecipitation of mineral phases, in particular intergranular cements, and can potentially affect the long term mechanical stability of the host formation. The study of these coupled chemical-mechanical reservoir rock responses can help identify and control unexpected emergent behavior associated with geological CO2 storage.Experiments show that micro-mechanical methods are useful in capturing a variety of mechanical parameters, including Young's modulus, hardness and fracture toughness. In particular, micro-mechanical measurements are well-suited for examining thin altered layers on the surfaces of rock specimens, as well as capturing variability on the scale of lithofacies. We performed indentation and scratching tests on sandstone and siltstone rocks altered in natural CO2-brine environments, as well as on analogous samples altered under high pressure, temperature, and dissolved CO2 conditions in a controlled laboratory experiment. We performed geochemical modeling to support the experimental observations, in particular to gain the insight into mineral dissolution/precipitation as a result of the rock-water-CO2reactions. The comparison of scratch measurements performed on specimens both unaltered and altered by CO2 over geologic time scales results in statistically different values for fracture toughness and scratch hardness, indicating that long term exposure to CO2 caused mechanical degradation of the reservoir rock. Geochemical modeling indicates that major geochemical change caused by CO2 invasion of Entrada sandstone is dissolution of hematite cement, and its replacement with siderite and dolomite during the alteration process.

Manson impact structure, Iowa: First geochemical results for drill core M-1

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Anderson, Raymond R.; Hartung, Jack B.; Reimold, Wolf Uwe

1993-01-01

The Manson Impact Structure is a large complex impact crater centered ca. S km north of the town of Manson, Iowa. It is the largest intact impact structure recognized in the United States (35 km in diameter). Its Ar-40/Ar-39 age is indistinguishable from that of the Cretaceous-Tertiary (K-T) boundary. The Manson structure may be one element of the events at the K-T boundary. The crater is completely covered by Quaternary glacial sedimentary deposits that are normally underlain by Cretaceous clastic sediments and flat-lying carbonate sediments of Phanerozoic age, as well as Proterozoic red clastic, metamorphic, volcanic, and plutonic rock sequences. The study of a reflection seismic profile, provided by Amoco, was critical in interpreting the structure. In the 35 km diameter zone that marks the extension of the crater the normal rock sequence is disturbed due to the impact, and at the center of the structure granitic basement rocks are present that have been uplifted from about 4 km depth. Our studies consist of detailed petrological and geochemical characterization of all cores, with emphasis on a detailed description of all rock types found in the core samples and their relationship to target rocks. Geochemical data on samples from the Manson M-1 core are presented.

Manson impact structure, Iowa: First geochemical results for drill core M-1

NASA Astrophysics Data System (ADS)

Koeberl, Christian; Anderson, Raymond R.; Hartung, Jack B.; Reimold, Wolf Uwe

1993-03-01

The Manson Impact Structure is a large complex impact crater centered ca. S km north of the town of Manson, Iowa. It is the largest intact impact structure recognized in the United States (35 km in diameter). Its Ar-40/Ar-39 age is indistinguishable from that of the Cretaceous-Tertiary (K-T) boundary. The Manson structure may be one element of the events at the K-T boundary. The crater is completely covered by Quaternary glacial sedimentary deposits that are normally underlain by Cretaceous clastic sediments and flat-lying carbonate sediments of Phanerozoic age, as well as Proterozoic red clastic, metamorphic, volcanic, and plutonic rock sequences. The study of a reflection seismic profile, provided by Amoco, was critical in interpreting the structure. In the 35 km diameter zone that marks the extension of the crater the normal rock sequence is disturbed due to the impact, and at the center of the structure granitic basement rocks are present that have been uplifted from about 4 km depth. Our studies consist of detailed petrological and geochemical characterization of all cores, with emphasis on a detailed description of all rock types found in the core samples and their relationship to target rocks. Geochemical data on samples from the Manson M-1 core are presented.

A coupled THC model of the FEBEX in situ test with bentonite swelling and chemical and thermal osmosis.

PubMed

Zheng, Liange; Samper, Javier; Montenegro, Luis

2011-09-25

The performance assessment of a geological repository for radioactive waste requires quantifying the geochemical evolution of the bentonite engineered barrier. This barrier will be exposed to coupled thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes. This paper presents a coupled THC model of the FEBEX (Full-scale Engineered Barrier EXperiment) in situ test which accounts for bentonite swelling and chemical and thermal osmosis. Model results attest the relevance of thermal osmosis and bentonite swelling for the geochemical evolution of the bentonite barrier while chemical osmosis is found to be almost irrelevant. The model has been tested with data collected after the dismantling of heater 1 of the in situ test. The model reproduces reasonably well the measured temperature, relative humidity, water content and inferred geochemical data. However, it fails to mimic the solute concentrations at the heater-bentonite and bentonite-granite interfaces because the model does not account for the volume change of bentonite, the CO(2)(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO(3)(-) and pH data cannot be explained solely by solute transport, calcite dissolution and protonation/deprotonation by surface complexation, suggesting that such data may be affected also by other reactions. Published by Elsevier B.V.

Evolution of modern eukaryotes in the context of Cryogenian geochemical, tectonic and climatic changes (Invited)

NASA Astrophysics Data System (ADS)

Bosak, T.; MacDonald, F. A.; Pruss, S. B.; Lahr, D.

2010-12-01

The Cryogenian period (850-635 Ma) is one of the most dynamic periods in Earth history; its strata host evidence of the break-up of a super-continent, multiple low-latitude glaciations, the reorganization of geochemical cycles, the radiation of eukaryotes, and the origin of animals. However, relationships between the evolving ecosystems during this time, global glaciations and the cycling of carbon, sulfur and oxygen remain poorly understood. This is due to the lack of studies that couple geochemical and micropaleontological records in a stratigraphic and sedimentological context and the paucity of studies of sections that span the entire interval. Here we describe our current work on the recently discovered microfossil record from carbonate rocks deposited between the two Cryogenian low-latitude glaciations (710-635 million years ago) including the Tayshir Formation in Mongolia and cap carbonates from the Rasthof Formation in Namibia. This record provides constraints on the severity of Sturtian low-latitude glaciation and shows the presence of various modern eukaryotic lineages in late Cryogenian ecosystems and the first occurrences of various shell-building organisms. These biological changes gave rise to an increasing complexity of food webs that may have fed the first animals and influenced the sinking and burial of organic matter, ushering the Neoproterozoic revolution in biogeochemical cycling.

Geochemical, aeromagnetic, and generalized geologic maps showing distribution and abundance of antimony and tungsten, Golconda and Iron Point quadrangles, Humboldt County, Nevada

USGS Publications Warehouse

Erickson, R.L.; Marsh, S.P.

1971-01-01

Detailed geologic and geochemical studies of the four 7 1/2-minute quadrangles that make up the Edna Mountain 15-minute quadrangle in Humboldt County, Nevada, were begun during the 1969 summer field season. The objectives of the project are to map the geology of this structurally complex area at 1:24,000 scale and to determine the regional distribution and abundance of metals in rocks of the area and the factors that control the distribution and abundance of those metals. Tungsten-bearing hot-spring tufa, metalliferous black shale in Ordovician rocks , base-metal and barite deposits in Paleozoic sedimentary rocks, and copper molydbenum in granodiorite plutons of Cretaceous age occur in the Edna Mountain area. None of these deposits have been of much economic significance, although tungsten was mined from the hot-spring deposits during World War II. 

Geochemical, aeromagnetic, and generalized geologic maps showing distribution and abundance of gold and copper, Golconda and Iron Point quadrangles, Humboldt County, Nevada

USGS Publications Warehouse

Erickson, R.L.; Marsh, S.P.

1971-01-01

Detailed geologic and geochemical studies of the four 7 1/2-minute quadrangles that make up the Edna Mountain 15-minute quadrangle in Humboldt County, Nevada, were begun during the 1969 summer field season.  The objectives of the project are to map the geology of this structurally complex area at 1:24,000 scale and to determine the regional distribution and abundance of metals in rocks of the area and the factors that control the distribution and abundance of those metals.  Tungsten-bearing hot-spring tufa, metalliferous black shale in Ordovician rocks, base-metal and barite deposits in Paleozoic sedimentary rocks, and copper-molybdenum in granodiorite plutons of Cretaceous age occur in the Edna Mountain area.  None of these deposits have been of much economic signigicance, although tungsten was mined from the hot-spring deposits during World War II.

Geochemical, aeromagnetic, and generalized geologic maps showing distribution and abundance of mercury and arsenic, Golconda and Iron Point quadrangles, Humboldt County, Nevada

USGS Publications Warehouse

Erickson, R.L.; Marsh, S.P.

1971-01-01

Detailed geologic and geochemical studies of the four 7 1/2-minute wuadrangles that make up the Edna Mountain 15-minute quadrangle in Humboldt County, Nevada, were begun druring the 1969 summer field season. The objectives of the project are to map the geology of this structurally complex area at 1:24,000 scale and to determine the regional distribution and abundance of metals in rocks of the area and the factors that control the distribution and abundance of those metals. Tungsten-bearing hot-spring tufa, metalliferous black shale in Ordovician rocks, base-metal and barite deposits in Paleozoic sedimentary rocks, and copper-molybdenum in granodiorite plutons of Creataceous age occur in the Edna Mountain dare. None of these deposits have been of much economic significance, although tungsten was mined from the hot-spring deposits during World War II. 

Late Pleistocene-Holocene volcanic activity in northern Victoria Land recorded in Ross Sea (Antarctica) marine sediments

NASA Astrophysics Data System (ADS)

Del Carlo, P.; Di Roberto, A.; Di Vincenzo, G.; Bertagnini, A.; Landi, P.; Pompilio, M.; Colizza, E.; Giordano, G.

2015-05-01

Eight pyroclastic fall deposits have been identified in cores of Late Pleistocene-Holocene marine sediments from the Ross Sea (Antarctica), and their components, granulometry and clast morphologies were analysed. Sedimentological, petrographic and geochemical analysis of clasts, with 40Ar-39Ar dating of alkali feldspar grains, indicate that during this period at least five explosive eruptions of mid to high intensity (plinian to subplinian) occurred, and that three of these eruptions took place from Mount Melbourne volcanic complex, between 137.1 ± 3.4 and 12 ka. Geochemical comparison of the studied tephra with micro- and crypto-tephra recovered from deep Antarctic ice cores and from nearby englacial tephra at Frontier Mountain indicates that eruptive activity in the Melbourne Volcanic Province of northern Victoria Land was intense during the Late Pleistocene-Holocene, but only a general area of provenance for the majority of the identified tephra can be identified.

Multielement extraction system for the determination of 18 trace elements in geochemical samples

USGS Publications Warehouse

Clark, J.R.; Viets, J.G.

1981-01-01

A Methyl isobutyl ketone-Amine synerGistic Iodide Complex (MAGIC) extraction system has been developed for use in geochemical exploration which separates a maximum number of trace elements from interfering matrices. Extraction curves for 18 of these trace elements are presented: Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, Tl, Sa, Pb, As, Sb, Bi, Se, and Te. The acid normality of the aqueous phase controls the extraction into the organic phase, and each of these 18 elements has a broad range of HCl normality over which H is quantitatively extracted, making H possible to determine all 18 trace elements from a single sample digestion or leach solution. The extract can be analyzed directly by flame atomic absorption or inductively coupled plasma emission spectroscopy. Most of these 18 elements can be determined by Nameless atomic absorption after special treatment of the organic extract.

Automatic measurements and computations for radiochemical analyses

USGS Publications Warehouse

Rosholt, J.N.; Dooley, J.R.

1960-01-01

In natural radioactive sources the most important radioactive daughter products useful for geochemical studies are protactinium-231, the alpha-emitting thorium isotopes, and the radium isotopes. To resolve the abundances of these thorium and radium isotopes by their characteristic decay and growth patterns, a large number of repeated alpha activity measurements on the two chemically separated elements were made over extended periods of time. Alpha scintillation counting with automatic measurements and sample changing is used to obtain the basic count data. Generation of the required theoretical decay and growth functions, varying with time, and the least squares solution of the overdetermined simultaneous count rate equations are done with a digital computer. Examples of the complex count rate equations which may be solved and results of a natural sample containing four ??-emitting isotopes of thorium are illustrated. These methods facilitate the determination of the radioactive sources on the large scale required for many geochemical investigations.

Geochemistry, petrology, and palynology of the Pond Creek coal bed, northern Pike and southern Martin counties, Kentucky

USGS Publications Warehouse

Hower, J.C.; Ruppert, L.F.; Eble, C.F.; Clark, W.L.

2005-01-01

The geochemistry, petrology, and palynology of the Duckmantian-age Pond Creek coal bed were investigated in northern Pike and southern Martin counties, eastern Kentucky. The coal bed exhibits significant vertical variation in the investigated geochemical parameters, with many diagenetic overprints of the original geochemistry. Included in the range of geochemical signatures are the presence of elements, particularly TiO2 and Zr, suggesting the detrital influences at the time of deposition of a low-vitrinite durain; a high CaO zone with elevated B/Be, both suggesting marine influence, in a lithotype in the middle of the coal bed; and the postdepositional emplacement of pyrite in the uppermost lithotype. Individual lithotypes, each representing distinct depositional environments, all complicated to some degree by diagentic overprints, comprise the complex history of the coal bed. ?? 2004 Elsevier B.V. All rights reserved.

Formation and tectonic evolution of the Cretaceous Jurassic Muslim Bagh ophiolitic complex, Pakistan: Implications for the composite tectonic setting of ophiolites

NASA Astrophysics Data System (ADS)

Khan, Mehrab; Kerr, Andrew C.; Mahmood, Khalid

2007-10-01

The Muslim Bagh ophiolitic complex Balochistan, Pakistan is comprised of an upper and lower nappe and represents one of a number of ophiolites in this region which mark the boundary between the Indian and Eurasian plates. These ophiolites were obducted onto the Indian continental margin around the Late Cretaceous, prior to the main collision between the Indian and Eurasian plates. The upper nappe contains mantle sequence rocks with numerous isolated gabbro plutons which we show are fed by dolerite dykes. Each pluton has a transitional dunite-rich zone at its base, and new geochemical data suggest a similar mantle source region for both the plutons and dykes. In contrast, the lower nappe consists of pillow basalts, deep-marine sediments and a mélange of ophiolitic rocks. The rocks of the upper nappe have a geochemical signature consistent with formation in an island arc environment whereas the basalts of the lower nappe contain no subduction component and are most likely to have formed at a mid-ocean ridge. The basalts and sediments of the lower nappe have been intruded by oceanic alkaline igneous rocks during the northward drift of the Indian plate. The two nappes of the Muslim Bagh ophiolitic complex are thus distinctively different in terms of their age, lithology and tectonic setting. The recognition of composite ophiolites such as this has an important bearing on the identification and interpretation of ophiolites where the plate tectonic setting is less well resolved.

Geochemical and physical drivers of microbial community structure in hot spring ecosystems

NASA Astrophysics Data System (ADS)

Havig, J. R.; Hamilton, T. L.; Boyd, E. S.; Meyer-Dombard, D. R.; Shock, E.

2012-12-01

Microbial communities in natural systems are typically characterized using samples collected from a single time point, thereby neglecting the temporal dynamics that characterize natural systems. The composition of these communities obtained from single point samples is then related to the geochemistry and physical parameters of the environment. Since most microbial life is adapted to a relatively narrow ecological niche (multiplicity of physical and chemical parameters that characterize a local habitat), these assessments provide only modest insight into the controls on community composition. Temporal variation in temperature or geochemical composition would be expected to add another dimension to the complexity of niche space available to support microbial diversity, with systems that experience greater variation supporting a greater biodiversity until a point where the variability is too extreme. . Hot springs often exhibit significant temporal variation, both in physical as well as chemical characteristics. This is a result of subsurface processes including boiling, phase separation, and differential mixing of liquid and vapor phase constituents. These characteristics of geothermal systems, which vary significantly over short periods of time, provide ideal natural laboratories for investigating how i) the extent of microbial community biodiversity and ii) the composition of those communities are shaped by temporal fluctuations in geochemistry. Geochemical and molecular samples were collected from 17 temporally variable hot springs across Yellowstone National Park, Wyoming. Temperature measurements using data-logging thermocouples, allowing accurate determination of temperature maximums, minimums, and ranges for each collection site, were collected in parallel, along with multiple geochemical characterizations as conditions varied. There were significant variations in temperature maxima (54.5 to 90.5°C), minima (12.5 to 82.5°C), and range (3.5 to 77.5°C) for the hot spring environments that spanned ranges of pH values (2.2 to 9.0) and geochemical compositions. We characterized the abundance, composition, and phylogenetic diversity of bacterial and archaeal 16S rRNA gene assemblages in sediment/biofilm samples collected from each site. 16S data can be used as proxy for metabolic dissimilarity. We predict that temporally fluctuating environments should provide additional complexity to the system (additional niche space) capable of supporting additional taxa, which should lead to greater 16S rRNA gene diversity. However, systems with too much variability should collapse the diversity. Thus, one would expect an optimal system for variability, with respect to 16S phylogenetic diversity. Community ecology tools were then applied to model the relative influence of physical and chemical characteristics (including temperature dynamics) on the local biodiversity. The results reveal unique insight into the role of temporal environmental variation in the development of biodiverse communities and provide a platform for predicting the response of an ecosystem to temperature perturbation.

A geochemical and geophysical reappraisal to the significance of the recent unrest at Campi Flegrei caldera (Southern Italy)

NASA Astrophysics Data System (ADS)

Moretti, Roberto; De Natale, Giuseppe; Troise, Claudia

2017-03-01

Volcanic unrest at calderas involves complex interaction between magma, hydrothermal fluids, and crustal stress and strain. Campi Flegrei caldera (CFc), located in the Naples (Italy) area and characterized by the highest volcanic risk on Earth for the extreme urbanization, undergoes unrest phenomena involving several meters of uplift and intense shallow microseismicity since several decades. Despite unrest episodes display in the last decade only moderate ground deformation and seismicity, current interpretations of geochemical data point to a highly pressurized hydrothermal system. We show that at CFc, the usual assumption of vapor-liquid coexistence in the fumarole plumes leads to largely overestimated hydrothermal pressures and, accordingly, interpretations of elevated unrest. By relaxing unconstrained geochemical assumptions, we infer an alternative model yielding better agreement between geophysical and geochemical observations. The model reconciles discrepancies between what observed (1) for two decades since the 1982-1984 large unrest, when shallow magma was supplying heat and fluids to the hydrothermal system, and (2) in the last decade. Compared to the 1980's unrest, the post-2005 phenomena are characterized by much lower aquifers overpressure and magmatic involvement, as indicated by geophysical data and despite large changes in geochemical indicators. Our interpretation points out a model in which shallow sills, intruded during 1969-1984, have completely cooled, so that fumarole emissions are affected now by deeper, CO2-richer, magmatic gases producing the modest heating and overpressure of the hydrothermal system. Our results have important implications on the short-term eruption hazard assessment and on the best strategies for monitoring and interpreting geochemical data.