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.

Using stable isotopes and major ions to identify hydrological processes and geochemical characteristics in a typical karstic basin, Guizhou, Southwest China.

PubMed

Han, Zhiwei; Tang, Changyuan; Wu, Pan; Zhang, Ruixue; Zhang, Chipeng

2014-01-01

The investigation of hydrological processes is very important for water resource development in karst basins. In order to understand these processes associated with complex hydrogeochemical evolution, a typical basin was chosen in Houzai, southwest China. The basin was hydrogeologically classified into three zones based on hydrogen and oxygen isotopes as well as the field surveys. Isotopic values were found to be enriched in zone 2 where paddy fields were prevailing with well-developed underground flow systems, and heavier than those in zone 1. Zone 3 was considered as the mixture of zones 1 and 2 with isotopic values falling in the range between the two zones. A conceptual hydrological model was thus proposed to reveal the probable hydrological cycle in the basin. In addition, major processes of long-term chemical weathering in the karstic basin were discussed, and reactions between water and carbonate rocks proved to be the main geochemical processes in karst aquifers.

Evolution of chemical and isotopic composition of inorganic carbon in a complex semi-arid zone environment: Consequences for groundwater dating using radiocarbon

NASA Astrophysics Data System (ADS)

Meredith, K. T.; Han, L. F.; Hollins, S. E.; Cendón, D. I.; Jacobsen, G. E.; Baker, A.

2016-09-01

Estimating groundwater age is important for any groundwater resource assessment and radiocarbon (14C) dating of dissolved inorganic carbon (DIC) can provide this information. In semi-arid zone (i.e. water-limited environments), there are a multitude of reasons why 14C dating of groundwater and traditional correction models may not be directly transferable. Some include; (1) the complex hydrological responses of these systems that lead to a mixture of different ages in the aquifer(s), (2) the varied sources, origins and ages of organic matter in the unsaturated zone and (3) high evaporation rates. These all influence the evolution of DIC and are not easily accounted for in traditional correction models. In this study, we determined carbon isotope data for; DIC in water, carbonate minerals in the sediments, sediment organic matter, soil gas CO2 from the unsaturated zone, and vegetation samples. The samples were collected after an extended drought, and again after a flood event, to capture the evolution of DIC after varying hydrological regimes. A graphical method (Han et al., 2012) was applied for interpretation of the carbon geochemical and isotopic data. Simple forward mass-balance modelling was carried out on key geochemical processes involving carbon and agreed well with observed data. High values of DIC and δ13CDIC, and low 14CDIC could not be explained by a simple carbonate mineral-CO2 gas dissolution process. Instead it is suggested that during extended drought, water-sediment interaction leads to ion exchange processes within the top ∼10-20 m of the aquifer which promotes greater calcite dissolution in saline groundwater. This process was found to contribute more than half of the DIC, which is from a mostly 'dead' carbon source. DIC is also influenced by carbon exchange between DIC in water and carbonate minerals found in the top 2 m of the unsaturated zone. This process occurs because of repeated dissolution/precipitation of carbonate that is dependent on the water salinity driven by drought and periodic flooding conditions. This study shows that although 14C cannot be directly applied as a dating tool in some circumstances, carbon geochemical/isotopic data can be useful in hydrological investigations related to identifying groundwater sources, mixing relations, recharge processes, geochemical evolution, and interaction with surface water.

Matlab Geochemistry: An open source geochemistry solver based on MRST

NASA Astrophysics Data System (ADS)

McNeece, C. J.; Raynaud, X.; Nilsen, H.; Hesse, M. A.

2017-12-01

The study of geological systems often requires the solution of complex geochemical relations. To address this need we present an open source geochemical solver based on the Matlab Reservoir Simulation Toolbox (MRST) developed by SINTEF. The implementation supports non-isothermal multicomponent aqueous complexation, surface complexation, ion exchange, and dissolution/precipitation reactions. The suite of tools available in MRST allows for rapid model development, in particular the incorporation of geochemical calculations into transport simulations of multiple phases, complex domain geometry and geomechanics. Different numerical schemes and additional physics can be easily incorporated into the existing tools through the object-oriented framework employed by MRST. The solver leverages the automatic differentiation tools available in MRST to solve arbitrarily complex geochemical systems with any choice of species or element concentration as input. Four mathematical approaches enable the solver to be quite robust: 1) the choice of chemical elements as the basis components makes all entries in the composition matrix positive thus preserving convexity, 2) a log variable transformation is used which transfers the nonlinearity to the convex composition matrix, 3) a priori bounds on variables are calculated from the structure of the problem, constraining Netwon's path and 4) an initial guess is calculated implicitly by sequentially adding model complexity. As a benchmark we compare the model to experimental and semi-analytic solutions of the coupled salinity-acidity transport system. Together with the reservoir simulation capabilities of MRST the solver offers a promising tool for geochemical simulations in reservoir domains for applications in a diversity of fields from enhanced oil recovery to radionuclide storage.

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.

Geochemical Controls on the Partitioning and Hydrological Transport of Metals in a Human Impacted, Non-Acidic, River System

NASA Astrophysics Data System (ADS)

Thorslund, J.; Jarsjo, J.; Wällstedt, T.; Morth, C. M.; Lychagin, M.; Chalov, S.

2014-12-01

The knowledge of coupled processes controlling the spreading and fate of metals in non-acidic river systems is currently much more limited than the knowledge of metal behavior under acidic conditions (e.g., in acid mine drainage systems). Critical geochemical controls governing metal speciation may thus differ substantially between acidic and non-acidic hydrological systems. We here aim at expanding the knowledge of metals in non-acidic river systems, by considering a high pH river, influenced by mining by the largest gold mining area in the Mongolian part of the transboundary Lake Baikal drainage basin. The combined impact of geochemical and hydrological processes is investigated, to be able to understand the solubility of various heavy metals, their partitioning between particulate and dissolved phase and its impact on overall transport. We show, through site specific measurements and a geochemical modelling approach, that the combined effects of precipitation of ferrihydrite and gibbsite and associated sorption complexes of several metals can explain the high impact of suspended transport relative to total transport often seen under non-acidic conditions. Our results also identifies the phosphate mineral Hydroxyapatite as a potential key sorption site for many metals, which has both site specific and general relevance for metal partitioning under non-acidic conditions. However, an adsorption database, which is currently unavailable for hydroxyapatite, needs to be developed for appropriate sorption quantification. Furthermore, Cd, Fe, Pb and Zn were particularly sensitive to increasing DOC concentrations, which increased the solubility of these metals due to metal-organic complexation. Modeling the sensitivity to changes in geochemical parameters showed that decreasing pH and increasing DOC concentrations in downstream regions would increase the dissolution and hence the toxicity and bioavailability of many pollutants of concern in the downstream ecosystem. In general, this study suggests that in non-acidic hydrological systems, both seasonality of DOC concentrations (which could vary by several 100%), changing DOC concentrations (resulting from climate and land use changes) and potential phosphate solids can majorly influence on the spreading and toxicity of several metals.

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.

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.

Early warning risk assessment for drinking water production: decoding subtle evidence

NASA Astrophysics Data System (ADS)

Merz, Christoph; Lischeid, Gunnar; Böttcher, Steven

2016-04-01

Due to increasing demands for high quality water for drinking water supply all over the world there is acute need for methods to detect possible threats to groundwater resources early. Especially drinking water production in complex geologic settings has a particularly high risk for unexpected degradation of the groundwater quality due to the unknown interplay between anthropogenically induced hydraulic changes and geochemical processes. This study investigates the possible benefit of the Principal Component Analysis (PCA) for groundwater and drinking water management using common sets of physicochemical monitoring data. The approach was used to identify the prevailing processes driving groundwater quality shifts and related threats, which might be masked in anthropogenically impacted aquifer systems. The approach was applied to a data set from a waterworks located in the state of Brandenburg, NE Germany, which has been operating since nearly four decades. The region faces confronting and increasing demands due to rising peri-urban settlements. The PCA subdivided the data set according to different strengths of effects induced by differing geochemical processes at different sites in the capture zone of the waterworks and varying in time. Thus a spatial assessment of these processes could be performed as well as a temporal assessment of long-term groundwater quality shifts in the extracted water. The analysis revealed that over the period of 16 years of water withdrawal the geochemistry of the extracted groundwater had become increasingly more dissimilar compared to the characteristics found at the majority of observation wells. This component could be identified as highly mineralized CaSO4 dominated water from unexamined deeper zones of the aquifer system. Due to the complex geochemical and hydraulic interactions in the system, this process was masked and was not evident in the data set without validation by the applied statistical analysis. The findings give a clear indication of a potential threat to the groundwater resources in this region with danger for drinking water contamination in a medium-term period.

Magmatic Complexes of the Vetlovaya Marginal Sea Paleobasin (Kamchatka): Composition and Geodynamic Setting

NASA Astrophysics Data System (ADS)

Tsukanov, N. V.; Saveliev, D. P.; Kovalenko, D. V.

2018-01-01

This study presents new geochemical and isotope data on igneous rocks of the Vetlovaya marginal sea paleobasin (part of the Late Mesozoic-Cenozoic margin of the northwestern Pacific). The results show that the rock complexes of this marginal sea basin comprise igneous rocks with geochemical compositions similar to those of normal oceanic tholeiites, enriched transitional tholeiites, and ocean island and back-arc basin basalts. Island-arc tholeiitic basalts are present only rarely. The specific geochemical signatures of these rocks are interpreted as being related to mantle heterogeneity and the geodynamic conditions in the basin.

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.

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.

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).

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.

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.

The curved 14C vs. δ13C relationship in dissolved inorganic carbon: A useful tool for groundwater age- and geochemical interpretations

USGS Publications Warehouse

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

2014-01-01

Determination of the 14C content of dissolved inorganic carbon (DIC) is useful for dating of groundwater. However, in addition to radioactive decay, the 14C content in DIC (14CDIC) can be affected by many geochemical and physical processes and numerous models have been proposed to refine radiocarbon ages of DIC in groundwater systems. Changes in the δ13C content of DIC (δ13CDIC) often can be used to deduce the processes that affect the carbon isotopic composition of DIC and the 14C value during the chemical evolution of groundwater. This paper shows that a curved relationship of 14CDIC vs. δ13CDIC will be observed for groundwater systems if (1) the change in δ13C value in DIC is caused by a first-order or pseudo-first-order process, e.g. isotopic exchange between DIC and solid carbonate, (2) the reaction/process progresses with the ageing of the groundwater, i.e. with decay of 14C in DIC, and (3) the magnitude of the rate of change in δ13C of DIC is comparable with that of 14C decay. In this paper, we use a lumped parameter method to derive a model based on the curved relationship between 14CDICand δ13CDIC. The derived model, if used for isotopic exchange between DIC and solid carbonate, is identical to that derived by Gonfiantini and Zuppi (2003). The curved relationship of 14CDIC vs. δ13CDIC can be applied to interpret the age of the DIC in groundwater. Results of age calculations using the method discussed in this paper are compared with those obtained by using other methods that calculate the age of DIC based on adjusted initial radiocarbon values for individual samples. This paper shows that in addition to groundwater age interpretation, the lumped parameter method presented here also provides a useful tool for geochemical interpretations, e.g. estimation of apparent rates of geochemical reactions and revealing the complexity of the geochemical environment.

Modelling geochemical and microbial consumption of dissolved oxygen after backfilling a high level radiactive waste repository.

PubMed

Yang, Changbing; Samper, Javier; Molinero, Jorge; Bonilla, Mercedes

2007-08-15

Dissolved oxygen (DO) left in the voids of buffer and backfill materials of a deep geological high level radioactive waste (HLW) repository could cause canister corrosion. Available data from laboratory and in situ experiments indicate that microbes play a substantial role in controlling redox conditions near a HLW repository. This paper presents the application of a coupled hydro-bio-geochemical model to evaluate geochemical and microbial consumption of DO in bentonite porewater after backfilling of a HLW repository designed according to the Swedish reference concept. In addition to geochemical reactions, the model accounts for dissolved organic carbon (DOC) respiration and methane oxidation. Parameters for microbial processes were derived from calibration of the REX in situ experiment carried out at the Aspö underground laboratory. The role of geochemical and microbial processes in consuming DO is evaluated for several scenarios. Numerical results show that both geochemical and microbial processes are relevant for DO consumption. However, the time needed to consume the DO trapped in the bentonite buffer decreases dramatically from several hundreds of years when only geochemical processes are considered to a few weeks when both geochemical reactions and microbially-mediated DOC respiration and methane oxidation are taken into account simultaneously.

On prediction and discovery of lunar ores

NASA Technical Reports Server (NTRS)

Haskin, Larry A.; Colson, Russell O.; Vaniman, David

1991-01-01

Sampling of lunar material and remote geochemical, mineralogical, and photogeologic sensing of the lunar surface, while meager, provide first-cut information about lunar composition and geochemical separation processes. Knowledge of elemental abundances in known lunar materials indicates which common lunar materials might serve as ores if there is economic demand and if economical extraction processes can be developed, remote sensing can be used to extend the understanding of the Moon's major geochemical separations and to locate potential ore bodies. Observed geochemical processes might lead to ores of less abundant elements under extreme local conditions.

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.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Modeling hydrologic controls on sulfur processes in sulfate-impacted wetland and stream sediments

NASA Astrophysics Data System (ADS)

Ng, G.-H. C.; Yourd, A. R.; Johnson, N. W.; Myrbo, A. E.

2017-09-01

Recent studies show sulfur redox processes in terrestrial settings are more important than previously considered, but much remains uncertain about how these processes respond to dynamic hydrologic conditions in natural field settings. We used field observations from a sulfate-impacted wetland and stream in the mining region of Minnesota (USA) to calibrate a reactive transport model and evaluate sulfur and coupled geochemical processes under contrasting hydrogeochemical scenarios. Simulations of different hydrological conditions showed that flux and chemistry differences between surface water and deeper groundwater strongly control hyporheic zone geochemical profiles. However, model results for the stream channel versus wetlands indicate sediment organic carbon content to be the more important driver of sulfate reduction rates. A complex nonlinear relationship between sulfate reduction rates and geochemical conditions is apparent from the model's higher sensitivity to sulfate concentrations in settings with higher organic content. Across all scenarios, simulated e- balance results unexpectedly showed that sulfate reduction dominates iron reduction, which is contrary to the traditional thermodynamic ladder but corroborates recent experimental findings by Hansel et al. (2015) that "cryptic" sulfur cycling could drive sulfate reduction in preference over iron reduction. Following the thermodynamic ladder, our models shows that high surface water sulfate slows methanogenesis in shallow sediments, but field observations suggest that sulfate reduction may not entirely suppress methane. Overall, our results show that sulfate reduction may serve as a major component making up and influencing terrestrial redox processes, with dynamic hyporheic fluxes controlling sulfate concentrations and reaction rates, especially in high organic content settings.

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

USGS Publications Warehouse

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

2011-01-01

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

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.

Geochemical effects on the behavior of LLW radionuclides in soil/groundwater environments

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

Krupka, K.M.; Sterne, R.J.

1995-12-31

Assessing the migration potential of radionuclides leached from low-level radioactive waste (LLW) and decommissioning sites necessitates information on the effects of sorption and precipitation on the concentrations of dissolved radionuclides. Such an assessment requires that the geochemical processes of aqueous speciation, complexation, oxidation/reduction, and ion exchange be taken into account. The Pacific Northwest National Laboratory (PNNL) is providing technical support to the U.S. Nuclear Regulatory Commission (NRC) for defining the solubility and sorption behavior of radionuclides in soil/ground-water environments associated with engineered cementitious LLW disposal systems and decommissioning sites. Geochemical modeling is being used to predict solubility limits for radionuclidesmore » under geochemical conditions associated with these environments. The solubility limits are being used as maximum concentration limits in performance assessment calculations describing the release of contaminants from waste sources. Available data were compiled regarding the sorption potential of radionuclides onto {open_quotes}fresh{close_quotes} cement/concrete where the expected pH of the cement pore waters will equal to or exceed 10. Based on information gleaned from the literature, a list of preferred minimum distribution coefficients (Kd`s) was developed for these radionuclides. The K{sub d} values are specific to the chemical environments associated with the evolution of the compositions of cement/concrete pore waters.« less

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

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.

Advances in interpretation of subsurface processes with time-lapse electrical imaging

USGS Publications Warehouse

Singha, Kaminit; Day-Lewis, Frederick D.; Johnson, Tim B.; Slater, Lee D.

2015-01-01

Electrical geophysical methods, including electrical resistivity, time-domain induced polarization, and complex resistivity, have become commonly used to image the near subsurface. Here, we outline their utility for time-lapse imaging of hydrological, geochemical, and biogeochemical processes, focusing on new instrumentation, processing, and analysis techniques specific to monitoring. We review data collection procedures, parameters measured, and petrophysical relationships and then outline the state of the science with respect to inversion methodologies, including coupled inversion. We conclude by highlighting recent research focused on innovative applications of time-lapse imaging in hydrology, biology, ecology, and geochemistry, among other areas of interest.

Advances in interpretation of subsurface processes with time-lapse electrical imaging

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

Singha, Kamini; Day-Lewis, Frederick D.; Johnson, Timothy C.

2015-03-15

Electrical geophysical methods, including electrical resistivity, time-domain induced polarization, and complex resistivity, have become commonly used to image the near subsurface. Here, we outline their utility for time-lapse imaging of hydrological, geochemical, and biogeochemical processes, focusing on new instrumentation, processing, and analysis techniques specific to monitoring. We review data collection procedures, parameters measured, and petrophysical relationships and then outline the state of the science with respect to inversion methodologies, including coupled inversion. We conclude by highlighting recent research focused on innovative applications of time-lapse imaging in hydrology, biology, ecology, and geochemistry, among other areas of interest.

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.

Biological reduction of chlorinated solvents: Batch-scale geochemical modeling

NASA Astrophysics Data System (ADS)

Kouznetsova, Irina; Mao, Xiaomin; Robinson, Clare; Barry, D. A.; Gerhard, Jason I.; McCarty, Perry L.

2010-09-01

Simulation of biodegradation of chlorinated solvents in dense non-aqueous phase liquid (DNAPL) source zones requires a model that accounts for the complexity of processes involved and that is consistent with available laboratory studies. This paper describes such a comprehensive modeling framework that includes microbially mediated degradation processes, microbial population growth and decay, geochemical reactions, as well as interphase mass transfer processes such as DNAPL dissolution, gas formation and mineral precipitation/dissolution. All these processes can be in equilibrium or kinetically controlled. A batch modeling example was presented where the degradation of trichloroethene (TCE) and its byproducts and concomitant reactions (e.g., electron donor fermentation, sulfate reduction, pH buffering by calcite dissolution) were simulated. Local and global sensitivity analysis techniques were applied to delineate the dominant model parameters and processes. Sensitivity analysis indicated that accurate values for parameters related to dichloroethene (DCE) and vinyl chloride (VC) degradation (i.e., DCE and VC maximum utilization rates, yield due to DCE utilization, decay rate for DCE/VC dechlorinators) are important for prediction of the overall dechlorination time. These parameters influence the maximum growth rate of the DCE and VC dechlorinating microorganisms and, thus, the time required for a small initial population to reach a sufficient concentration to significantly affect the overall rate of dechlorination. Self-inhibition of chlorinated ethenes at high concentrations and natural buffering provided by the sediment were also shown to significantly influence the dechlorination time. Furthermore, the analysis indicated that the rates of the competing, nonchlorinated electron-accepting processes relative to the dechlorination kinetics also affect the overall dechlorination time. Results demonstrated that the model developed is a flexible research tool that is able to provide valuable insight into the fundamental processes and their complex interactions during bioremediation of chlorinated ethenes in DNAPL source zones.

Microbial facies distribution and its geological and geochemical controls at the Hanford 300 area

NASA Astrophysics Data System (ADS)

Hou, Z.; Nelson, W.; Stegen, J.; Murray, C. J.; Arntzen, E.

2015-12-01

Efforts have been made by various scientific disciplines to study hyporheic zones and characterize their associated processes. One way to approach the study of the hyporheic zone is to define facies, which are elements of a (hydrobio) geologic classification scheme that groups components of a complex system with high variability into a manageable set of discrete classes. In this study, we try to classify the hyporheic zone based on the geology, geochemistry, microbiology, and understand their interactive influences on the integrated biogeochemical distributions and processes. A number of measurements have been taken for 21 freeze core samples along the Columbia River bank in the Hanford 300 Area, and unique datasets have been obtained on biomass, pH, number of microbial taxa, percentage of N/C/H/S, microbial activity parameters, as well as microbial community attributes/modules. In order to gain a complete understanding of the geological control on these variables and processes, the explanatory variables are set to include quantitative gravel/sand/mud/silt/clay percentages, statistical moments of grain size distributions, as well as geological (e.g., Folk-Wentworth) and statistical (e.g., hierarchical) clusters. The dominant factors for major microbial and geochemical variables are identified and summarized using exploratory data analysis approaches (e.g., principal component analysis, hierarchical clustering, factor analysis, multivariate analysis of variance). The feasibility of extending the facies definition and its control of microbial and geochemical properties to larger scales is discussed.

Uranium redox transition pathways in acetate-amended sediments

USGS Publications Warehouse

Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

2013-01-01

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

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 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.

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.

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.

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.

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.

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.

Chaperones in maturation of molybdoenzymes: Why specific is better than general?

PubMed

Lemaire, Olivier N; Bouillet, Sophie; Méjean, Vincent; Iobbi-Nivol, Chantal; Genest, Olivier

2017-03-04

Molybdoenzymes play essential functions in living organisms and, as a result, in various geochemical cycles. It is thus crucial to understand how these complex proteins become highly efficient enzymes able to perform a wide range of catalytic activities. It has been established that specific chaperones are involved during their maturation process. Here, we raise the question of the involvement of general chaperones acting in concert with dedicated chaperones or not.

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.

Symplectite in spinel lherzolite xenoliths from the Little Hungarian Plain, Western Hungary: A key for understanding the complex history of the upper mantle of the Pannonian Basin

NASA Astrophysics Data System (ADS)

Falus, György; Szabó, Csaba; Kovács, István; Zajacz, Zoltán; Halter, Werner

2007-03-01

Two spinel lherzolite xenoliths from Hungary that contain pyroxene-spinel symplectites have been studied using EPMA, Laser ablation ICP-MS and universal stage. Based on their geochemical and structural characteristics, the xenoliths represent two different domains of the shallow subcontinental lithospheric mantle beneath the Pannonian Basin. The occurrence of symplectites is attributed to the former presence and subsequent breakdown of garnets due to significant pressure decrease related to lithospheric thinning. This implies that both mantle domains were once part of the garnet lherzolitic upper mantle and had a similar history during the major extension that formed the Pannonian Basin. Garnet breakdown resulted in distinct geochemical characteristics in the adjacent clinopyroxene crystals in both xenoliths. This is manifested by enrichment in HREE, Y, Zr and Hf towards the clinopyroxene porphyroclast rims and also in the neoblasts with respect to porphyroclast core compositions. This geochemical feature, together with the development and preservation of the texturally very sensitive symplectites, enables us to determine the relative timing of mantle processes. Our results indicate that garnets had been metastable in the spinel lherzolite environment and their breakdown to pyroxene and spinel is one of the latest processes that took place within the upper mantle before the xenoliths were brought to the surface.

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

Decreasing Kd uncertainties through the application of thermodynamic sorption models.

PubMed

Domènech, Cristina; García, David; Pękala, Marek

2015-09-15

Radionuclide retardation processes during transport are expected to play an important role in the safety assessment of subsurface disposal facilities for radioactive waste. The linear distribution coefficient (Kd) is often used to represent radionuclide retention, because analytical solutions to the classic advection-diffusion-retardation equation under simple boundary conditions are readily obtainable, and because numerical implementation of this approach is relatively straightforward. For these reasons, the Kd approach lends itself to probabilistic calculations required by Performance Assessment (PA) calculations. However, it is widely recognised that Kd values derived from laboratory experiments generally have a narrow field of validity, and that the uncertainty of the Kd outside this field increases significantly. Mechanistic multicomponent geochemical simulators can be used to calculate Kd values under a wide range of conditions. This approach is powerful and flexible, but requires expert knowledge on the part of the user. The work presented in this paper aims to develop a simplified approach of estimating Kd values whose level of accuracy would be comparable with those obtained by fully-fledged geochemical simulators. The proposed approach consists of deriving simplified algebraic expressions by combining relevant mass action equations. This approach was applied to three distinct geochemical systems involving surface complexation and ion-exchange processes. Within bounds imposed by model simplifications, the presented approach allows radionuclide Kd values to be estimated as a function of key system-controlling parameters, such as the pH and mineralogy. This approach could be used by PA professionals to assess the impact of key geochemical parameters on the variability of radionuclide Kd values. Moreover, the presented approach could be relatively easily implemented in existing codes to represent the influence of temporal and spatial changes in geochemistry on Kd values. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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

PubMed

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

2017-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Evolution of Icelandic Central Volcanoes: Evidence from the Austurhorn Plutonic and Vestmannaeyjar Volcanic Complexes

DTIC Science & Technology

1989-09-01

felsic magmas into a laterally extensive warm mafic chamber. Experiments with aqueous solutions suggest that buoyant felsic magma will rise as a plume ...crustal influences and processes . It is widely accepted that the Iceland mantle plume , which supplies this region with copious basalt magmas, is...currently located near Kverkfjoll in the center of the country (e.g., Vink, 1984; figure 1.2). Plume material is geochemically distinct from the mantle

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.

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.

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

Stable isotope study of antimony deposits in the Muratdagi region, western Turkey

NASA Astrophysics Data System (ADS)

Gokçe, A.; Spiro, B.

1994-09-01

The Muratdagi region is rich in antimony deposits having the following common characteristics: post Miocene age, location on the down-thrown blocks next to normal faults, in the vicinity of active or fossil thermal springs, and in contact with carbonate rocks. The isotopic composition of — 7‰. SMOW of the mineralizing fluid calculated from the measured ° 18O of quartz and the fluid inclusion microthermometry, is indicative of meteoric water origin. The ° 13C of the inclusion CO2 of — 19.1 to — 25.4‰ PDB is indicative of interaction with organic material-graphite. The ° 34S of stibnite — 3.6 to — 0.7‰ is, in view of the mineral assemblage, indicative of magmatic origin of the sulphur. A tightly confined set of structural, lithological, hydrological and geochemical features define a sequence of geochemical processes; formation of acid and reducing fluid, leaching and transport of antimony complexes and precipitation of stibnite within defined lithological units. The set of processes seems to have taken place within a space of 5000 m lateral and 1000 m vertical extension.

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.

An array processing system for lunar geochemical and geophysical data

NASA Technical Reports Server (NTRS)

Eliason, E. M.; Soderblom, L. A.

1977-01-01

A computerized array processing system has been developed to reduce, analyze, display, and correlate a large number of orbital and earth-based geochemical, geophysical, and geological measurements of the moon on a global scale. The system supports the activities of a consortium of about 30 lunar scientists involved in data synthesis studies. The system was modeled after standard digital image-processing techniques but differs in that processing is performed with floating point precision rather than integer precision. Because of flexibility in floating-point image processing, a series of techniques that are impossible or cumbersome in conventional integer processing were developed to perform optimum interpolation and smoothing of data. Recently color maps of about 25 lunar geophysical and geochemical variables have been generated.

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.

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.

First Principle Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface and Mineral/Aqueous Fluid Interface

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

Chen, Ying; Bylaska, Eric J.; Weare, John H.

Reactions in the mineral surface/reservoir fluid interface control many geochemical processes such as the dissolution and growth of minerals (Yanina and Rosso 2008), heterogeneous oxidation/reduction (Hochella 1990, Brown 2001, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008), and inorganic respiration (Newman 2010). Key minerals involved in these processes are the transition metal oxides and oxyhydroxides (e.g., hematite, Fe2O3, and goethite, FeOOH)(Brown, Henrich et al. 1999, Brown 2001, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008). To interpret and predict these processes, it is necessary to have a high level of understanding of the interactions between themore » formations containing these minerals and their reservoir fluids. However, these are complicated chemical events occurring under a wide range of T, P, and X conditions and the interpretation is complicated by the highly heterogeneous nature of natural environments (Hochella 1990, Hochella, Lower et al. 2008, Navrotsky, Mazeina et al. 2008) and the electronic and structural complexity of the oxide materials involved(Cox 1992, Kotliar and Vollhardt 2004, Navrotsky, Mazeina et al. 2008). In addition, also because of the complexity of the minerals involved and the heterogeneous nature of natural systems, the direct observation of these reactions at the atomic level is experimentally extremely difficult. Theoretical simulations will provide important support for analysis of the geochemistry of the mineral surface/fluid region as well as provide essential tools to extrapolate laboratory measurements to the field environment.« less

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

SeSBench - An initiative to benchmark reactive transport models for environmental subsurface processes

NASA Astrophysics Data System (ADS)

Jacques, Diederik

2017-04-01

As soil functions are governed by a multitude of interacting hydrological, geochemical and biological processes, simulation tools coupling mathematical models for interacting processes are needed. Coupled reactive transport models are a typical example of such coupled tools mainly focusing on hydrological and geochemical coupling (see e.g. Steefel et al., 2015). Mathematical and numerical complexity for both the tool itself or of the specific conceptual model can increase rapidly. Therefore, numerical verification of such type of models is a prerequisite for guaranteeing reliability and confidence and qualifying simulation tools and approaches for any further model application. In 2011, a first SeSBench -Subsurface Environmental Simulation Benchmarking- workshop was held in Berkeley (USA) followed by four other ones. The objective is to benchmark subsurface environmental simulation models and methods with a current focus on reactive transport processes. The final outcome was a special issue in Computational Geosciences (2015, issue 3 - Reactive transport benchmarks for subsurface environmental simulation) with a collection of 11 benchmarks. Benchmarks, proposed by the participants of the workshops, should be relevant for environmental or geo-engineering applications; the latter were mostly related to radioactive waste disposal issues - excluding benchmarks defined for pure mathematical reasons. Another important feature is the tiered approach within a benchmark with the definition of a single principle problem and different sub problems. The latter typically benchmarked individual or simplified processes (e.g. inert solute transport, simplified geochemical conceptual model) or geometries (e.g. batch or one-dimensional, homogeneous). Finally, three codes should be involved into a benchmark. The SeSBench initiative contributes to confidence building for applying reactive transport codes. Furthermore, it illustrates the use of those type of models for different environmental and geo-engineering applications. SeSBench will organize new workshops to add new benchmarks in a new special issue. Steefel, C. I., et al. (2015). "Reactive transport codes for subsurface environmental simulation." Computational Geosciences 19: 445-478.

Nano is the next big thing: Revealing geochemical processes with atom probe microscopy

NASA Astrophysics Data System (ADS)

Reddy, Steven; Saxey, David; Rickard, William; Fougerouse, Denis; Peterman, Emily; van Riessen, Arie; Johnson, Tim

2017-04-01

Characterizing compositional variations in minerals at the nanometre scale has the potential to yield fundamental insights into a range of geological processes associated with nucleation and mineral growth and the subsequent modification of mineral compositions by processes such as diffusion, deformation and recrystallization. However, there are few techniques that allow the quantitative measurement of low abundance trace elements and isotopes signatures at the nanometre scale. Atom probe microscopy is one such technique that has been widely used in the study of metals and, in the last decade, semiconductors. However, the development and application of atom probe microscopy to minerals is in its infancy and only a handful of published studies exist in the literature. Here, we provide an introduction to atom probe microscopy and its potential use in geological studies using two examples from both undeformed and deformed zircon (ZrSiO4). In the first example, we use atom probe microscopy to show that discordant data from the core of an undeformed 2.1 Ga zircon, metamorphosed at granulite facies conditions 150 Myr ago, contains distinct Pb reservoirs that represent both the crystallisation and metamorphic 207Pb/206Pb ages. Crystallisation ages are preserved within ˜10 nm diameter dislocation loops that formed during annealing of radiation-damaged zircon during the prograde path of the metamorphic event. The results highlight the potential for resolving the chronology of multiple, distinct Pb reservoirs within isotopically complex zircon and provide an explanation for varying amounts of discordance within individual zircon grains. In the second example, we illustrate complex trace element distributions associated with near-instantaneous deformation of a shocked zircon during the ˜1.17 Ga Stac Fada bolide impact. Substitutional and interstitial ions show correlated segregation, indicating coupling between different mobility mechanisms associated with the rapid formation and migration of oxygen vacancies and dislocations into low energy configurations. The results of these two studies show how quantification of elemental and isotopic variations at the nanoscale may reveal fundamental new insights into geochemical processes that underpin the interpretation of geochemical data collected at the microscale. Furthermore, these new data highlight the important role of crystal defects, even in undeformed zircon, in the chemical modification of zircon, and allow the interplay amongst radiation damage, recrystallization and deformation to be assessed.

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.

Relation of compositions of deep fluids in geothermal activity of Pleistocene-Holocene volcanic fields of Lesser Caucasus

NASA Astrophysics Data System (ADS)

Meliksetian, Khachatur; Lavrushin, Vassily; Shahinyan, Hrach; Aidarkozhina, Altin; Navasardyan, Gevorg; Ermakov, Alexander; Zakaryan, Shushan; Prasolov, Edward; Manucharyan, Davit; Gyulnazaryan, Shushan; Grigoryan, Edmond

2017-04-01

It is widely accepted, that geothermal activity in the conductive heat flow processes, such as volcanism and hydrothermal activity, is manifestation of the thermal mass transfer process in the Earth's crust, where geothermal and geochemical processes are closely connected. Therefore, geochemistry and isotope compositions of thermal mineral waters within and on periphery of volcanic clusters may represent key indicators for better understanding of geothermal activity in geodynamically active zones. Geochemical features of heat and mass transport in hydrothermal systems related to active volcanic and fault systems in continental collision related orogenic elevated plateaus such as Anatolian-Armenian-Iranian highlands are still poorly understood. In this contribution we attempt to fill these gaps in our knowledge of relations of geochemical and geothermal processes in collision zones. We present new data on chemical compositions, trace element geochemistry of thermal waters of Lesser Caucasus, (Armenia) as well as isotope analysis of free gases such as {}3He/{}4He, {}40Ar/{}36Ar, δ{}13?(CO{}2), nitrogen δ{}15N(N{}2) and oxygen and hydrogen isotopes in water phases (δD, δ{}18O). To reveal some specific features of formation of fluid systems related to thermal activity in the areas of collision related active volcanism and active geodynamics a complex geochemical (SiO{}2, K-Na, Na-Li, Li-Mg) and isotope geothermometers (δ{}18O(CaCO{}3) - δ{}18O(H{}2O)) were applied. The distribution of δ{}13?(??{}2) values in free gases of mineral waters of Armenia demonstrates that gases related to Quaternary volcanic fields are characterized by relatively light δ{}13?(CO{}2) values close to mantle derived gases, while on periphery of volcanic systems relatively heavy values of δ{}13?(CO{}2) indicate strong influence of metamorphic and sedimentary derived carbon dioxide. Distribution of nitrogen isotopes δ{}15N(N{}2) demonstrate an inverse correlation with δ{}13?(CO{}2) values and similarly to carbon dioxide indicate presence of metamorphic nitrogen on the periphery and strong influence of atmospheric (and mantle derived) nitrogen within volcanic fields. Results of geochemical and isotope investigations, as well as estimated temperatures of the formation of the mineral compositions of thermal waters demonstrate, that these studied hydrothermal systems originated within thermal anomaly fields associated with young (Pleistocene-Holocene) volcanic fields in Armenia. Basing on geochemical and isotope data, as well as on estimations of temperatures of water formation, calculated using various geothermometers, thermal anomaly fields, related to young volcanic activity and faults, within Armenian and neighboring areas of Lesser Caucasus are outlined. These results are used to reveal potential and promising areas for geothermal energy exploration in Armenia. This research is completed in framework of joint Armenian-Russian research grant funded by State Committee of Science of Armenia (grant #15RF-076) and Russian Foundation for Basic Research (grant#15-55-05069).

Geochemistry and the Understanding of Groundwater Systems

NASA Astrophysics Data System (ADS)

Glynn, P. D.; Plummer, L. N.; Weissmann, G. S.; Stute, M.

2009-12-01

Geochemical techniques and concepts have made major contributions to the understanding of groundwater systems. Advances continue to be made through (1) development of measurement and characterization techniques, (2) improvements in computer technology, networks and numerical modeling, (3) investigation of coupled geologic, hydrologic, geochemical and biologic processes, and (4) scaling of individual observations, processes or subsystem models into larger coherent model frameworks. Many applications benefit from progress in these areas, such as: (1) understanding paleoenvironments, in particular paleoclimate, through the use of groundwater archives, (2) assessing the sustainability (recharge and depletion) of groundwater resources, and (3) their vulnerability to contamination, (4) evaluating the capacity and consequences of subsurface waste isolation (e.g. geologic carbon sequestration, nuclear and chemical waste disposal), (5) assessing the potential for mitigation/transformation of anthropogenic contaminants in groundwater systems, and (6) understanding the effect of groundwater lag times in ecosystem-scale responses to natural events, land-use changes, human impacts, and remediation efforts. Obtaining “representative” groundwater samples is difficult and progress in obtaining “representative” samples, or interpreting them, requires new techniques in characterizing groundwater system heterogeneity. Better characterization and simulation of groundwater system heterogeneity (both physical and geochemical) is critical to interpreting the meaning of groundwater “ages”; to understanding and predicting groundwater flow, solute transport, and geochemical evolution; and to quantifying groundwater recharge and discharge processes. Research advances will also come from greater use and progress (1) in the application of environmental tracers to ground water dating and in the analysis of new geochemical tracers (e.g. compound specific isotopic analyses, noble gas isotopes, analyses of natural organic tracers), (2) in inverse geochemical and hydrological modeling, (3) in the understanding and simulation of coupled biological, geological, geochemical and hydrological processes, and (4) in the description and quantification of processes occurring at the boundaries of groundwater systems (e.g. unsaturated zone processes, groundwater/surface water interactions, impacts of changing geomorphology and vegetation). Improvements are needed in the integration of widely diverse information. Better techniques are needed to construct coherent conceptual frameworks from individual observations, simulated or reconstructed information, process models, and intermediate scale models. Iterating between data collection, interpretation, and the application of forward, inverse, and statistical modeling tools is likely to provide progress in this area. Quantifying groundwater system processes by using an open-system thermodynamic approach in a common mass- and energy-flow framework will also facilitate comparison and understanding of diverse processes.

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

Isotopic constraints on contamination processes in the Tonian Goiás Stratiform Complex

NASA Astrophysics Data System (ADS)

Giovanardi, Tommaso; Mazzucchelli, Maurizio; Lugli, Federico; Girardi, Vicente A. V.; Correia, Ciro T.; Tassinari, Colombo C. G.; Cipriani, Anna

2018-06-01

The Tonian Goiás Stratiform Complex (TGSC, Goiás, central Brazil), is one of the largest mafic-ultramafic layered complexes in the world, emplaced during the geotectonic events that led to the Gondwana accretion. In this study, we present trace elements and in-situ U/Pb-Lu-Hf analyses of zircons and 87Sr/86Sr ratios of plagioclases from anorthosites and gabbros of the TGSC. Although formed by three isolated bodies (Cana Brava, Niquelândia and Barro Alto), and characterized by a Lower and Upper Sequence (LS and US), our new U/Pb zircon data confirm recent geochemical, geochronological, and structural evidences that the TGSC has originated from a single intrusive body in the Neoproterozoic. New Hf and Sr isotope ratios construe a complex contamination history for the TGSC, with different geochemical signatures in the two sequences. The low Hf and high Sr isotope ratios of the Lower Sequence (εHf(t) from -4.2 down to -27.5; 87Sr/86Sr = 0.706605-0.729226), suggest the presence of a crustal component and are consistent with contamination from meta-pelitic and calc-silicate rocks found as xenoliths within the Sequence. The more radiogenic Hf isotope ratios and low Sr isotope composition of the Upper Sequence (εHf(t) from 11.3 down to -8.4; 87Sr/86Sr = 0.702368-0.702452), suggest a contamination from mantle-derived metabasalts in agreement with the occurrences of amphibolite xenoliths in the US stratigraphy. The differential contamination of the two sequences is explained by the intrusion of the TGSC in a stratified crust dominated by metasedimentary rocks in its deeper part and metavolcanics at shallower levels. Moreover, the differential thermal gradient in the two crystallizing sequences might have contributed to the preservation and recrystallization of inherited zircon grains in the US and total dissolution or magmatic overgrowth of the LS zircons via melt/rock reaction processes.

A review of single-sample-based models and other approaches for radiocarbon dating of dissolved inorganic carbon in groundwater

USGS Publications Warehouse

Han, L. F; Plummer, Niel

2016-01-01

Numerous methods have been proposed to estimate the pre-nuclear-detonation 14C content of dissolved inorganic carbon (DIC) recharged to groundwater that has been corrected/adjusted for geochemical processes in the absence of radioactive decay (14C0) - a quantity that is essential for estimation of radiocarbon age of DIC in groundwater. The models/approaches most commonly used are grouped as follows: (1) single-sample-based models, (2) a statistical approach based on the observed (curved) relationship between 14C and δ13C data for the aquifer, and (3) the geochemical mass-balance approach that constructs adjustment models accounting for all the geochemical reactions known to occur along a groundwater flow path. This review discusses first the geochemical processes behind each of the single-sample-based models, followed by discussions of the statistical approach and the geochemical mass-balance approach. Finally, the applications, advantages and limitations of the three groups of models/approaches are discussed.The single-sample-based models constitute the prevailing use of 14C data in hydrogeology and hydrological studies. This is in part because the models are applied to an individual water sample to estimate the 14C age, therefore the measurement data are easily available. These models have been shown to provide realistic radiocarbon ages in many studies. However, they usually are limited to simple carbonate aquifers and selection of model may have significant effects on 14C0 often resulting in a wide range of estimates of 14C ages.Of the single-sample-based models, four are recommended for the estimation of 14C0 of DIC in groundwater: Pearson's model, (Ingerson and Pearson, 1964; Pearson and White, 1967), Han & Plummer's model (Han and Plummer, 2013), the IAEA model (Gonfiantini, 1972; Salem et al., 1980), and Oeschger's model (Geyh, 2000). These four models include all processes considered in single-sample-based models, and can be used in different ranges of 13C values.In contrast to the single-sample-based models, the extended Gonfiantini & Zuppi model (Gonfiantini and Zuppi, 2003; Han et al., 2014) is a statistical approach. This approach can be used to estimate 14C ages when a curved relationship between the 14C and 13C values of the DIC data is observed. In addition to estimation of groundwater ages, the relationship between 14C and δ13C data can be used to interpret hydrogeological characteristics of the aquifer, e.g. estimating apparent rates of geochemical reactions and revealing the complexity of the geochemical environment, and identify samples that are not affected by the same set of reactions/processes as the rest of the dataset. The investigated water samples may have a wide range of ages, and for waters with very low values of 14C, the model based on statistics may give more reliable age estimates than those obtained from single-sample-based models. In the extended Gonfiantini & Zuppi model, a representative system-wide value of the initial 14C content is derived from the 14C and δ13C data of DIC and can differ from that used in single-sample-based models. Therefore, the extended Gonfiantini & Zuppi model usually avoids the effect of modern water components which might retain ‘bomb’ pulse signatures.The geochemical mass-balance approach constructs an adjustment model that accounts for all the geochemical reactions known to occur along an aquifer flow path (Plummer et al., 1983; Wigley et al., 1978; Plummer et al., 1994; Plummer and Glynn, 2013), and includes, in addition to DIC, dissolved organic carbon (DOC) and methane (CH4). If sufficient chemical, mineralogical and isotopic data are available, the geochemical mass-balance method can yield the most accurate estimates of the adjusted radiocarbon age. The main limitation of this approach is that complete information is necessary on chemical, mineralogical and isotopic data and these data are often limited.Failure to recognize the limitations and underlying assumptions on which the various models and approaches are based can result in a wide range of estimates of 14C0 and limit the usefulness of radiocarbon as a dating tool for groundwater. In each of the three generalized approaches (single-sample-based models, statistical approach, and geochemical mass-balance approach), successful application depends on scrutiny of the isotopic (14C and 13C) and chemical data to conceptualize the reactions and processes that affect the 14C content of DIC in aquifers. The recently developed graphical analysis method is shown to aid in determining which approach is most appropriate for the isotopic and chemical data from a groundwater system.

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.

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.

Understanding Crystal Populations: The Role of Textural Analysis in Determining Magmatic Timescales

NASA Astrophysics Data System (ADS)

Jerram, D. A.

2006-12-01

Crystal populations in igneous rocks that erupt at the Earths surface act as records of magma chamber processes at depth, predominantly recording episodes of growth/nucleation and geochemical changes within the host body. Detailed inspection of such crystal populations, however, reveals a complex crystal cargo that comprises crystals which have grown directly from the host, crystals that have spent one or more protracted periods being isolated from the host magma and crystals that originated from a completely different magma body and/or country rock. To further interrogate this crystal cargo we can use textural analysis techniques to fully quantify the crystal population and gather important information about the population, such as crystal morphology, spatial distribution and size relationships. When quantified, such data can be used to better constrain the different components of the resultant crystal population and how they relate to each other. Additionally, by combining textural analysis information with geochemical analysis, a powerful measure of magma timescales and magma chamber processes results. In this contribution the different types of textural analysis techniques in 2D and 3D are introduced with examples from both plutonic and volcanic systems presented to highlight the roll of this approach to quantifying magma timescales.

Magma genesis, storage and eruption processes at Aluto volcano, Ethiopia: lessons from remote sensing, gas emissions and geochemistry

NASA Astrophysics Data System (ADS)

Hutchison, William; Biggs, Juliet; Mather, Tamsin; Pyle, David; Gleeson, Matthew; Lewi, Elias; Yirgu, Gezahgen; Caliro, Stefano; Chiodini, Giovanni; Fischer, Tobias

2016-04-01

One of the most intriguing aspects of magmatism during the transition from continental rifting to sea-floor spreading is that large silicic magmatic systems develop within the rift zone. In the Main Ethiopian Rift (MER) these silicic volcanoes not only pose a significant hazard to local populations but they also sustain major geothermal resources. Understanding the journey magma takes from source to surface beneath these volcanoes is vital for determining its eruption style and for better evaluating the geothermal resources that these complexes host. We investigate Aluto, a restless silicic volcano in the MER, and combine a wide range of geochemical and geophysical techniques to constrain magma genesis, storage and eruption processes and shed light on magmatic-hydrothermal-tectonic interactions. Magma genesis and storage processes at Aluto were evaluated using new whole-rock geochemical data from recent eruptive products. Geochemical modelling confirms that Aluto's peralkaline rhyolites, that constitute the bulk of recent erupted products, are generated from protracted fractionation (>80 %) of basalt that is compositionally similar to rift-related basalts found on the margins of the complex. Crustal melting did not play a significant role in rhyolite genesis and melt storage depths of ~5 km can reproduce almost all aspects of their geochemistry. InSAR methods were then used to investigate magma storage and fluid movement at Aluto during an episode of ground deformation that took place between 2008 and 2010. Combining new SAR imagery from different viewing geometries we identified an accelerating uplift pulse and found that source models support depths of magmatic and/or fluid intrusion at ~5 km for the uplift and shallower depths of ~4 km for the subsidence. Finally, gas samples collected on Aluto in 2014 were used to evaluate magma and fluid transport processes. Our results show that gases are predominantly emanating from major fault zones on Aluto and that they display a clear magmatic carbon signature of -4.2 to -4.5 ‰. This provides compelling evidence that the magmatic and hydrothermal reservoirs of Aluto are physically connected. Bringing the new data sets together provides an integrated picture of the plumbing system of this restless rift volcano. Aluto's silicic magmas are generated and stored at depths of ~5 km. Magmatic intrusion and/or fluid injection in the cap of this magmatic reservoir drives edifice wide inflation while subsequent deflation is related to magmatic degassing and/or cooling of the geothermal reservoir at shallower depths. Tectonic faults that dissect the complex are a key component of this plumbing system and by connecting the deep reservoirs to the surface they not only provide important degassing pathways but will almost certainly be exploited during future eruptive events.

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

Geochemical consequences of flow differentiation in a multiple injection dike (Trinity ophiolite, N. California)

USGS Publications Warehouse

Brouxel, M.

1991-01-01

A clinopyroxene-rich dike of the Trinity ophiolite sheeted-dike complex shows three different magmatic pulses, probably injected in a short period of time (no well developed chilled margin) and important variations of the clinopyroxene and plagioclase percentages between its core (highly porphyritic) and margins (aphyric). This variation, interpreted as related to a flow differentiation phenomenon (mechanical phenocryst redistribution), has important geochemical consequences. It produces increases in the FeO, MgO, CaO, Cr and Ni contents from the margin to the core, together with increases in the clinopyroxene percentage, and decreases in the SiO2, Zr, Y, Nb and REE contents together with a decrease in the percentage of the fine-grained groundmass toward the core of the dike. This mineralogical redistribution, which also affects the incompatible trace element ratios because of the difference in plagioclase and clinopyroxene mineral/liquid partition coefficients, illustrate the importance of fractionation processes outside of a magma chamber. ?? 1991.

Popigai Impact Structure Modeling: Morphology and Worldwide Ejecta

NASA Technical Reports Server (NTRS)

Ivanov, B. A.; Artemieva, N. A.; Pierazzo, E.

2004-01-01

The approx. 100 km in diameter, 35.7 0.2 Ma old Popigai structure [1], northern Siberia (Russia), is the best-preserved of the large terrestrial complex crater structures containing a central-peak ring [2- 4]. Although remotely located, the excellent outcrops, large number of drill cores, and wealth of geochemical data make Popigai ideal for the general study of the cratering processes. It is most famous for its impact-diamonds [2,5]. Popigai is the best candidate for the source crater of the worldwide late Eocene ejecta [6,7].

Final Report (BMWi Project No.: 02 E 10971): Joint project: Retention of radionuclides relevant for final disposal in natural clay rock and saline systems - Subproject 2: Geochemical behavior and transport of radionuclides in saline systems in the prese

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

Schmeide, Katja; Fritsch, Katharina; Lippold, Holger

2016-02-29

The objective of this project was to study the influence of increased salinities on interaction processes in the system radionuclide – organics – clay – aquifer. For this, complexation, redox, sorption, and diffusion studies were performed under variation of the ionic strength (up to 4 mol kg -1) and the background electrolyte (NaCl, CaCl 2, MgCl 2).

Generation of Acid Mine Lakes Associated with Abandoned Coal Mines in Northwest Turkey.

PubMed

Sanliyuksel Yucel, Deniz; Balci, Nurgul; Baba, Alper

2016-05-01

A total of five acid mine lakes (AMLs) located in northwest Turkey were investigated using combined isotope, molecular, and geochemical techniques to identify geochemical processes controlling and promoting acid formation. All of the investigated lakes showed typical characteristics of an AML with low pH (2.59-3.79) and high electrical conductivity values (1040-6430 μS/cm), in addition to high sulfate (594-5370 mg/l) and metal (aluminum [Al], iron [Fe], manganese [Mn], nickel [Ni], and zinc [Zn]) concentrations. Geochemical and isotope results showed that the acid-generation mechanism and source of sulfate in the lakes can change and depends on the age of the lakes. In the relatively older lakes (AMLs 1 through 3), biogeochemical Fe cycles seem to be the dominant process controlling metal concentration and pH of the water unlike in the younger lakes (AMLs 4 and 5). Bacterial species determined in an older lake (AML 2) indicate that biological oxidation and reduction of Fe and S are the dominant processes in the lakes. Furthermore, O and S isotopes of sulfate indicate that sulfate in the older mine lakes may be a product of much more complex oxidation/dissolution reactions. However, the major source of sulfate in the younger mine lakes is in situ pyrite oxidation catalyzed by Fe(III) produced by way of oxidation of Fe(II). Consistent with this, insignificant fractionation between δ(34) [Formula: see text] and δ(34) [Formula: see text] values indicated that the oxidation of pyrite, along with dissolution and precipitation reactions of Fe(III) minerals, is the main reason for acid formation in the region. Overall, the results showed that acid generation during early stage formation of an AML associated with pyrite-rich mine waste is primarily controlled by the oxidation of pyrite with Fe cycles becoming the dominant processes regulating pH and metal cycles in the later stages of mine lake development.

Numerical Modelling of Speleothem and Dripwater Chemistry: Interpreting Coupled Trace Element and Isotope Proxies for Climate Reconstructions

NASA Astrophysics Data System (ADS)

Owen, R.; Day, C. C.; Henderson, G. M.

2016-12-01

Speleothem palaeoclimate records are widely used but are often difficult to interpret due to the geochemical complexity of the soil-karst-cave system. Commonly analysed proxies (e.g. δ18O, δ13C and Mg/Ca) may be affected by multiple processes along the water flow path from atmospheric moisture source through to the cave drip site. Controls on speleothem chemistry include rainfall and aerosol chemistry, bedrock chemistry, temperature, soil pCO2, the degree of open-system dissolution and prior calcite precipitation. Disentangling the effects of these controls is necessary to fully interpret speleothem palaeoclimate records. To quantify the effects of these processes, we have developed an isotope-enabled numerical model based on the geochemical modelling software PHREEQC. The model calculates dripwater chemistry and isotopes through equilibrium bedrock dissolution and subsequent iterative CO2 degassing and calcite precipitation. This approach allows forward modelling of dripwater and speleothem proxies, both chemical (e.g. Ca concentration, pH, Mg/Ca and Sr/Ca ratios) and isotopic (e.g. δ18O, δ13C, δ44Ca and radiocarbon content), in a unified framework. Potential applications of this model are varied and the model may be readily expanded to include new isotope systems or processes. Here we focus on calculated proxy co-variation due to changes in model parameters. Examples include: - The increase in Ca concentration, decrease in δ13C and increase in radiocarbon content as bedrock dissolution becomes more open-system. - Covariation between δ13C, δ44Ca and trace metal proxies (e.g. Mg/Ca) predicted by changing prior calcite precipitation. - The effect of temperature change on all proxies through the soil-karst-cave system. Separating the impact of soil and karst processes on geochemical proxies allows more quantitative reconstruction of the past environment, and greater understanding in modern cave monitoring studies.

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.

Si-Metasomatism During Serpentinization of Jurassic Ultramafic Sea-floor: a Comparative Study

NASA Astrophysics Data System (ADS)

Vogel, M.; Frueh-Green, G. L.; Boschi, C.; Schwarzenbach, E. M.

2014-12-01

The Bracco-Levanto ophiolitic complex (northwestern Italy) represents one of the largest and better-exposed ophiolitic successions in the Northern Apennines. It is considered to be a fragment of heterogeneous Jurassic lithosphere that records tectono-magmatic and alteration histories similar to those documented along the Mid-Atlantic Ridge (MAR), such as at the 15°20'N area and the Atlantis Massif at 30°N. Structural and petrological studies on these rocks provide constraints on metamorphic/deformation processes during formation and hydrothermal alteration of the Jurassic oceanic lithosphere. We present a petrological and geochemical study of serpentinization processes and fluid-rock interaction in the Bracco-Levanto ophiolitic complex and compare these to published data from modern oceanic hydrothermal systems, such as the Lost City hydrothermal field hosted in serpentinites on the Atlantis Massif. Major element and mineral compositional data allow us to distinguish a multiphase history of alteration characterized by: (1) widespread Si-metasomatism during progressive serpentinization, and (2) multiple phases of veining and carbonate precipitation associated with circulation of seawater in the shallow ultramafic-dominated portions of the Jurassic seafloor, resulting in the formation of ophicalcites. In detail, regional variations in Si, Mg and Al content are observed in zones of ophicalcite formation, indicating metasomatic reactions and Si-Al transport during long-lived fluid-rock interaction and channelling of hydrothermal fluids. Rare earth element and isotopic analysis indicate that the Si-rich fluids are derived from alteration of pyroxenes to talc and tremolite in ultramafic rocks at depth. Comparison with serpentinites from the Atlantis Massif and 15°20'N indicates a similar degree of Si-enrichment in the modern seafloor and suggests that Si-metasomatism may be a fundamental process associated with serpentinization at slow-spreading ridge environments. However, in contrast to metasomatic processes at the MAR, we find no geochemical evidence for a gabbroic source of the fluids, and thus, processes leading to Si-rich fluids can be variable in these environments.

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.

Laboratory simulation of organic geochemical processes.

NASA Technical Reports Server (NTRS)

Eglinton, G.

1972-01-01

Discussion of laboratory simulations that are important to organic geochemistry in that they provide direct evidence relating to geochemical cycles involving carbon. Reviewed processes and experiments include reactions occurring in the geosphere, particularly, short-term diagenesis of biolipids and organochlorine pesticides in estuarine muds, as well as maturation of organic matter in ancient sediments.

Microbial respiration and dissolution precipitation reactions of minerals: thermo-kinetics and reactive transport modelling

NASA Astrophysics Data System (ADS)

Azaroual, M. M.; Parmentier, M.; Andre, L.; Croiset, N.; Pettenati, M.; Kremer, S.

2010-12-01

Microbial processes interact closely with abiotic geochemical reactions and mineralogical transformations in several hydrogeochemical systems. Reactive transport models are aimed to analyze these complex mechanisms integrating as well as the degradation of organic matter as the redox reactions involving successive terminal electron acceptors (TEAPs) mediated by microbes through the continuum of unsaturated zone (soil) - saturated zone (aquifer). The involvement of microbial processes in reactive transport in soil and subsurface geologic greatly complicates the mastery of the major mechanisms and the numerical modelling of these systems. The introduction of kinetic constraints of redox reactions in aqueous phase requires the decoupling of equilibrium reactions and the redefinition of mass balance of chemical elements including the concept of basis species and secondary species of thermodynamic databases used in geochemical modelling tools. An integrated methodology for modelling the reactive transport has been developed and implemented to simulate the transfer of arsenic, denitrification processes and the role of metastable aqueous sulfur species with pyrite and organic matter as electron donors entities. A mechanistic rate law of microbial respiration in various geochemical environments was used to simulate reactive transport of arsenic, nitrate and organic matter combined to the generalized rate law of mineral dissolution - precipitation reactions derived from the transition state theory was used for dissolution - precipitation of silica, aluminosilicate, carbonate, oxyhydroxide, and sulphide minerals. The kinetic parameters are compiled from the literature measurements based on laboratory constrained experiments and field observations. Numerical simulations, using the geochemical software PHREEQC, were performed aiming to identify the key reactions mediated by microbes in the framework of in the first hand the concept of the unsaturated - saturated zones of an artificial recharge of deep aquifers system and in a second hand an acid mine drainage system. A large amount of data is available on the old mine site of Cheni (France). This field data on acid mine drainage are compared to a thermokinetic model including biological kinetics, precipitation-dissolution kinetics and surface complexation on ferrihydrite. The kinetic parameters are from literature and from a fitting on batch biological experiments. The integrated approach combining reaction kinetics and biogeochemical thermodynamic constraints is successfully applied to denitrification experiments in the presence of acetate and pyrite conducted in the laboratory for batch and column systems. The powerful of this coupled approach allows a fine description of the different transition species from nitrate to nitrogen. The fitted kinetic parameters established for modelling these laboratory results are thus extended to simulate the denitrification processes in a field case where organic matter and pyrite FeS2 are the electron donors and O2, NO3, Fe(OH)3, SO4 are the electron acceptors in the framework of a continuum UZ - SZ aiming to identify the stabilized redox zones of acid mine drainage. The detailed results obtained on two actual case studies will be presented.

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.

PEaCH4 v.2.0: A modelling platform to predict early diagenetic processes in marine sediments with a focus on biogenic methane - Case study: Offshore Namibia

NASA Astrophysics Data System (ADS)

Arning, Esther T.; Häußler, Steffen; van Berk, Wolfgang; Schulz, Hans-Martin

2016-07-01

The modelling of early diagenetic processes in marine sediments is of interest in marine science, and in the oil and gas industry, here, especially with respect to methane occurrence and gas hydrate formation as resources. Early diagenesis in marine sediments evolves from a complex web of intertwining (bio)geochemical reactions. It comprises microbially catalysed reactions and inorganic mineral-water-gas interactions. A model that will describe and consider all of these reactions has to be complex. However, it should be user-friendly, as well as to be applicable for a broad community and not only for experts in the field of marine chemistry. The presented modelling platform PeaCH4 v.2.0 combines both aspects, and is Microsoft Excel©-based. The modelling tool is PHREEQC (version 2), a computer programme for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. The conceptual PEaCH4 model is based on the conversion of sediment-bound degradable organic matter. PEaCH4 v.2.0 was developed to quantify and predict early diagenetic processes in marine sediments with the focus on biogenic methane formation and its phase behaviour, and allows carbon mass balancing. In regard to the irreversible degradation of organic matter, it comprises a "reaction model" and a "kinetic model" to predict methane formation. Both approaches differ in their calculations and outputs as the "kinetic model" considers the modelling time to integrate temperature dependent biogenic methane formation in its calculations, whereas the "reaction model" simply relies on default organic matter degradation. With regard to the inorganic mineral-water-gas interactions, which are triggered by irreversible degradation of organic matter, PEaCH4 v.2.0 is based on chemical equilibrium thermodynamics, appropriate mass-action laws, and their temperature dependent equilibrium constants. The programme is exemplarily presented with the example of upwelling sediments off Namibia, ODP Leg 175, Site 1082. The application demonstrates that the modelling platform PEaCH4 v.2.0 provides a user-friendly, but complex scientific tool that delivers retraceable information about early diagenetic processes and products in marine sediments.

Scaling laws and properties of compositional data

NASA Astrophysics Data System (ADS)

Buccianti, Antonella; Albanese, Stefano; Lima, AnnaMaria; Minolfi, Giulia; De Vivo, Benedetto

2016-04-01

Many random processes occur in geochemistry. Accurate predictions of the manner in which elements or chemical species interact each other are needed to construct models able to treat presence of random components. Geochemical variables actually observed are the consequence of several events, some of which may be poorly defined or imperfectly understood. Variables tend to change with time/space but, despite their complexity, may share specific common traits and it is possible to model them stochastically. Description of the frequency distribution of the geochemical abundances has been an important target of research, attracting attention for at least 100 years, starting with CLARKE (1889) and continued by GOLDSCHMIDT (1933) and WEDEPOHL (1955). However, it was AHRENS (1954a,b) who focussed on the effect of skewness distributions, for example the log-normal distribution, regarded by him as a fundamental law of geochemistry. Although modeling of frequency distributions with some probabilistic models (for example Gaussian, log-normal, Pareto) has been well discussed in several fields of application, little attention has been devoted to the features of compositional data. When compositional nature of data is taken into account, the most typical distribution models for compositions are the Dirichlet and the additive logistic normal (or normal on the simplex) (AITCHISON et al. 2003; MATEU-FIGUERAS et al. 2005; MATEU-FIGUERAS and PAWLOWSKY-GLAHN 2008; MATEU-FIGUERAS et al. 2013). As an alternative, because compositional data have to be transformed from simplex space to real space, coordinates obtained by the ilr transformation or by application of the concept of balance can be analyzed by classical methods (EGOZCUE et al. 2003). In this contribution an approach coherent with the properties of compositional information is proposed and used to investigate the shape of the frequency distribution of compositional data. The purpose is to understand data-generation processes from the perspective of compositional theory. The approach is based on the use of the isometric log-ratio transformation, characterized by theoretical and practical advantages, but requiring a more complex geochemical interpretation compared with the investigation of single variables. The proposed methodology directs attention to model the frequency distributions of more complex indices, linking all the terms of the composition to better represent the dynamics of geochemical processes. An example of its application is presented and discussed by considering topsoil geochemistry of Campania Region (southern Italy). The investigated multi-element data archive contains, among others, Al, As, B, Ba, Ca, Co, Cr, Cu, Fe, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, Sr, Th, Ti, V and Zn (mg/kg) contents determined in 3535 new topsoils as well as information on coordinates, geology, land cover. (BUCCIANTI et al., 2015). AHRENS, L. ,1954a. Geochim. Cosm. Acta 6, 121-131. AHRENS, L., 1954b. Geochim. Cosm. Acta 5, 49-73. AITCHISON, J., et al., 2003. Math Geol 35(6), 667-680. BUCCIANTI et al., 2015. Jour. Geoch. Explor., 159, 302-316. CLARKE, F., 1889. Phil. Society of Washington Bull. 11, 131-142. EGOZCUE, J.J. et al., 2003. Math Geol 35(3), 279-300. MATEU-FIGUERAS, G. et al, (2005), Stoch. Environ. Res. Risk Ass. 19(3), 205-214.

Sr/Ca and Mg/Ca in Glycymeris glycymeris (Bivalvia) shells from the Iberian upwelling system: Ontogeny and environmental control

NASA Astrophysics Data System (ADS)

Freitas, Pedro; Richardson, Christopher; Chenery, Simon; Monteiro, Carlos; Butler, Paul; Reynolds, David; Scourse, James; Gaspar, Miguel

2017-04-01

Bivalve shells have a great potential as high-resolution geochemical proxy archives of marine environmental conditions. In addition, sclerochronology of long-lived bivalve species (e.g. Arctica islandica) provides a timeline of absolutely dated shell material for geochemical analysis that can extend into the past beyond the lifetime of single individuals through the use of replicated crossmatched centennial to millennial chronologies. However, the interpretation of such records remains extremely challenging and complex, with multiple environmental and biological processes affecting element incorporation in the shell (e.g. crystal fabrics, organic matrix, biomineralization mechanisms and physiological processes). As a result, the effective use of bivalve shell elemental/Ca ratios as palaeoenvironmental proxies has been limited, often to species-specific applications or applications restricted to particular environmental settings. The dog-cockle, Glycymeris glycymeris, is a relatively long-lived bivalve (up to 200 years) that occurs in coarse-grained subtidal sediments of coastal shelf seas of Europe and North West Africa. Glycymeris glycymeris shells provide a valuable, albeit not fully explored, archive to reconstruct past environmental variability in an area lacking sclerochronological studies due to the rarity of long-lived bivalves and lack of coral reefs. In this study, we evaluate the potential of Sr/Ca and Mg/Ca ratios in G. glycymeris shells as geochemical proxies of upwelling conditions in the Iberian Upwelling System, the northern section of the Canary Current Eastern Boundary Upwelling System. Sr/Ca and Mg/Ca generally co-varied significantly and a clear ontogenetic, non-environmental related change in Sr/Ca and Ba/Ca variability was observed. High Sr/Ca and Mg/Ca ratios in older shells (> 10 years old) were found to be associated with the occurrence of growth lines deposited during the winter reduction in shell growth. Nevertheless, Sr/Ca and Mg/Ca variation in older shells was synchronous with contemporary environmental conditions, i.e. upwelling intensity and salinity. The use of Sr or Mg in G. glycymeris shells as valid geochemical environmental proxies in the Iberian Upwelling System remains complex and requires further research to unravel environmental and physiological/biomineralization controls. This study was financed by the Portuguese Fundação para a Ciência e Tecnologia (FCT) GLYCY Project (contract PTDC/AAC-CLI/118003/2010) and a sabbatical grant to PSF (Ref: SFRH/BSAB/127786/2016), co-supported by POCH and the European Social Fund. Funding for consumable costs was provided by Bangor University.

Elements of complexity in subsurface modeling, exemplified with three case studies

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

Freedman, Vicky L.; Truex, Michael J.; Rockhold, Mark

2017-04-03

There are complexity elements to consider when applying subsurface flow and transport models to support environmental analyses. Modelers balance the benefits and costs of modeling along the spectrum of complexity, taking into account the attributes of more simple models (e.g., lower cost, faster execution, easier to explain, less mechanistic) and the attributes of more complex models (higher cost, slower execution, harder to explain, more mechanistic and technically defensible). In this paper, modeling complexity is examined with respect to considering this balance. The discussion of modeling complexity is organized into three primary elements: 1) modeling approach, 2) description of process, andmore » 3) description of heterogeneity. Three examples are used to examine these complexity elements. Two of the examples use simulations generated from a complex model to develop simpler models for efficient use in model applications. The first example is designed to support performance evaluation of soil vapor extraction remediation in terms of groundwater protection. The second example investigates the importance of simulating different categories of geochemical reactions for carbon sequestration and selecting appropriate simplifications for use in evaluating sequestration scenarios. In the third example, the modeling history for a uranium-contaminated site demonstrates that conservative parameter estimates were inadequate surrogates for complex, critical processes and there is discussion on the selection of more appropriate model complexity for this application. All three examples highlight how complexity considerations are essential to create scientifically defensible models that achieve a balance between model simplification and complexity.« less

Elements of complexity in subsurface modeling, exemplified with three case studies

NASA Astrophysics Data System (ADS)

Freedman, Vicky L.; Truex, Michael J.; Rockhold, Mark L.; Bacon, Diana H.; Freshley, Mark D.; Wellman, Dawn M.

2017-09-01

There are complexity elements to consider when applying subsurface flow and transport models to support environmental analyses. Modelers balance the benefits and costs of modeling along the spectrum of complexity, taking into account the attributes of more simple models (e.g., lower cost, faster execution, easier to explain, less mechanistic) and the attributes of more complex models (higher cost, slower execution, harder to explain, more mechanistic and technically defensible). In this report, modeling complexity is examined with respect to considering this balance. The discussion of modeling complexity is organized into three primary elements: (1) modeling approach, (2) description of process, and (3) description of heterogeneity. Three examples are used to examine these complexity elements. Two of the examples use simulations generated from a complex model to develop simpler models for efficient use in model applications. The first example is designed to support performance evaluation of soil-vapor-extraction remediation in terms of groundwater protection. The second example investigates the importance of simulating different categories of geochemical reactions for carbon sequestration and selecting appropriate simplifications for use in evaluating sequestration scenarios. In the third example, the modeling history for a uranium-contaminated site demonstrates that conservative parameter estimates were inadequate surrogates for complex, critical processes and there is discussion on the selection of more appropriate model complexity for this application. All three examples highlight how complexity considerations are essential to create scientifically defensible models that achieve a balance between model simplification and complexity.

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.

Transfer of rare earth elements from natural metalliferous (copper and cobalt rich) soils into plant shoot biomass of metallophytes from Katanga (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Pourret, Olivier; Lange, Bastien; Jitaru, Petru; Mahy, Grégory; Faucon, Michel-Pierre

2014-05-01

The geochemical behavior of rare earth elements (REE) is generally assessed for the characterization of the geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. REE behavior is investigated according to their concentrations normalized with respect to the upper continental crust. In this study, the geochemical fingerprint of REE in plant shoot biomass of an unique metallicolous flora (i.e., Crepidorhopalon tenuis and Anisopappus chinensis) was investigated. The plants originate from extremely copper and cobalt rich soils, deriving from Cu and Co outcrops in Katanga, Democratic Republic of Congo. Some of the species investigated in this study are able to accumulate high amounts of Cu and Co in shoot hence being considered as Cu and Co hyperaccumulators. Therefore, assessing the behavior of REE may lead to a better understanding of the mechanisms of metal accumulation by this flora. The data obtained in this study indicate that REE uptake by plants is not primarily controlled by their concentration and speciation in the soil as previously shown in the literature (Brioschi et al. 2013). Indeed, the REE patterns in shoots are relatively flat whereas soils patterns are Middle REE enriched. In addition, it is worth noting that Eu enrichments occur in aerial parts of the plants. These positive Eu anomalies suggest that Eu3 + can form stable organic complexes replacing Ca2 + in several biological processes as in xylem fluids associated with the general nutrient flux. Therefore, is is possible that the Eu mobility in these fluids is enhanced by its reductive speciation as Eu2 +. Eventually, the geochemical behavior of REE illustrates that metals accumulation in aerial parts of C. tenuis and A. chinensis is mainly driven by dissolved complexation. Brioschi, L., Steinmann, M., Lucot, E., Pierret, M., Stille, P., Prunier, J., Badot, P., 2013. Transfer of rare earth elements (REE) from natural soil to plant systems: implications for the environmental availability of anthropogenic REE. Plant and Soil, 366, 143-163.

Actinide geochemistry: from the molecular level to the real system.

PubMed

Geckeis, Horst; Rabung, Thomas

2008-12-12

Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid-liquid interface reactions to obtain molecular level speciation insight. We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto gamma-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S-O-An(III)(OH)x(2-x)(H2O)5-x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions. The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide-colloid interaction. Kinetic stabilization of colloid bound actinides can be due to inclusion into inorganic colloid matrix or by macromolecular rearrangement in case of organic, humic/fulvic like colloids. Only a combination of spectroscopy, microscopy and classical batch sorption experiments can help to elucidate the actinide-colloid interaction mechanisms and thus contribute to the assessment of colloids for radionuclide migration.

Geochemical differentiation processes for arc magma of the Sengan volcanic cluster, Northeastern Japan, constrained from principal component analysis

NASA Astrophysics Data System (ADS)

Ueki, Kenta; Iwamori, Hikaru

2017-10-01

In this study, with a view of understanding the structure of high-dimensional geochemical data and discussing the chemical processes at work in the evolution of arc magmas, we employed principal component analysis (PCA) to evaluate the compositional variations of volcanic rocks from the Sengan volcanic cluster of the Northeastern Japan Arc. We analyzed the trace element compositions of various arc volcanic rocks, sampled from 17 different volcanoes in a volcanic cluster. The PCA results demonstrated that the first three principal components accounted for 86% of the geochemical variation in the magma of the Sengan region. Based on the relationships between the principal components and the major elements, the mass-balance relationships with respect to the contributions of minerals, the composition of plagioclase phenocrysts, geothermal gradient, and seismic velocity structure in the crust, the first, the second, and the third principal components appear to represent magma mixing, crystallizations of olivine/pyroxene, and crystallizations of plagioclase, respectively. These represented 59%, 20%, and 6%, respectively, of the variance in the entire compositional range, indicating that magma mixing accounted for the largest variance in the geochemical variation of the arc magma. Our result indicated that crustal processes dominate the geochemical variation of magma in the Sengan volcanic cluster.

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

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

Zheng, L.; Samper, J.; Montenegro, L.

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 collectedmore » 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{sub 2}(g) degassing and the transport of vapor from the bentonite into the granite. The inferred HCO{sub 3}{sup -} 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.« less

Model simulations of a field experiment on cation exchange-affected multicomponent solute transport in a sandy aquifer

NASA Astrophysics Data System (ADS)

Bjerg, Poul L.; Ammentorp, Hans C.; Christensen, Thomas H.

1993-04-01

A large-scale and long-term field experiment on cation exchange in a sandy aquifer has been modelled by a three-dimensional geochemical transport model. The geochemical model includes cation-exchange processes using a Gaines-Thomas expression, the closed carbonate system and the effects of ionic strength. Information on geology, hydrogeology and the transient conservative solute transport behaviour was obtained from a dispersion study in the same aquifer. The geochemical input parameters were carefully examined. CEC and selectivity coefficients were determined on the actual aquifer material by batch experiments and by the composition of the cations on the exchange complex. Potassium showed a non-ideal exchange behaviour with KCa selectivity coefficients indicating dependency on equivalent fraction and K + concentration in the aqueous phase. The model simulations over a distance of 35 m and a period of 250 days described accurately the observed attenuation of Na and the expelled amounts of Ca and Mg. Also, model predictions of plateau zones, formed by interaction with the background groundwater, in general agreed satisfactorily with the observations. Transport of K was simulated over a period of 800 days due to a substantially attenuation in the aquifer. The observed and the predicted breakthrough curves showed a reasonable accordance taking the duration of the experiment into account. However, some discrepancies were observed probably caused by the revealed non-ideal exchange behaviour of K +.

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

USGS Publications Warehouse

Parkhurst, David L.; Wissmeier, Laurin

2015-01-01

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

Small-scale geochemical cycles and the distribution of uranium in central and north Florida organic deposits

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

Bond, P.A.

1993-03-01

The global geochemical cycle for an element tracks its path from its various sources to its sinks via processes of weathering and transportation. The cycle may then be quantified in a necessarily approximate manner. The geochemical cycle (thus quantified) reveals constraints (known and unknown) on an element's behavior imposed by the various processes which act on it. In the context of a global geochemical cycle, a continent becomes essentially a source term. If, however, an element's behavior is examined in a local or regional context, sources and their related sinks may be identified. This suggests that small-scale geochemical cycles maymore » be superimposed on global geochemical cycles. Definition of such sub-cycles may clarify the distribution of an element in the earth's near-surface environment. In Florida, phosphate minerals of the Hawthorn Group act as a widely distributed source of uranium. Uranium is transported by surface- and ground-waters. Florida is the site of extensive wetlands and peatlands. The organic matter associated with these deposits adsorbs uranium and may act as a local sink depending on its hydrogeologic setting. This work examines the role of organic matter in the distribution of uranium in the surface and shallow subsurface environments of central and north Florida.« less

Integration of Geophysical and Geochemical Data

NASA Astrophysics Data System (ADS)

Yamagishi, Y.; Suzuki, K.; Tamura, H.; Nagao, H.; Yanaka, H.; Tsuboi, S.

2006-12-01

Integration of geochemical and geophysical data would give us a new insight to the nature of the Earth. It should advance our understanding for the dynamics of the Earth's interior and surface processes. Today various geochemical and geophysical data are available on Internet. These data are stored in various database systems. Each system is isolated and provides own format data. The goal of this study is to display both the geochemical and geophysical data obtained from such databases together visually. We adopt Google Earth as the presentation tool. Google Earth is virtual globe software and is provided free of charge by Google, Inc. Google Earth displays the Earth's surface using satellite images with mean resolution of ~15m. We display any graphical features on Google Earth by KML format file. We have developed softwares to convert geochemical and geophysical data to KML file. First of all, we tried to overlay data from Georoc and PetDB and seismic tomography data on Google Earth. Georoc and PetDB are both online database systems for geochemical data. The data format of Georoc is CSV and that of PetDB is Microsoft Excel. The format of tomography data we used is plain text. The conversion software can process these different file formats. The geochemical data (e. g. compositional abundance) is displayed as a three-dimensional column on the Earth's surface. The shape and color of the column mean the element type. The size and color tone vary according to the abundance of the element. The tomography data can be converted into a KML file for each depth. This overlay plot of geochemical data and tomography data should help us to correlate internal temperature anomalies to geochemical anomalies, which are observed at the surface of the Earth. Our tool can convert any geophysical and geochemical data to a KML as long as the data is associated with longitude and latitude. We are going to support more geophysical data formats. In addition, we are currently trying to obtain scientific insights for the Earth's interior based on the view of both geophysical and geochemical data on Google Earth.

The effects of sorting by aeolian processes on the geochemical characteristics of surface materials: a wind tunnel experiment

NASA Astrophysics Data System (ADS)

Wang, Xunming; Lang, Lili; Hua, Ting; Zhang, Caixia; Li, Hui

2018-03-01

The geochemical characteristics of aeolian and surface materials in potential source areas of dust are frequently employed in environmental reconstructions as proxies of past climate and as source tracers of aeolian sediments deposited in downwind areas. However, variations in the geochemical characteristics of these aeolian deposits that result from near-surface winds are currently poorly understood. In this study, we collected surface samples from the Ala Shan Plateau (a major potential dust source area in Central Asia) to determine the influence of aeolian processes on the geochemical characteristics of aeolian transported materials. Correlation analyses show that compared with surface materials, the elements in transported materials (e.g., Cu, As, Pb, Mn, Zn, Al, Ca, Fe, Ga, K, Mg, P, Rb, Co, Cr, Na, Nb, Si, and Zr) were subjected to significant sorting by aeolian processes, and the sorting also varied among different particle size fractions and elements. Variations in wind velocity were significantly correlated with the contents of Cr, Ga, Sr, Ca, Y, Nd, Zr, Nb, Ba, and Al, and with the Zr/Al, Zr/Rb, K/Ca, Sr/Ca, Rb/Sr, and Ca/Al ratios. Given the great variation in the geochemical characteristics of materials transported under different aeolian processes relative to those of the source materials, these results indicate that considerable uncertainty may be introduced to analyses by using surface materials to trace the potential source areas of aeolian deposits that accumulate in downwind areas.

Complexation of carboxylate on smectite surfaces.

PubMed

Liu, Xiandong; Lu, Xiancai; Zhang, Yingchun; Zhang, Chi; Wang, Rucheng

2017-07-19

We report a first principles molecular dynamics (FPMD) study of carboxylate complexation on clay surfaces. By taking acetate as a model carboxylate, we investigate its inner-sphere complexes adsorbed on clay edges (including (010) and (110) surfaces) and in interlayer space. Simulations show that acetate forms stable monodentate complexes on edge surfaces and a bidentate complex with Ca 2+ in the interlayer region. The free energy calculations indicate that the complexation on edge surfaces is slightly more stable than in interlayer space. By integrating pK a s and desorption free energies of Al coordinated water calculated previously (X. Liu, X. Lu, E. J. Meijer, R. Wang and H. Zhou, Geochim. Cosmochim. Acta, 2012, 81, 56-68; X. Liu, J. Cheng, M. Sprik, X. Lu and R. Wang, Geochim. Cosmochim. Acta, 2014, 140, 410-417), the pH dependence of acetate complexation has been revealed. It shows that acetate forms inner-sphere complexes on (110) in a very limited mildly acidic pH range while it can complex on (010) in the whole common pH range. The results presented in this study form a physical basis for understanding the geochemical processes involving clay-organics interactions.

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.

Iodine and selenium in natural water, their fixation on geochemical barriers in soils and rocks and explanation of I and Se behavior in water-solid phase system using thermodynamic modeling

NASA Astrophysics Data System (ADS)

Korobova, Elena; Ryzhenko, Boris; Cherkasova, Elena; Sedykh, Ivelina; Korsakova, Nadezhda; Berezkin, Victor; Kolmykova, Lyudmila; Danilova, Valentina; Khushvakhtova, Sabzbakhor

2014-05-01

Iodine and selenium are essential for normal functioning of thyroid gland. Their natural deficiency in areas subjected to radioiodine contamination during nuclear tests and accidents may increase the risk of thyroid cancer among the most sensitive groups of population. Deficiency is caused by both the low abundance of microelements in the environmental components of the local food chain and their fixation on geochemical barriers due to such processes as chemical transformation, sorption, chemisorption, complexing. The studies of iodine and selenium distribution in soils, herbs and drinking water in rural settlements of the Bryansk oblast' confirmed low level of iodine and selenium content in local soils, plants and water and revealed different character of their distribution in soils and waters formed in geochemically different conditions of water migration in areas of fluvioglacial, moraine and loess-like soil forming rocks (the polesje, moraine and opolje landscapes correspondingly). Iodine content in top horizons of the soils developed on loess-like sediments and rich in organic matter was considerably higher as compared to those formed on sandy moraine or fluvioglacial sediments. For selenium the difference was not pronounced. Iodine was noted for positive correlation with Corg and fixation in the soil profile on carbonate barrier. A negative correlation was found between selenium content in grasses and in topsoil of subordinated elementary landscapes characterized by waterlogged and reduction conditions in soils. Thermodynamic modeling performed for 47 water samples on the basis of their chemical composition helped to explain the established patterns of iodine and selenium behavior in soil-water system. It demonstrated the possibility of existence of CaI+ and MgI+ complexes in water and sedimentation of FeSe(cr) in presence of a considerable amount of Fe2+. Iodine complexation with Ca and Mg ions may explain its further fixation on carbonate barrier in soils, and selenium sedimentation may decrease its availability to plants in gley kinds of soils elsewhere. It may be suggested that the organic water-soluble iodine complexes typical for polesije landscapes and the mineral ones in opolje landscapes could have increased the mobility of radioiodine isotopes and their transfer to food chains in the contaminated areas. The work was supported the Russian Foundation for Basic Research (grants 10-05-01148 and 13-05-00823).

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.

How do Kakortokites form? Additional evidence from the Ilimaussaq Complex, S. Greenland

NASA Astrophysics Data System (ADS)

Hunt, E. J.; Finch, A. A.; Donaldson, C. H.

2012-04-01

The Ilímaussaq Complex, South Greenland, contains some of the most evolved igneous rocks in the world and is widely considered to represent one of the largest deposits of rare-earth elements, Ta, Nb and Zr. Our work is focused on the kakortokite layered series at the base of the complex. The layered series is composed of 29 repetitive 3-layer units (named -11 to +17, Bohse et al. 1971), successively enriched in arfvedsonite, eudialyte and nepheline. Despite a large body of work on the development of the kakortokite series, no consensus on the process/processes that produced the layering has been forthcoming. We present the preliminary findings of a combined petrographical, quantitative textural and geochemical analysis on the kakortokite series, initially focused on layer 0. Although many of the hypotheses for the formation of these rocks invoke a pressure change, the enrichment of the series in volatile constituents (CH4 and H; Konnerup-Madsen, 2001) has led many authors to suggest crystallisation occurred in a closed system, with processes of gravitational settling formed the layering. Crystal size distribution (CSD) analysis, performed on hand-digitised photomicrographs, provides insight into processes of crystal nucleation and growth. The results indicate that simple cumulate settling is untenable for layer 0. Instead the plot gradients indicate that the arfvedsonite in the black kakortokite crystallised in situ above a sharp boundary to the white kakortokite. The CSD plots for the alkali feldspars indicate secondary nucleation occurred, with the small crystal size fraction forming in situ. The feldspar phenocrysts also exhibit embayment textures indicating partial resorption. These graphs are consistent with a model whereby an influx of hotter magma results in the partial thermal erosion of the underlying white kakortokite, followed by in situ crystallisation of arfvedsonite above the melt infiltration boundary, followed by in situ crystallisation of eudialyte. Then nepheline and alkali feldspar crystallised through multiple modes of nucleation, developing the characteristic layering. Geochemical trends described by Pfaff et al. (2008) support an open system replenishment model during the formation of layer 0, and potentially also layers +4 and +8. To further this work we intend to apply this combined approach to investigate the formation of individual layers, scaling these processes into a model for the development of the Ilímaussaq complex. Bohse et al. (1971). Rapport Grønlands Geologiske Undergesølgelse, 36, 43 pp. Konnerup-Madsen (2001). Geology Greenland Surv. Bull., 190, 159-166. Pfaff et al. (2008). Lithos, 106, 280-296.

Tok-Algoma magmatic complex of the Selenga-Stanovoi Superterrain in the Central Asian fold belt: Age and tectonic setting

NASA Astrophysics Data System (ADS)

Kotov, A. B.; Larin, A. M.; Salnikova, E. B.; Velikoslavinskii, S. D.; Sorokin, A. A.; Sorokin, A. P.; Yakovleva, S. Z.; Anisimova, I. V.; Tolmacheva, E. V.

2012-05-01

According to the results of U-Pb geochronological investigations, the hornblende subalkali diorite rocks making up the Tok-Algoma Complex in the eastern part of the Selenga-Stanovoi Superterrain of the Central Asian fold belt were formed in the Middle Jurassic rather than in the Middle Archean as was suggested previously. Thus, the age of the regional amphibolite facies metamorphism manifested itself in the Ust'-Gilyui rock sequence of the Stanovoi Complex and that superimposed on granitoids of the Tok-Algoma Complex is Mesozoic rather than Early Precambrian. The geochemical features of the Tok-Algoma granitoids are indicative of the fact that they were formed in the geodynamic setting of the active continental margin or a mature island arc. Hence, it is possible to suggest that the subduction processes along the southern boundary between the Selenga-Stanovoi Superterrain and the Mongolian-Okhotsk ocean basin in the Middle Jurassic resulted in the formation of a magmatic belt of over 500 km in length.

Steric hindrance and the enhanced stability of light rare-earth elements in hydrothermal fluids

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2009-01-01

A series of X-ray absorption spectroscopy (XAS) experiments were made to determine the structure and stability of aqueous REE (La, Nd, Gd, and Yb) chloride complexes to 500 ??C and 520 MPa. The REE3+ ions exhibit inner-sphere chloroaqua complexation with a steady increase of chloride coordination with increasing temperature in the 150 to 500 ??C range. Furthermore, the degree of chloride coordination of REE3+ inner-sphere chloroaqua complexes decreases significantly from light to heavy REE. These results indicate that steric hindrance drives the reduction of chloride coordination of REE3+ inner-sphere chloroaqua complexes from light to heavy REE. This results in greater stability and preferential transport of light REE3+ over heavy REE3+ ions in saline hydrothermal fluids. Accordingly, the preferential mobility of light REE directly influences the relative abundance of REE in rocks and minerals and thus needs to be considered in geochemical modeling of petrogenetic and ore-forming processes affected by chloride-bearing hydrothermal fluids.

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.

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

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

Flynn, Elaine D.; Catalano, Jeffrey G.

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests thatmore » this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni 2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.« less

Geochemical Monitoring Considerations for the FutureGen 2.0 Project

DOE PAGES

Amonette, James E.; Johnson, Timothy A.; Spencer, Clayton F.; ...

2014-12-31

Geochemical monitoring is an essential component of a suite of monitoring technologies designed to evaluate CO2 mass balance and detect possible loss of containment at the FutureGen 2.0 geologic sequestration site near Jacksonville, IL. This presentation gives an overview of the potential geochemical approaches and tracer technologies that were considered, and describes the evaluation process by which the most cost-effective and robust of these were selected for implementation

Dissecting the Hydrobiogeochemical Box

NASA Astrophysics Data System (ADS)

Wang, Y.; Alves Meira Neto, A.; Sengupta, A.; Root, R. A.; Dontsova, K.; Troch, P. A. A.; Chorover, J.

2015-12-01

Soil genesis is a coupled hydrologic and biogeochemical process that involves the interaction of weathering rock surfaces and water. Due to strong nonlinear coupling, it is extremely difficult to predict biogeochemical changes from hydrological modeling in natural field systems. A fully controlled and monitored system with known initial conditions could be utilized to isolate variables and simplify these natural processes. To investigate the initial weathering of host rock to soil, we employed a 10° sloping soil lysimeter containing one cubic meter of crushed and homogenized basaltic rock. A major experiment of the Periodic Tracer Hierarchy (PERTH) method (Harman and Kim, 2014) coupled with its bonus experiment were performed in the past two years. These experimental applications successfully described the transit-time distribution (TTD) of a tracer-enriched water breakthrough curve in this unique hydrological system (Harman, 2015). With intensive irrigation and high volume of water storage throughout the experiments, rapid biological changes have been observed on the soil surface, such as algal and grass growth. These observations imply that geochemical hotspots may be established within the soil lysimeter. To understand the detailed 2D spatial distribution of biogeochemical changes, 100 selected and undisturbed soil blocks, among a total 1000 sub-gridded equal sized, are tested with several geochemical tools. Each selected soil block was subjected to elemental analysis by pXRF to determine if elemental migration is detectable in the dynamic proto-soil development. Synchrotron XRD quantification with Reitveld refinement will follow to clarify mineralogical transformations in the soil blocks. The combined techniques aim to confirm the development of geochemical hotspots; and link these findings with previous hydrological findings from the PERTH experiment as well as other hydrological modeling, such as conducted with Hydrus and CATHY. This work provides insight to the detailed correlations between hydrological and biogeochemical processes during incipient soil formation, as well as aiding the development of advanced tools and methods to study complex Earth-system dynamics.

Characterization and quantification of suspended sediment sources to the Manawatu River, New Zealand.

PubMed

Vale, S S; Fuller, I C; Procter, J N; Basher, L R; Smith, I E

2016-02-01

Knowledge of sediment movement throughout a catchment environment is essential due to its influence on the character and form of our landscape relating to agricultural productivity and ecological health. Sediment fingerprinting is a well-used tool for evaluating sediment sources within a fluvial catchment but still faces areas of uncertainty for applications to large catchments that have a complex arrangement of sources. Sediment fingerprinting was applied to the Manawatu River Catchment to differentiate 8 geological and geomorphological sources. The source categories were Mudstone, Hill Subsurface, Hill Surface, Channel Bank, Mountain Range, Gravel Terrace, Loess and Limestone. Geochemical analysis was conducted using XRF and LA-ICP-MS. Geochemical concentrations were analysed using Discriminant Function Analysis and sediment un-mixing models. Two mixing models were used in conjunction with GRG non-linear and Evolutionary optimization methods for comparison. Discriminant Function Analysis required 16 variables to correctly classify 92.6% of sediment sources. Geological explanations were achieved for some of the variables selected, although there is a need for mineralogical information to confirm causes for the geochemical signatures. Consistent source estimates were achieved between models with optimization techniques providing globally optimal solutions for sediment quantification. Sediment sources was attributed primarily to Mudstone, ≈38-46%; followed by the Mountain Range, ≈15-18%; Hill Surface, ≈12-16%; Hill Subsurface, ≈9-11%; Loess, ≈9-15%; Gravel Terrace, ≈0-4%; Channel Bank, ≈0-5%; and Limestone, ≈0%. Sediment source apportionment fits with the conceptual understanding of the catchment which has recognized soft sedimentary mudstone to be highly susceptible to erosion. Inference of the processes responsible for sediment generation can be made for processes where there is a clear relationship with the geomorphology, but is problematic for processes which occur within multiple terrains. Copyright © 2015 Elsevier B.V. All rights reserved.

Complementing approaches to demonstrate chlorinated solvent biodegradation in a complex pollution plume: Mass balance, PCR and compound-specific stable isotope analysis

NASA Astrophysics Data System (ADS)

Courbet, Christelle; Rivière, Agnès; Jeannottat, Simon; Rinaldi, Sandro; Hunkeler, Daniel; Bendjoudi, Hocine; de Marsily, Ghislain

2011-11-01

This work describes the use of different complementing methods (mass balance, polymerase chain reaction assays and compound-specific stable isotope analysis) to demonstrate the existence and effectiveness of biodegradation of chlorinated solvents in an alluvial aquifer. The solvent-contaminated site is an old chemical factory located in an alluvial plain in France. As most of the chlorinated contaminants currently found in the groundwater at this site were produced by local industries at various times in the past, it is not enough to analyze chlorinated solvent concentrations along a flow path to convincingly demonstrate biodegradation. Moreover, only a few data were initially available to characterize the geochemical conditions at this site, which were apparently complex at the source zone due to (i) the presence of a steady oxygen supply to the groundwater by irrigation canal losses and river infiltration and (ii) an alkaline pH higher than 10 due to former underground lime disposal. A demonstration of the existence of biodegradation processes was however required by the regulatory authority within a timeframe that did not allow a full geochemical characterization of such a complex site. Thus a combination of different fast methods was used to obtain a proof of the biodegradation occurrence. First, a mass balance analysis was performed which revealed the existence of a strong natural attenuation process (biodegradation, volatilization or dilution), despite the huge uncertainty on these calculations. Second, a good agreement was found between carbon isotopic measurements and PCR assays (based on 16S RNA gene sequences and functional genes), which clearly indicated reductive dechlorination of different hydrocarbons (Tetrachloroethene—PCE-, Trichloroethene—TCE-, 1,2- cisDichloroethene— cis-1,2-DCE-, 1,2- transDichloroethene— trans-1,2-DCE-, 1,1-Dichloroethene—1,1-DCE-, and Vinyl Chloride—VC) to ethene. According to these carbon isotope measurements, although TCE biodegradation seems to occur only in the upgradient part of the studied zone, DCE and VC dechlorination (originating from the initial TCE dechlorination) occurs along the entire flowpath. TCE reductase was not detected among the Dehalococcoides bacteria identified by quantitative PCR (qPCR), while DCE and VC reductases were present in the majority of the population. Reverse transcriptase PCR assays (rt-PCR) also indicated that bacteria and their DCE and VC reductases were active. Mass balance calculations showed moreover that 1,1-DCE was the predominant DCE isomer produced by TCE dechlorination in the upgradient part of the site. Consequently, coupling rt-PCR assays with isotope measurements removes the uncertainties inherent in a simple mass balance approach, so that when the three methods are used jointly, they allow the identification and quantification of natural biodegradation, even under apparently complex geochemical and hydraulic conditions.

Investigation of recharge dynamics and flow paths in a fractured crystalline aquifer in semi-arid India using borehole logs: implications for managed aquifer recharge

NASA Astrophysics Data System (ADS)

Alazard, M.; Boisson, A.; Maréchal, J.-C.; Perrin, J.; Dewandel, B.; Schwarz, T.; Pettenati, M.; Picot-Colbeaux, G.; Kloppman, W.; Ahmed, S.

2016-02-01

The recharge flow paths in a typical weathered hard-rock aquifer in a semi-arid area of southern India were investigated in relation to structures associated with a managed aquifer recharge (MAR) scheme. Despite the large number of MAR structures, the mechanisms of recharge in their vicinity are still unclear. The study uses a percolation tank as a tool to identify the input signal of the recharge and uses multiple measurements (piezometric time series, electrical conductivity profiles in boreholes) compared against heat-pulse flowmeter measurements and geochemical data (major ions and stable isotopes) to examine recharge flow paths. The recharge process is a combination of diffuse piston flow and preferential flow paths. Direct vertical percolation appears to be very limited, in contradiction to the conceptual model generally admitted where vertical flow through saprolite is considered as the main recharge process. The horizontal component of the flow leads to a strong geochemical stratification of the water column. The complex recharge pattern, presented in a conceptual model, leads to varied impacts on groundwater quality and availability in both time and space, inducing strong implications for water management, water quality evolution, MAR monitoring and longer-term socio-economic costs.

Potential accumulation of contaminated sediments in a reservoir of a high-Andean watershed: Morphodynamic connections with geochemical processes

NASA Astrophysics Data System (ADS)

Contreras, María. Teresa; Müllendorff, Daniel; Pastén, Pablo; Pizarro, Gonzalo E.; Paola, Chris; Escauriaza, Cristián.

2015-05-01

Rapid changes due to anthropic interventions in high-altitude environments, such as the Altiplano region in South America, require new approaches to understand the connections between physical and geochemical processes. Alterations of the water quality linked to the river morphology can affect the ecosystems and human development in the long term. The future construction of a reservoir in the Lluta River, located in northern Chile, will change the spatial distribution of arsenic-rich sediments, which can have significant effects on the lower parts of the watershed. In this investigation, we develop a coupled numerical model to predict and evaluate the interactions between morphodynamic changes in the Lluta reservoir, and conditions that can potentially desorb arsenic from the sediments. Assuming that contaminants are mobilized under anaerobic conditions, we calculate the oxygen concentration within the sediments to study the interactions of the delta progradation with the potential arsenic release. This work provides a framework for future studies aimed to analyze the complex connections between morphodynamics and water quality, when contaminant-rich sediments accumulate in a reservoir. The tool can also help to design effective risk management and remediation strategies in these extreme environments. This article was corrected on 15 JUNE 2015. See the end of the full text for details.

Eruptive stratigraphy of the Tatara-San Pedro complex, 36°S, sourthern volcanic zone, Chilean Andes: reconstruction method and implications for magma evolution at long-lived arc volcanic centers

USGS Publications Warehouse

Dungan, M.A.; Wulff, A.; Thompson, R.

2001-01-01

The Quaternary Tatara-San Pedro volcanic complex (36°S, Chilean Andes) comprises eight or more unconformity-bound volcanic sequences, representing variably preserved erosional remnants of volcanic centers generated during 930 ky of activity. The internal eruptive histories of several dominantly mafic to intermediate sequences have been reconstructed, on the basis of correlations of whole-rock major and trace element chemistry of flows between multiple sampled sections, but with critical contributions from photogrammetric, geochronologic, and paleomagnetic data. Many groups of flows representing discrete eruptive events define internal variation trends that reflect extrusion of heterogeneous or rapidly evolving magna batches from conduit-reservoir systems in which open-system processes typically played a large role. Long-term progressive evolution trends are extremely rare and the magma compositions of successive eruptive events rarely lie on precisely the same differentiation trend, even where they have evolved from similar parent magmas by similar processes. These observations are not consistent with magma differentiation in large long-lived reservoirs, but they may be accommodated by diverse interactions between newly arrived magma inputs and multiple resident pockets of evolved magma and / or crystal mush residing in conduit-dominated subvolcanic reservoirs. Without constraints provided by the reconstructed stratigraphic relations, the framework for petrologic modeling would be far different. A well-established eruptive stratigraphy may provide independent constraints on the petrologic processes involved in magma evolution-simply on the basis of the specific order in which diverse, broadly cogenetic magmas have been erupted. The Tatara-San Pedro complex includes lavas ranging from primitive basalt to high-SiO2 rhyolite, and although the dominant erupted magma type was basaltic andesite ( 52-55 wt % SiO2) each sequence is characterized by unique proportions of mafic, intermediate, and silicic eruptive products. Intermediate lava compositions also record different evolution paths, both within and between sequences. No systematic long-term pattern is evident from comparisons at the level of sequences. The considerable diversity of mafic and evolved magmas of the Tatara-San Pedro complex bears on interpretations of regional geochemical trends. The variable role of open-system processes in shaping the compositions of evolved Tatara-San Pedro complex magmas, and even some basaltic magmas, leads to the conclusion that addressing problems such as are magma genesis and elemental fluxes through subduction zones on the basis of averaged or regressed reconnaissance geochemical datasets is a tenuous exercise. Such compositional indices are highly instructive for identifying broad regional trends and first-order problems, but they should be used with extreme caution in attempts to quantify processes and magma sources, including crustal components, implicated in these trends.

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.

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

USGS Publications Warehouse

Amos, Richard T.; Mayer, K. Ulrich

2006-01-01

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O2 to waters otherwise depleted in O2. Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH4 partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.

Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

NASA Astrophysics Data System (ADS)

Amos, Richard T.; Ulrich Mayer, K.

2006-09-01

In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O 2 to waters otherwise depleted in O 2. Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given conditions more than 50% of all produced CH 4 partitions to the gas phase or is aerobically oxidised near the water table, suggesting that these processes should be accounted for when assessing the rate and extent of methanogenic degradation of hydrocarbons.

Post-magmatic structural evolution of the Troodos Ophiolite Pillow Lavas revealed by microthermometry within vein precipitates, with application to Alpine-Mediterranean supra-subduction zone settings

NASA Astrophysics Data System (ADS)

Klöcking, M.; White, N. J.; Maclennan, J.; Fitton, J. G.

2016-12-01

The Troodos ophiolite, Cyprus, is one of the best preserved ophiolites. Based on geochemical data a supra-subduction zone (SSZ) setting was proposed. Microtextures and fluid inclusions of veins and vesicles within the Pillow Lavas record the post-magmatic structural and geochemical evolution of this SSZ beginning at 75 Ma. Three different vein types from the Upper and Lower Pillow Lavas are distinguished and imply vein precipitation under a dominant extensional regime: (1) syntaxial calcite-, quartz- and zeolite-bearing veins are interpreted as mineralized extension fractures that were pervaded by seawater. This advective fluid flow in an open system changed later into a closed system characterized by geochemical self-organization. (2) Blocky and (3) antitaxial fibrous calcite veins are associated with brecciation due to hydrofracturing and diffusion-crystallization processes, respectively. Based on aqueous fluid inclusion chemistry with seawater salinities in all studied vein types, representative fluid inclusion isochores crossed with calculated litho- and hydrostatic pressure conditions yield mineral precipitation temperatures between 180 and 210 °C, for veins and vesicles hosted in the Upper and Lower Pillow Lavas. This points to a heat source for the circulating seawater and implies that vein and vesicle minerals precipitated shortly after pillow lava crystallization under dominant isobaric cooling conditions. Compared to previous suggestions derived from secondary mineralization a less steep geothermal gradient of 200 °C from the Sheeted Dyke Complex to the Pillow Lavas of the Troodos SSZ is proposed. Further fossil and recent SSZ like the Mirdita ophiolite, Albania, the South-Anatolian ophiolites, Turkey, and the Izu-Bonin fore arc, respectively, reveal similar volcanic sequences. Vein samples recovered during International Ocean Discovery Program expedition 351 and 352 in the Izu-Bonin back and fore arc, respectively, indicate also seawater infiltration into fractures but low-temperature (<150 °C) mineral precipitation. This comparison of spatially and temporally unrelated vein systems contributes to the understanding of post-magmatic structural and geochemical processes in SSZ. This study was granted by the Austrian Science Fund (FWF-P 27982-N29).

Post-magmatic structural evolution of the Troodos Ophiolite Pillow Lavas revealed by microthermometry within vein precipitates, with application to Alpine-Mediterranean supra-subduction zone settings

NASA Astrophysics Data System (ADS)

Kurz, W.; Quandt, D.; Micheuz, P.; Krenn, K.

2017-12-01

The Troodos ophiolite, Cyprus, is one of the best preserved ophiolites. Based on geochemical data a supra-subduction zone (SSZ) setting was proposed. Microtextures and fluid inclusions of veins and vesicles within the Pillow Lavas record the post-magmatic structural and geochemical evolution of this SSZ beginning at 75 Ma. Three different vein types from the Upper and Lower Pillow Lavas are distinguished and imply vein precipitation under a dominant extensional regime: (1) syntaxial calcite-, quartz- and zeolite-bearing veins are interpreted as mineralized extension fractures that were pervaded by seawater. This advective fluid flow in an open system changed later into a closed system characterized by geochemical self-organization. (2) Blocky and (3) antitaxial fibrous calcite veins are associated with brecciation due to hydrofracturing and diffusion-crystallization processes, respectively. Based on aqueous fluid inclusion chemistry with seawater salinities in all studied vein types, representative fluid inclusion isochores crossed with calculated litho- and hydrostatic pressure conditions yield mineral precipitation temperatures between 180 and 210 °C, for veins and vesicles hosted in the Upper and Lower Pillow Lavas. This points to a heat source for the circulating seawater and implies that vein and vesicle minerals precipitated shortly after pillow lava crystallization under dominant isobaric cooling conditions. Compared to previous suggestions derived from secondary mineralization a less steep geothermal gradient of 200 °C from the Sheeted Dyke Complex to the Pillow Lavas of the Troodos SSZ is proposed. Further fossil and recent SSZ like the Mirdita ophiolite, Albania, the South-Anatolian ophiolites, Turkey, and the Izu-Bonin fore arc, respectively, reveal similar volcanic sequences. Vein samples recovered during International Ocean Discovery Program expedition 351 and 352 in the Izu-Bonin back and fore arc, respectively, indicate also seawater infiltration into fractures but low-temperature (<150 °C) mineral precipitation. This comparison of spatially and temporally unrelated vein systems contributes to the understanding of post-magmatic structural and geochemical processes in SSZ. This study was granted by the Austrian Science Fund (FWF-P 27982-N29).

Anthropogenic Increase Of Soil Erosion In The Gangetic Plain Revealed By Geochemical Budget Of Erosion

NASA Astrophysics Data System (ADS)

Galy, V.; France-Lanord, C.; Galy, A.; Gaillardet, J.

2007-12-01

Tectonic and climatic factors are the key natural variables controlling the erosion through complex interactions. Nonetheless, over the last few hundred years, human activity also exerts a dominant control in response to extensive land use. The geochemical budget of erosion allows the balance between the different erosion processes to be quantified. The chemical composition of river sediment results from the chemical composition of the source rock modified by (1) weathering reactions occurring during erosion and (2) physical segregation during transport. If erosion is at steady state, the difference between the chemical composition of source rocks and that of river sediments must therefore be counterbalanced by the dissolved flux. However, climatic variations or anthropic impact can induce changes in the erosion distribution in a given basin resulting in non steady state erosion. Using a mass balance approach, the comparison of detailed geochemical data on river sediments with the current flux of dissolved elements allows the steady state hypothesis to be tested. In this study, we present a geochemical budget of weathering for the Ganga basin, one of the most densely populated basin in the world, based on detailed sampling of Himalayan rivers and of the Ganga in the delta. Sampling includes depth profile in the river, to assess the variability generated by transport processes. Himalayan river sediments are described by the dilution of an aluminous component (micas + clays + feldspars) by quartz. Ganga sediments on the other hand correspond to the mixing of bedload, similar to coarse Himalayan sediments, with an aluminous component highly depleted in alkaline elements. Compared with the dissolved flux, the depletion of alkaline elements in Ganga sediments shows that the alkaline weathering budget is imbalanced. This imbalance results from an overabundance of fine soil material in the Ganga sediment relative to other less weathered material directly derived from Himalaya. Based on the average composition of the suspended load and of floodplain soils, we estimate that 250x106 t/yr i.e. 5 t/ha/yr is eroded from soil surfaces of the Ganga floodplain. This enhanced soil erosion is likely triggered by intense deforestation and change in land use due to increasing human activity in the basin.

A geochemical examination of humidity cell tests

USGS Publications Warehouse

Maest, Ann; Nordstrom, D. Kirk

2017-01-01

Humidity cell tests (HCTs) are long-term (20 to >300 weeks) leach tests that are considered by some to be the among the most reliable geochemical characterization methods for estimating the leachate quality of mined materials. A number of modifications have been added to the original HCT method, but the interpretation of test results varies widely. We suggest that the HCTs represent an underutilized source of geochemical data, with a year-long test generating approximately 2500 individual chemical data points. The HCT concentration peaks and valleys can be thought of as a “chromatogram” of reactions that may occur in the field, whereby peaks in concentrations are associated with different geochemical processes, including sulfate salt dissolution, sulfide oxidation, and dissolution of rock-forming minerals, some of which can neutralize acid. Some of these reactions occur simultaneously, some do not, and geochemical modeling can be used to help distinguish the dominant processes. Our detailed examination, including speciation and inverse modeling, of HCTs from three projects with different geology and mineralization shows that rapid sulfide oxidation dominates over a limited period of time that starts between 40 and 200 weeks of testing. The applicability of laboratory tests results to predicting field leachate concentrations, loads, or rates of reaction has not been adequately demonstrated, although early flush releases and rapid sulfide oxidation rates in HCTs should have some relevance to field conditions. Knowledge of possible maximum solute concentrations is needed to design effective treatment and mitigation approaches. Early flush and maximum sulfide oxidation results from HCTs should be retained and used in environmental models. Factors that complicate the use of HCTs include: sample representation, time for microbial oxidizers to grow, sample storage before testing, geochemical reactions that add or remove constituents, and the HCT results chosen for use in modeling the environmental performance at mine sites. Improved guidance is needed for more consistent interpretation and use of HCT results that rely on identifying: the geochemical processes; the mineralogy, including secondary mineralogy; the available surface area for reactions; and the influence of hydrologic processes on leachate concentrations in runoff, streams, and groundwater.

Geochemical Modeling of Carbon Sequestration, MMV, and EOR in the Illinois Basin

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.; Mehnert, E.

2009-01-01

The Illinois State Geologic Survey is conducting several ongoing CO2 sequestration projects that require geochemical models to gain an understanding of the processes occurring in the subsurface. The ISGS has collected brine and freshwater samples associated with an enhanced oil recovery project in the Loudon oil field. Geochemical modeling allows us to understand reactions with carbonate and silicate minerals in the reservoir, and the effects they have had on brine composition. For the Illinois Basin Decatur project, geochemical models should allow predictions of the reactions that will take place before CO2 injection begins. ?? 2009 Elsevier Ltd. All rights reserved.

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

USGS Publications Warehouse

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

2009-01-01

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

New insight into unstable hillslopes hydrology from hydrogeochemical modelling.

NASA Astrophysics Data System (ADS)

Bertrand, C.; Marc, V.; Malet, J.-P.

2010-05-01

In the black marl outcrops of the French South Alps, sub surface flow conditions are considered as the main triggering factor for initiation and reactivation of landslides. The problem is traditionally addressed in term of hydrological processes (how does percolation to the water table occur?) but in some cases the origin of water is also in question. Direct rainfall is generally assumed as the only water source for groundwater recharge in shallow hillslope aquifers. The bedrock is also supposed impervious and continuous. Yet the geological environment of the study area is very complex owing to the geological history of this alpine sector. The autochthonous callovo-oxfordian black marl bedrock is highly tectonized (Maquaire et al., 2003) and may be affected by large, possibly draining discontinuities. A deep water inflow at the slip surface may at least locally result in increase the pore pressure and decrease the effective shearing resistance of the landslide material. In the active slow-moving landslide of Super-Sauze (Malet and Maquaire, 2003), this question has been addressed using hydrochemical investigations. The groundwater was sampled during five field campaigns uniformly spread out over the year from a network of boreholes. Water chemistry data were completed by geochemical and mineralogical analyses of the marl material. The major hydro-geochemical processes over area proved (1) mixing processes, (2) pyrite alteration, (3) dissolution/precipitation of carbonates and (4) cations exchange (de Montety et al., 2007). A geochemical modelling was carried out using the model Phreeqc (Parkhurst and Appelo, version 2.15, 2008) to check how suitable was observed water chemistry with the reservoir characteristics. The modelling exercise was based on a kinetics approach of soil-water interactions. The model simulates the rock alteration by the dissolution of the primary minerals and the precipitation of new phases. Initial parameters were obtained from geochemical and mineralogical analyses or from the literature (kinetics constants). The simulations showed that pH, sulphate and calcium concentrations in groundwater could be reproduced from reasonable assumptions. However, the observed high concentrations in magnesium and sodium were not correctly simulated by the model. Furthermore, a particular anomaly in the Na+ concentration was observed in the most active part of the landslide. Lastly, isotopic investigation showed that groundwater 3H content in this sector was significantly lower than groundwater content in the other parts of the landslide and lower than the mean rainwater content. This result showed that the mean groundwater age in the active part was probably higher than elsewhere in the landslide. All these arguments led us to conclude that groundwater was locally recharged with saline waters from areas outside the watershed, coming up through the bedrock using major discontinuities. This assumption is in agreement with the geological context. de Montety, V., V. Marc, C. Emblanch, J.-P. Malet, C. Bertrand, O. Maquaire, and T. A. Bogaard, 2007, Identifying the origin of groundwater and flow processes in complex landslides affecting black marls: insights from a hydrochemical survey.: Earth Surface Processes and Landforms, v. 32, p. 32-48. Malet, J.-P. and Maquaire, O., 2003. Black marl earthflows mobility and long-term seasonal dynamic in southeastern France. In: Picarelli, L. (Ed). Proceedings of the International Conference on Fast Slope Movements: Prediction and Prevention for Risk Mitigation. Patron Editore, Bologna: 333-340. Maquaire, O., Malet, J.-P., Remaître, A., Locat, J., Klotz, S. and Guillon, J., 2003. Instability conditions of marly hillslopes: towards landsliding or gullying? The case of the Barcelonnette Bassin, South East France. Engineering Geology, 70(1-2): 109-130. Parkhurst, D.L. and Appelo, C.A.J., 1999, User's guide to PHREEQC (version 2)--A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations: U.S. Geological Survey Water-Resources Investigations Report 99-4259, 312 p.

Integrating Hydrogeological, Microbiological, and Geochemical Data Using a Multi-Component Reactive Transport Model: Quantifying the Biogeochemical Evolution of Redox Zones in a Contaminated Aquifer

NASA Astrophysics Data System (ADS)

McGuire, J. T.; Phanikumar, M. S.; Long, D. T.; Hyndman, D. W.

2003-12-01

Hydrogeological, microbiological, and geochemical processes operating in a shallow sandy aquifer contaminated by waste fuels and chlorinated solvents were integrated using high-resolution mechanistic models. A 3-D, transient, reactive transport model was developed to quantitatively describe coupled processes via thermodynamic and kinetic arguments. The model was created by linking the hydrodynamic model MODFLOW (McDonald and Harbaugh, 1988), with advection, dispersion and user defined kinetic reactions based on RT3D 2.0, (Clement and Jones, 1998) and geochemical model PHREEQC (Parkhurst and Appelo, 1999). This model, BGTK3D 2.0, describes 1) the biodegradation of organic matter based on the influence of transport processes on microbial growth, 2) the complex suite of biogeochemical reactions operating in the aquifer, and 3) sharp chemical gradients. Some key features of this model are an ability to incorporate realistic solid phases to test hypotheses regarding mineral-water interactions, and an ability to accurately describe small-scale biogeochemical cycling (cm variability) observed in the field without oscillations or excessive numerical damping. BGTK3D was used to test hypotheses regarding the evolution of redox chemistry in a contaminated aquifer. The conceptual model that terminal electron accepting processes (TEAPs) distribute themselves sequentially into redox zones down flow path in aqueous systems is often used to interpret how and at what rates organic compounds will be degraded in the environment. Geochemical and microbiological data collected from a mixed contaminant plume at the former Wurtsmith AFB in Oscoda, Michigan suggests that under steady-state, mature plume conditions, traditional redox zonation may not be a realistic model of the distribution of TEAPs and therefore may not be the best model to evaluate the potential degradation of organic compounds. Based on these data, a conceptual model of TEAP evolution in contaminated systems was established. This model proposes that during initial plume development terminal electron acceptors O2, Fe3+, NO3, and SO4, are consumed sequentially based on thermodynamic arguments until a balance between organic degradation rates and source inputs and thus a stable plume length can be achieved. Once this "mature" state has been achieved, distinct redox zones can no longer be sustained and methanogenesis will dominate except in portions of the aquifer impacted by recharge water and diffusion of TEAs from all sides. Under these conditions, TEAPs will not proceed sequentially.

A Generalized Model for Transport of Contaminants in Soil by Electric Fields

PubMed Central

Paz-Garcia, Juan M.; Baek, Kitae; Alshawabkeh, Iyad D.; Alshawabkeh, Akram N.

2012-01-01

A generalized model applicable to soils contaminated with multiple species under enhanced boundary conditions during treatment by electric fields is presented. The partial differential equations describing species transport are developed by applying the law of mass conservation to their fluxes. Transport, due to migration, advection and diffusion, of each aqueous component and complex species are combined to produce one partial differential equation hat describes transport of the total analytical concentrations of component species which are the primary dependent variables. This transport couples with geochemical reactions such as aqueous equilibrium, sorption, precipitation and dissolution. The enhanced model is used to simulate electrokinetic cleanup of lead and copper contaminants at an Army Firing Range. Acid enhancement is achieved by the use of adipic acid to neutralize the basic front produced for the cathode electrochemical reaction. The model is able to simulate enhanced application of the process by modifying the boundary conditions. The model showed that kinetics of geochemical reactions, such as metals dissolution/leaching and redox reactions might be significant for realistic prediction of enhanced electrokinetic extraction of metals in real world applications. PMID:22242884

TAPIR--Finnish national geochemical baseline database.

PubMed

Jarva, Jaana; Tarvainen, Timo; Reinikainen, Jussi; Eklund, Mikael

2010-09-15

In Finland, a Government Decree on the Assessment of Soil Contamination and Remediation Needs has generated a need for reliable and readily accessible data on geochemical baseline concentrations in Finnish soils. According to the Decree, baseline concentrations, referring both to the natural geological background concentrations and the diffuse anthropogenic input of substances, shall be taken into account in the soil contamination assessment process. This baseline information is provided in a national geochemical baseline database, TAPIR, that is publicly available via the Internet. Geochemical provinces with elevated baseline concentrations were delineated to provide regional geochemical baseline values. The nationwide geochemical datasets were used to divide Finland into geochemical provinces. Several metals (Co, Cr, Cu, Ni, V, and Zn) showed anomalous concentrations in seven regions that were defined as metal provinces. Arsenic did not follow a similar distribution to any other elements, and four arsenic provinces were separately determined. Nationwide geochemical datasets were not available for some other important elements such as Cd and Pb. Although these elements are included in the TAPIR system, their distribution does not necessarily follow the ones pre-defined for metal and arsenic provinces. Regional geochemical baseline values, presented as upper limit of geochemical variation within the region, can be used as trigger values to assess potential soil contamination. Baseline values have also been used to determine upper and lower guideline values that must be taken into account as a tool in basic risk assessment. If regional geochemical baseline values are available, the national guideline values prescribed in the Decree based on ecological risks can be modified accordingly. The national geochemical baseline database provides scientifically sound, easily accessible and generally accepted information on the baseline values, and it can be used in various environmental applications. Copyright 2010 Elsevier B.V. All rights reserved.

Effect of organic complexing agents on the interactions of Cs(+), Sr(2+) and UO(2)(2+) with silica and natural sand.

PubMed

Reinoso-Maset, Estela; Worsfold, Paul J; Keith-Roach, Miranda J

2013-05-01

Sorption processes play a key role in controlling radionuclide migration through subsurface environments and can be affected by the presence of anthropogenic organic complexing agents found at contaminated sites. The effect of these complexing agents on radionuclide-solid phase interactions is not well known. Therefore the aim of this study was to examine the processes by which EDTA, NTA and picolinate affect the sorption kinetics and equilibria of Cs(+), Sr(2+) and UO2(2+) onto natural sand. The caesium sorption rate and equilibrium were unaffected by the complexing agents. Strontium however showed greater interaction with EDTA and NTA in the presence of desorbed matrix cations than geochemical modelling predicted, with SrNTA(-) enhancing sorption and SrEDTA(2-) showing lower sorption than Sr(2+). Complexing agents reduced UO2(2+) sorption to silica and enhanced the sorption rate in the natural sand system. Elevated concentrations of picolinate reduced the sorption of Sr(2+) and increased the sorption rate of UO2(2+), demonstrating the potential importance of this complexing agent. These experiments provide a direct comparison of the sorption behaviour of Cs(+), Sr(2+) and UO2(2+)onto natural sand and an assessment of the relative effects of EDTA, NTA and picolinate on the selected elements. Copyright © 2013 Elsevier Ltd. All rights reserved.

Geochronology and geochemistry of basaltic rocks from the Sartuohai ophiolitic mélange, NW China: Implications for a Devonian mantle plume within the Junggar Ocean

NASA Astrophysics Data System (ADS)

Yang, Gaoxue; Li, Yongjun; Santosh, M.; Yang, Baokai; Yan, Jing; Zhang, Bing; Tong, Lili

2012-10-01

The West Junggar domain in NW China is a distinct tectonic unit of the Central Asian Orogenic Belt (CAOB). It is composed of Paleozoic ophiolitic mélanges, arcs and accretionary complexes. The Sartuohai ophiolitic mélange in the eastern West Junggar forms the northeastern part of the Darbut ophiolitic mélange, which contains serpentinized harzburgite, pyroxenite, dunite, cumulate, pillow lava, abyssal radiolarian chert and podiform chromite, overlain by the Early Carboniferous volcano-sedimentary rocks. In this paper we report new geochronological and geochemical data from basaltic and gabbroic blocks embedded within the Sartuohai ophiolitic mélange, to assess the possible presence of a Devonian mantle plume in the West Junggar, and evaluate the petrogenesis and implications for understanding of the Paleozoic continental accretion of CAOB. Zircon U-Pb analyses from the alkali basalt and gabbro by laser ablation inductively coupled plasma mass spectrometry yielded weighted mean ages of 375 ± 2 Ma and 368 ± 11 Ma. Geochemically, the Sartuohai ophiolitic mélange includes at least two distinct magmatic units: (1) a Late Devonian fragmented ophiolite, which were produced by ca. 2-10% spinel lherzolite partial melting in arc-related setting, and (2) contemporary alkali lavas, which were derived from 5% to 10% garnet + minor spinel lherzolite partial melting in an oceanic plateau or a seamount. Based on detailed zircon U-Pb dating and geochemical data for basalts and gabbros from the Sartuohai ophiolitic mélange, in combination with previous work, indicate a complex evolution by subduction-accretion processes from the Devonian to the Carboniferous. Furthermore, the alkali basalts from the Sartuohai ophiolitic mélange might be correlated to a Devonian mantle plume-related magmatism within the Junggar Ocean. If the plume model as proposed here is correct, it would suggest that mantle plume activity significantly contributed to the crustal growth in the CAOB.

Authigenic carbonate formation at hydrocarbon seeps in continental margin sediments: A comparative study

USGS Publications Warehouse

Naehr, T.H.; Eichhubl, P.; Orphan, V.J.; Hovland, M.; Paull, C.K.; Ussler, W.; Lorenson, T.D.; Greene, H. Gary

2007-01-01

Authigenic carbonates from five continental margin locations, the Eel River Basin, Monterey Bay, Santa Barbara Basin, the Sea of Okhotsk, and the North Sea, exhibit a wide range of mineralogical and stable isotopic compositions. These precipitates include aragonite, low- and high-Mg calcite, and dolomite. The carbon isotopic composition of carbonates varies widely, ranging from -60??? to +26???, indicating complex carbon sources that include 13C-depleted microbial and thermogenic methane and residual, 13C-enriched, bicarbonate. A similarly large variability of ??18O values (-5.5??? to +8.9???) demonstrates the geochemical complexity of these sites, with some samples pointing toward an 18O-enriched oxygen source possibly related to advection of 18O-enriched formation water or to the decomposition of gas hydrate. Samples depleted in 18O are consistent with formation deeper in the sediment or mixing of pore fluids with meteoric water during carbonate precipitation. A wide range of isotopic and mineralogical variation in authigenic carbonate composition within individual study areas but common trends across multiple geographic areas suggest that these parameters alone are not indicative for certain tectonic or geochemical settings. Rather, the observed variations probably reflect local controls on the flux of carbon and other reduced ions, such as faults, fluid conduits, the presence or absence of gas hydrate in the sediment, and the temporal evolution of the local carbon reservoir. Areas with seafloor carbonates that indicate formation at greater depth below the sediment-water interface must have undergone uplift and erosion in the past or are still being uplifted. Consequently, the occurrence of carbonate slabs on the seafloor in areas of active hydrocarbon seepage is commonly an indicator of exhumation following carbonate precipitation in the shallow subsurface. Therefore, careful petrographic and geochemical analyses are critical components necessary for the correct interpretation of processes related to hydrocarbon seepage in continental margin environments and elsewhere. ?? 2007 Elsevier Ltd. All rights reserved.

Complex resistivity signatures of ethanol biodegradation in porous media

USGS Publications Warehouse

Personna, Yves Robert; Slater, Lee; Ntarlagiannis, Dimitrios; Werkema, Dale D.; Szabo, Zoltan

2013-01-01

Numerous adverse effects are associated with the accidental release of ethanol (EtOH) and its persistence in the subsurface. Geophysical techniques may permit non-invasive, real time monitoring of microbial degradation of hydrocarbon. We performed complex resistivity (CR) measurements in conjunction with geochemical data analysis on three microbial-stimulated and two control columns to investigate changes in electrical properties during EtOH biodegradation processes in porous media. A Debye Decomposition approach was applied to determine the chargeability (m), normalized chargeability (mn) and time constant (τ) of the polarization magnitude and relaxation length scale as a function of time. The CR responses showed a clear distinction between the bioaugmented and control columns in terms of real (σ′) and imaginary (σ″) conductivity, phase (ϕ) and apparent formation factor (Fapp). Unlike the control columns, a substantial decrease in σ′ and increase in Fapp occurred at an early time (within 4 days) of the experiment for all three bioaugmented columns. The observed decrease in σ′ is opposite to previous studies on hydrocarbon biodegradation. These columns also exhibited increases in ϕ (up to ~ 9 mrad) and σ″ (up to two order of magnitude higher) 5 weeks after microbial inoculation. Variations in m and mn were consistent with temporal changes in ϕ and σ″ responses, respectively. Temporal geochemical changes and high resolution scanning electron microscopy imaging corroborated the CR findings, thus indicating the sensitivity of CR measurements to EtOH biodegradation processes. Our results offer insight into the potential application of CR measurements for long-term monitoring of biogeochemical and mineralogical changes during intrinsic and induced EtOH biodegradation in the subsurface.

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

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

Hyporheic zone influences on concentration-discharge relationships in a headwater sandstone stream

NASA Astrophysics Data System (ADS)

Hoagland, Beth; Russo, Tess A.; Gu, Xin; Hill, Lillian; Kaye, Jason; Forsythe, Brandon; Brantley, Susan L.

2017-06-01

Complex subsurface flow dynamics impact the storage, routing, and transport of water and solutes to streams in headwater catchments. Many of these hydrogeologic processes are indirectly reflected in observations of stream chemistry responses to rain events, also known as concentration-discharge (CQ) relations. Identifying the relative importance of subsurface flows to stream CQ relationships is often challenging in headwater environments due to spatial and temporal variability. Therefore, this study combines a diverse set of methods, including tracer injection tests, cation exchange experiments, geochemical analyses, and numerical modeling, to map groundwater-surface water interactions along a first-order, sandstone stream (Garner Run) in the Appalachian Mountains of central Pennsylvania. The primary flow paths to the stream include preferential flow through the unsaturated zone ("interflow"), flow discharging from a spring, and groundwater discharge. Garner Run stream inherits geochemical signatures from geochemical reactions occurring along each of these flow paths. In addition to end-member mixing effects on CQ, we find that the exchange of solutes, nutrients, and water between the hyporheic zone and the main stream channel is a relevant control on the chemistry of Garner Run. CQ relationships for Garner Run were compared to prior results from a nearby headwater catchment overlying shale bedrock (Shale Hills). At the sandstone site, solutes associated with organo-mineral associations in the hyporheic zone influence CQ, while CQ trends in the shale catchment are affected by preferential flow through hillslope swales. The difference in CQ trends document how the lithology and catchment hydrology control CQ relationships.

An integrated monitoring network for hydrologic, geochemical, and sediment fluxes to characterize carbon-mineral fate in the Christina River Basin Critical Zone Observatory

NASA Astrophysics Data System (ADS)

Sawyer, A. H.; Karwan, D. L.; Lazareva, O.

2011-12-01

Organic carbon (C) -mineral complexation mechanism plays an important role in C sequestration within watersheds. The primary goal of the Christina River Basin Critical Zone Observatory in SE Pennsylvania and N Delaware, USA (one of six National Science Foundation-funded observatories) is to quantify net carbon sink or source due to mineral production and transport and its dependence on land use. This effort requires an interdisciplinary understanding of carbon and mineral fluxes across interfaces between soil, aquifer, floodplain, and river. We have established a monitoring network that targets hydrologic, geochemical, and sedimentological transport processes across channel-floodplain-aquifer interfaces within White Clay Creek Watershed. Within the channel, suspended material is sampled and analyzed for organic and mineral composition as well as geochemical fingerprints. Surface water and groundwater are analyzed for C, Fe, and Mn chemistry. Within the floodplain, in-situ sensors monitor soil moisture, pressure, temperature, conductivity, and redox potential. Integrated data analysis should yield estimates of water and solute fluxes between the vadose zone, riparian aquifer, and stream. Our preliminary data show that storm events are important for carbon and mineral fluxes-suspended material in surface water changes in source and composition throughout the storm. Meanwhile, the variation in stream stage drives surface water-groundwater exchange, facilitating changes in redox potential and providing opportunity for enhanced transport and reactions involving C, Fe, and Mn in the riparian aquifer.

Strategies to predict metal mobility in surficial mining environments

USGS Publications Warehouse

Smith, Kathleen S.

2007-01-01

This report presents some strategies to predict metal mobility at mining sites. These strategies are based on chemical, physical, and geochemical information about metals and their interactions with the environment. An overview of conceptual models, metal sources, and relative mobility of metals under different geochemical conditions is presented, followed by a discussion of some important physical and chemical properties of metals that affect their mobility, bioavailability, and toxicity. The physical and chemical properties lead into a discussion of the importance of the chemical speciation of metals. Finally, environmental and geochemical processes and geochemical barriers that affect metal speciation are discussed. Some additional concepts and applications are briefly presented at the end of this report.

Hydrological mixing and geochemical processes characterization in an estuarine/mangrove system using environmental tracers in Babitonga Bay (Santa Catarina, Brazil)

NASA Astrophysics Data System (ADS)

Barros Grace, Virgínia; Mas-Pla, Josep; Oliveira Novais, Therezinha; Sacchi, Elisa; Zuppi, Gian Maria

2008-03-01

The hydrologic complex of Babitonga Bay (Brazil) forms a vast environmental complex where agriculture, shellfish farming, and industries coexist with a unique natural area of Atlantic rain forest and mangrove systems. The origin of different continental hydrological components, the environmental transition between saline and freshwaters, and the influence of the seasonality on Babitonga Bay waters are evaluated using isotopes and chemistry. End-member mixing analysis is used to explore hydrological processes in the bay. We show that a mixing of waters from different origins takes place in the bay modifying its chemical characteristics. Furthermore, biogeochemical processes related to well-developed mangrove systems are responsible for an efficient bromide uptake, which limit its use as a tracer as commonly used in non-biologically active environments. Seasonal behaviours are also distinguished from our datasets. The rainy season (April) provides a homogenization of the hydrological processes that is not seen after the dry season (October), when larger spatial differences appear and when the effects of biological processes on the bay hydrochemistry are more dynamic, or can be better recognized. Moreover, Cl/Br and stable isotopes of water molecule allow a neat definition of the hydrological and biogeochemical processes that control chemical composition in coastal and transition areas.

Gamma spectrometry application of the Kola Peninsula (in Russian)

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

Golovin, I.V.; Kolesnik, N.N.; Antipov, V.S.

1973-03-01

The methods and results are reported of a spectrometric study, carried out with the SP-3 instrument in Pre-Cambrian fornnations in the northwest ranges of Kola Peninsula for clarification of the radiochemical characteristics of the rocks of the region and of the distribution characteristics of radioactive elements in Cu-Ni mineralizations. It was established that the content of radioactive elements in the rocks varies within a wide interval and corresponds basically to the Vinogradov content. The radioactive element content in typical metamorphic and magmatic complexes and sulfide ores was determined. The spectrometric method can be used for the solution of various geologicalmore » problems. It is particularly useful for studying the separation of strata, the genesis of magmatic and metamorphic complexes, and the metamorphic and geochemical zonality and granitization processes. (tr-auth)« less

Geochemical and Mineralogical Indicators for Aqueous Processes on the West Spur of the Columbia Hills in Gusev Crater

NASA Technical Reports Server (NTRS)

Ming, D. W.; Morris, R. V.; Gellert, R.; Yen, A.; Bell, J. F., III; Blaney, D.; Christensen, P. R.; Crumpler, L.; Chu, P.; Farrand, W. H.

2005-01-01

The primary objective of the MER Spirit and Opportunity Rovers is to identify and investigate rocks, outcrops, and soils that have the highest possible chance of preserving evidence of water activity on Mars. The Athena Science Instrument Payload onboard the two rovers has provided geochemical and mineralogical information that indicates a variety of aqueous processes and various degrees of alteration at the two landing sites.

Chemical Structure and Molecular Dimension As Controls on the Inherent Stability of Charcoal in Boreal Forest Soil

NASA Astrophysics Data System (ADS)

Hockaday, W. C.; Kane, E. S.; Ohlson, M.; Huang, R.; Von Bargen, J.; Davis, R.

2014-12-01

Efforts have been made by various scientific disciplines to study hyporheic zones and characterize their associated processes. One way to approach the study of the hyporheic zone is to define facies, which are elements of a (hydrobio) geologic classification scheme that groups components of a complex system with high variability into a manageable set of discrete classes. In this study, we try to classify the hyporheic zone based on the geology, geochemistry, microbiology, and understand their interactive influences on the integrated biogeochemical distributions and processes. A number of measurements have been taken for 21 freeze core samples along the Columbia River bank in the Hanford 300 Area, and unique datasets have been obtained on biomass, pH, number of microbial taxa, percentage of N/C/H/S, microbial activity parameters, as well as microbial community attributes/modules. In order to gain a complete understanding of the geological control on these variables and processes, the explanatory variables are set to include quantitative gravel/sand/mud/silt/clay percentages, statistical moments of grain size distributions, as well as geological (e.g., Folk-Wentworth) and statistical (e.g., hierarchical) clusters. The dominant factors for major microbial and geochemical variables are identified and summarized using exploratory data analysis approaches (e.g., principal component analysis, hierarchical clustering, factor analysis, multivariate analysis of variance). The feasibility of extending the facies definition and its control of microbial and geochemical properties to larger scales is discussed.

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.

Hiereachical Bayesian Model for Combining Geochemical and Geophysical Data for Environmental Applications Software

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

Chen, Jinsong

2013-05-01

Development of a hierarchical Bayesian model to estimate the spatiotemporal distribution of aqueous geochemical parameters associated with in-situ bioremediation using surface spectral induced polarization (SIP) data and borehole geochemical measurements collected during a bioremediation experiment at a uranium-contaminated site near Rifle, Colorado. The SIP data are first inverted for Cole-Cole parameters including chargeability, time constant, resistivity at the DC frequency and dependence factor, at each pixel of two-dimensional grids using a previously developed stochastic method. Correlations between the inverted Cole-Cole parameters and the wellbore-based groundwater chemistry measurements indicative of key metabolic processes within the aquifer (e.g. ferrous iron, sulfate, uranium)more » were established and used as a basis for petrophysical model development. The developed Bayesian model consists of three levels of statistical sub-models: 1) data model, providing links between geochemical and geophysical attributes, 2) process model, describing the spatial and temporal variability of geochemical properties in the subsurface system, and 3) parameter model, describing prior distributions of various parameters and initial conditions. The unknown parameters are estimated using Markov chain Monte Carlo methods. By combining the temporally distributed geochemical data with the spatially distributed geophysical data, we obtain the spatio-temporal distribution of ferrous iron, sulfate and sulfide, and their associated uncertainity information. The obtained results can be used to assess the efficacy of the bioremediation treatment over space and time and to constrain reactive transport models.« 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.

Is rhizosphere remediation sufficient for sustainable revegetation of mine tailings?

PubMed

Huang, Longbin; Baumgartl, Thomas; Mulligan, David

2012-07-01

Revegetation of mine tailings (fine-grained waste material) starts with the reconstruction of root zones, consisting of a rhizosphere horizon (mostly topsoil and/or amended tailings) and the support horizon beneath (i.e. equivalent to subsoil - mostly tailings), which must be physically and hydro-geochemically stable. This review aims to discuss key processes involved in the development of functional root zones within the context of direct revegetation of tailings and introduces a conceptual process of rehabilitating structure and function in the root zones based on a state transition model. Field studies on the revegetation of tailings (from processing base metal ore and bauxite residues) are reviewed. Particular focus is given to tailings' properties that limit remediation effectiveness. Aspects of root zone reconstruction and vegetation responses are also discussed. When reconstructing a root zone system, it is critical to restore physical structure and hydraulic functions across the whole root zone system. Only effective and holistically restored systems can control hydro-geochemical mobility of acutely and chronically toxic factors from the underlying horizon and maintain hydro-geochemical stability in the rhizosphere. Thereafter, soil biological capacity and ecological linkages (i.e. carbon and nutrient cycling) may be rehabilitated to integrate the root zones with revegetated plant communities into sustainable plant ecosystems. A conceptual framework of system transitions between the critical states of root zone development has been proposed. This will illustrate the rehabilitation process in root zone reconstruction and development for direct revegetation with sustainable plant communities. Sustainable phytostabilization of tailings requires the systematic consideration of hydro-geochemical interactions between the rhizosphere and the underlying supporting horizon. It further requires effective remediation strategies to develop hydro-geochemically stable and biologically functional root zones, which can facilitate the recovery of the microbial community and ecological linkages with revegetated plant communities.

Geochemistry of siliciclastic rocks in the Peninsular, Chugach, and Prince William terranes: Implications for the tectonic evolution of south central Alaska

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

Gilbert, S.A.; Casey, J.F.; Bradley, D.

1992-01-01

According to some interpretations, south-central Alaska consists of a series of unrelated terranes juxtaposed by dominantly strike-slip motions some time after formation. Alternatively, these so-called terranes may be related components of a seaward-facing arc, forearc, and accretionary prism. To shed new light on the tectonic history of this area, 150 samples of siliciclastic rocks were analyzed for major, trace, and rare earth elements (REE). Shales were sampled from the Upper Cretaceous Matanuska and Paleogene Chickaloon Fms. of the Peninsular Terrane (forearc basin); argillaceous melange matrix from the Mesozoic McHugh Complex and slate from turbidites of the Upper Cretaceous Valdez Groupmore » of the Chugach Terrane (landward part of accretionary prism); and slate from turbidites of the Paleogene Orea Group of the Prince William Terrane (seaward part of accretionary prism). One tectonic model that may fit these geochemical data requires an early linkage between the Peninsular and Chugach-Prince William composite terranes. The geochemical signatures suggest that the McHugh Complex was derived from a mafic volcanic source and may represent an early accretionary stage of sediments derived from an oceanic arc. The progressive continental enrichment of the Valdez and Orca Groups may reflect later accretionary processes during and/or after the collision of the Talkectna arc with the North American continent. The similar increasingly continental source documented in the geochemistry of the forearc basin shales of the Matanuska and Chickaloon Fms. may suggest: that the presently defined Peninsular, Chugach, and Prince William terranes collectively represent one continuously evolving, seaward facing arc, forearc, and accretionary prism complex.« less

Low-frequency electrical properties.

USGS Publications Warehouse

Olhoeft, G.R.

1985-01-01

In the interpretation of induced polarization data, it is commonly assumed that metallic mineral polarization dominantly or solely causes the observed response. However, at low frequencies, there is a variety of active chemical processes which involve the movement or transfer of electrical charge. Measurements of electrical properties at low frequencies (such as induced polarization) observe such movement of charge and thus monitor many geochemical processes at a distance. Examples in which this has been done include oxidation-reduction of metallic minerals such as sulfides, cation exchange on clays, and a variety of clay-organic reactions relevant to problems in toxic waste disposal and petroleum exploration. By using both the frequency dependence and nonlinear character of the complex resistivity spectrum, these reactions may be distinguished from each other and from barren or reactionless materials.-Author

Granitoids of different geodynamic settings of Baikal region (Russia) their geochemical evolution and origin

NASA Astrophysics Data System (ADS)

Antipin, Viktor; Sheptyakova, Natalia

2016-04-01

In the southern folded framing of the Siberian craton the granitoid magmatism of different ages involves batholiths, small low-depth intrusions and intrusion-dyke belts with diverse mineral and geochemical characteristics of rocks. Granitoid formation could be related to the Early Paleozoic collision stage and intra-plate magmatism of the Late Paleozoic age of the geologic development of Baikal area. The Early Paleozoic granitoids of Khamar-Daban Ridge and Olkhon region revealed their closeness in age and composition. They were referred to syncollision S-type formations derived from gneiss-schistose substratum of metamorphic sequences. The magmatic rocks were classified into various geochemical types comprising formations of normal Na-alkalinity (migmatites and plagiogranites), calc-alkaline and subalkaline (K-Na granitoids, granosyenites and quartz syenites) series. It is significant, that plagiomigmatites and plagiogranites in all elements repeat the shape of the chart of normalized contents marked for trend of K-Na granitoids, but at considerably lower level of concentrations of all elements. This general pattern of element distribution might indicate similar anatectic origin of both granitoid types, but from crustal substrata distinguished by composition and geochemical features. Comparative geochemical analysis pointed out that the source of melts of the Early Paleozoic granitoids of the Olkhon (505-477 Ma) and Khamar-Daban (516-490 Ma) complexes of the Baikal region could be the crustal substratum, which is obviously the criterion for their formation in the collisional geodynamic setting. Using the Late Paleozoic subalkaline magmatism proceeding at the Khamar-Daban Range (Khonzurtay pluton, 331 Ma) as an example, it was found that the formation of monzodiorite-syenite-leucogranite series was considerably contributed by the processes of hybridism and assimilation through mixing of the upper mantle basaltoid magma derived melts of granitic composition. The involvement of the deep source is indicated by low Rb/Sr ratios and 87Sr/86Sr ratio (0.70592±0.00021) in rocks (Kazimirovskiy, 2006). The intra-plate biotite granites and leucogranites are represented by rare-metal geochemical type of rocks (311-321 Ma). Geochemical evolution promoted an increase of F, Li, Rb, Cs, Sn, Be, Ta, and Pb and a decrease of Ba, Sr, Zn, Zr, Th, and U contents in rare-metal granites, that reflects their formation from deeply differentiated residual magma. The substance of the lower crust could have the composition of biotite-bearing granulites rich in lithophyle rare elements. It is noteworthy, that the composition and isotope-geochemical features of the supposed magma-forming substratum correspond to the characteristics of the ancient Precambrian continental crust of the Southern Baikal region. These conclusions agree with the results of preceding studies of rare-metal granites in the other regions of Central Asia (Kovalenko et al, 1999). Research has been supported by RNF grant № 15-17-10010.

Origin and age of the Eisenkappel gabbro to granite suite (Carinthia, SE Austrian Alps)

PubMed Central

Miller, C.; Thöni, M.; Goessler, W.; Tessadri, R.

2011-01-01

The northern part of the Karawanken plutonic belt is a gabbro–granite complex located just north of the Periadriatic lineament near the Slovenian–Austrian border. Petrographic and geochemical studies of the Eisenkappel intrusive complex indicate that this multiphase plutonic suite developed by a combination of crystal accumulation, fractional crystallization and assimilation processes, magma mixing and mingling. The mafic rocks are alkaline and have within-plate geochemical characteristics, indicating anorogenic magmatism in an extensional setting and derivation from an enriched mantle source. The mafic melts triggered partial melting of the crust and the formation of granite. The granitic rocks are alkalic, metaluminous and have the high Fe/Fe + Mg characteristics of within-plate plutons. Temperature and pressure conditions, derived from amphibole-plagioclase and different amphibole thermobarometers, suggest that the analysed Eisenkappel gabbros crystallized at around 1000 ± 20 °C and 380–470 MPa, whereas the granitic rock crystallized at T ≤ 800 ± 20 °C and ≤ 350 MPa. Mineral-whole rock Sm–Nd analyses of two cumulate gabbros yielded 249 ± 8.4 Ma and 250 ± 26 Ma (εNd: + 3.6), garnet-whole rock Sm–Nd analyses of two silicic samples yielded well-constrained ages of 238.4 ± 1.9 Ma and 242.1 ± 2.1 Ma (εNd: − 2.6). PMID:26525511

Occurrence and multivariate exploratory analysis of the natural radioactivity anomaly in the south coastal region of Kenya

NASA Astrophysics Data System (ADS)

Kaniu, M. I.; Angeyo, K. H.; Darby, I. G.

2018-05-01

Characterized by a variety of rock formations, namely alkaline, igneous and sedimentary that contain significant deposits of monazite and pyrochlore ores, the south coastal region of Kenya may be regarded as highly heterogeneous with regard to its geochemistry, mineralogy as well as geological morphology. The region is one of the several alkaline carbonatite complexes of Kenya that are associated with high natural background radiation and therefore radioactivity anomaly. However, this high background radiation (HBR) anomaly has hardly been systematically assessed and delineated with regard to the spatial, geological, geochemical as well as anthropogenic variability and co-dependencies. We conducted wide-ranging in-situ gamma-ray spectrometric measurements in this area. The goal of the study was to assess the radiation exposure as well as determine the underlying natural radioactivity levels in the region. In this paper we report the occurrence, exploratory analysis and modeling to assess the multivariate geo-dependence and spatial variability of the radioactivity and associated radiation exposure. Unsupervised principal component analysis and ternary plots were utilized in the study. It was observed that areas which exhibit HBR anomalies are located along the south coast paved road and in the Mrima-Kiruku complex. These areas showed a trend towards enhanced levels of 232Th and 238U and low 40K. The spatial variability of the radioactivity anomaly was found to be mainly constrained by anthropogenic activities, underlying geology and geochemical processes in the terrestrial environment.

Inorganic and organic geochemical fingerprinting of sediment sources and ocean circulation on a complex continental margin (São Paulo Bight, Brazil)

NASA Astrophysics Data System (ADS)

Michaelovitch de Mahiques, Michel; Jörg Hanebuth, Till Jens; Hanae Nagai, Renata; Caruso Bícego, Marcia; Lopes Figueira, Rubens Cesar; Mello Sousa, Silvia Helena; Burone, Leticia; Franco-Fraguas, Paula; Taniguchi, Satie; Barbosa Salaroli, Alexandre; Pereira Dias, Gilberto; Menezes Prates, Denise; Fernandes Freitas, Maria Eugenia

2017-03-01

In this study, we use inorganic (metal) and organic (bulk and molecular) markers in sediment samples of the south-eastern Brazilian margin to investigate the response of geochemical fingerprints to the complex hydrodynamic processes present in the area. Results indicate the potential of export of terrigenous siliciclastic and organic constituents to the upper slope, even in an area with limited fluvial supply.

Metal contents and especially the ln(Ti / Al) and ln(Fe / K) ratios make it possible to recognise the extension of shelf sediments toward the upper slope. Potassium, here expressed as ln(K / Sc) and ln(K / Al) ratios used as proxies of illite-kaolinite variations, proved to be an important parameter, especially because it allowed us to decipher the imprint of the northward flow of the Intermediate Western Boundary Current (IWBC) in comparison to the southward flows of the Brazil Current (BC) and Deep Western Boundary Current (DWBC). Using organic matter analyses, we were able to evaluate the extent of terrestrial contributions to the outer shelf and slope, even without the presence of significant fluvial input. In addition, molecular markers signify a slight increase in the input of C4-derived plants to the slope sediments, transported from distant areas by the main alongshore boundary currents, indicating that the terrestrial fraction of the organic matter deposited on the slope has a distinct origin when compared to shelf sediments.

Modeling the effectiveness of U(VI) biomineralization in dual-porosity porous media

NASA Astrophysics Data System (ADS)

Rotter, B. E.; Barry, D. A.; Gerhard, J. I.; Small, J. S.

2011-05-01

SummaryUranium contamination is a serious environmental concern worldwide. Recent attention has focused on the in situ immobilization of uranium by stimulation of dissimilatory metal-reducing bacteria (DMRB). The objective of this work was to investigate the effectiveness of this approach in heterogeneous and structured porous media, since such media may significantly affect the geochemical and microbial processes taking place in contaminated sites, impacting remediation efficiency during biostimulation. A biogeochemical reactive transport model was developed for uranium remediation by immobile-region-resident DMRB in two-region porous media. Simulations were used to investigate the parameter sensitivities of the system over wide-ranging geochemical, microbial and groundwater transport conditions. The results suggest that optimal biomineralization is generally likely to occur when the regional mass transfer timescale is less than one-thirtieth the value of the volumetric flux timescale, and/or the organic carbon fermentation timescale is less than one-thirtieth the value of the advective timescale, and/or the mobile region porosity ranges between equal to and four times the immobile region porosity. Simulations including U(VI) surface complexation to Fe oxides additionally suggest that, while systems exhibiting U(VI) surface complexation may be successfully remediated, they are likely to display different degrees of remediation efficiency over varying microbial efficiency, mobile-immobile mass transfer, and porosity ratios. Such information may aid experimental and field designs, allowing for optimized remediation in dual-porosity (two-region) biostimulated DMRB U(VI) remediation schemes.

Assessment of In-Situ Reductive Dechlorination Using Compound-Specific Stable Isotopes, Functional-Gene Pcr, and Geochemical Data

PubMed Central

Carreón-Diazconti, Concepción; Santamaría, Johanna; Berkompas, Justin; Field, James A.; Brusseau, Mark L.

2010-01-01

Isotopic analysis and molecular-based bioassay methods were used in conjunction with geochemical data to assess intrinsic reductive dechlorination processes for a chlorinated-solvent contaminated site in Tucson, Arizona. Groundwater samples were obtained from monitoring wells within a contaminant plume comprising tetrachloroethene and its metabolites trichloroethene, cis-1,2-dichloroethene, vinyl chloride, and ethene, as well as compounds associated with free-phase diesel present at the site. Compound specific isotope (CSI) analysis was performed to characterize biotransformation processes influencing the transport and fate of the chlorinated contaminants. PCR analysis was used to assess the presence of indigenous reductive dechlorinators. The target regions employed were the 16s rRNA gene sequences of Dehalococcoides sp. and Desulfuromonas sp., and DNA sequences of genes pceA, tceA, bvcA, and vcrA, which encode reductive dehalogenases. The results of the analyses indicate that relevant microbial populations are present and that reductive dechlorination is presently occurring at the site. The results further show that potential degrader populations as well as biotransformation activity is non-uniformly distributed within the site. The results of laboratory microcosm studies conducted using groundwater collected from the field site confirmed the reductive dechlorination of tetrachloroethene to dichloroethene. This study illustrates the use of an integrated, multiple-method approach for assessing natural attenuation at a complex chlorinated-solvent contaminated site. PMID:19603638

Microscale Biosignatures and Abiotic Mineral Authigenesis in Little Hot Creek, California

PubMed Central

Kraus, Emily A.; Beeler, Scott R.; Mors, R. Agustin; Floyd, James G.; Stamps, Blake W.; Nunn, Heather S.; Stevenson, Bradley S.; Johnson, Hope A.; Shapiro, Russell S.; Loyd, Sean J.; Spear, John R.; Corsetti, Frank A.

2018-01-01

Hot spring environments can create physical and chemical gradients favorable for unique microbial life. They can also include authigenic mineral precipitates that may preserve signs of biological activity on Earth and possibly other planets. The abiogenic or biogenic origins of such precipitates can be difficult to discern, therefore a better understanding of mineral formation processes is critical for the accurate interpretation of biosignatures from hot springs. Little Hot Creek (LHC) is a hot spring complex located in the Long Valley Caldera, California, that contains mineral precipitates composed of a carbonate base (largely submerged) topped by amorphous silica (largely emergent). The precipitates occur in close association with microbial mats and biofilms. Geological, geochemical, and microbiological data are consistent with mineral formation via degassing and evaporation rather than direct microbial involvement. However, the microfabric of the silica portion is stromatolitic in nature (i.e., wavy and finely laminated), suggesting that abiogenic mineralization has the potential to preserve textural biosignatures. Although geochemical and petrographic evidence suggests the calcite base was precipitated via abiogenic processes, endolithic microbial communities modified the structure of the calcite crystals, producing a textural biosignature. Our results reveal that even when mineral precipitation is largely abiogenic, the potential to preserve biosignatures in hot spring settings is high. The features found in the LHC structures may provide insight into the biogenicity of ancient Earth and extraterrestrial rocks.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation.

PubMed

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand; Apte, Shree Kumar

2016-08-15

Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Interaction of Uranium with Bacterial Cell Surfaces: Inferences from Phosphatase-Mediated Uranium Precipitation

PubMed Central

Kulkarni, Sayali; Misra, Chitra Seetharam; Gupta, Alka; Ballal, Anand

2016-01-01

ABSTRACT Deinococcus radiodurans and Escherichia coli expressing either PhoN, a periplasmic acid phosphatase, or PhoK, an extracellular alkaline phosphatase, were evaluated for uranium (U) bioprecipitation under two specific geochemical conditions (GCs): (i) a carbonate-deficient condition at near-neutral pH (GC1), and (ii) a carbonate-abundant condition at alkaline pH (GC2). Transmission electron microscopy revealed that recombinant cells expressing PhoN/PhoK formed cell-associated uranyl phosphate precipitate under GC1, whereas the same cells displayed extracellular precipitation under GC2. These results implied that the cell-bound or extracellular location of the precipitate was governed by the uranyl species prevalent at that particular GC, rather than the location of phosphatase. MINTEQ modeling predicted the formation of predominantly positively charged uranium hydroxide ions under GC1 and negatively charged uranyl carbonate-hydroxide complexes under GC2. Both microbes adsorbed 6- to 10-fold more U under GC1 than under GC2, suggesting that higher biosorption of U to the bacterial cell surface under GC1 may lead to cell-associated U precipitation. In contrast, at alkaline pH and in the presence of excess carbonate under GC2, poor biosorption of negatively charged uranyl carbonate complexes on the cell surface might have resulted in extracellular precipitation. The toxicity of U observed under GC1 being higher than that under GC2 could also be attributed to the preferential adsorption of U on cell surfaces under GC1. This work provides a vivid description of the interaction of U complexes with bacterial cells. The findings have implications for the toxicity of various U species and for developing biological aqueous effluent waste treatment strategies. IMPORTANCE The present study provides illustrative insights into the interaction of uranium (U) complexes with recombinant bacterial cells overexpressing phosphatases. This work demonstrates the effects of aqueous speciation of U on the biosorption of U and the localization pattern of uranyl phosphate precipitated as a result of phosphatase action. Transmission electron microscopy revealed that location of uranyl phosphate (cell associated or extracellular) was primarily influenced by aqueous uranyl species present under the given geochemical conditions. The data would be useful for understanding the toxicity of U under different geochemical conditions. Since cell-associated precipitation of metal facilitates easy downstream processing by simple gravity-based settling down of metal-loaded cells, compared to cumbersome separation techniques, the results from this study are of considerable relevance to effluent treatment using such cells. PMID:27287317

Microbial Iron Cycling in Acidic Geothermal Springs of Yellowstone National Park: Integrating Molecular Surveys, Geochemical Processes, and Isolation of Novel Fe-Active Microorganisms

PubMed Central

Kozubal, Mark A.; Macur, Richard E.; Jay, Zackary J.; Beam, Jacob P.; Malfatti, Stephanie A.; Tringe, Susannah G.; Kocar, Benjamin D.; Borch, Thomas; Inskeep, William P.

2012-01-01

Geochemical, molecular, and physiological analyses of microbial isolates were combined to study the geomicrobiology of acidic iron oxide mats in Yellowstone National Park. Nineteen sampling locations from 11 geothermal springs were studied ranging in temperature from 53 to 88°C and pH 2.4 to 3.6. All iron oxide mats exhibited high diversity of crenarchaeal sequences from the Sulfolobales, Thermoproteales, and Desulfurococcales. The predominant Sulfolobales sequences were highly similar to Metallosphaera yellowstonensis str. MK1, previously isolated from one of these sites. Other groups of archaea were consistently associated with different types of iron oxide mats, including undescribed members of the phyla Thaumarchaeota and Euryarchaeota. Bacterial sequences were dominated by relatives of Hydrogenobaculum spp. above 65–70°C, but increased in diversity below 60°C. Cultivation of relevant iron-oxidizing and iron-reducing microbial isolates included Sulfolobus str. MK3, Sulfobacillus str. MK2, Acidicaldus str. MK6, and a new candidate genus in the Sulfolobales referred to as Sulfolobales str. MK5. Strains MK3 and MK5 are capable of oxidizing ferrous iron autotrophically, while strain MK2 oxidizes iron mixotrophically. Similar rates of iron oxidation were measured for M. yellowstonensis str. MK1 and Sulfolobales str. MK5. Biomineralized phases of ferric iron varied among cultures and field sites, and included ferric oxyhydroxides, K-jarosite, goethite, hematite, and scorodite depending on geochemical conditions. Strains MK5 and MK6 are capable of reducing ferric iron under anaerobic conditions with complex carbon sources. The combination of geochemical and molecular data as well as physiological observations of isolates suggests that the community structure of acidic Fe mats is linked with Fe cycling across temperatures ranging from 53 to 88°C. PMID:22470372

Current approaches for the assessment of in situ biodegradation.

PubMed

Bombach, Petra; Richnow, Hans H; Kästner, Matthias; Fischer, Anko

2010-04-01

Considering the high costs and technical difficulties associated with conventional remediation strategies, in situ biodegradation has become a promising approach for cleaning up contaminated aquifers. To verify if in situ biodegradation of organic contaminants is taking place at a contaminated site and to determine if these processes are efficient enough to replace conventional cleanup technologies, a comprehensive characterization of site-specific biodegradation processes is essential. In recent years, several strategies including geochemical analyses, microbial and molecular methods, tracer tests, metabolite analysis, compound-specific isotope analysis, and in situ microcosms have been developed to investigate the relevance of biodegradation processes for cleaning up contaminated aquifers. In this review, we outline current approaches for the assessment of in situ biodegradation and discuss their potential and limitations. We also discuss the benefits of research strategies combining complementary methods to gain a more comprehensive understanding of the complex hydrogeological and microbial interactions governing contaminant biodegradation in the field.

Performance of a Zerovalent Iron Reactive Barrier for the Treatment of Arsenic in Groundwater: Part 2. Geochemical Modeling and Solid Phase Studies

EPA Science Inventory

Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic plays a key role in directing arsenic...

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.

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

USGS Publications Warehouse

Clark, D.W.

1995-01-01

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

Geochemical evolution of groundwater in the Mud Lake area, eastern Idaho, USA

USGS Publications Warehouse

Rattray, Gordon W.

2015-01-01

Groundwater with elevated dissolved-solids concentrations—containing large concentrations of chloride, sodium, sulfate, and calcium—is present in the Mud Lake area of Eastern Idaho. The source of these solutes is unknown; however, an understanding of the geochemical sources and processes controlling their presence in groundwater in the Mud Lake area is needed to better understand the geochemical sources and processes controlling the water quality of groundwater at the Idaho National Laboratory. The geochemical sources and processes controlling the water quality of groundwater in the Mud Lake area were determined by investigating the geology, hydrology, land use, and groundwater geochemistry in the Mud Lake area, proposing sources for solutes, and testing the proposed sources through geochemical modeling with PHREEQC. Modeling indicated that sources of water to the eastern Snake River Plain aquifer were groundwater from the Beaverhead Mountains and the Camas Creek drainage basin; surface water from Medicine Lodge and Camas Creeks, Mud Lake, and irrigation water; and upward flow of geothermal water from beneath the aquifer. Mixing of groundwater with surface water or other groundwater occurred throughout the aquifer. Carbonate reactions, silicate weathering, and dissolution of evaporite minerals and fertilizer explain most of the changes in chemistry in the aquifer. Redox reactions, cation exchange, and evaporation were locally important. The source of large concentrations of chloride, sodium, sulfate, and calcium was evaporite deposits in the unsaturated zone associated with Pleistocene Lake Terreton. Large amounts of chloride, sodium, sulfate, and calcium are added to groundwater from irrigation water infiltrating through lake bed sediments containing evaporite deposits and the resultant dissolution of gypsum, halite, sylvite, and bischofite.

Adaptive Multiscale Modeling of Geochemical Impacts on Fracture Evolution

NASA Astrophysics Data System (ADS)

Molins, S.; Trebotich, D.; Steefel, C. I.; Deng, H.

2016-12-01

Understanding fracture evolution is essential for many subsurface energy applications, including subsurface storage, shale gas production, fracking, CO2 sequestration, and geothermal energy extraction. Geochemical processes in particular play a significant role in the evolution of fractures through dissolution-driven widening, fines migration, and/or fracture sealing due to precipitation. One obstacle to understanding and exploiting geochemical fracture evolution is that it is a multiscale process. However, current geochemical modeling of fractures cannot capture this multi-scale nature of geochemical and mechanical impacts on fracture evolution, and is limited to either a continuum or pore-scale representation. Conventional continuum-scale models treat fractures as preferential flow paths, with their permeability evolving as a function (often, a cubic law) of the fracture aperture. This approach has the limitation that it oversimplifies flow within the fracture in its omission of pore scale effects while also assuming well-mixed conditions. More recently, pore-scale models along with advanced characterization techniques have allowed for accurate simulations of flow and reactive transport within the pore space (Molins et al., 2014, 2015). However, these models, even with high performance computing, are currently limited in their ability to treat tractable domain sizes (Steefel et al., 2013). Thus, there is a critical need to develop an adaptive modeling capability that can account for separate properties and processes, emergent and otherwise, in the fracture and the rock matrix at different spatial scales. Here we present an adaptive modeling capability that treats geochemical impacts on fracture evolution within a single multiscale framework. Model development makes use of the high performance simulation capability, Chombo-Crunch, leveraged by high resolution characterization and experiments. The modeling framework is based on the adaptive capability in Chombo which not only enables mesh refinement, but also refinement of the model-pore scale or continuum Darcy scale-in a dynamic way such that the appropriate model is used only when and where it is needed. Explicit flux matching provides coupling betwen the scales.

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

Effects of metal-soil contact time on the extraction of mercury from soils.

PubMed

Ma, Lan; Zhong, Huan; Wu, Yong-Gui

2015-03-01

To investigate the mercury aging process in soils, soil samples were spiked with inorganic mercury (Hg(II)) or methylated mercury (MeHg) and incubated for 2, 7, 14 or 28 days in the laboratory. Potential availability of mercury, assessed by bovine serum albumin (BSA) or calcium chloride (CaCl2) extraction, decreased by 2-19 times for Hg(II) or 2-6 times for MeHg, when the contact time increased from 2 to 28 days. Decreased Hg(II) extraction could be explained by Hg(II) geochemical fractionation, i.e., Hg(II) migrated from more mobile fractions (water soluble and stomach acid soluble fractions) to refractory ones (organo-complexed, strongly complexed and residual fractions) over time, resulting in more stable association of Hg(II) with soils. In addition, decrease of mercury extraction was more evident in soils with lower organic content in most treatments, suggesting that organic matter may potentially play an important role in mercury aging process. In view of the significant decreased Hg(II) or MeHg extraction with prolonged contact time, mercury aging process should be taken into account when assessing risk of mercury in contaminated soils.

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.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India.

PubMed

Gurumurthy, G P; Balakrishna, K; Tripti, M; Audry, Stéphane; Riotte, Jean; Braun, J J; Udaya Shankar, H N

2014-04-01

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Uranium speciation in biofilms studied by laser fluorescence techniques.

PubMed

Arnold, Thuro; Grossmann, Kay; Baumann, Nils

2010-03-01

Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behaviour. The mechanisms of these processes are currently not understood, because the complexity of such biofilms creates many discrete geochemical microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical properties, e.g. pH and dissolved oxygen concentration, the presence of organic molecules, e.g. metabolites, and many more, all of which may affect metal speciation. To obtain such information, which is necessary for performance assessment studies or the development of new cost-effective strategies for cleaning waste waters, it is very important to develop new non-invasive methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques have some superior features, above all very high sensitivity for fluorescent heavy metals. An approach combining confocal laser scanning microscopy and laser-induced fluorescence spectroscopy for study of the interactions of biofilms with uranium is presented. It was found that coupling these techniques furnishes a promising tool for in-situ non-invasive study of fluorescent heavy metals within biofilm systems. Information on uranium speciation and uranium redox states can be obtained.

Characterization and Beneficiation Studies of a Low Grade Bauxite Ore

NASA Astrophysics Data System (ADS)

Rao, D. S.; Das, B.

2014-10-01

A low grade bauxite sample of central India was thoroughly characterized with the help of stereomicroscope, reflected light microscope and electron microscope using QEMSCAN. A few hand picked samples were collected from different places of the mine and were subjected to geochemical characterization studies. The geochemical studies indicated that most of the samples contain high silica and low alumina, except a few which are high grade. Mineralogically the samples consist of bauxite (gibbsite and boehmite), ferruginous mineral phases (goethite and hematite), clay and silicate (quartz), and titanium bearing minerals like rutile and ilmenite. Majority of the gibbsite, boehmite and gibbsitic oolites contain clay, quartz and iron and titanium mineral phases within the sample as inclusions. The sample on an average contains 39.1 % Al2O3 and 12.3 % SiO2, and 20.08 % of Fe2O3. Beneficiation techniques like size classification, sorting, scrubbing, hydrocyclone and magnetic separation were employed to reduce the silica content suitable for Bayer process. The studies indicated that, 50 % by weight with 41 % Al2O3 containing less than 5 % SiO2 could be achieved. The finer sized sample after physical beneficiation still contains high silica due to complex mineralogical associations.

Sewage contamination in the upper Mississippi River as measured by the fecal sterol, coprostanol

USGS Publications Warehouse

Writer, J.H.; Leenheer, J.A.; Barber, L.B.; Amy, G.L.; Chapra, S.C.

1995-01-01

The molecular sewage indicator, coprostanol, was measured in bed sediments of the Mississippi River for the purpose of determining sewage contamination. Coprostanol is a non-ionic, non-polar, organic molecule that associates with sediments in surface waters, and concentrations of coprostanol in bed sediments provide an indication of long-term sewage loads. Because coprostanol concentrations are dependent on particle size and percent organic carbon, a ratio between coprostanol (sewage sources) and cholestanol + cholesterol (sewage and non-sewage sources) was used to remove the biases related to particle size and percent organic carbon. The dynamics of contaminant transport in the Upper Mississippi River are influenced by both hydrologic and geochemical parameters. A mass balance model incorporating environmental parameters such as river and tributary discharge, suspended sediment concentration, fraction of organic carbon, sedimentation rates, municipal discharges and coprostanol decay rates was developed that describes coprostanol concentrations and therefore, expected patterns of municipal sewage effects on the Upper Mississippi River. Comparison of the computed and the measured coprostanol concentrations provides insight into the complex hydrologic and geochemical processes of contaminant transport and the ability to link measured chemical concentrations with hydrologic characteristics of the Mississippi River.

Magma mixing and high fountaining during the 1959 Kīlauea Iki eruption, Hawai‘i

USGS Publications Warehouse

Sides, I.; Edmonds, M.; Maclennan, J.; Houghton, Bruce F.; Swanson, Don; Steele-MacInnis, M.J.

2014-01-01

The 1959 Kīlauea Iki eruption provides a unique opportunity to investigate the process of shallow magma mixing, its impact on the magmatic volatile budget and its role in triggering and driving episodes of Hawaiian fountaining. Melt inclusions hosted by olivine record a continuous decrease in H2O concentration through the 17 episodes of the eruption, while CO2 concentrations correlate with the degree of post-entrapment crystallization of olivine on the inclusion walls. Geochemical data, when combined with the magma budget and with contemporaneous eruption observations, show complex mixing between episodes involving hot, geochemically heterogeneous melts from depth, likely carrying exsolved vapor, and melts which had erupted at the surface, degassed and drained-back into the vent. The drained-back melts acted as a coolant, inducing rapid cooling of the more primitive melts and their olivines at shallow depths and inducing crystallization and vesiculation and triggering renewed fountaining. A consequence of the mixing is that the melts became vapor-undersaturated, so equilibration pressures cannot be inferred from them using saturation models. After the melt inclusions were trapped, continued growth of vapor bubbles, caused by enhanced post-entrapment crystallization, sequestered a large fraction of CO2 from the melt within the inclusions. This study, while cautioning against accepting melt inclusion CO2 concentrations “as measured” in mixed magmas, also illustrates that careful analysis and interpretation of post-entrapment modifications can turn this apparent challenge into a way to yield novel useful insights into the geochemical controls on eruption intensity.

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.

Project Report: Undergraduate Student Research Program (USRP)

NASA Technical Reports Server (NTRS)

Gavin, Patricia

2011-01-01

To better understand geochemical processes occurring on Europa's seafloor, we investigated the effects of varying Fe?content in the seafloor rock and varying temperature. Iron is important in such geochemical processes as the production of methane through serpentinization (e.g. Allen and Seyfried, 2003) and can be a nutrient for microbes (Russell and Hall, 2006; Park and Kim, 2001). It can also offer clues as to the state of differentiation of Europa's core/mantle. If Europa is fully differentiated and contains an iron core, we would expect there to be little iron in the mantle and ocean floor whereas a homogeneous Europa would have iron evenly dispersed throughout the ocean floor. Furthermore, the composition of the ocean is a result of water?rock interactions at the seafloor. This project investigated the effects of temperature on geochemical processes, comparing high temperature (> 250oC) hydrothermal vents (Kelley et al., 2001) to lower temperature (20oC) cold seeps (e.g. Orphan et al., 2002).

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.

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.

H2-rich fluids from serpentinization: Geochemical and biotic implications

PubMed Central

Sleep, N. H.; Meibom, A.; Fridriksson, Th.; Coleman, R. G.; Bird, D. K.

2004-01-01

Metamorphic hydration and oxidation of ultramafic rocks produces serpentinites, composed of serpentine group minerals and varying amounts of brucite, magnetite, and/or FeNi alloys. These minerals buffer metamorphic fluids to extremely reducing conditions that are capable of producing hydrogen gas. Awaruite, FeNi3, forms early in this process when the serpentinite minerals are Fe-rich. Olivine with the current mantle Fe/Mg ratio was oxidized during serpentinization after the Moon-forming impact. This process formed some of the ferric iron in the Earth's mantle. For the rest of Earth's history, serpentinites covered only a small fraction of the Earth's surface but were an important prebiotic and biotic environment. Extant methanogens react H2 with CO2 to form methane. This is a likely habitable environment on large silicate planets. The catalytic properties of FeNi3 allow complex organic compounds to form within serpentinite and, when mixed with atmospherically produced complex organic matter and waters that circulated through basalts, constitutes an attractive prebiotic substrate. Conversely, inorganic catalysis of methane by FeNi3 competes with nascent and extant life. PMID:15326313

Geochemical and Isotopic (Sr, U) Tracing of Weathering Processes Controlling the Recent Geochemical Evolution of Soil Solutions in the Strengbach Catchment (Vosges, France)

NASA Astrophysics Data System (ADS)

Chabaux, F. J.; Prunier, J.; Pierret, M.; Stille, P.

2012-12-01

The characterization of the present-day weathering processes controlling the chemical composition of waters and soils in natural ecosystems is an important issue to predict and to model the response of ecosystems to recent environmental changes. It is proposed here to highlight the interest of a multi-tracer geochemical approach combining measurement of major and trace element concentrations along with U and Sr isotopic ratios to progress in this topic. This approach has been applied to the small granitic Strengbah Catchment, located in the Vosges Mountain (France), used and equipped as a hydro-geochemical observatory since 1986 (Observatoire Hydro-Géochimique de l'Environnement; http://ohge.u-strasbg.fr). This study includes the analysis of major and trace element concentrations and (U-Sr) isotope ratios in soil solutions collected within two soil profiles located on two experimental plots of this watershed, as well as the analysis of soil samples and vegetation samples from these two plots The depth variation of elemental concentration of soil solutions confirms the important influence of the vegetation cycling on the budget of Ca, K, Rb and Sr, whereas Mg and Si budget in soil solutions are quasi exclusively controlled by weathering processes. Variation of Sr, and U isotopic ratios with depth also demonstrates that the sources and biogeochemical processes controlling the Sr budget of soil solutions is different in the uppermost soil horizons and in the deeper ones, and clearly influence by the vegetation cycling.

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.

Vestiges of Submarine Serpentinization Recorded in the Microbiology of Continental Ophiolite Complexes

NASA Astrophysics Data System (ADS)

Schrenk, M. O.; Sabuda, M.; Brazelton, W. J.; Twing, K. I.

2017-12-01

The study of serpentinization-influenced microbial ecosystems at and below the seafloor has accelerated in recent years with multidisciplinary drilling expeditions to the Atlantis Massif (X357), Southwest Indian Ridge (X360) and Mariana Forearc (X366). In parallel, a number of studies have surveyed serpentinizing systems in ophiolite complexes which host a range of geologic histories, geochemical characteristics, fluid pathways, and consequently microbiology. As ophiolite complexes originate as seafloor materials, it is likely that a microbiological record of seafloor serpentinization processes is maintained through the emplacement and weathering of continental serpentinites. This hypothesis was evaluated through a global comparison of continental serpentinite springs and groundwater, ranging from highly brackish (saline) to freshwater. One of the most saline sites, known as the Coast Range Ophiolite Microbial Observatory (CROMO), was used as a point-of-comparison to marine serpentinizing systems, such as the Lost City Hydrothermal Field. Although there was little taxonomic overlap between microbial populations in marine and terrestrial systems, both communities harbored an abundance of genes involved in sulfur metabolism, including sulfide oxidation, thiosulfate disproportionation, and sulfate reduction. The phylogeny of key genes involved in these metabolic processes was evaluated relative to published studies and compared between sites. Together, these data provide insights into both the functioning of microbial communities in modern-day serpentinizing systems, and the transport processes that disperse microorganisms between marine and terrestrial serpentinites.

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).

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.

Metagenomic and stable isotopic analyses of modern freshwater microbialites in Cuatro Ciénegas, Mexico.

PubMed

Breitbart, Mya; Hoare, Ana; Nitti, Anthony; Siefert, Janet; Haynes, Matthew; Dinsdale, Elizabeth; Edwards, Robert; Souza, Valeria; Rohwer, Forest; Hollander, David

2009-01-01

Ancient biologically mediated sedimentary carbonate deposits, including stromatolites and other microbialites, provide insight into environmental conditions on early Earth. The primary limitation to interpreting these records is our lack of understanding regarding microbial processes and the preservation of geochemical signatures in contemporary microbialite systems. Using a combination of metagenomic sequencing and isotopic analyses, this study describes the identity, metabolic potential and chemical processes of microbial communities from living microbialites from Cuatro Ciénegas, Mexico. Metagenomic sequencing revealed a diverse, redox-dependent microbial community associated with the microbialites. The microbialite community is distinct from other marine and freshwater microbial communities, and demonstrates extensive environmental adaptation. The microbialite metagenomes contain a large number of genes involved in the production of exopolymeric substances and the formation of biofilms, creating a complex, spatially structured environment. In addition to the spatial complexity of the biofilm, microbial activity is tightly controlled by sensory and regulatory systems, which allow for coordination of autotrophic and heterotrophic processes. Isotopic measurements of the intracrystalline organic matter demonstrate the importance of heterotrophic respiration of photoautotrophic biomass in the precipitation of calcium carbonate. The genomic and stable isotopic data presented here significantly enhance our evolving knowledge of contemporary biomineralization processes, and are directly applicable to studies of ancient microbialites.

Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

NASA Astrophysics Data System (ADS)

Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

2003-04-01

Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

An integrated geophysical and geochemical exploration of critical zone weathering on opposing montane hillslope

NASA Astrophysics Data System (ADS)

Singha, K.; Navarre-Sitchler, A.; Bandler, A.; Pommer, R. E.; Novitsky, C. G.; Holbrook, S.; Moore, J.

2017-12-01

Quantifying coupled geochemical and hydrological properties and processes that operate in the critical zone is key to predicting rock weathering and subsequent transmission and storage of water in the shallow subsurface. Geophysical data have the potential to elucidate geochemical and hydrologic processes across landscapes over large spatial scales that are difficult to achieve with point measurements alone. Here, we explore the connections between weathering and fracturing, as measured from integrated geochemical and geophysical borehole data and seismic velocities on north- and south-facing aspects within one watershed in the Boulder Creek Critical Zone Observatory. We drilled eight boreholes up to 13 m deep on north- and south-facing aspects within Upper Gordon Gulch, and surface seismic refraction data were collected near these wells to explore depths of regolith and bedrock, as well as anisotropic characteristics of the subsurface material due to fracturing. Optical televiewer data were collected in these wells to infer the dominant direction of fracturing and fracture density in the near surface to corroborate with the seismic data. Geochemical samples were collected from four of these wells and a series of shallow soil pits for bulk chemistry, clay fraction, and exchangeable cation concentrations to identify depths of chemically altered saprolite. Seismic data show that depth to unweathered bedrock, as defined by p-wave seismic velocity, is slightly thicker on the north-facing slopes. Geochemical data suggest that the depth to the base of saprolite ranges from 3-5 m, consistent with a p-wave velocity value of 1200 m/s. Based on magnitude and anisotropy of p-wave velocities together with optical televiewer data, regolith on north-facing slopes is thought to be more fractured than south-facing slopes, while geochemical data indicate that position on the landscape is another important characteristic in determining depths of weathering. We explore the importance of fracture opening in controlling both saprolite and regolith thickness within this watershed.

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.

Interaction between municipal solid waste leachate and Bauru aquifer system: a study case in Brazil.

PubMed

de Faria, Gabriel Messias Moura; Mondelli, Giulliana

2017-12-01

Leachate contamination is a chronic and urgent problem present in municipal solid waste (MSW) landfill. Geochemical mathematical models in this work was suitable to study the dynamics of the leachate from an MSW landfill located in the Midwest of Sao Paulo, Brazil, a region with high precipitation and temperature and rich in chalcophile compounds and lithophile compounds, despite contamination with nitrogenous compounds. After 13 years of local aquifer monitoring, some groundwater samplings in Feb. 2004, Aug. 2007, Nov. 2009, and Feb. 2014 were chosen to be simulated. The hydrolysis is the main process at the landfill, together with absorption, adsorption, complexation, dilution, cation exchange, and oxidation, besides nitrification, reoxidation, and reduction.

Acid-Sulfate Alteration at Gusev Crater and Across Mars: High-SiO2 Residues and Ferric Sulfate Precipitates

NASA Technical Reports Server (NTRS)

Morris, R. V.; Catalano, J. G.; Klingelhoefer, G.; Schroeder, C.; Gellert, R.; Clark, B. C.; Ming, D. W.; Yen, A. S.; Arvidson, R. E.; Cohen, B. A.;

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

In the recent years researchers have enjoyed noticeable improvements of portable analytical and geophysical methods, which allow studying floodplain architecture and deciphering pollutant distribution more easily than ever before. Our area of interest was floodplain of the Ploučnice River, particularly a pollution hotspot in Boreček, severely impacted by U mining between the 1970s and late 1980s, in particular a "radioactive flood" in 1981. In the area, we used hand drill coring and in situ (field) analysis of so acquired sediments by handheld X-ray fluorescence spectrometer (XRF), which gave us information about depth profiles of pollutants (Ba, U, Zn) and the Al/Si and Zr/Rb ratios, i.e., proxies for sediment lithology. We found that spatial distribution of pollutants (control by depth and position in the floodplain) is apparently complex and discontinuous. In some places, contamination is buried by a couple decimetres of less polluted sediments, while in other places the peak pollution is near surface, apparently without a straightforward connection with the surface topography and the distance to the river channel. We thus examined the floodplain architecture, the internal structure of the floodplain using two geophysical methods. First of them, dipole electromagnetic profiling (DEMP, also denoted EMP, MP, or Slingram) quickly acquires average electric resistivity in top strata in selected areas, which was actually top 3 m with our particular instrument. Second, electric resistivity tomography (ERT) produces much more detailed information on resistivity with depth resolution of ca 0.5 m to the depth of ca 5 m in selected lines. ERT thus allows identifying boundaries of electric resistivity domains (sediment bodies) and DEMP their spatial distribution. Based on the obtained data, we divided the floodplain to five segments with specific topography, pollution characteristics, and electric resistivity. We suppose that those segments are lithogenetic floodplain units. Those findings must, however, be checked by sediment examination and analysis in selected points. We processed the crucial characteristics obtained by geochemical mapping, namely depth of maximum pollution, amount of contamination, and lithology (Al/Si and Zr/Rb ratios), using geostatistics. Moreover, some parts of floodplain were dated by optically stimulated luminescence (OSL) which revealed, that recycling of top decimetres of floodplain fine fill (silts) in Boreček site has proceeded relatively recently (in decades and centuries) as compared to deeper lying coarser (sandy) strata (millennia). The results of geochemical mapping show complexity of pollution hotspots and need of their integrated interpretation. Key words: Dipole electromagneting profilling, electric resistivity tomography, floodplain contamination, geochemical mapping

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...

Exploratory and spatial data analysis (EDA-SDA) for determining regional background levels and anomalies of potentially toxic elements in soils from Catorce-Matehuala, Mexico

USGS Publications Warehouse

Chiprés, J.A.; Castro-Larragoitia, J.; Monroy, M.G.

2009-01-01

The threshold between geochemical background and anomalies can be influenced by the methodology selected for its estimation. Environmental evaluations, particularly those conducted in mineralized areas, must consider this when trying to determinate the natural geochemical status of a study area, quantifying human impacts, or establishing soil restoration values for contaminated sites. Some methods in environmental geochemistry incorporate the premise that anomalies (natural or anthropogenic) and background data are characterized by their own probabilistic distributions. One of these methods uses exploratory data analysis (EDA) on regional geochemical data sets coupled with a geographic information system (GIS) to spatially understand the processes that influence the geochemical landscape in a technique that can be called a spatial data analysis (SDA). This EDA-SDA methodology was used to establish the regional background range from the area of Catorce-Matehuala in north-central Mexico. Probability plots of the data, particularly for those areas affected by human activities, show that the regional geochemical background population is composed of smaller subpopulations associated with factors such as soil type and parent material. This paper demonstrates that the EDA-SDA method offers more certainty in defining thresholds between geochemical background and anomaly than a numeric technique, making it a useful tool for regional geochemical landscape analysis and environmental geochemistry studies.

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

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

Pan, Feng; McPherson, Brian J.; Kaszuba, John

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

Evaluation of CO 2 -Fluid-Rock Interaction in Enhanced Geothermal Systems: Field-Scale Geochemical Simulations

DOE PAGES

Pan, Feng; McPherson, Brian J.; Kaszuba, John

2017-01-01

Recent studies suggest that using supercritical CO 2 (scCO 2 ) instead of water as a heat transmission fluid in Enhanced Geothermal Systems (EGS) may improve energy extraction. While CO 2 -fluid-rock interactions at “typical” temperatures and pressures of subsurface reservoirs are fairly well known, such understanding for the elevated conditions of EGS is relatively unresolved. Geochemical impacts of CO 2 as a working fluid (“CO 2 -EGS”) compared to those for water as a working fluid (H 2 O-EGS) are needed. The primary objectives of this study are (1) constraining geochemical processes associated with CO 2 -fluid-rock interactions undermore » the high pressures and temperatures of a typical CO 2 -EGS site and (2) comparing geochemical impacts of CO 2 -EGS to geochemical impacts of H 2 O-EGS. The St. John’s Dome CO 2 -EGS research site in Arizona was adopted as a case study. A 3D model of the site was developed. Net heat extraction and mass flow production rates for CO 2 -EGS were larger compared to H 2 O-EGS, suggesting that using scCO 2 as a working fluid may enhance EGS heat extraction. More aqueous CO 2 accumulates within upper- and lower-lying layers than in the injection/production layers, reducing pH values and leading to increased dissolution and precipitation of minerals in those upper and lower layers. Dissolution of oligoclase for water as a working fluid shows smaller magnitude in rates and different distributions in profile than those for scCO 2 as a working fluid. It indicates that geochemical processes of scCO 2 -rock interaction have significant effects on mineral dissolution and precipitation in magnitudes and distributions.« less

Surrogate model approach for improving the performance of reactive transport simulations

NASA Astrophysics Data System (ADS)

Jatnieks, Janis; De Lucia, Marco; Sips, Mike; Dransch, Doris

2016-04-01

Reactive transport models can serve a large number of important geoscientific applications involving underground resources in industry and scientific research. It is common for simulation of reactive transport to consist of at least two coupled simulation models. First is a hydrodynamics simulator that is responsible for simulating the flow of groundwaters and transport of solutes. Hydrodynamics simulators are well established technology and can be very efficient. When hydrodynamics simulations are performed without coupled geochemistry, their spatial geometries can span millions of elements even when running on desktop workstations. Second is a geochemical simulation model that is coupled to the hydrodynamics simulator. Geochemical simulation models are much more computationally costly. This is a problem that makes reactive transport simulations spanning millions of spatial elements very difficult to achieve. To address this problem we propose to replace the coupled geochemical simulation model with a surrogate model. A surrogate is a statistical model created to include only the necessary subset of simulator complexity for a particular scenario. To demonstrate the viability of such an approach we tested it on a popular reactive transport benchmark problem that involves 1D Calcite transport. This is a published benchmark problem (Kolditz, 2012) for simulation models and for this reason we use it to test the surrogate model approach. To do this we tried a number of statistical models available through the caret and DiceEval packages for R, to be used as surrogate models. These were trained on randomly sampled subset of the input-output data from the geochemical simulation model used in the original reactive transport simulation. For validation we use the surrogate model to predict the simulator output using the part of sampled input data that was not used for training the statistical model. For this scenario we find that the multivariate adaptive regression splines (MARS) method provides the best trade-off between speed and accuracy. This proof-of-concept forms an essential step towards building an interactive visual analytics system to enable user-driven systematic creation of geochemical surrogate models. Such a system shall enable reactive transport simulations with unprecedented spatial and temporal detail to become possible. References: Kolditz, O., Görke, U.J., Shao, H. and Wang, W., 2012. Thermo-hydro-mechanical-chemical processes in porous media: benchmarks and examples (Vol. 86). Springer Science & Business Media.

Is rhizosphere remediation sufficient for sustainable revegetation of mine tailings?

PubMed Central

Huang, Longbin; Baumgartl, Thomas; Mulligan, David

2012-01-01

Background Revegetation of mine tailings (fine-grained waste material) starts with the reconstruction of root zones, consisting of a rhizosphere horizon (mostly topsoil and/or amended tailings) and the support horizon beneath (i.e. equivalent to subsoil – mostly tailings), which must be physically and hydro-geochemically stable. This review aims to discuss key processes involved in the development of functional root zones within the context of direct revegetation of tailings and introduces a conceptual process of rehabilitating structure and function in the root zones based on a state transition model. Scope Field studies on the revegetation of tailings (from processing base metal ore and bauxite residues) are reviewed. Particular focus is given to tailings' properties that limit remediation effectiveness. Aspects of root zone reconstruction and vegetation responses are also discussed. Conclusions When reconstructing a root zone system, it is critical to restore physical structure and hydraulic functions across the whole root zone system. Only effective and holistically restored systems can control hydro-geochemical mobility of acutely and chronically toxic factors from the underlying horizon and maintain hydro-geochemical stability in the rhizosphere. Thereafter, soil biological capacity and ecological linkages (i.e. carbon and nutrient cycling) may be rehabilitated to integrate the root zones with revegetated plant communities into sustainable plant ecosystems. A conceptual framework of system transitions between the critical states of root zone development has been proposed. This will illustrate the rehabilitation process in root zone reconstruction and development for direct revegetation with sustainable plant communities. Sustainable phytostabilization of tailings requires the systematic consideration of hydro-geochemical interactions between the rhizosphere and the underlying supporting horizon. It further requires effective remediation strategies to develop hydro-geochemically stable and biologically functional root zones, which can facilitate the recovery of the microbial community and ecological linkages with revegetated plant communities. PMID:22648878

Geochemical Insights Into Lithospheric Melting and Instability in the Bufumbira Volcanic Field of the Western Rift, Uganda

NASA Astrophysics Data System (ADS)

Pitcavage, E.; Furman, T.; Nelson, W. R.

2016-12-01

The East African Rift System (EARS) is the earth's largest continental divergent boundary and is an unparalleled natural laboratory for understanding magmatic processes related to continental rifting. A fundamental unresolved question in EARS magmatism is the degree to which volcanism and rifting are influenced by Cenozoic plume-related melting rather than older, tectonically-driven metasomatism. In the latter scenario, metasomatism by carbonatite or silicate magmas and/or fluids that accompanies tectonic events such as the Proterozoic Pan-African Orogeny will create geochemical heterogeneities and rheological weaknesses in the sub-continental lithospheric mantle (SCLM). In the Western Rift, abundant alkaline mafic lavas record significant contributions from metasomatized SCLM. Modification, destabilization and foundering of metasomatized SCLM has an increasingly recognized role in continental magmatism worldwide. Lithospheric drip magmatism occurs when foundered lithosphere devolatilizes and melts on descent. Lithospheric thinning is one consequence of this process, and may play a role in physical aspects of rifting. Geochemical and geophysical evidence that drip magmatism has occurred in several areas of the EARS, including Turkana, Chyulu Hills, and Oligocene HT2 flood basalts in Afar, suggests that this process is fundamentally related to the onset of successful rifting. We use geochemical characteristics of primitive lavas from the Bufumbira volcanic field in the Western Rift's Virunga Province to demonstrate that ancient, tectonically-driven metasomatism modified the SCLM and contributes to recent volcanism. Further, we identify geochemical signatures which indicate that lithospheric drip melting is the primary petrogenetic process generating these lavas. Sr-Nd-Pb-Hf isotopic data show that the northern portion of the Western Rift, including Bufumbira, requires magma sources distinct from the rest of the EARS. Trace element data show that Bufumbira lavas are derived from depths within the garnet stability field and that source mineralogy includes phlogopite with potential amphibole and zircon; and that extent of melting increased with depth of melting, a signature of lithospheric drip.

Hydrological and geochemical processes constraining groundwater salinity in wetland areas related to evaporitic (karst) systems. A case study from Southern Spain

NASA Astrophysics Data System (ADS)

Gil-Márquez, J. M.; Barberá, J. A.; Andreo, B.; Mudarra, M.

2017-01-01

Chemical and isotopic evolution of groundwater in an evaporite karst plateau (including wetland areas and saline to hyper-saline springs) located at S Spain was studied. Physicochemical parameters, major ions and stable isotopes were analyzed in rain, brine spring, wetland and leakage water samples, from which the most common mineral saturation indexes were computed and geochemical and isotopic modelling were performed. Results show an apparent relationship between the elevation of brine springs and their water mineralization, indicating that drainage at higher altitude may be associated to gravity-driven flows, since brackish groundwater is isotopically fractionated due to evaporation. On the other hand, the lower altitude springs could drain deeper flows with longer residence time, resulting in highly mineralized and warmer (briny) groundwater. The dissolution of halite and gypsum has proved to be the main geochemical processes, which are favored by the great ionic strength of groundwater. Calcite precipitation occurs in brackish waters draining wetlands, being boosted by common ion effect (when CaSO4 waters are present) and solute concentration caused by evaporation. Modelling results strongly support the hypothesis that most of the selected springs geochemically evolve in a common (S-N) flowpath. The methods used in this research contribute to a better understanding of the hydrogeological processes occurring in the studied evaporitic system, but also in equivalent hydrological environments worldwide.

Modeling biogechemical reactive transport in a fracture zone

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

Molinero, Jorge; Samper, Javier; Yang, Chan Bing, and Zhang, Guoxiang

2005-01-14

A coupled model of groundwater flow, reactive solute transport and microbial processes for a fracture zone of the Aspo site at Sweden is presented. This is the model of the so-called Redox Zone Experiment aimed at evaluating the effects of tunnel construction on the geochemical conditions prevailing in a fracture granite. It is found that a model accounting for microbially-mediated geochemical processes is able to reproduce the unexpected measured increasing trends of dissolved sulfate and bicarbonate. The model is also useful for testing hypotheses regarding the role of microbial processes and evaluating the sensitivity of model results to changes inmore » biochemical parameters.« less

New Geochemical Analyses Reveal Crustal Accretionary Processes at The Overlapping Spreading Center Near 3 N East Pacific Rise

NASA Astrophysics Data System (ADS)

Smithka, I. N.; Perfit, M. R.

2013-12-01

Mid-ocean ridges (MORs) are the sites of oceanic lithosphere creation and construction. Ridge discontinuities are a global phenomenom but are not as well understood as ridge axes. Geochemical analyses provide insights into upper mantle processes since elements fractionate with melting and freezing as well as reside in material to retain source signature. Lavas collected from ridge discontinuities consist of greater chemical diversity and represent variations in source, melting parameters, and local crustal processes. The small overlapping spreading center (OSC) near the third parallel north on the East Pacific Rise has been superficially analyzed previously, but here we present new isotope analyses and expand our understanding of MOR processes and processes near OSCs. Initial analyses of lavas collected in 2000 on AHA-NEMO2 revealed normal MOR basalt trends in rare earth element enrichments as well as in major element concentrations. Crystal fractionation varies along the tips of both axes, with MgO and TiO2 concentrations increasing towards the OSC basin. Newly analyzed Sr, Nd, and Pb isotope ratios will further constrain the nature of geochemical diversity along axis. As the northern tip seems to be propagating and the southern tip dying, lavas collected from each may reflect two different underlying mantle melting and magma storage processes.

Unraveling the role of liquids during chondrule formation processes

NASA Astrophysics Data System (ADS)

Varela, Maria Eugenia; Zinner, Ernst

2018-01-01

The process/es involved in chondrule formation cover a wide range of mechanisms whose nature is still unknown. Our attention is focused on solar nebula processes mainly in untangling the origin of the initial liquid droplets that turn into chondrules. To do this, we start deciphering the processes under which the chondritic constituents of glass-rich, PO and POP chondrules from the Unequilibrated Ordinary Chondrite (UOC) Tieschitz L/H3.6 could have been formed. One constituent is the initial refractory liquid. This chilled liquid, presented as primary glass inclusions in olivine or as glass mesostasis, has trace element abundances with unfractionated patterns and lacks the chemical signature that is expected from a geochemical (liquid-crystal) fractionation. The unfractionated crystal-liquid distribution coefficients observed in the glass-rich, PO and POP chondrules indicate that formation of these objects was not dominated by an igneous process. In addition, the good correlation of elements with different geochemical and cosmochemical properties (e.g., Yb and La-Ce) that spread around the primordial ratio, indicate that a cosmochemical (condensation) instead of a geochemical process may have been involved in the origin of this refractory liquid. We end up discussing a secondary process: the alkali-Ca exchange reaction that could have taken place within a cooling nebula at sub-solidus temperatures. The extent to which these solid/gas exchange reactions took place will determine the final composition of the chondrules.

Alaska Geochemical Database (AGDB)-Geochemical data for rock, sediment, soil, mineral, and concentrate sample media

USGS Publications Warehouse

Granitto, Matthew; Bailey, Elizabeth A.; Schmidt, Jeanine M.; Shew, Nora B.; Gamble, Bruce M.; Labay, Keith A.

2011-01-01

The Alaska Geochemical Database (AGDB) was created and designed to compile and integrate geochemical data from Alaska in order to facilitate geologic mapping, petrologic studies, mineral resource assessments, definition of geochemical baseline values and statistics, environmental impact assessments, and studies in medical geology. This Microsoft Access database serves as a data archive in support of present and future Alaskan geologic and geochemical projects, and contains data tables describing historical and new quantitative and qualitative geochemical analyses. The analytical results were determined by 85 laboratory and field analytical methods on 264,095 rock, sediment, soil, mineral and heavy-mineral concentrate samples. Most samples were collected by U.S. Geological Survey (USGS) personnel and analyzed in USGS laboratories or, under contracts, in commercial analytical laboratories. These data represent analyses of samples collected as part of various USGS programs and projects from 1962 to 2009. In addition, mineralogical data from 18,138 nonmagnetic heavy mineral concentrate samples are included in this database. The AGDB includes historical geochemical data originally archived in the USGS Rock Analysis Storage System (RASS) database, used from the mid-1960s through the late 1980s and the USGS PLUTO database used from the mid-1970s through the mid-1990s. All of these data are currently maintained in the Oracle-based National Geochemical Database (NGDB). Retrievals from the NGDB were used to generate most of the AGDB data set. These data were checked for accuracy regarding sample location, sample media type, and analytical methods used. This arduous process of reviewing, verifying and, where necessary, editing all USGS geochemical data resulted in a significantly improved Alaska geochemical dataset. USGS data that were not previously in the NGDB because the data predate the earliest USGS geochemical databases, or were once excluded for programmatic reasons, are included here in the AGDB and will be added to the NGDB. The AGDB data provided here are the most accurate and complete to date, and should be useful for a wide variety of geochemical studies. The AGDB data provided in the linked database may be updated or changed periodically. The data on the DVD and in the data downloads provided with this report are current as of date of publication.

Improved Geothermometry Through Multivariate Reaction-path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators: Final Report

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

Mattson, Earl; Smith, Robert; Fujita, Yoshiko

2015-03-01

The project was aimed at demonstrating that the geothermometric predictions can be improved through the application of multi-element reaction path modeling that accounts for lithologic and tectonic settings, while also accounting for biological influences on geochemical temperature indicators. The limited utilization of chemical signatures by individual traditional geothermometer in the development of reservoir temperature estimates may have been constraining their reliability for evaluation of potential geothermal resources. This project, however, was intended to build a geothermometry tool which can integrate multi-component reaction path modeling with process-optimization capability that can be applied to dilute, low-temperature water samples to consistently predict reservoirmore » temperature within ±30 °C. The project was also intended to evaluate the extent to which microbiological processes can modulate the geochemical signals in some thermal waters and influence the geothermometric predictions.« less

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Analysis of gold(I/III)-complexes by HPLC-ICP-MS demonstrates gold(III) stability in surface waters.

PubMed

Ta, Christine; Reith, Frank; Brugger, Joël; Pring, Allan; Lenehan, Claire E

2014-05-20

Understanding the form in which gold is transported in surface- and groundwaters underpins our understanding of gold dispersion and (bio)geochemical cycling. Yet, to date, there are no direct techniques capable of identifying the oxidation state and complexation of gold in natural waters. We present a reversed phase ion-pairing HPLC-ICP-MS method for the separation and determination of aqueous gold(III)-chloro-hydroxyl, gold(III)-bromo-hydroxyl, gold(I)-thiosulfate, and gold(I)-cyanide complexes. Detection limits for the gold species range from 0.05 to 0.30 μg L(-1). The [Au(CN)2](-) gold cyanide complex was detected in five of six waters from tailings and adjacent monitoring bores of working gold mines. Contrary to thermodynamic predictions, evidence was obtained for the existence of Au(III)-complexes in circumneutral, hypersaline waters of a natural lake overlying a gold deposit in Western Australia. This first direct evidence for the existence and stability of Au(III)-complexes in natural surface waters suggests that Au(III)-complexes may be important for the transport and biogeochemical cycling of gold in surface environments. Overall, these results show that near-μg L(-1) enrichments of Au in environmental waters result from metastable ligands (e.g., CN(-)) as well as kinetically controlled redox processes leading to the stability of highly soluble Au(III)-complexes.

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

NASA Astrophysics Data System (ADS)

Korobova, Elena; Romanov, Sergey

2013-04-01

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

Oil and gas produced water as a growth medium for microalgae cultivation: A review and feasibility analysis

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

Sullivan Graham, Enid Joan; Dean, Cynthia Ann; Yoshida, Thomas M.

Scale-up of microalgal biotechnology to provide large quantities of biofuel, lipids, and coproducts is not fully developed because of the large needs for nutrients, water, land, solar insolation, and CO 2/carbon supplies. Wastewaters, including oil and gas produced water (PW), may supply a portion of these needs in regions with insufficient fresh water resources. PW is a challenging water resource for this use because of variable salinity, geochemical complexity, and the presence of biologically toxic components. In this paper we review PW volumes, quality, and use in media for microalgae production in the southwestern US, Australia, and Oman. We alsomore » include data from the southwestern US, referencing previously unpublished results from the National Alliance for Biofuels and Bioproducts (NAABB) consortium research project. We include a Supplementary Information section that explores cultivation of multiple microalgae species in PW and examines the carbon utilization process, all work performed in support of the NAABB field program. Strains of algae tested in the reviewed papers include Nannochloropsis, Dunalliella, Scenedesmus, and several mixed or unknown cultures. We conclude that the use of PW in algae cultivation is feasible, if the additional complexity of the water resource is accounted for in developing media formulations and in understanding metals uptake by the algae. We recommend additional work to standardize growth testing in PW, better and more thorough chemical analysis, and geochemical modeling of the PW used in media. As a result, expanded strain testing in PW media will identify improved strains tolerant of PW in algae cultivation.« less

Oil and gas produced water as a growth medium for microalgae cultivation: A review and feasibility analysis

DOE PAGES

Sullivan Graham, Enid Joan; Dean, Cynthia Ann; Yoshida, Thomas M.; ...

2017-02-16

Scale-up of microalgal biotechnology to provide large quantities of biofuel, lipids, and coproducts is not fully developed because of the large needs for nutrients, water, land, solar insolation, and CO 2/carbon supplies. Wastewaters, including oil and gas produced water (PW), may supply a portion of these needs in regions with insufficient fresh water resources. PW is a challenging water resource for this use because of variable salinity, geochemical complexity, and the presence of biologically toxic components. In this paper we review PW volumes, quality, and use in media for microalgae production in the southwestern US, Australia, and Oman. We alsomore » include data from the southwestern US, referencing previously unpublished results from the National Alliance for Biofuels and Bioproducts (NAABB) consortium research project. We include a Supplementary Information section that explores cultivation of multiple microalgae species in PW and examines the carbon utilization process, all work performed in support of the NAABB field program. Strains of algae tested in the reviewed papers include Nannochloropsis, Dunalliella, Scenedesmus, and several mixed or unknown cultures. We conclude that the use of PW in algae cultivation is feasible, if the additional complexity of the water resource is accounted for in developing media formulations and in understanding metals uptake by the algae. We recommend additional work to standardize growth testing in PW, better and more thorough chemical analysis, and geochemical modeling of the PW used in media. As a result, expanded strain testing in PW media will identify improved strains tolerant of PW in algae cultivation.« less

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.

Enrichment of fluoride in groundwater under the impact of saline water intrusion at the salt lake area of Yuncheng basin, northern China

NASA Astrophysics Data System (ADS)

Gao, Xubo; Wang, Yanxin; Li, Yilian; Guo, Qinghai

2007-12-01

Long-term intake of high-fluoride groundwater causes endemic fluorosis. This study, for the first time, discovered that the salt lake water intrusion into neighboring shallow aquifers might result in elevation of fluoride content of the groundwater. Two cross-sections along the groundwater flow paths were selected to study the geochemical processes controlling fluoride concentration in Yuncheng basin, northern China. There are two major reasons for the observed elevation of fluoride content: one is the direct contribution of the saline water; the other is the undersaturation of the groundwater with respect to fluorite due to salt water intrusion, which appears to be more important reason. The processes of the fluorine activity reduction and the change of Na/Ca ratio in groundwater induced by the intrusion of saline water favor further dissolution of fluorine-bearing mineral, and it was modeled using PHREEQC. With the increase in Na concentration (by adding NaCl or Na2SO4 as Na source, calcium content kept invariable), the increase of NaF concentration was rapid at first and then became slower; and the concentrations of HF, HF{2/-}, CaF+, and MgF+ were continuously decreasing. The geochemical conditions in the study area are advantageous to the complexation of F- with Na+ and the decline of saturation index of CaF2, regardless of the water type (Cl-Na or SO4-Na type water).

Geochemical Interpretation of Collision Volcanism

NASA Astrophysics Data System (ADS)

Pearce, Julian

2014-05-01

Collision volcanism can be defined as volcanism that takes place during an orogeny from the moment that continental subduction starts to the end of orogenic collapse. Its importance in the Geological Record is greatly underestimated as collision volcanics are easily misinterpreted as being of volcanic arc, extensional or mantle plume origin. There are many types of collision volcanic province: continent-island arc collision (e.g. Banda arc); continent-active margin collision (e.g. Tibet, Turkey-Iran); continent-rear-arc collision (e.g. Bolivia); continent-continent collision (e.g. Tuscany); and island arc-island arc collision (e.g. Taiwan). Superimposed on this variability is the fact that every orogeny is different in detail. Nonetheless, there is a general theme of cyclicity on different time scales. This starts with syn-collision volcanism resulting from the subduction of an ocean-continent transition and continental lithosphere, and continues through post-collision volcanism. The latter can be subdivided into orogenic volcanism, which is related to thickened crust, and post-orogenic, which is related to orogenic collapse. Typically, but not always, collision volcanism is preceded by normal arc volcanism and followed by normal intraplate volcanism. Identification and interpretation of collision volcanism in the Geologic Record is greatly facilitated if a dated stratigraphic sequence is present so that the petrogenic evolution can be traced. In any case, the basis of fingerprinting collision terranes is to use geochemical proxies for mantle and subduction fluxes, slab temperatures, and depths and degrees of melting. For example, syn-collision volcanism is characterized by a high subduction flux relative to mantle flux because of the high input flux of fusible sediment and crust coupled with limited mantle flow, and because of high slab temperatures resulting from the decrease in subduction rate. The resulting geochemical patterns are similar regardless of collision type with extreme LILE and significant HFSE enrichment relative to MORB and with large negative Nb-Ta and Ti anomalies. Post-collision volcanism is usually ascribed to combinations of slab detachment, delamination, and slab roll back (orogenic) and extension (post-orogenic). The magma source is typically conductively-heated, sub-continental mantle lithosphere with composition and depth of melting depending on the nature and evolution of the collision zone in question. Geochemical patterns may be similar to those of syn-collision basalts or of intraplate, continental basalts - or transitional between these. This variability in space and time, though problematic for geochemical fingerprinting, can give clues to the polarity and development of the collision zone, for example by highlighting the distribution of subduction-modified mantle lithosphere and hence of pre-collision subduction zones. One characteristic common to this setting is a high crustal input resulting from the presence of a hot, thick 'crustal chemical filter' which is evident on geochemical projections that highlight AFC-type processes. Using this, and other, geochemical features it is possible to develop methodologies to at least partly see through the complexity of collision terranes.

Column Testing and 1D Reactive Transport Modeling to Evaluate Uranium Plume Persistence Processes

NASA Astrophysics Data System (ADS)

Johnson, R. H.; Morrison, S.; Morris, S.; Tigar, A.; Dam, W. L.; Dayvault, J.

2015-12-01

At many U.S. Department of Energy Office of Legacy Management sites, 100 year natural flushing was selected as a remedial option for groundwater uranium plumes. However, current data indicate that natural flushing is not occurring as quickly as expected and solid-phase and aqueous uranium concentrations are persistent. At the Grand Junction, Colorado office site, column testing was completed on core collected below an area where uranium mill tailings have been removed. The total uranium concentration in this core was 13.2 mg/kg and the column was flushed with laboratory-created water with no uranium and chemistry similar to the nearby Gunnison River. The core was flushed for a total of 91 pore volumes producing a maximum effluent uranium concentration of 6,110 μg/L at 2.1 pore volumes and a minimum uranium concentration of 36.2 μg/L at the final pore volume. These results indicate complex geochemical reactions at small pore volumes and a long tailing affect at greater pore volumes. Stop flow data indicate the occurrence of non-equilibrium processes that create uranium concentration rebound. These data confirm the potential for plume persistence, which is occurring at the field scale. 1D reactive transport modeling was completed using PHREEQC (geochemical model) and calibrated to the column test data manually and using PEST (inverse modeling calibration routine). Processes of sorption, dual porosity with diffusion, mineral dissolution, dispersion, and cation exchange were evaluated separately and in combination. The calibration results indicate that sorption and dual porosity are major processes in explaining the column test data. These processes are also supported by fission track photographs that show solid-phase uranium residing in less mobile pore spaces. These procedures provide valuable information on plume persistence and secondary source processes that may be used to better inform and evaluate remedial strategies, including natural flushing.

A review of structural patterns and melting processes in the Archean craton of West Greenland: Evidence for crustal growth at convergent plate margins as opposed to non-uniformitarian models

NASA Astrophysics Data System (ADS)

Polat, Ali; Wang, Lu; Appel, Peter W. U.

2015-11-01

The Archean craton of West Greenland consists of many fault-bounded Eoarchean to Neoarchean tectonic terranes (crustal blocks). These tectonic terranes are composed mainly of tonalite-trondhjemite-granodiorite (TTG) gneisses, granitic gneisses, metavolcanic-dominated supracrustal belts, layered anorthositic complexes, and late- to post-tectonic granites. Rock assemblages and geochemical signatures in these terranes suggest that they represent fragments of dismembered oceanic island arcs, consisting mainly of TTG plutons, tholeiitic to calc-alkaline basalts, boninites, picrites, and cumulate layers of ultramafic rocks, gabbros, leucogabbros and anorthosites, with minor sedimentary rocks. The structural characteristics of the terrane boundaries are consistent with the assembly of these island arcs through modern style of horizontal tectonics, suggesting that the Archean craton of West Greenland grew at convergent plate margins. Several supracrustal belts that occur at or near the terrane boundaries are interpreted as relict accretionary prisms. The terranes display fold and thrust structures and contain numerous 10 cm to 20 m wide bifurcating, ductile shear zones that are characterized by a variety of structures including transposed and redistributed isoclinal folds. Geometrically these structures are similar to those occurring on regional scales, suggesting that the Archean craton of West Greenland can be interpreted as a continental scale accretionary complex, such as the Paleozoic Altaids. Melting of metavolcanic rocks during tectonic thickening in the arcs played an important role in the generation of TTGs. Non-uniformitarian models proposed for the origin of Archean terranes have no analogs in the geologic record and are inconsistent with structural, lithological, petrological and geochemical data collected from Archean terranes over the last four decades. The style of deformation and generation of felsic rocks on outcrop scales in the Archean craton of West Greenland and the Mesozoic Sulu orogenic belt of eastern China are similar, consistent with the formation of Archean continental crust by subduction zone processes.

Pleistocene hydrology of North America: The role of ice sheets in reorganizing groundwater flow systems

NASA Astrophysics Data System (ADS)

Person, Mark; McIntosh, Jennifer; Bense, Victor; Remenda, V. H.

2007-09-01

While the geomorphic consequences of Pleistocene megafloods have been known for some time, it has been only in the past 2 decades that hydrogeologists and glaciologists alike have begun to appreciate the important impact that ice sheet-aquifer interactions have had in controlling subsurface flow patterns, recharge rates, and the distribution of fresh water in confined aquifer systems across North America. In this paper, we document the numerous lines of geochemical, isotopic, and geomechanical evidence of ice sheet hydrogeology across North America. We also review the mechanical, thermal, and hydrologic processes that control subsurface fluid migration beneath ice sheets. Finite element models of subsurface fluid flow, permafrost formation, and ice sheet loading are presented to investigate the coupled nature of transport processes during glaciation/deglaciation. These indicate that recharge rates as high as 10 times modern values occurred as the Laurentide Ice Sheet overran the margins of sedimentary basins. The effects of ice sheet loading and permafrost formation result in complex transient flow patterns within aquifers and confining units alike. Using geochemical and environmental isotopic data, we estimate that the volume of glacial meltwater emplaced at the margins of sedimentary basins overrun by the Laurentide Ice Sheet totals about 3.7 × 104 km3, which is about 0.2% of the volume of the Laurentide Ice Sheet. Subglacial infiltration estimates based on continental-scale hydrologic models are even higher (5-10% of meltwater generated). These studies in sum call into question the widely held notion that groundwater flow patterns within confined aquifer systems are controlled primarily by the water table configuration during the Pleistocene. Rather, groundwater flow patterns were likely much more complex and transient in nature than has previously been thought. Because Pleistocene recharge rates are believed to be highly variable, these studies have profound implications for water resource managers charged with determining sustainable pumping rates from confined aquifers that host ice sheet meltwater.

A reactive transport model for mercury fate in soil--application to different anthropogenic pollution sources.

PubMed

Leterme, Bertrand; Blanc, Philippe; Jacques, Diederik

2014-11-01

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg(2+) to Hg(0) was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg(2+) with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg(2+) sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.

Identification of the Hydrogeochemical Processes in Groundwater Using Classic Integrated Geochemical Methods and Geostatistical Techniques, in Amol-Babol Plain, Iran

PubMed Central

Sheikhy Narany, Tahoora; Ramli, Mohammad Firuz; Aris, Ahmad Zaharin; Sulaiman, Wan Nor Azmin; Juahir, Hafizan; Fakharian, Kazem

2014-01-01

Hydrogeochemical investigations had been carried out at the Amol-Babol Plain in the north of Iran. Geochemical processes and factors controlling the groundwater chemistry are identified based on the combination of classic geochemical methods with geographic information system (GIS) and geostatistical techniques. The results of the ionic ratios and Gibbs plots show that water rock interaction mechanisms, followed by cation exchange, and dissolution of carbonate and silicate minerals have influenced the groundwater chemistry in the study area. The hydrogeochemical characteristics of groundwater show a shift from low mineralized Ca-HCO3, Ca-Na-HCO3, and Ca-Cl water types to high mineralized Na-Cl water type. Three classes, namely, C1, C2, and C3, have been classified using cluster analysis. The spatial distribution maps of Na+/Cl−, Mg2+/Ca2+, and Cl−/HCO3 − ratios and electrical conductivity values indicate that the carbonate and weathering of silicate minerals played a significant role in the groundwater chemistry on the southern and western sides of the plain. However, salinization process had increased due to the influence of the evaporation-precipitation process towards the north-eastern side of the study area. PMID:24523640

U.S. Geological Survey applied research studies of the Cheyenne River system, South Dakota; description and collation of data, water years 1985-86

USGS Publications Warehouse

Goddard, Kimball E.

1988-01-01

The Cheyenne River system in Western South Dakota has been impacted by the discharge of about 100 million metric tons of gold-mill tailings to Whitewood Creek near Lead, South Dakota. In April 1985, the U.S. Geological Survey initiated an extensive series of research studies to investigate the magnitude of the impact and to define important processes acting on the contaminated sediments present in the system. The report presents all data collected during the 1985 and 1986 water years for these research studies. Some of the data included have been published previously. Hydrologic, geochemical, and biologic data are available for sites on Whitewood Creek, the Belle Fourche and Cheyenne Rivers, and for the Cheyenne River arm of Lake Oahe. Data complexity varies from routine discharge and water quality to very complex photon-correlation spectroscopy and energy-dispersive x-ray analysis. Methods for sample collection, handling and preservation, and laboratory analysis are also presented. No interpretations or complex statistical summaries are included. (USGS)

Modeling low-temperature geochemical processes: Chapter 2

USGS Publications Warehouse

Nordstrom, D. Kirk; Campbell, Kate M.

2014-01-01

This chapter provides an overview of geochemical modeling that applies to water–rock interactions under ambient conditions of temperature and pressure. Topics include modeling definitions, historical background, issues of activity coefficients, popular codes and databases, examples of modeling common types of water–rock interactions, and issues of model reliability. Examples include speciation, microbial redox kinetics and ferrous iron oxidation, calcite dissolution, pyrite oxidation, combined pyrite and calcite dissolution, dedolomitization, seawater–carbonate groundwater mixing, reactive-transport modeling in streams, modeling catchments, and evaporation of seawater. The chapter emphasizes limitations to geochemical modeling: that a proper understanding and ability to communicate model results well are as important as completing a set of useful modeling computations and that greater sophistication in model and code development is not necessarily an advancement. If the goal is to understand how a particular geochemical system behaves, it is better to collect more field data than rely on computer codes.

Geochemical cycles of atmospheric gases

NASA Technical Reports Server (NTRS)

Walker, J. C. G.; Drever, J. I.

1988-01-01

The processes that control the atmosphere and atmospheric changes are reviewed. The geochemical cycles of water vapor, nitrogen, carbon dioxide, oxygen, and minor atmospheric constituents are examined. Changes in atmospheric chemistry with time are discussed using evidence from the rock record and analysis of the present atmosphere. The role of biological evolution in the history of the atmosphere and projected changes in the future atmosphere are considered.

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.

Hydraulic and geochemical framework of the Idaho National Engineering and Environmental Laboratory vadose zone

USGS Publications Warehouse

Nimmo, John R.; Rousseau, Joseph P.; Perkins, Kim S.; Stollenwerk, Kenneth G.; Glynn, Pierre D.; Bartholomay, Roy C.; Knobel, LeRoy L.

2004-01-01

Questions of major importance for subsurface contaminant transport at the Idaho National Engineering and Environmental Laboratory (INEEL) include (i) travel times to the aquifer, both average or typical values and the range of values to be expected, and (ii) modes of contaminant transport, especially sorption processes. The hydraulic and geochemical framework within which these questions are addressed is dominated by extreme heterogeneity in a vadose zone and aquifer consisting of interbedded basalts and sediments. Hydraulically, major issues include diverse possible types of flow pathways, extreme anisotropy, preferential flow, combined vertical and horizontal flow, and temporary saturation or perching. Geochemically, major issues include contaminant mobility as influenced by redox conditions, the concentration of organic and inorganic complexing solutes and other local variables, the interaction with infiltrating waters and with the contaminant source environment, and the aqueous speciation of contaminants such as actinides. Another major issue is the possibility of colloid transport, which inverts some of the traditional concepts of mobility, as sorbed contaminants on mobile colloids may be transported with ease compared with contaminants that are not sorbed. With respect to the goal of minimizing aquifer concentrations of contaminants, some characteristics of the vadose zone are essentially completely favorable. Examples include the great thickness (200 m) of the vadose zone, and the presence of substantial quantities of fine sediments that can retard contaminant transport both hydraulically and chemically. Most characteristics, however, have both favorable and unfavorable aspects. For example, preferential flow, as promoted by several notable features of the vadose zone at the INEEL, can provide fast, minimally sorbing pathways for contaminants to reach the aquifer easily, but it also leads to a wide dispersal of contaminants in a large volume of subsurface material, thus increasing the opportunity for dilution and sorption.

Chemolithotrophy in the continental deep subsurface: Sanford Underground Research Facility (SURF), USA

PubMed Central

Osburn, Magdalena R.; LaRowe, Douglas E.; Momper, Lily M.; Amend, Jan P.

2014-01-01

The deep subsurface is an enormous repository of microbial life. However, the metabolic capabilities of these microorganisms and the degree to which they are dependent on surface processes are largely unknown. Due to the logistical difficulty of sampling and inherent heterogeneity, the microbial populations of the terrestrial subsurface are poorly characterized. In an effort to better understand the biogeochemistry of deep terrestrial habitats, we evaluate the energetic yield of chemolithotrophic metabolisms and microbial diversity in the Sanford Underground Research Facility (SURF) in the former Homestake Gold Mine, SD, USA. Geochemical data, energetic modeling, and DNA sequencing were combined with principle component analysis to describe this deep (down to 8100 ft below surface), terrestrial environment. SURF provides access into an iron-rich Paleoproterozoic metasedimentary deposit that contains deeply circulating groundwater. Geochemical analyses of subsurface fluids reveal enormous geochemical diversity ranging widely in salinity, oxidation state (ORP 330 to −328 mV), and concentrations of redox sensitive species (e.g., Fe2+ from near 0 to 6.2 mg/L and Σ S2- from 7 to 2778μg/L). As a direct result of this compositional buffet, Gibbs energy calculations reveal an abundance of energy for microorganisms from the oxidation of sulfur, iron, nitrogen, methane, and manganese. Pyrotag DNA sequencing reveals diverse communities of chemolithoautotrophs, thermophiles, aerobic and anaerobic heterotrophs, and numerous uncultivated clades. Extrapolated across the mine footprint, these data suggest a complex spatial mosaic of subsurface primary productivity that is in good agreement with predicted energy yields. Notably, we report Gibbs energy normalized both per mole of reaction and per kg fluid (energy density) and find the later to be more consistent with observed physiologies and environmental conditions. Further application of this approach will significantly expand our understanding of the deep terrestrial biosphere. PMID:25429287

Alaska Geochemical Database, Version 2.0 (AGDB2)--including “best value” data compilations for rock, sediment, soil, mineral, and concentrate sample media

USGS Publications Warehouse

Granitto, Matthew; Schmidt, Jeanine M.; Shew, Nora B.; Gamble, Bruce M.; Labay, Keith A.

2013-01-01

The Alaska Geochemical Database Version 2.0 (AGDB2) contains new geochemical data compilations in which each geologic material sample has one “best value” determination for each analyzed species, greatly improving speed and efficiency of use. Like the Alaska Geochemical Database (AGDB, http://pubs.usgs.gov/ds/637/) before it, the AGDB2 was created and designed to compile and integrate geochemical data from Alaska in order to facilitate geologic mapping, petrologic studies, mineral resource assessments, definition of geochemical baseline values and statistics, environmental impact assessments, and studies in medical geology. This relational database, created from the Alaska Geochemical Database (AGDB) that was released in 2011, serves as a data archive in support of present and future Alaskan geologic and geochemical projects, and contains data tables in several different formats describing historical and new quantitative and qualitative geochemical analyses. The analytical results were determined by 85 laboratory and field analytical methods on 264,095 rock, sediment, soil, mineral and heavy-mineral concentrate samples. Most samples were collected by U.S. Geological Survey personnel and analyzed in U.S. Geological Survey laboratories or, under contracts, in commercial analytical laboratories. These data represent analyses of samples collected as part of various U.S. Geological Survey programs and projects from 1962 through 2009. In addition, mineralogical data from 18,138 nonmagnetic heavy-mineral concentrate samples are included in this database. The AGDB2 includes historical geochemical data originally archived in the U.S. Geological Survey Rock Analysis Storage System (RASS) database, used from the mid-1960s through the late 1980s and the U.S. Geological Survey PLUTO database used from the mid-1970s through the mid-1990s. All of these data are currently maintained in the National Geochemical Database (NGDB). Retrievals from the NGDB were used to generate most of the AGDB data set. These data were checked for accuracy regarding sample location, sample media type, and analytical methods used. This arduous process of reviewing, verifying and, where necessary, editing all U.S. Geological Survey geochemical data resulted in a significantly improved Alaska geochemical dataset. USGS data that were not previously in the NGDB because the data predate the earliest U.S. Geological Survey geochemical databases, or were once excluded for programmatic reasons, are included here in the AGDB2 and will be added to the NGDB. The AGDB2 data provided here are the most accurate and complete to date, and should be useful for a wide variety of geochemical studies. The AGDB2 data provided in the linked database may be updated or changed periodically.

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.

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.

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.

Quantifying Linkages between Biogeochemical Processes in a Contaminated Aquifer-Wetland System Using Multivariate Statistics and HP1

NASA Astrophysics Data System (ADS)

Arora, B.; Mohanty, B. P.; McGuire, J. T.

2009-12-01

Fate and transport of contaminants in saturated and unsaturated zones in the subsurface is controlled by complex biogeochemical processes such as precipitation, sorption-desorption, ion-exchange, redox, etc. In dynamic systems such as wetlands and anaerobic aquifers, these processes are coupled and can interact non-linearly with each other. Variability in measured hydrological, geochemical and microbiological parameters thus corresponds to multiple processes simultaneously. To infer the contributing processes, it is important to eliminate correlations and to identify inter-linkages between factors. The objective of this study is to develop quantitative relationships between hydrological (initial and boundary conditions, hydraulic conductivity ratio, and soil layering), geochemical (mineralogy, surface area, redox potential, and organic matter) and microbiological factors (MPN) that alter the biogeochemical processes at the column scale. Data used in this study were collected from controlled flow experiments in: i) two homogeneous soil columns, ii) a layered soil column, iii) a soil column with embedded clay lenses, and iv) a soil column with embedded clay lenses and one central macropore. The soil columns represent increasing level of soil structural heterogeneity to better mimic the Norman Landfill research site. The Norman Landfill is a closed municipal facility with prevalent organic contamination. The sources of variation in the dataset were explored using multivariate statistical techniques and dominant biogeochemical processes were obtained using principal component analysis (PCA). Furthermore, artificial neural networks (ANN) coupled with HP1 was used to develop mathematical rules identifying different combinations of factors that trigger, sustain, accelerate/decelerate, or discontinue the biogeochemical processes. Experimental observations show that infiltrating water triggers biogeochemical processes in all soil columns. Similarly, slow release of water from low permeability clay lenses sustain biogeochemical cycling for a longer period of time than in homogeneous soil columns. Preliminary results indicate: i) certain variables (anion, cation concentrations, etc.) do not follow normal or lognormal distributions even at the column scale, ii) strong correlations exist between parameters related to redox geochemistry (pH with S2- concentrations), and iii) PCA can identify dominant processes (e.g. iron and sulfate reduction) occurring in the system by grouping together causative variables (e.g. dominant TEAPs).

Deconvolving the Fate of Carbon in Coastal Sediments

NASA Astrophysics Data System (ADS)

Van der Voort, Tessa S.; Mannu, Utsav; Blattmann, Thomas M.; Bao, Rui; Zhao, Meixun; Eglinton, Timothy I.

2018-05-01

Coastal oceans play a crucial role in the global carbon cycle, and are increasingly affected by anthropogenic forcing. Understanding carbon cycling in coastal environments is hindered by convoluted sources and myriad processes that vary over a range of spatial and temporal scales. In this study, we deconvolve the complex mosaic of organic carbon manifested in Chinese Marginal Sea (CMS) sediments using a novel numerical clustering algorithm based on 14C and total OC content. Results reveal five regions that encompass geographically distinct depositional settings. Complementary statistical analyses reveal contrasting region-dependent controls on carbon dynamics and composition. Overall, clustering is shown to be highly effective in demarcating areas of distinct organic facies by disentangling intertwined organic geochemical patterns resulting from superimposed effects of OC provenance, reworking and deposition on a shelf region exhibiting pronounced spatial heterogeneity. This information will aid in constraining region-specific budgets of carbon burial and carbon cycle processes.

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

Zoran, Maria; Savastru, Roxana; Savastru, Dan

This paper presents a complex multidisciplinary approach concept to explain the nature of short-term earthquake precursors observed in land surface, atmosphere, ionosphere and magnetosphere for strong intermediate depth earthquakes recorded in Vrancea region in Romania. A developed Lithosphere-Surfacesphere-Atmosphere-Ionosphere (LSAI) coupling model can explain most of these presignals as a synergy between different anomalies of geophysical/geochemical parameters. These anomalies prior to medium to strong earthquakes are attributed to the thermodynamic, degassing and ionization processes in the Earth-Atmosphere system and micro-fracturing in the rocks especially along area’s active faults. The main outcome of this paper is an unified concept for systematic validationmore » of different types of earthquake precursors of which Land Surface Temperature (LST), outgoing Long wave Radiation (OLR), Surface Latent Heat Flux (SLHF), Air Temperature (AT), radon gas concentration, ionospheric Total Electron Content (TEC) are the most reliable parameters within the chain of the processes described by LSAI model.« less

Geochemical Data Package for Performance Assessment Calculations Related to the Savannah River Site

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

Kaplan, Daniel I.

The Savannah River Site (SRS) disposes of low-level radioactive waste (LLW) and stabilizes high-level radioactive waste (HLW) tanks in the subsurface environment. Calculations used to establish the radiological limits of these facilities are referred to as Performance Assessments (PA), Special Analyses (SA), and Composite Analyses (CA). The objective of this document is to revise existing geochemical input values used for these calculations. This work builds on earlier compilations of geochemical data (2007, 2010), referred to a geochemical data packages. This work is being conducted as part of the on-going maintenance program of the SRS PA programs that periodically updates calculationsmore » and data packages when new information becomes available. Because application of values without full understanding of their original purpose may lead to misuse, this document also provides the geochemical conceptual model, the approach used for selecting the values, the justification for selecting data, and the assumptions made to assure that the conceptual and numerical geochemical models are reasonably conservative (i.e., bias the recommended input values to reflect conditions that will tend to predict the maximum risk to the hypothetical recipient). This document provides 1088 input parameters for geochemical parameters describing transport processes for 64 elements (>740 radioisotopes) potentially occurring within eight subsurface disposal or tank closure areas: Slit Trenches (ST), Engineered Trenches (ET), Low Activity Waste Vault (LAWV), Intermediate Level (ILV) Vaults, Naval Reactor Component Disposal Areas (NRCDA), Components-in-Grout (CIG) Trenches, Saltstone Facility, and Closed Liquid Waste Tanks. The geochemical parameters described here are the distribution coefficient, Kd value, apparent solubility concentration, k s value, and the cementitious leachate impact factor.« less

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

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.

Magma transport in sheet intrusions of the Alnö carbonatite complex, central Sweden.

PubMed

Andersson, Magnus; Almqvist, Bjarne S G; Burchardt, Steffi; Troll, Valentin R; Malehmir, Alireza; Snowball, Ian; Kübler, Lutz

2016-06-10

Magma transport through the Earth's crust occurs dominantly via sheet intrusions, such as dykes and cone-sheets, and is fundamental to crustal evolution, volcanic eruptions and geochemical element cycling. However, reliable methods to reconstruct flow direction in solidified sheet intrusions have proved elusive. Anisotropy of magnetic susceptibility (AMS) in magmatic sheets is often interpreted as primary magma flow, but magnetic fabrics can be modified by post-emplacement processes, making interpretation of AMS data ambiguous. Here we present AMS data from cone-sheets in the Alnö carbonatite complex, central Sweden. We discuss six scenarios of syn- and post-emplacement processes that can modify AMS fabrics and offer a conceptual framework for systematic interpretation of magma movements in sheet intrusions. The AMS fabrics in the Alnö cone-sheets are dominantly oblate with magnetic foliations parallel to sheet orientations. These fabrics may result from primary lateral flow or from sheet closure at the terminal stage of magma transport. As the cone-sheets are discontinuous along their strike direction, sheet closure is the most probable process to explain the observed AMS fabrics. We argue that these fabrics may be common to cone-sheets and an integrated geology, petrology and AMS approach can be used to distinguish them from primary flow fabrics.

Complexity and Productivity Differentiation Models of Metallogenic Indicator Elements in Rocks and Supergene Media Around Daijiazhuang Pb-Zn Deposit in Dangchang County, Gansu Province

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

He, Jin-zhong, E-mail: viewsino@163.com; Yao, Shu-zhen; Zhang, Zhong-ping

2013-03-15

With the help of complexity indices, we quantitatively studied multifractals, frequency distributions, and linear and nonlinear characteristics of geochemical data for exploration of the Daijiazhuang Pb-Zn deposit. Furthermore, we derived productivity differentiation models of elements from thermodynamics and self-organized criticality of metallogenic systems. With respect to frequency distributions and multifractals, only Zn in rocks and most elements except Sb in secondary media, which had been derived mainly from weathering and alluviation, exhibit nonlinear distributions. The relations of productivity to concentrations of metallogenic elements and paragenic elements in rocks and those of elements strongly leached in secondary media can be seenmore » as linear addition of exponential functions with a characteristic weak chaos. The relations of associated elements such as Mo, Sb, and Hg in rocks and other elements in secondary media can be expressed as an exponential function, and the relations of one-phase self-organized geological or metallogenic processes can be represented by a power function, each representing secondary chaos or strong chaos. For secondary media, exploration data of most elements should be processed using nonlinear mathematical methods or should be transformed to linear distributions before processing using linear mathematical methods.« less

Magma transport in sheet intrusions of the Alnö carbonatite complex, central Sweden

PubMed Central

Andersson, Magnus; Almqvist, Bjarne S. G.; Burchardt, Steffi; Troll, Valentin R.; Malehmir, Alireza; Snowball, Ian; Kübler, Lutz

2016-01-01

Magma transport through the Earth’s crust occurs dominantly via sheet intrusions, such as dykes and cone-sheets, and is fundamental to crustal evolution, volcanic eruptions and geochemical element cycling. However, reliable methods to reconstruct flow direction in solidified sheet intrusions have proved elusive. Anisotropy of magnetic susceptibility (AMS) in magmatic sheets is often interpreted as primary magma flow, but magnetic fabrics can be modified by post-emplacement processes, making interpretation of AMS data ambiguous. Here we present AMS data from cone-sheets in the Alnö carbonatite complex, central Sweden. We discuss six scenarios of syn- and post-emplacement processes that can modify AMS fabrics and offer a conceptual framework for systematic interpretation of magma movements in sheet intrusions. The AMS fabrics in the Alnö cone-sheets are dominantly oblate with magnetic foliations parallel to sheet orientations. These fabrics may result from primary lateral flow or from sheet closure at the terminal stage of magma transport. As the cone-sheets are discontinuous along their strike direction, sheet closure is the most probable process to explain the observed AMS fabrics. We argue that these fabrics may be common to cone-sheets and an integrated geology, petrology and AMS approach can be used to distinguish them from primary flow fabrics. PMID:27282420

Hydrogeomorphic and ecological control on carbonate dissolution in a patterned landscape in South Florida

NASA Astrophysics Data System (ADS)

Dong, X.; Heffernan, J. B.; Murray, A. B.; Cohen, M. J.; Martin, J. B.

2016-12-01

The evolution of the critical zone both shapes and reflects hydrologic, geochemical, and ecological processes. These interactions are poorly understood in karst landscapes with highly soluble bedrock. In this study, we used the regular-dispersed wetland basins of Big Cypress National Preserve in Florida as a focal case to model the hydrologic, geochemical, and biological mechanisms that affect soil development in karst landscapes. We addressed two questions: (1) What is the minimum timescale for wetland basin development, and (2) do changes in soil depth feed back on dissolution processes and if so by what mechanism? We developed an atmosphere-water-soil model with coupled water-solute transport, incorporating major ion equilibria and kinetic non-equilibrium chemistry, and biogenic acid production via roots distributed through the soil horizon. Under current Florida climate, weathering to a depth of 2 m (a typical depth of wetland basins) would take 4000 6000 yrs, suggesting that landscape pattern could have origins as recent as the most recent stabilization of sea level. Our model further illustrates that interactions between ecological and hydrologic processes influence the rate and depth-dependence of weathering. Absent inundation, dissolution rate decreased exponentially with distance from the bedrock to groundwater table. Inundation generally increased bedrock dissolution, but surface water chemistry and residence time produced complex and non-linear effects on dissolution rate. Biogenic acidity accelerated the dissolution rate by 50 and 1,000 times in inundated and exposed soils. Phase portrait analysis indicated that exponential decreases in bedrock dissolution rate with soil depth could produce stable basin depths. Negative feedback between hydro-period and total basin volume could stabilize the basin radius, but the lesser strength of this mechanism may explain the coalescence of wetland basins observed in some parts of the Big Cypress Landscape.

Geochemical data for Colorado soils-Results from the 2006 state-scale geochemical survey

USGS Publications Warehouse

Smith, David B.; Ellefsen, Karl J.; Kilburn, James E.

2010-01-01

In 2006, soil samples were collected at 960 sites (1 site per 280 square kilometers) throughout the state of Colorado. These samples were collected from a depth of 0-15 centimeters and, following a near-total multi-acid digestion, were analyzed for a suite of more than 40 major and trace elements. The resulting data set provides a baseline for the natural variation in soil geochemistry for Colorado and forms the basis for detecting changes in soil composition that might result from natural processes or anthropogenic activities. This report describes the sampling and analytical protocols used and makes available all the soil geochemical data generated in the study.

Mercury Slovenian soils: High, medium and low sample density geochemical maps

NASA Astrophysics Data System (ADS)

Gosar, Mateja; Šajn, Robert; Teršič, Tamara

2017-04-01

Regional geochemical survey was conducted in whole territory of Slovenia (20273 km2). High, medium and low sample density surveys were compared. High sample density represented the regional geochemical data set supplemented by local high-density sampling data (irregular grid, n=2835). Medium-density soil sampling was performed in a 5 x 5 km grid (n=817) and low-density geochemical survey was conducted in a sampling grid 25 x 25 km (n=54). Mercury distribution in Slovenian soils was determined with models of mercury distribution in soil using all three data sets. A distinct Hg anomaly in western part of Slovenia is evident on all three models. It is a consequence of 500-years of mining and ore processing in the second largest mercury mine in the world, the Idrija mine. The determined mercury concentrations revealed an important difference between the western and the eastern parts of the country. For the medium scale geochemical mapping is the median value (0.151 mg /kg) for western Slovenia almost 2-fold higher than the median value (0.083 mg/kg) in eastern Slovenia. Besides the Hg median for the western part of Slovenia exceeds the Hg median for European soil by a factor of 4 (Gosar et al., 2016). Comparing these sample density surveys, it was shown that high sampling density allows the identification and characterization of anthropogenic influences on a local scale, while medium- and low-density sampling reveal general trends in the mercury spatial distribution, but are not appropriate for identifying local contamination in industrial regions and urban areas. The resolution of the pattern generated is the best when the high-density survey on a regional scale is supplemented with the geochemical data of the high-density surveys on a local scale. References: Gosar, M, Šajn, R, Teršič, T. Distribution pattern of mercury in the Slovenian soil: geochemical mapping based on multiple geochemical datasets. Journal of geochemical exploration, 2016, 167/38-48.

Mineral compositions of plutonic rocks from the Lewis Hills massif, Bay of Islands ophiolite

NASA Technical Reports Server (NTRS)

Smith, Susan E.; Elthon, Don

1988-01-01

Mineral compositions of residual and cumulate rocks from the Lewis Hills massif of the Bay of Islands ophiolite complex are reported and interpreted in the context of magnetic processes involved in the geochemical evolution of spatially associated diabase dikes. The mineral compositions reflect greater degrees of partial melting than most abyssal peridotites do and appear to represent the most depleted end of abyssal peridotite compositions. Subsolidus equilibration between Cr-Al spinal and olivine generally has occurred at temperatures of 700 to 900 C. The spinel variations agree with the overall fractionation of basaltic magmas producing spinels with progressively lower Cr numbers. The compositions of clinopyroxenes suggest that the fractionation of two different magma series produced the various cumulate rocks.

Influence of geochemical processes on hydrochemistry and irrigation suitability of groundwater in part of semi-arid Deccan Plateau, India

NASA Astrophysics Data System (ADS)

Vasu, Duraisamy; Singh, Surendra Kumar; Tiwary, Pramod; Sahu, Nisha; Ray, Sanjay Kumar; Butte, Pravin; Duraisami, Veppangadu Perumal

2017-11-01

Major ion geochemistry was used to characterise the chemical composition of groundwater in part of semi-arid Deccan plateau region to understand the geochemical evolution and to evaluate the groundwater quality for irrigation. The study area comprises peninsular gneissic complex of Archean age, younger granites and basaltic alluvium. Forty-nine georeferenced groundwater samples were collected and analysed for major ions. The ionic sequence based on relative proportions was Na+ > Mg2+ > Ca2+ > SO4 2- > HCO3 - > Cl- > CO3 2- > BO3 3- > K+. High Na+, Mg2+ and Ca2+ were generally associated with basaltic alluvial formation, whereas pH, electrical conductivity (EC) and total dissolved salts (TDS) were found to be higher in granitic formations. High standard deviation for EC, TDS, Na+, Ca2+ and Mg2+ indicated the dispersion of ionic concentration throughout the study area. Four major hydrochemical facies identified were Na-Mg-HCO3 type; Mg-Na-HCO3 type; Na-Mg-Ca-SO4 and Mg-Na-Ca-SO4 type. The graphical plots indicated that the groundwater chemistry was influenced by rock-water interaction, silicate weathering and reverse ion exchange. Sodium-dominated waters might have impeded the hydraulic properties of soils as a result of long-term irrigation.

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.

Geochemical and isotopic determination of deep groundwater contributions and salinity to the shallow groundwater and surface water systems, Mesilla Basin, New Mexico, Texas, and Mexico

NASA Astrophysics Data System (ADS)

Robertson, A.; Carroll, K. C.; Kubicki, C.; Purtshert, R.

2017-12-01

The Mesilla Basin/Conejos-Médanos aquifer system, extending from southern New Mexico to Chihuahua, Mexico, is a priority transboundary aquifer under the 2006 United States­-Mexico Transboundary Aquifer Assessment Act. Declining water levels, deteriorating water quality, and increasing groundwater use by municipal, industrial, and agricultural users on both sides of the international border raise concerns about long-term aquifer sustainability. Relative contributions of present-day and "paleo" recharge to sustainable fresh groundwater yields has not been determined and evidence suggests that a large source of salinity at the distal end of the Mesilla Basin is saline discharge from deep groundwater flow. The magnitude and distribution of those deep saline flow paths are not determined. The contribution of deep groundwater to discharge and salinity in the shallow groundwater and surface water of the Mesilla Basin will be determined by collecting discrete groundwater samples and analyzing for aqueous geochemical and isotopic tracers, as well as the radioisotopes of argon and krypton. Analytes include major ions, trace elements, the stable isotopes of water, strontium and boron isotopes, uranium isotopes, the carbon isotopes of dissolved inorganic carbon, noble gas concentrations and helium isotope ratios. Dissolved gases are extracted and captured from groundwater wells using membrane contactors in a process known as ultra-trace sampling. Gas samples are analyzed for radioisotope ratios of krypton by the ATTA method and argon by low-level counting. Effectiveness of the ultra-trace sampling device and method was evaluated by comparing results of tritium concentrations to the krypton-85 content. Good agreement between the analyses, especially in samples with undetectable tritium, indicates that the ultra-trace procedure is effective and confirms that introduction of atmospheric air has not occurred. The geochemistry data indicate a complex system of geochemical endmembers, and mixing between these endmembers. Ongoing work seeks to better constrain groundwater ages and mixing models through the coupled use of conventional aqueous geochemical and isotopic analysis and the ultra-trace constituents.

[Landscape structure and ecological coupling analysis of ecotone on the west Sonnen Plain].

PubMed

Song, Changchun; Deng, Wei; Song, Xinshan

2003-09-01

Ecotone is a special zone in the landscape, which is very susceptive to the changes in environmental conditions, and hence, is prone to the disturbance by unfavorable conditions. Human activity has a series of positive and negative effects on it, and greatly changes the geo-chemical process in the ecosystem. In the ecosystem, especially in the ecotone, different systems and regimes are interconnected and inter-determined. For the sustainable development of ecosystem and the protection and rational utilization of resources, it is of great importance to study this internal relationship and to seek rational regulation and control measures. With the ecotone in the west Songnen Plain as an example, and based on the studies of the topography, physiognomy, soil, vegetation, and their geographic distribution in the ecotone., this paper explained the structure of the ecological landscape, and quantitatively analyzed the ecological geo-chemical processes under different landscape conditions. In addition, this paper also tried to make coupling analyses to the ecologic succession and the landscape geo-chemical environment. Under current conditions, the succession of plant communities and the shift of soil landscape geo-chemical conditions in the west Songnen Plain are almost co-instantaneous, and these two factors can inter-determined under certain conditions.

Bacterial communities associated with subsurface geochemical processes in continental serpentinite springs.

PubMed

Brazelton, William J; Morrill, Penny L; Szponar, Natalie; Schrenk, Matthew O

2013-07-01

Reactions associated with the geochemical process of serpentinization can generate copious quantities of hydrogen and low-molecular-weight organic carbon compounds, which may provide energy and nutrients to sustain subsurface microbial communities independently of the photosynthetically supported surface biosphere. Previous microbial ecology studies have tested this hypothesis in deep sea hydrothermal vents, such as the Lost City hydrothermal field. This study applied similar methods, including molecular fingerprinting and tag sequencing of the 16S rRNA gene, to ultrabasic continental springs emanating from serpentinizing ultramafic rocks. These molecular surveys were linked with geochemical measurements of the fluids in an interdisciplinary approach designed to distinguish potential subsurface organisms from those derived from surface habitats. The betaproteobacterial genus Hydrogenophaga was identified as a likely inhabitant of transition zones where hydrogen-enriched subsurface fluids mix with oxygenated surface water. The Firmicutes genus Erysipelothrix was most strongly correlated with geochemical factors indicative of subsurface fluids and was identified as the most likely inhabitant of a serpentinization-powered subsurface biosphere. Both of these taxa have been identified in multiple hydrogen-enriched subsurface habitats worldwide, and the results of this study contribute to an emerging biogeographic pattern in which Betaproteobacteria occur in near-surface mixing zones and Firmicutes are present in deeper, anoxic subsurface habitats.

Bacterial Communities Associated with Subsurface Geochemical Processes in Continental Serpentinite Springs

PubMed Central

Morrill, Penny L.; Szponar, Natalie; Schrenk, Matthew O.

2013-01-01

Reactions associated with the geochemical process of serpentinization can generate copious quantities of hydrogen and low-molecular-weight organic carbon compounds, which may provide energy and nutrients to sustain subsurface microbial communities independently of the photosynthetically supported surface biosphere. Previous microbial ecology studies have tested this hypothesis in deep sea hydrothermal vents, such as the Lost City hydrothermal field. This study applied similar methods, including molecular fingerprinting and tag sequencing of the 16S rRNA gene, to ultrabasic continental springs emanating from serpentinizing ultramafic rocks. These molecular surveys were linked with geochemical measurements of the fluids in an interdisciplinary approach designed to distinguish potential subsurface organisms from those derived from surface habitats. The betaproteobacterial genus Hydrogenophaga was identified as a likely inhabitant of transition zones where hydrogen-enriched subsurface fluids mix with oxygenated surface water. The Firmicutes genus Erysipelothrix was most strongly correlated with geochemical factors indicative of subsurface fluids and was identified as the most likely inhabitant of a serpentinization-powered subsurface biosphere. Both of these taxa have been identified in multiple hydrogen-enriched subsurface habitats worldwide, and the results of this study contribute to an emerging biogeographic pattern in which Betaproteobacteria occur in near-surface mixing zones and Firmicutes are present in deeper, anoxic subsurface habitats. PMID:23584766

Pore-Scale Geochemical Reactivity Associated with CO2 Storage: New Frontiers at the Fluid-Solid Interface.

PubMed

Noiriel, Catherine; Daval, Damien

2017-04-18

The reactivity of carbonate and silicate minerals is at the heart of porosity and pore geometry changes in rocks injected with CO 2 , which ultimately control the evolution of flow and transport properties of fluids in porous and/or fractured geological reservoirs. Modeling the dynamics of CO 2 -water-rock interactions is challenging because of the resulting large geochemical disequilibrium, the reservoir heterogeneities, and the large space and time scales involved in the processes. In particular, there is a lack of information about how the macroscopic properties of a reservoir, e.g., the permeability, will evolve as a result of geochemical reactions at the molecular scale. Addressing this point requires a fundamental understanding of how the microstructures influence the macroscopic properties of rocks. The pore scale, which ranges from a few nanometers to centimeters, has stood out as an essential scale of observation of geochemical processes in rocks. Transport or surface reactivity limitations due to the pore space architecture, for instance, are best described at the pore scale itself. It can be also considered as a mesoscale for aggregating and increasing the gain of fundamental understanding of microscopic interfacial processes. Here we focus on the potential application of a combination of physicochemical measurements coupled with nanoscale and microscale imaging techniques during laboratory experiments to improve our understanding of the physicochemical mechanisms that occur at the fluid-solid interface and the dynamics of the coupling between the geochemical reactions and flow and transport modifications at the pore scale. Imaging techniques such as atomic force microscopy, vertical scanning interferometry, focused ion beam transmission electron microscopy, and X-ray microtomography, are ideal for investigating the reactivity dynamics of these complex materials. Minerals and mineral assemblages, i.e., rocks, exhibit heterogeneous and anisotropic reactivity, which challenges the continuum description of porous media and assumptions required for reactive transport modeling at larger scales. The conventional approach, which consists of developing dissolution rate laws normalized to the surface area, should be revisited to account for both the anisotropic crystallographic structure of minerals and the transport of chemical species near the interface, which are responsible for the intrinsic evolution of the mineral dissolution rate as the reaction progresses. In addition, the crystal morphology and the mineral assemblage composition, texture, and structural heterogeneities are crucial in determining whether the permeability and transport properties of the reservoir will be altered drastically or maintain the sealing properties required to ensure the safe sequestration of CO 2 for hundreds of years. Investigating the transport properties in nanometer- to micrometer-thick amorphous Si-rich surface layers (ASSLs), which develop at the fluid-mineral interface in silicates, provides future direction, as ASSLs may prevent contact between the dissolving solids and the pore fluid, potentially inhibiting the dissolution/carbonation process. Equally, at a larger scale, the growth of micrometer- to millimeter-thick alteration layers, which result from the difference in reactivity between silicates and carbonates, slows the transport in the vicinity of the fluid-solid interface in polymineralic rocks, thus limiting the global reactivity of the carbonate matrix. In contrast, in pure limestone, the global reactivity of the monomineralic rock decreases because the flow localization promotes the local reactivity within the forming channels, thus enhancing permeability changes compared with more homogeneous dissolution of the rock matrix. These results indicate that the transformation of the rock matrix should control the evolution of the transport properties in reservoirs injected with CO 2 to the same extent as the intrinsic chemical reactivity of the minerals and the reservoir hydrodynamics. This process, which is currently not captured by large-scale modeling of reactive transport, should benefit from the increasing capabilities of noninvasive and nondestructive characterization tools for pore-scale processes, ultimately constraining reactive transport modeling and improving the reliability of predictions.

Tracking channel-floodplain sediment exchange with conservative and non-conservative geochemical tracers

NASA Astrophysics Data System (ADS)

Belmont, Patrick; Stout, Justin

2013-04-01

Fine sediment is routed through landscapes and channel networks in a highly unsteady and non-uniform manner, potentially experiencing deposition and re-suspension many times during transport from source to sink. Developing a better understanding of sediment routing at the landscape scale is an intriguing challenge from a modeling perspective because it requires consideration of a multitude of processes that interact and vary in space and time. From an applied perspective, an improved understanding of sediment routing is essential for predicting how conservation and restoration practices within a watershed will influence water quality, to support land and water management decisions. Two key uncertainties in predicting sediment routing at the landscape scale are 1) determining the proportion of suspended sediment that is derived from terrestrial (soil) erosion versus channel (bank) erosion, and 2) constraining the proportion of sediment that is temporarily stored and re-suspended within the channel-floodplain complex. Sediment fingerprinting that utilizes a suite of conservative and non-conservative geochemical tracers associated with suspended sediment can provide insight regarding both of these key uncertainties. Here we present a model that tracks suspended sediment with associated conservative and non-conservative geochemical tracers. The model assumes that particle residence times are described by a bimodal distribution wherein some fraction of sediment is transported through the system in a relatively short time (< 1 year) and the remainder experiences temporary storage (of variable duration) within the channel-floodplain complex. We use the model to explore the downstream evolution of non-conservative tracers under equilibrium conditions (i.e., exchange between the channel and floodplain is allowed, but no net change in channel-floodplain storage can occur) to illustrate how the process of channel-floodplain storage and re-suspension can potentially bias interpretation of sediment fingerprinting results. We then apply the model to explain measurements of meteoric Beryllium-10, Lead-210, and Cesium-137 associated with suspended sediment in two very different rivers, one incising (Le Sueur River, south-central Minnesota, USA) and the other aggrading (Root River, southeastern Minnesota, USA) in response to base level fall and rise, respectively. The Le Sueur River exhibits a remarkably narrow range of tracer concentrations in source areas, which include agricultural fields, alluvial banks, and bluffs. Suspended sediment samples collected immediately above and below the 30 km long incising reach show a systematic shift in terrestrial sources in the downstream direction, indicated by changes in Beryllium-10 concentrations. The Root River indicates a more variable erosion history, with significant variability of Beryllium-10 concentrations in source areas (agricultural fields, forested hillslopes, and alluvial floodplains and terraces) and inverted Beryllium-10 depth profiles (higher concentrations at depth, suggesting unsteady erosion and significant storage of legacy sediment). Both rivers show a systematic disparity in normalized concentrations of conservative versus non-conservative tracers, indicating that significant storage and re-suspension occurs in both systems as the sediment is routed through the channel-floodplain complex.

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.

H2-rich fluids from serpentinization: geochemical and biotic implications.

PubMed

Sleep, N H; Meibom, A; Fridriksson, Th; Coleman, R G; Bird, D K

2004-08-31

Metamorphic hydration and oxidation of ultramafic rocks produces serpentinites, composed of serpentine group minerals and varying amounts of brucite, magnetite, and/or FeNi alloys. These minerals buffer metamorphic fluids to extremely reducing conditions that are capable of producing hydrogen gas. Awaruite, FeNi3, forms early in this process when the serpentinite minerals are Fe-rich. Olivine with the current mantle Fe/Mg ratio was oxidized during serpentinization after the Moon-forming impact. This process formed some of the ferric iron in the Earth's mantle. For the rest of Earth's history, serpentinites covered only a small fraction of the Earth's surface but were an important prebiotic and biotic environment. Extant methanogens react H2 with CO2 to form methane. This is a likely habitable environment on large silicate planets. The catalytic properties of FeNi3 allow complex organic compounds to form within serpentinite and, when mixed with atmospherically produced complex organic matter and waters that circulated through basalts, constitutes an attractive prebiotic substrate. Conversely, inorganic catalysis of methane by FeNi3 competes with nascent and extant life. Copyright 2004 The National Academy of Sciencs of the USA

PFLOTRAN: Reactive Flow & Transport Code for Use on Laptops to Leadership-Class Supercomputers

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

Hammond, Glenn E.; Lichtner, Peter C.; Lu, Chuan

PFLOTRAN, a next-generation reactive flow and transport code for modeling subsurface processes, has been designed from the ground up to run efficiently on machines ranging from leadership-class supercomputers to laptops. Based on an object-oriented design, the code is easily extensible to incorporate additional processes. It can interface seamlessly with Fortran 9X, C and C++ codes. Domain decomposition parallelism is employed, with the PETSc parallel framework used to manage parallel solvers, data structures and communication. Features of the code include a modular input file, implementation of high-performance I/O using parallel HDF5, ability to perform multiple realization simulations with multiple processors permore » realization in a seamless manner, and multiple modes for multiphase flow and multicomponent geochemical transport. Chemical reactions currently implemented in the code include homogeneous aqueous complexing reactions and heterogeneous mineral precipitation/dissolution, ion exchange, surface complexation and a multirate kinetic sorption model. PFLOTRAN has demonstrated petascale performance using 2{sup 17} processor cores with over 2 billion degrees of freedom. Accomplishments achieved to date include applications to the Hanford 300 Area and modeling CO{sub 2} sequestration in deep geologic formations.« less

Tectono-seismic characteristics of faults in the shallow portion of an accretionary prism

NASA Astrophysics Data System (ADS)

Hirono, Tetsuro; Ishikawa, Tsuyoshi

2018-01-01

To understand the tectono-seismic evolution of faults in the shallow part of a subduction-accretion system, we examined major faults in a fossil accretionary prism, the Emi Group (Hota Group), Boso Peninsula, Japan, by performing multiple structural, geochemical, and mineralogical analyses. Because the strata are relatively shallow (burial depth, 1-4 km), early stage deformation related to subduction, accretion, and uplifting processes is well preserved in three dominant fault zones. On the basis of both previous findings and our geochemical and mineralogical results, we inferred that early stage faulting in a near-trench setting under high pore fluid pressure and second stage faulting at relatively deep along subduction corresponded to aseismic deformations, as shown by velocity strengthening characteristics; and during late stage faulting, probably in association with accretion and uplift processes, a high-temperature fluid, revealed by a geochemical temperature proxy, triggered fault weakening by a thermal pressurization mechanism, and potentially led to the generation of a tsunami.

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 controls on vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Geochemical controls of vanadium accumulation in fossil fuels

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1989-01-01

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Molybdenum mineralization related to the Yangtze's lower crust and differentiation in the Dabie Orogen: Evidence from the geochemical features of the Yaochong porphyry Mo deposit

NASA Astrophysics Data System (ADS)

Liu, Qing-Quan; Li, Bin; Shao, Yong-Jun; Lu, An-Huai; Lai, Jian-Qing; Li, Yong-Feng; Luo, Zheng-Zhuan

2017-06-01

The Dabie Orogen is a world-class case for large amounts of Mo mineralization in that it contains at least 10 porphyry Mo deposits with Mo metal reserves over 3 Mt from the time period of 156-110 Ma. However, the principal mechanism for the Mo mineralization remains controversial due to the lack of a precise definition of its source and shallow ore-forming process, which is essential to understand these rare large Mo deposits. Detailed geochronology, geochemistry, and isotopic data for ore-related granites and minerals were analyzed in order to place constraints on the massive Mo mineralization in the Dabie Orogen in eastern China. The Yaochong molybdenum orebodies were hosted in the transition belt and alteration zone between the granitic stocks and the Dabie Complex and were characterized as numerous veinlets with potassic, phyllic and propylitic alterations. The buried Yaochong granitic intrusions and associated molybdenum mineralization yield Early Cretaceous ages of magmatic activities at ca. 138 Ma and extremely similar Re-Os isotope ages for the corresponding Mo metallogenic event at ca. 137 Ma. The Yaochong monzogranite and granite porphyry belong to the highly fractionated I-type granites, which are believed to be derived from the dominantly Yangtze's lower crust mixed with the Northern Dabie Complex due to their geochemical and isotope features. The elemental diversity and isotopic homogeneity suggest that the formation of the Yaochong monzogranite involved the fractionation of biotite, garnet and minor feldspar and accessory minerals combined with a weak crustal assimilation process. In contrast, the granite porphyry was possibly generated by the partial melting of the same mixed lower continental crust via the differentiation process involving the fractionation of feldspar, apatite, and/or titanite. Fractional crystallization processes can significantly elevate the molybdenum concentration in the residual melts. The biotite fractional crystallization results in removal of molybdenum from the vestigial magma since molybdenum is compatible with it, which may account for the barren monzogranite with a low-grade molybdenum mineralization. The ore-bearing granite porphyry has more source materials from the Yangtze's lower crust, which may have contributed most of the molybdenum for the porphyry-related molybdenum deposits in the Dabie metallogenic zone. This porphyry molybdenum aggregation may have been deposited in a post-collision or intracontinental extensional setting.

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 ...

Geochemical patterns and microbial contribution to iron plaque formation in the rice plant rhizosphere

NASA Astrophysics Data System (ADS)

Maisch, Markus; Murata, Chihiro; Unger, Julia; Kappler, Andreas; Schmidt, Caroline

2015-04-01

Rice is the major food source for more than half of the world population and 80 percent of the worldwide rice cultivation is performed on water logged paddy soils. The establishment of reducing conditions in the soil and across the soil-water interface not only stimulates the microbial production and release of the greenhouse gas methane. These settings also create optimal conditions for microbial iron(III) reduction and therefore saturate the system with reduced ferrous iron. Through the reduction and dissolution of ferric minerals that are characterized by their high surface activity, sorbed nutrients and contaminants (e.g. arsenic) will be mobilized and are thus available for uptake by plants. Rice plants have evolved a strategy to release oxygen from their roots in order to prevent iron toxification in highly ferrous environments. The release of oxygen to the reduced paddy soil causes ferric iron plaque formation on the rice roots and finally increases the sorption capacity for toxic metals. To this date the geochemical and microbiological processes that control the formation of iron plaque are not deciphered. It has been hypothesized that iron(II)-oxidizing bacteria play a potential role in the iron(III) mineral formation along the roots. However, not much is known about the actual processes, mineral products, and geochemical gradients that establish within the rhizosphere. In the present study we have developed a growth set-up that allows the co-cultivation of rice plants and iron(II)-oxidizing bacteria, as well as the visual observation and in situ measurement of geochemical parameters. Oxygen and dissolved iron(II) gradients have been measured using microelectrodes and show geochemical hot spots that offer optimal growth conditions for microaerophilic iron(II) oxidizers. First mineral identification attempts of iron plaque have been performed using Mössbauer spectroscopy and microscopy. The obtained results on mineraology and crystallinity have been compared to mineralogical data from purely biotic (microaerophilic) and abiotic iron mineral formation processes.

Hydrologic and geochemical data assimilation at the Hanford 300 Area

NASA Astrophysics Data System (ADS)

Chen, X.; Hammond, G. E.; Murray, C. J.; Zachara, J. M.

2012-12-01

In modeling the uranium migration within the Integrated Field Research Challenge (IFRC) site at the Hanford 300 Area, uncertainties arise from both hydrologic and geochemical sources. The hydrologic uncertainty includes the transient flow boundary conditions induced by dynamic variations in Columbia River stage and the underlying heterogeneous hydraulic conductivity field, while the geochemical uncertainty is a result of limited knowledge of the geochemical reaction processes and parameters, as well as heterogeneity in uranium source terms. In this work, multiple types of data, including the results from constant-injection tests, borehole flowmeter profiling, and conservative tracer tests, are sequentially assimilated across scales within a Bayesian framework to reduce the hydrologic uncertainty. The hydrologic data assimilation is then followed by geochemical data assimilation, where the goal is to infer the heterogeneous distribution of uranium sources using uranium breakthrough curves from a desorption test that took place at high spring water table. We demonstrate in our study that Ensemble-based data assimilation techniques (Ensemble Kalman filter and smoother) are efficient in integrating multiple types of data sequentially for uncertainty reduction. The computational demand is managed by using the multi-realization capability within the parallel PFLOTRAN simulator.

Geochemical modeling of trivalent chromium migration in saline-sodic soil during Lasagna process: impact on soil physicochemical properties.

PubMed

Lukman, Salihu; Bukhari, Alaadin; Al-Malack, Muhammad H; Mu'azu, Nuhu D; Essa, Mohammed H

2014-01-01

Trivalent Cr is one of the heavy metals that are difficult to be removed from soil using electrokinetic study because of its geochemical properties. High buffering capacity soil is expected to reduce the mobility of the trivalent Cr and subsequently reduce the remedial efficiency thereby complicating the remediation process. In this study, geochemical modeling and migration of trivalent Cr in saline-sodic soil (high buffering capacity and alkaline) during integrated electrokinetics-adsorption remediation, called the Lasagna process, were investigated. The remedial efficiency of trivalent Cr in addition to the impacts of the Lasagna process on the physicochemical properties of the soil was studied. Box-Behnken design was used to study the interaction effects of voltage gradient, initial contaminant concentration, and polarity reversal rate on the soil pH, electroosmotic volume, soil electrical conductivity, current, and remedial efficiency of trivalent Cr in saline-sodic soil that was artificially spiked with Cr, Cu, Cd, Pb, Hg, phenol, and kerosene. Overall desirability of 0.715 was attained at the following optimal conditions: voltage gradient 0.36 V/cm; polarity reversal rate 17.63 hr; soil pH 10.0. Under these conditions, the expected trivalent Cr remedial efficiency is 64.75%.

Geochemical Modeling of Trivalent Chromium Migration in Saline-Sodic Soil during Lasagna Process: Impact on Soil Physicochemical Properties

PubMed Central

Bukhari, Alaadin; Al-Malack, Muhammad H.; Mu'azu, Nuhu D.; Essa, Mohammed H.

2014-01-01

Trivalent Cr is one of the heavy metals that are difficult to be removed from soil using electrokinetic study because of its geochemical properties. High buffering capacity soil is expected to reduce the mobility of the trivalent Cr and subsequently reduce the remedial efficiency thereby complicating the remediation process. In this study, geochemical modeling and migration of trivalent Cr in saline-sodic soil (high buffering capacity and alkaline) during integrated electrokinetics-adsorption remediation, called the Lasagna process, were investigated. The remedial efficiency of trivalent Cr in addition to the impacts of the Lasagna process on the physicochemical properties of the soil was studied. Box-Behnken design was used to study the interaction effects of voltage gradient, initial contaminant concentration, and polarity reversal rate on the soil pH, electroosmotic volume, soil electrical conductivity, current, and remedial efficiency of trivalent Cr in saline-sodic soil that was artificially spiked with Cr, Cu, Cd, Pb, Hg, phenol, and kerosene. Overall desirability of 0.715 was attained at the following optimal conditions: voltage gradient 0.36 V/cm; polarity reversal rate 17.63 hr; soil pH 10.0. Under these conditions, the expected trivalent Cr remedial efficiency is 64.75 %. PMID:25152905

Compilation of field methods used in geochemical prospecting by the U.S. Geological Survey

USGS Publications Warehouse

Lakin, Hubert William; Ward, Frederick Norville; Almond, Hy

1952-01-01

The field methods described in this report are those currently used in geochemical prospecting by the U. S. Geological Survey. Some have been published, others are being processed for publication, while others are still being investigated. The purpose in compiling these methods is to make them readily available in convenient form. The methods have not been thoroughly tested and none is wholly satisfactory. Research is being continued.

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.

The hydrothermal system of the Domuyo volcanic complex (Argentina): A conceptual model based on new geochemical and isotopic evidences

NASA Astrophysics Data System (ADS)

Tassi, F.; Liccioli, C.; Agusto, M.; Chiodini, G.; Vaselli, O.; Calabrese, S.; Pecoraino, G.; Tempesti, L.; Caponi, C.; Fiebig, J.; Caliro, S.; Caselli, A.

2016-12-01

The Domuyo volcanic complex (Neuquén Province, Argentina) hosts one of the most promising geothermal systems of Patagonia, giving rise to thermal manifestations discharging hot and Cl--rich fluids. This study reports a complete geochemical dataset of gas and water samples collected in three years (2013, 2014 and 2015) from the main fluid discharges of this area. The chemical and isotopic composition (δD-H2O and δ18O-H2O) of waters indicates that rainwater and snow melting are the primary recharge of a hydrothermal reservoir located at relative shallow depth (400-600 m) possibly connected to a second deeper (2-3 km) reservoir. Reactive magmatic gases are completely scrubbed by the hydrothermal aquifer(s), whereas interaction of meteoric waters at the surface causes a significant air contamination and dilution of the fluid discharges located along the creeks at the foothill of the Cerro Domuyo edifice. Thermal discharges located at relatively high altitude ( 3150 m a.s.l.), namely Bramadora, are less affected by this process, as also shown by their relatively high R/Ra values (up to 6.91) pointing to the occurrence of an actively degassing magma batch located at an unknown depth. Gas and solute geothermometry suggests equilibrium temperatures up to 220-240 °C likely referred to the shallower hydrothermal reservoir. These results, confirming the promising indications of the preliminary surveys carried out in the 1980‧s, provide useful information for a reliable estimation of the geothermal potential of this extinct volcanic system, although a detailed geophysical measurements is required for the correct estimation of depth and dimensions of the fluid reservoir(s).

Geochemical baseline studies and relations between water quality and streamflow in the upper Blackfoot Watershed, Montana: data for July 1997-December 1998

USGS Publications Warehouse

Nagorski, Sonia A.; Moore, Johnnie N.; Smith, David B.

2001-01-01

We used ultraclean sampling techniques to study the solute (operationally defined as <0.2 ?m) surface water geochemistry at five sites along the Upper Blackfoot River and four sites along the Landers Fork, some in more detail and more regularly than others. We collected samples also from Hogum Creek, a tributary to the Blackfoot, from Copper Creek, a tributary to the Landers Fork, and from ground water seeps contributing to the flow along the Landers Fork. To better define the physical dynamics of the hydrologic system and to determine geochemical loads, we measured streamflow at all the sites where we took samples for water quality analysis. The Upper Blackfoot River, which drains historic mines ca. 20 Km upstream of the study area, had higher trace metal concentrations than did the Landers Fork, which drains the pristine Scapegoat Wilderness area. In both rivers, many of the major elements were inversely related to streamflow, and at some sites, several show a hysteresis effect in which the concentrations were lower on the rising limb of the hydrograph than on the falling limb. However, many of the trace elements followed far more irregular trends, especially in the Blackfoot River. Elements such as As, Cu, Fe, Mn, S, and Zn exhibited complex and variable temporal patterns, which included almost no response to streamflow differences, increased concentrations following a summer storm and at the start of snowmelt in the spring, and/or increased concentrations throughout the course of spring runoff. In summary, complex interactions between the timing and magnitude of streamflow with physical and chemical processes within the watershed appeared to greatly influence the geochemistry at the sites, and streamflow values alone were not good predictors of solute concentrations in the rivers.

River-spring connectivity and hydrogeochemical interactions in a shallow fractured rock formation. The case study of Fuensanta river valley (Southern Spain)

NASA Astrophysics Data System (ADS)

Barberá, J. A.; Andreo, B.

2017-04-01

In upland catchments, the hydrology and hydrochemistry of streams are largely influenced by groundwater inflows, at both regional and local scale. However, reverse conditions (groundwater dynamics conditioned by surface water interferences), although less described, may also occur. In this research, the local river-spring connectivity and induced hydrogeochemical interactions in intensely folded, fractured and layered Cretaceous marls and marly-limestones (Fuensanta river valley, S Spain) are discussed based on field observations, tracer tests and hydrodynamic and hydrochemical data. The differential flow measurements and tracing experiments performed in the Fuensanta river permitted us to quantify the surface water losses and to verify its direct hydraulic connection with the Fuensanta spring. The numerical simulations of tracer breakthrough curves suggest the existence of a groundwater flow system through well-connected master and tributary fractures, with fast and multi-source flow components. Furthermore, the multivariate statistical analysis conducted using chemical data from the sampled waters, the geochemical study of water-rock interactions and the proposed water mixing approach allowed the spatial characterization of the chemistry of the springs and river/stream waters draining low permeable Cretaceous formations. Results corroborated that the mixing of surface waters, as well as calcite dissolution and CO2 dissolution/exsolution, are the main geochemical processes constraining Fuensanta spring hydrochemistry. The estimated contribution of the tributary surface waters to the spring flow during the research period was approximately 26-53% (Fuensanta river) and 47-74% (Convento stream), being predominant the first component during high flow and the second one during the dry season. The identification of secondary geochemical processes (dolomite and gypsum dissolution and dedolomitization) in Fuensanta spring waters evidences the induced hydrogeochemical changes resulting from the allogenic recharge. This research highlights the usefulness of an integrated approach based on river and spring flow examination, dye tracing interpretation and regression and multivariate statistical analysis using hydrochemical data for surface water-groundwater interaction assessment in fractured complex environments worldwide, whose implementation becomes critical for an appropriate groundwater policy.

New Zealand as a Potential Source of Mineral Dust to the Atmosphere and Ocean during Glacial Periods

NASA Astrophysics Data System (ADS)

Koffman, B. G.; Goldstein, S. L.; Winckler, G.; Kaplan, M. R.; Bolge, L.; Cai, Y.; Recasens, C.; Koffman, T. N. B.

2017-12-01

The geochemical composition of sediments and dust can be used to trace their provenance, thereby providing insights into a range of Earth surface processes. During past glacial climates, much of the South Island of New Zealand (NZ) was blanketed by temperate erosive glacier systems, which significantly would have enhanced sediment production, including from associated active outwash plains. Such glacially-derived mineral dust from NZ may have impacted climate and ecological systems. In addition, dust and sediment can be used to trace downstream aeolian and oceanic transport. To this end, we systematically characterized the geochemical compositions of likely sediment- and dust-producing regions from the NZ South Island. We observe a strong relationship between sediment geochemical composition and geologic setting. Specifically, sediments from the central South Island, including the Canterbury Plains and Mackenzie Basin, where glaciers eroded mainly the Torlesse Greywacke, have a relatively homogenous isotopic composition, with 87Sr/86Sr = 0.7095-0.7165, ɛNd = -6.5 to -4.0, 206Pb/204Pb = 18.75-19.04, 207Pb/204Pb = 15.65-15.68, 208Pb/204Pb = 38.68-38.93. Southern South Island sediment sources, including southern Otago and Southland, show younger crust formation ages and more variable Sr and Nd isotopic compositions, reflecting the presence of Paleozoic volcanic complexes. Here 87Sr/86Sr = 0.7041-0.7140, ɛNd = -4.0 to +5.3, 206Pb/204Pb = 18.71-18.92, 207Pb/204Pb = 15.62-15.65, 208Pb/204Pb = 38.44-38.87. During the Last Glacial Maximum (LGM), glacial outwash and associated fluvial systems downstream were greatly expanded relative to present day, which could have provided regions for dust deflation - especially given a sea level lowering of 130 m. Due to processes linked to glaciations and lower sea levels, we suggest that the NZ South Island, though limited in extent compared to larger southern landmasses, may still have served as an important source of detritus during ice age climates.

Synthetical Analysis for Morphology, biological Species, and stable Isotopes (SAMSI) of single-cell planktonic foraminifer

NASA Astrophysics Data System (ADS)

Ujiie, Y.; Kimoto, K.; Ishimura, T.

2017-12-01

Planktonic foraminifers are widely used in the studies of paleontology and paleoceanography, because the morphology of their calcareous shells is enough highly variable to identify the morphospecies and the chemical composition of the shells reflect ambient seawater condition. Although the morphospecies were believed to represent environments associating with latitudinal temperature range of the world ocean, molecular phylogeographic studies have unveiled the presence of multiple biological species in a single morphospecies and their species-specific distributions. This implicates the actual complexity of planktonic foraminiferal ecology. Conversely, these biological species have a high potential for providing novel ecological and environmental information to us. In order to reassess the morphological and geochemical characters of biological species, the DNA extraction method with the guanidium isothiocyanate buffer was developed to preserve the calcareous shells. The present study carefully tested the physical and chemical damages of the DNA extraction process to the shells, by our novel approaches with geochemical analysis of the shells after non-destructive analysis for morphometrics on a same specimen. First, we checked the changes of the shell densities between pre- and post-DNA extraction by using the micro-focus X-ray CT (MXCT) scanning. Based on the simultaneous measurement of a sample and the standard material, we confirmed no significant changes to the shell densities through the DNA extraction process. As a next step, we compared stable oxygen and carbon isotopes among individuals of three sample sets: (1) no chemical and incubation as control, (2) incubation in the DNA extraction buffer at 65-70°C for 40 minutes as standard way, and (3) incubation in the DNA extraction buffer at 65-70°C for 120 minutes, by using the microscale isotopic analytical system (MICAL3c). Consequently, there were no significant differences among the three sample sets. These examinations clearly certified that we define morphological and geochemical features from same specimens after genetic identification. Thus, our novel approach (SAMSI) provides future studies to establish the accurate ecological and environmental proxies both in the modern and past oceans.

Tidally driven water column hydro-geochemistry in a remediating acidic wetland

NASA Astrophysics Data System (ADS)

Johnston, Scott G.; Keene, Annabelle F.; Bush, Richard T.; Sullivan, Leigh A.; Wong, Vanessa N. L.

2011-10-01

SummaryManaged tidal inundation is a newly evolved technique for remediating coastal acid sulphate soil (CASS) wetlands. However, there remains considerable uncertainty regarding the hydro-geochemical pathways and spatiotemporal dynamics of residual H + and metal(loid) mobilisation into the tidal fringe surface waters of these uniquely iron-rich landscapes. Here, we examine the hydrology and water column chemistry across the intertidal slope of a remediating CASS wetland during several tide cycles. There was extreme spatial and temporal dynamism in water column chemistry, with pH fluctuating by ˜3 units (˜3.5-6.5) during a single tide cycle. Acute acidity was spatially confined to the upper intertidal slope, reflecting surface sediment properties, and tidal overtopping is an important pathway for mobilisation of residual H + and Al 3+ to the water column. Marine derived HCO3- was depleted from surface waters migrating across the intertidal slope and a strong gradient in HCO3- was observed from the tidal fringe to the adjacent tributary channel and nearby estuary. Tidal forcing generated oscillating hydraulic gradients in the shallow fringing aquifer, favouring ebb-tide seepage and driving rapid, heterogeneous advection of groundwater on the lower intertidal slope via surface connected macropores. A combination of diffusive and advective flux across the sediment-water interface led to persistent, elevated surface water Fe 2+ (˜10-1000 μM). The geochemical processes associated with Fe 2+ mobilisation displayed distinct spatial zonation, with low pH, proton-promoted desorption occurring on the upper intertidal slope, whilst circum-neutral pH, Fe(III)-reducing processes dominated the lower intertidal slope. Arsenic was also mobilised into surface waters on the lower intertidal slope under moderate pH (˜6.0) conditions and was strongly positively correlated with Fe 2+. Saturation index values for aragonite were substantially depressed (-1 to -5) and significantly negatively correlated with elevation, thereby presenting a barrier to re-colonisation of the upper intertidal slope by calcifying benthic organisms. These findings highlight the spatially complex hydrological and geochemical controls on surface water quality that can occur in tidally inundated acid sulphate soil environments.

Geochemical Processes Data Package for the Vadose Zone in the Single-Shell Tank Waste Management Areas at the Hanford Site

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

Cantrell, Kirk J.; Zachara, John M.; Dresel, P. Evan

This data package discusses the geochemistry of vadose zone sediments beneath the single-shell tank farms at the U.S. Department of Energy’s (DOE’s) Hanford Site. The purpose of the report is to provide a review of the most recent and relevant geochemical process information available for the vadose zone beneath the single-shell tank farms and the Integrated Disposal Facility. Two companion reports to this one were recently published which discuss the geology of the farms (Reidel and Chamness 2007) and groundwater flow and contamination beneath the farms (Horton 2007).

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.

An Integrated 3D Hydrogeological, Geophysical, and Microbiological Investigation of Geochemical Gradients in a Pristine Aquifer Located in Laurentian Hills, ON, Canada

NASA Astrophysics Data System (ADS)

Shirokova, V.; Graves, L.; Stojanovic, S.; Enright, A. M.; Bank, C.; Ferris, F. G.

2013-12-01

A pristine glaciofluvial aquifer displaying naturally occurring geochemical gradients was investigated using hydrogeological, geophysical, and microbiological methods. A network of 25 piezometers was used to collect samples for groundwater chemical analysis, including parameters such as total iron (Fe), ferrous iron (Fe2+), sulphate (SO42-), sulfur (S2-), ammonium (NH4+), nitrate (NO3-), nitrite (NO2-), silica (SiO2), phosphate (PO43-), pH, and oxidation reduction potential (ORP). Ion concentration values between piezometers were interpolated using kriging and inverse distance weighting. Yearly analysis of the network shows spatially and temporally persistent plumes of iron and sulfur. A 3D model of the aquifer was compiled to aid in the understanding of the nature and origin of the geochemical gradients. The resulting maps showed zones with high concentrations of dissolved total iron (predominantly soluble ferric iron and complexed iron compounds), followed immediately downgradient by a high concentration of ferrous iron. Similarly, zones of high sulfide concentration were followed by areas of high sulfate concentration. There was some overlap between the iron and sulfur plumes, and ion concentrations were higher in years with a lower water table elevation. Metagenomic analysis revealed a diverse microbial community in the sediment, capable of the biogeochemical cycling of iron, sulfur, and nitrogen. The aquifer basin, as bounded by a till aquitard, was delineated using ground penetrating radar tomography from 45 lines. The plumes corresponded to an area where there is large, channel-like depression in the till boundary. Flow vectors from hydrogeological modelling indicated increased velocity followed by a slowing and convergence of groundwater in this location. Resistivity values from 20 lines varied in general from high values (2000-6000 Ohm.m) above 1-2 m to lower values (less than 1000 Ohm.m) below 2 to a 5m depth. The resistivity surveys consistently showed low resistivity values in areas of ionic enrichment, the location of the geochemical plumes, and high resistivity values at the top of the vadose zone including below dry sand outcrops. Fluorescent microscopy suggests the plumes are associated with attached subsurface bacteria dominated by species such as Gallionella and Leptothrix. These bacteria are likely responsible for conductive anomalies (<200 Ohm.m), observed in the resistivity models, that were at the centre of areas with high ionic concentrations. The above aquifer chemical network is currently being computationally simulated, and attempts are being made to determine the extents to which biotic and abiotic processes contribute to the formation of the geochemical gradients.

Statistical tables and charts showing geochemical variation in the Mesoproterozoic Big Creek, Apple Creek, and Gunsight formations, Lemhi group, Salmon River Mountains and Lemhi Range, central Idaho

USGS Publications Warehouse

Lindsey, David A.; Tysdal, Russell G.; Taggart, Joseph E.

2002-01-01

The principal purpose of this report is to provide a reference archive for results of a statistical analysis of geochemical data for metasedimentary rocks of Mesoproterozoic age of the Salmon River Mountains and Lemhi Range, central Idaho. Descriptions of geochemical data sets, statistical methods, rationale for interpretations, and references to the literature are provided. Three methods of analysis are used: R-mode factor analysis of major oxide and trace element data for identifying petrochemical processes, analysis of variance for effects of rock type and stratigraphic position on chemical composition, and major-oxide ratio plots for comparison with the chemical composition of common clastic sedimentary rocks.

Geochemical evidence for the formation of the Moon by impact induced fission of the proto-Earth

NASA Technical Reports Server (NTRS)

Waenke, H.; Dreibus, G.

1984-01-01

Geochemical evidence is discussed which advocates the theory that the Moon was formed by impact induced fission of the Earth. The Earth's mantle exhibits a number of geochemical peculiarities which make our planet a unique object in the solar system. Terrestrial basalts are compared with those from the Eucrite parent body and the Shergotty parent body. Also the Moon's composition is very close to the Earth's in all details except the lower FeO content which is explained. Evidence is discussed for the plausible physical process of formation of the Moon by impact induced fission. Also the theory that impact induced fission occurred at the moment at which accretion of the Earth was not totally complete is briefly discussed.

Geochemistry of the Springfield Plateau aquifer of the Ozark Plateaus Province in Arkansas, Kansas, Missouri and Oklahoma, USA

USGS Publications Warehouse

Adamski, J.C.

2000-01-01

Geochemical data indicate that the Springfield Plateau aquifer, a carbonate aquifer of the Ozark Plateaus Province in central USA, has two distinct hydrochemical zones. Within each hydrochemical zone, water from springs is geochemically and isotopically different than water from wells. Geochemical data indicate that spring water generally interacts less with the surrounding rock and has a shorter residence time, probably as a result of flowing along discrete fractures and solution openings, than water from wells. Water type throughout most of the aquifer was calcium bicarbonate, indicating that carbonate-rock dissolution is the primary geochemical process occurring in the aquifer. Concentrations of calcium, bicarbonate, dissolved oxygen and tritium indicate that most ground water in the aquifer recharged rapidly and is relatively young (less than 40 years). In general, field-measured properties, concentrations of many chemical constituents, and calcite saturation indices were greater in samples from the northern part of the aquifer (hydrochemical zone A) than in samples from the southern part of the aquifer (hydrochemical zone B). Factors affecting differences in the geochemical composition of ground water between the two zones are difficult to identify, but could be related to differences in chert content and possibly primary porosity, solubility of the limestone, and amount and type of cementation between zone A than in zone B. In addition, specific conductance, pH, alkalinity, concentrations of many chemical constituents and calcite saturation indices were greater in samples from wells than in samples from springs in each hydrochemical zone. In contrast, concentrations of dissolved oxygen, nitrite plus nitrate, and chloride generally were greater in samples from springs than in samples from wells. Water from springs generally flows rapidly through large conduits with minimum water-rock interactions. Water from wells flow through small fractures, which restrict flow and increase water-rock interactions. As a result, springs tend to be more susceptible to surface contamination than wells. The results of this study have important implications for the geochemical and hydrogeological processes of similar carbonate aquifers in other geographical locations. Copyright (C) 2000 John Wiley and Sons, Ltd.Geochemical data indicate that the Springfield Plateau carbonate aquifer has two distinct hydrochemical zones. With each hydrochemical zone, water from springs is geochemically and isotopically different from the water from wells. Spring water generally interacts less with the surrounding rock and has a shorter residence time, probably as a result of flowing along discrete fractures and solution openings, than water from wells. Factors affecting the differences in the geochemical composition of groundwater between the two zones are difficult to identify, but could be related to differences in chert content and possibly primary porosity, solubility of the limestone, and amount and type of cementation between zones.

Geochemical processes controlling fate and transport of arsenic in acid mine drainage (AMD) and natural systems.

PubMed

Cheng, Hefa; Hu, Yuanan; Luo, Jian; Xu, Bin; Zhao, Jianfu

2009-06-15

Acid mine drainage (AMD) is often accompanied with elevated concentrations of arsenic, in the forms of arsenite, As(III), and/or arsenate, As(V), due to the high affinity of arsenic for sulfide mineral ores. This review summarizes the major geochemical processes controlling the release, speciation, fate, and distribution of inorganic arsenic in mine drainage and natural systems. Arsenic speciation depends highly on redox potential and pH of the solution, and arsenite can be oxidized to the less toxic arsenate form. Homogeneous oxidation of arsenite occurs rather slowly while its heterogeneous oxidation on mineral surfaces can greatly enhance the reaction rates. Little evidence suggests that precipitation reaction limits the concentrations of arsenic in natural water, while co-precipitation may lead to rapid arsenic removal when large amount of iron hydroxides precipitate out of the aqueous phase upon neutralization of the mine drainage. Both arsenate and arsenite adsorb on common metal oxides and clay minerals through formation of inner-sphere and/or outer-sphere complexes, controlling arsenic concentration in natural water bodies. Arsenite adsorbs less strongly than arsenate in the typical pH range of natural water and is more mobile. Part of the adsorbed arsenic species can be exchanged by common anions (e.g., PO(4)(3-) and SO(4)(2-)), especially phosphate, which leads to their re-mobilization. Understanding the geochemistry of arsenic is helpful for predicting its mobility and fate in AMD and natural systems, and for designing of cost-effective remediation/treatment strategies to reduce the occurrence and risk of arsenic contamination.

Characterization of Unconventional Reservoirs: CO2 Induced Petrophysics

NASA Astrophysics Data System (ADS)

Verba, C.; Goral, J.; Washburn, A.; Crandall, D.; Moore, J.

2017-12-01

As concerns about human-driven CO2 emissions grow, it is critical to develop economically and environmentally effective strategies to mitigate impacts associated with fossil energy. Geologic carbon storage (GCS) is a potentially promising technique which involves the injection of captured CO2 into subsurface formations. Unconventional shale formations are attractive targets for GCS while concurrently improving gas recovery. However, shales are inherently heterogeneous, and minor differences can impact the ability of the shale to effectively adsorb and store CO2. Understanding GCS capacity from such endemic heterogeneities is further complicated by the complex geochemical processes which can dynamically alter shale petrophysics. We investigated the size distribution, connectivity, and type (intraparticle, interparticle, and organic) of pores in shale; the mineralogy of cores from unconventional shale (e.g. Bakken); and the changes to these properties under simulated GCS conditions. Electron microscopy and dual beam focused ion beam scanning electron microscopy were used to reconstruct 2D/3D digital matrix and pore structures. Comparison of pre and post-reacted samples gives insights into CO2-shale interactions - such as the mechanism of CO2 sorption in shales- intended for enhanced oil recovery and GCS initiatives. These comparisons also show how geochemical processes proceed differently across shales based on their initial diagenesis. Results show that most shale pore sizes fall within meso-macro pore classification (> 2 nm), but have variable porosity and organic content. The formation of secondary minerals (calcite, gypsum, and halite) may play a role in the infilling of fractures and pore spaces in the shale, which may reduce permeability and inhibit the flow of fluids.

Unraveling Vital Effects: Photosynthesis of Symbiotic Algae in Foraminifera Hosts

NASA Astrophysics Data System (ADS)

Fish, C.; Phelps, S. R.; Goes, J. I.; Hoenisch, B.

2015-12-01

B/Ca and boron isotope proxies recorded in the calcium carbonate shells of planktic foraminifera are sensitive to seawater acidity. We seek to understand how the biology of the organism affects the geochemical signals, as planktic foraminifera shells differ in their chemical composition from inorganic calcite and also between foraminifer species. These differences are most likely related to physiological processes like respiration, calcification, and photosynthesis in symbiont-bearing foraminifera. The modifications of geochemical signals by these biological parameters are termed vital effects. Our study is based on the hypothesis that the B/Ca and δ11B offsets observed in planktic foraminifer shells are primarily due to the photosynthetic activity of their symbionts, which may elevate the microenvironmental pH to different degrees in different foraminifer species. Using fast repetition rate fluorometry, chlorophyll α analyses and symbiont counts, we investigated the symbiont-photosynthetic activity associated with three foraminifera species - Globigerinoides ruber, G. sacculifer, and Orbulina universa. Boron proxy systematics in these species suggest that photosynthetic activity should be greater in G. ruber compared to G. sacculifer and O. universa, but this is not confirmed by our study. While symbiont photosynthesis undoubtedly explains microenvironmental pH-elevation and boron proxy systematics in symbiont-bearing compared to symbiont-barren foraminifer species, additional processes must be responsible for the boron geochemical offsets between symbiont-bearing species. Respiration of the symbiont-host association and the calcification process are most likely candidates that require further analysis. Our study highlights the potential danger of misinterpreting geochemical signals in biological organisms when the biology of the organism in question is not entirely understood.

Linking geochemical processes in mud volcanoes with arsenic mobilization driven by organic matter.

PubMed

Liu, Chia-Chuan; Kar, Sandeep; Jean, Jiin-Shuh; Wang, Chung-Ho; Lee, Yao-Chang; Sracek, Ondra; Li, Zhaohui; Bundschuh, Jochen; Yang, Huai-Jen; Chen, Chien-Yen

2013-11-15

The present study deals with geochemical characterization of mud fluids and sediments collected from Kunshuiping (KSP), Liyushan (LYS), Wushanting (WST), Sinyangnyuhu (SYNH), Hsiaokunshui (HKS) and Yenshuikeng (YSK) mud volcanoes in southwestern Taiwan. Chemical constituents (cations, anions, trace elements, organic carbon, humic acid, and stable isotopes) in both fluids and mud were analyzed to investigate the geochemical processes and spatial variability among the mud volcanoes under consideration. Analytical results suggested that the anoxic mud volcanic fluids are highly saline, implying connate water as the probable source. The isotopic signature indicated that δ(18)O-rich fluids may be associated with silicate and carbonate mineral released through water-rock interaction, along with dehydration of clay minerals. Considerable amounts of arsenic in mud irrespective of fluid composition suggested possible release through biogeochemical processes in the subsurface environment. Sequential extraction of As from the mud indicated that As was mostly present in organic and sulphidic phases, and adsorbed on amorphous Mn oxyhydroxides. Volcanic mud and fluids are rich in organic matter (in terms of organic carbon), and the presence of humic acid in mud has implications for the binding of arsenic. Functional groups of humic acid also showed variable sources of organic matter among the mud volcanoes being examined. Because arsenate concentration in the mud fluids was found to be independent from geochemical factors, it was considered that organic matter may induce arsenic mobilization through an adsorption/desorption mechanism with humic substances under reducing conditions. Organic matter therefore plays a significant role in the mobility of arsenic in mud volcanoes. Copyright © 2012 Elsevier B.V. All rights reserved.

Magma transport and metasomatism in the mantle: a critical review of current geochemical models

USGS Publications Warehouse

Nielson, J.E.; Wilshire, H.G.

1993-01-01

Conflicting geochemical models of metasomatic interactions between mantle peridotite and melt all assume that mantle reactions reflect chromatographic processes. Examination of field, petrological, and compositional data suggests that the hypothesis of chromatographic fractionation based on the supposition of large-scale percolative processes needs review and revision. Well-constrained rock and mineral data from xenoliths indicate that many elements that behave incompatibly in equilibrium crystallization processes are absorbed immediately when melts emerge from conduits into depleted peridotite. After reacting to equilibrium with the peridotite, melt that percolates away from the conduit is largely depleted of incompatible elements. Continued addition of melts extends the zone of equilibrium farther from the conduit. Such a process resembles ion-exchange chromatography for H2O purification, rather than the model of chromatographic species separation. -from Authors

Time Evolution of the Basse Terre Island (Guadeloupe, French West Indies) Effusive Volcanism from New K-Ar Cassignol-Gillot Ages.

NASA Astrophysics Data System (ADS)

Samper, A.; Quidelleur, X.; Mollex, D.; Komorowski, J. C.; Boudon, G.

2004-12-01

Radiometric dating and geochemistry of effusive volcanics have been combined with geomorphological observations in order to provide a general evolution model of the volcanic island of Basse Terre, Guadeloupe (French West Indies). More than forty new Cassignol-Gillot K-Ar ages distributed within the entire island, together with the twenty ages (Blanc, 1983; Carlut et al., 2000) previously obtained with the same technique, makes the Guadeloupe Island the best place to study the evolution of volcanic processes within the Lesser Antilles Arc. Dating was performed on the carefully separated groundmass in order to avoid K loss due to weathering and excess argon carried by mafic minerals. Ages obtained are relatively younger than previously thought on Basse Terre and range from a few ka to 2.79+-0.04 Ma. When available, the paleomagnetic polarity of the dated flows agree with the GPTS and a very good coherence of ages is observed for each massif. Our results demonstrate the general north to south migration of volcanism through time. It correlates with the main volcanic stages previously identified. The 2.75 Ma Basal Complex, the 1.81+-0.03 _ 1.15+-0.02 Ma Septentrional Chain, the 1.02+-0.02 Ma _ 0.606+-0.02 Ma Axial Chain, the 442+-6 _ 207+-28 ka Mateliane _ Sans Toucher Complex and the < 200 ka Complex of La Grande Decouverte, which outlines a relative continuity in the Basse Terre magmatism. Lavas are mainly basaltic andesites and andesites although a few basalt and dacite have also been dated. All of them are characterized by low MgO values (< 6 %), tholeiitic to calc-alkaline REE chondrite-normalized patterns and are of both low K and medium K affinity. Lavas display geochemical characteristics similar to that of the central islands of the Lesser Antilles arc. Within Basse Terre, geochemical characteristics are relatively constant through time, indicating no major change of volcanic processes during the whole subaerial activity. Finally the detailed chronological framework now available provides new constraints for estimating rates of edification and destruction at the island scale and, more generally, to help better understand the evolution of the still active Guadeloupe island Soufriere volcano.

Garnets within geode-like serpentinite veins: Implications for element transport, hydrogen production and life-supporting environment formation

NASA Astrophysics Data System (ADS)

Plümper, Oliver; Beinlich, Andreas; Bach, Wolfgang; Janots, Emilie; Austrheim, Håkon

2014-09-01

Geochemical micro-environments within serpentinizing systems can abiotically synthesize hydrocarbons and provide the ingredients required to support life. Observations of organic matter in microgeode-like hydrogarnets found in Mid-Atlantic Ridge serpentinites suggest these garnets possibly represent unique nests for the colonization of microbial ecosystems within the oceanic lithosphere. However, little is known about the mineralogical and geochemical processes that allow such unique environments to form. Here we present work on outcrop-scale vein networks from an ultramafic massif in Norway that contain massive amounts of spherulitic garnets (andradite), which help to constrain such processes. Vein andradite spherulites are associated with polyhedral serpentine, brucite, Ni-Fe alloy (awaruite), and magnetite indicative of low temperature (<200 °C) alteration under low fO2 and low aSiO2,aq geochemical conditions. Together with the outcrop- and micro-scale analysis geochemical reaction path modeling shows that there was limited mass transport and fluid flow over a large scale. Once opened the veins remained isolated (closed system), forming non-equilibrium microenvironments that allowed, upon a threshold supersaturation, the rapid crystallization (seconds to weeks) of spherulitic andradite. The presence of polyhedral serpentine spheres indicates that veins were initially filled with a gel-like protoserpentine phase. In addition, massive Fe oxidation associated with andradite formation could have generated as much as 600 mmol H2,aq per 100 cm3 vein. Although no carboneous matter was detected, the vein networks fulfill the reported geochemical criteria required to generate abiogenic hydrocarbons and support microbial communities. Thus, systems similar to those investigated here are of prime interest when searching for life-supporting environments within the deep subsurface.

Nanogeochemistry: Size-dependent mineral-fluid interface chemistry

NASA Astrophysics Data System (ADS)

Wang, Y.

2012-12-01

Nanostructures and nanometer mineral phases, both widely present in geologic materials, can potentially affect many geochemical processes. It is known that at nanometer scales a material tends to exhibit chemical properties distinct from the corresponding bulk phase. Understanding of this size-dependent property change will help us to bridge the existing knowledge gap between the molecular level understanding and the macro-scale laboratory/field observations of a geochemical process. In this presentation, I will review of the recent progresses in nanoscience and provide a perspective on how these progresses can potentially impact geochemical studies. My presentation will be focused the following areas: (1) the characterization of nanostructures in natural systems, (2) the study of fluids and chemical species in nanoconfinement, (3) the effects of nanopores on geochemical reaction and mass transfers, and (4) the use nanostructured materials for environmental management. I will demonstrate that the nanopore confinement can significantly modify geochemical reactions in porous geologic media. As the pore size is reduced to a few nanometers, the difference between surface acidity constants of a mineral (pK2 - pK1) decreases, giving rise to a higher surface charge density on a nanopore surface than that on an unconfined mineral-water interface. The change in surface acidity constants results in a shift of ion sorption edges and enhances ion sorption on nanopore surfaces. This effect causes preferential enrichment of trace elements in nanopores. I will then discuss the implications of this emergent nanometer-scale property to radionuclide transport and carbon dioxide storage in geologic media. This work was performed at Sandia National Laboratories, which is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the DOE under contract DE-AC04-94AL8500.

Introduction to the structures and processes of subduction zones

NASA Astrophysics Data System (ADS)

Zheng, Yong-Fei; Zhao, Zi-Fu

2017-09-01

Subduction zones have been the focus of many studies since the advent of plate tectonics in 1960s. Workings within subduction zones beneath volcanic arcs have been of particular interest because they prime the source of arc magmas. The results from magmatic products have been used to decipher the structures and processes of subduction zones. In doing so, many progresses have been made on modern oceanic subduction zones, but less progresses on ancient oceanic subduction zones. On the other hand, continental subduction zones have been studied since findings of coesite in metamorphic rocks of supracrustal origin in 1980s. It turns out that high-pressure to ultrahigh-pressure metamorphic rocks in collisional orogens provide a direct target to investigate the tectonism of subduction zones, whereas oceanic and continental arc volcanic rocks in accretionary orogens provide an indirect target to investigate the geochemistry of subduction zones. Nevertheless, metamorphic dehydration and partial melting at high-pressure to ultrahigh-pressure conditions are tectonically applicable to subduction zone processes at forearc to subarc depths, and crustal metasomatism is the physicochemical mechanism for geochemical transfer from the slab to the mantle in subduction channels. Taken together, these provide us with an excellent opportunity to find how the metamorphic, metasomatic and magmatic products are a function of the structures and processes in both oceanic and continental subduction zones. Because of the change in the thermal structures of subduction zones, different styles of metamorphism, metasomatism and magmatism are produced at convergent plate margins. In addition, juvenile and ancient crustal rocks have often suffered reworking in episodes independent of either accretionary or collisional orogeny, leading to continental rifting metamorphism and thus rifting orogeny for mountain building in intracontinental settings. This brings complexity to distinguish the syn-subduction processes and products from post-subduction processes and products. Nevertheless, available results indicate that our definition and understanding of subduction zone processes and products can be advanced by the convergence of observations and interpretations from geochemical, geological, geophysical and geodynamic studies of both oceanic and continental subduction zones. Therefore, insights into subduction zones can be provided by intergration of different approaches from different targets in the near future.

Introduction to the structures and processes of subduction zones

NASA Astrophysics Data System (ADS)

Zheng, Yong-Fei; Zhao, Zi-Fu

2017-09-01

Subduction zones have been the focus of many studies since the advent of plate tectonics in 1960s. Workings within subduction zones beneath volcanic arcs have been of particular interest because they prime the source of arc magmas. The results from magmatic products have been used to decipher the structures and processes of subduction zones. In doing so, many progresses have been made on modern oceanic subduction zones, but less progresses on ancient oceanic subduction zones. On the other hand, continental subduction zones have been studied since findings of coesite in metamorphic rocks of supracrustal origin in 1980s. It turns out that high-pressure to ultrahigh-pressure metamorphic rocks in collisional orogens provide a direct target to investigate the tectonism of subduction zones, whereas oceanic and continental arc volcanic rocks in accretionary orogens provide an indirect target to investigate the geochemistry of subduction zones. Nevertheless, metamorphic dehydration and partial melting at high-pressure to ultrahigh-pressure conditions are tectonically applicable to subduction zone processes at forearc to subarc depths, and crustal metasomatism is the physicochemical mechanism for geochemical transfer from the slab to the mantle in subduction channels. Taken together, these provide us with an excellent opportunity to find how the metamorphic, metasomatic and magmatic products are a function of the structures and processes in both oceanic and continental subduction zones. Because of the change in the thermal structures of subduction zones, different styles of metamorphism, metasomatism and magmatism are produced at convergent plate margins. In addition, juvenile and ancient crustal rocks have often suffered reworking in episodes independent of either accretionary or collisional orogeny, leading to continental rifting metamorphism and thus rifting orogeny for mountain building in intracontinental settings. This brings complexity to distinguish the syn-subduction processes and products from post-subduction processes and products. Nevertheless, available results indicate that our definition and understanding of subduction zone processes and products can be advanced by the convergence of observations and interpretations from geochemical, geological, geophysical and geodynamic studies of both oceanic and continental subduction zones. Therefore, insights into subduction zones can be provided by integration of different approaches from different targets in the near future.

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.

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

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

2015-01-01

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

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.

What do we really know about early diagenesis of non-marine carbonates?

NASA Astrophysics Data System (ADS)

De Boever, Eva; Brasier, Alexander T.; Foubert, Anneleen; Kele, Sándor

2017-11-01

Non-marine carbonate rocks including cave, spring, stream, calcrete and lacustrine-palustrine sediments, are susceptible to early diagenetic processes. These can profoundly alter the carbonate fabric and affect paleoclimatic proxies. This review integrates recent insights into diagenesis of non-marine carbonates and in particular the variety of early diagenetic processes, and presents a conceptual framework to address them. With ability to study at smaller and smaller scales, down to nanometers, one can now observe diagenesis taking place the moment initial precipitates have formed, and continuing thereafter. Diagenesis may affect whole rocks, but it typically starts in nano- and micro-environments. The potential for diagenetic alteration depends on the reactivity of the initial precipitate, commonly being metastable phases like vaterite, Ca-oxalates, hydrous Mg-carbonates and aragonite with regard to the ambient fluid. Furthermore, organic compounds commonly play a crucial role in hosting these early transformations. Processes like neomorphism (inversion and recrystallization), cementation and replacement generally result in an overall coarsening of the fabric and homogenization of the wide range of complex, primary microtextures. If early diagenetic modifications are completed in a short time span compared to the (annual to millennial) time scale of interest, then recorded paleoenvironmental signals and trends could still acceptably reflect original, depositional conditions. However, even compact, non-marine carbonate deposits may behave locally and temporarily as open systems to crystal-fluid exchange and overprinting of one or more geochemical proxies is not unexpected. Looking to the future, relatively few studies have examined the behaviour of promising geochemical records, such as clumped isotope thermometry and (non-conventional) stable isotopes, in well-constrained diagenetic settings. Ongoing and future in-vitro and in-situ experimental approaches will help to investigate and detangle sequences of intermediate, diagenetic products, processes and controls, and to quantify rates of early diagenesis, bridging a gap between nanoscale, molecular lab studies and the fossil field rock record of non-marine carbonates.

Volcanology and mineral deposits

USGS Publications Warehouse

Lipman, P.W.

1990-01-01

In contrast, old volcanic regions, which host many of the world's major hydrothermal-vein, porphyry, and massive-sulfide ore deposits, have been studied mainly by economic geologists, regional stratigraphers, and structural geologists who have limited familiarity with the complexities of volcanic processes. Such "dead" volcanoes, ranging in age from a few million million years (tertiary) to a few billion years (Precambrian), are commonly incompletely and discontinuously preserved due to rapid erosion of originally high-standing volcanic edifices. They can be difficult to date reliably, especially in terms of the time scales of individual volcanic events, and are variably hydrothermally altered-impeding high-resolution petrologic and geochemical studies. Many volcanologists, geochemists, and geophysicists who work on active volcanoes accordingly have been reluctant to become involved in studies of such less tractable rocks. 

U.S. Geological Survey applied research studies of the Cheyenne River System, South Dakota; description and collation of data, water years 1987-88

USGS Publications Warehouse

Goddard, K. E.

1990-01-01

The Cheyenne River System in western South Dakota has been impacted by the discharge of about 100 million metric tons of gold-mill tailings to Whitewood Creek near Lead, South Dakota. In April 1985, the U.S. Geological Survey initiated an extensive series of research studies to investigate the magnitude of the impact and to define important processes acting on the contaminated sediments present in the system. The report presents all data collected during the 1987 and 1988 water years for these research studies. Some of the data included have been published previously. Data collected in the 1985 and 1986 water years have been published in a companion report (U.S. Geological Survey Open-File Report 88-484). Hydrologic, geochemical, and biologic data are available for sites on Whitewood Creek, and the Belle Fourche and Cheyenne Rivers. Data complexity varies from routine discharge and water-quality to very complex energy-dispersive x-ray analysis. Methods for sample collection, handling and preservation, and laboratory analysis are also presented. No interpretations or complex statistical summaries are included. (See also W89-08390) (USGS)

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.

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.

Chemical modeling constraints on Martian surface mineralogies formed in an early, warm, wet climate, and speculations on the occurrence of phosphate minerals in the Martian regolith

NASA Technical Reports Server (NTRS)

Plumlee, Geoffrey S.; Ridley, W. Ian; Debraal, Jeffrey D.

1992-01-01

This is one in a series of reports summarizing our chemical modeling studies of water-rock-gas interactions at the martian surface through time. The purpose of these studies is to place constraints on possible mineralogies formed at the martian surface and to model the geochemical implications of martian surficial processes proposed by previous researchers. Plumlee and Ridley summarize geochemical processes that may have occurred as a result of inferred volcano- and impact-driven hydrothermal activity on Mars. DeBraal et al. model the geochemical aspects of water-rock interactions and water evaporation near 0 C, as a prelude to future calculations that will model sub-0 C brine-rock-clathrate interactions under the current martian climate. In this report, we discuss reaction path calculations that model chemical processes that may have occurred at the martian surface in a postulated early, warm, wet climate. We assume a temperature of 25 C in all our calculations. Processes we model here include (1) the reaction of rainwater under various ambient CO2 and O2 pressures with basaltic rocks at the martian surface, (2) the formation of acid rain by volcanic gases such as HCl and SO2, (3) the reactions of acid rain with basaltic surficial materials, and (4) evaporation of waters resulting from rainwater-basalt interactions.

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.

Geochemical and Isotopic Evidences of the Magmatic Sources in the Eastern Sector of the Trans-Mexican Volcanic Belt: Xihuingo-Chichicuautla Volcanic Field

NASA Astrophysics Data System (ADS)

Valadez, S.; Martinez-serrano, R.; Juarez-Lopez, K.; Solis-Pichardo, G.; Perez-Arvizu, O.

2011-12-01

The study of magmatism in the Trans-Mexican Volcanic Belt (TMVB) has great importance due to several features such as its obliquity with respect to the Middle American Trench and its petrological and geochemical variability, which are not common in most typical volcanic arcs. Although several papers have contributed significantly to the understanding of most important magmatic processes in this province, there are still several questions such as the characterization of magmatic sources. In the present work, we provide new stratigraphic, petrographic, geochemical and Sr, Nd and Pb isotopic data as well as some K-Ar age determinations from the Xihuingo-Chichicuautla volcanic field (XCVF), located at the eastern part of the TMVB, with the aim to identify the magmatic sources that produced the main volcanic rocks. The volcanic structures in the XCVF are divided in two main groups according to the petrographic and geochemical compositions: 1) dacitic domes, andesitic lava flows and some dacitic-rhyolitic ignimbrites and 2) scoria cones, shield volcanoes and associated lava flows of basalt to basaltic-andesite composition. Distribution of most volcanic structures is probably controlled by NE-SW fault and fractures system. This fault system was studied by other authors who established that volcanic activity started ca. 13.5 Ma ago, followed by a volcanic hiatus of ca. 10 Ma, and the late volcanic activity began ca. 3 to 1 Ma. In this work we dated 2 rock samples by K-Ar method, which yielded ages of 402 and 871 Ka, which correspond to the most recent volcanic activity in this study area. The volcanic rocks of the XCVF display compositions from basalts to rhyolites but in general all rocks show trace element patterns typical of magmatic arcs. However, we can identify two main magmatic sources: a depleted magmatic source represented by dacitic-andesitic rocks which present a LILE enrichment with respect to HFSE indicating that a magmatic source was modified by fluids derived from the subduction processes. These magmas probably suffered fractional crystallization and minor assimilation in the continental crust. Sr, Nd isotopic compositions for this first group display the most radiogenic values (87Sr/86Sr from 0.7046 to 0.7047 and ɛNd from 2.2 to 2.8). The second source for the basaltic-andesite and basalt could be associated with an enriched mantle. These rocks present a minor LILE enrichment with respect to HSFE, and Sr and Nd isotopic values less radiogenic than the felsic rocks of the first group (87Sr/86Sr from 0.7040 to 0.7045 and ɛNd from 3.1 to 4.8). According to these evidences we can establish that the magmas emplaced in the study area were produced from a heterogeneous mantle source with complex magmatic processes combined with different interaction degrees between the magmas and continental crust.

Compositional variation within thick (>10 m) flow units of Mauna Kea Volcano cored by the Hawaii Scientific Drilling Project

NASA Astrophysics Data System (ADS)

Huang, Shichun; Vollinger, Michael J.; Frey, Frederick A.; Rhodes, J. Michael; Zhang, Qun

2016-07-01

Geochemical analyses of stratigraphic sequences of lava flows are necessary to understand how a volcano works. Typically one sample from each lava flow is collected and studied with the assumption that this sample is representative of the flow composition. This assumption may not be valid. The thickness of flows ranges from <1 to >100 m. Geochemical heterogeneity in thin flows may be created by interaction with the surficial environment whereas magmatic processes occurring during emplacement may create geochemical heterogeneities in thick flows. The Hawaii Scientific Drilling Project (HSDP) cored ∼3.3 km of basalt erupted at Mauna Kea Volcano. In order to determine geochemical heterogeneities in a flow, multiple samples from four thick (9.3-98.4 m) HSDP flow units were analyzed for major and trace elements. We found that major element abundances in three submarine flow units are controlled by the varying proportion of olivine, the primary phenocryst phase in these samples. Post-magmatic alteration of a subaerial flow led to loss of SiO2, CaO, Na2O, K2O and P2O5, and as a consequence, contents of immobile elements, such as Fe2O3 and Al2O3, increase. The mobility of SiO2 is important because Mauma Kea shield lavas divide into two groups that differ in SiO2 content. Post-magmatic mobility of SiO2 adds complexity to determining if these groups reflect differences in source or process. The most mobile elements during post-magmatic subaerial and submarine alteration are K and Rb, and Ba, Sr and U were also mobile, but their abundances are not highly correlated with K and Rb. The Ba/Th ratio has been used to document an important role for a plagioclase-rich source component for basalt from the Galapagos, Iceland and Hawaii. Although Ba/Th is anomalously high in Hawaiian basalt, variation in Ba abundance within a single flow shows that it is not a reliable indicator of a deep source component. In contrast, ratios involving elements that are typically immobile, such as La/Nb, La/Th, Nb/Th, Ce/Pb, Sr/Nd, La/Sm, Sm/Yb, Nb/Zr, Nb/Y and La/Yb, are uniform within the units, and they can be used to constrain petrogenetic processes. Nevertheless all elements are mobile under some conditions. For example, a surprising result is that relative to other samples, the uppermost sample collected from subaerial flow Unit 70, less than 1 m below the flow surface, is depleted in P, HREE and Y relative to all other samples from this flow unit. This result is complementary to the P, REE and Y enrichment found in subaerial lava flows from several Hawaiian shields, e.g., Kahoolawe and Koolau Volcanoes. These enrichments require mobilization of REE and followed by deposition a P-rich mineral.

Chemical weathering from the CoDA (Compositional Data Analysis) point of view: new insights for the Alpine rivers geochemistry

NASA Astrophysics Data System (ADS)

Gozzi, Caterina; Buccianti, Antonella; Frondini, Francesco

2017-04-01

The aim of this contribution is to explore the relationship among weathering reactions, the sample space of compositional data and fractals by means of distributional analysis. Weathering reactions represent the transfer of heat and entropy to the environment in geochemical cycles. Chemical weathering is a key process for understanding the global cycle of elements, both on long and short-terms and chemical weathering rates are complex functions of many factors including dissolution kinetics of minerals, mechanical erosion, lithology. Compositional data express the relative (proportional) abundance of chemical elements/species in a given total (i.e. volume or weight) so that compositions pertaining to the peculiar geometry of the simplex sample space. Fractals are temporal or spatial objects with self-similarity and scale invariance, so that internal structures repeat themselves over multiple levels of magnification or scales of measurement. Gibbs's free energy and the application of the Law Mass Action can be used to model weathering reactions, under the hypothesis of chemical equilibrium. Compositional data are obtained in the analytical phase after the determination of the concentrations of chemicals in sampled solid, liquid or gaseous materials. Fractals can be measured by using their fractal dimensions. The presence of fractal structures can be observed when the frequency distribution of isometric log-ratio coordinates is investigated, showing the logarithm of the cumulative number of samples exceeding a certain coordinate value plotted against the coordinate value itself. Isometric log-ratio coordinates (or balances) can be constructed by using the sequential binary partition (SBP) method. The balances can be identified to maintain, as far as possible, the similarity with a corresponding weathering reaction (Buccianti & Zuo, 2016). As an alternative, balances can be derived after the multivariate investigation of the variance-covariance structure of the compositional matrix. In both cases the idea is to probe the behaviour of geochemical processes to be analysed in time or space. An application example is presented for the chemistry of the surficial waters of the Alpine region (Donnini et al., 2016). The emergence of fractal structures indicates the presence of dissipative systems, which require complexity, large numbers of inter-connected elements and stochasticity requiring caution in the use of classical spatial methods to represent geochemical phenomena. Buccianti A. & Zuo R., 2016. Weathering reactions and isometric log-ratio coordinates: Do they speak to each other? Applied Geochemistry, 75, 189-199. Donnini M., Frondini F., Probst J.L., Probst A., Cardellini C., Marchesini I., Guzzetti F., 2016. Chemical weathering and consumption of atmospheric carbon dioxide in the Alpine region. Global and Planetary Change, 136 (2016) 65-81.

Preliminary evaluation of the ground-water-flow system in the Twin Cities Metropolitan area, Minnesota

USGS Publications Warehouse

Guswa, John H.; Siegel, Donald I.; Gillies, Daniel C.

1982-01-01

Areal distribution of calcium, sodium, sulfate, and chloride concentrations were analyzed to provide information on the hydrologic and geochemical relationships between aquifers. Ground water is generally of the calcium magnesium bicarbonate type. Concentration of dissolved solids in water from the Jordan Sandstone and Mount Simon-Hinckley aquifer generally decreases from southwest to northeast across the study area. This decrease probably reflects differences in the quality of recharge water and geochemical processes within the aquifers, such as ion exchange.

Significance of elevated K/Rb ratios in lower crustal rocks

NASA Technical Reports Server (NTRS)

Frost, B. Ronald; Frost, Carol D.

1988-01-01

The granulite uncertainty principle, which states that it is difficult or impossible to determine with certainty the maximum geopressure and geotemperature that a granulite has experienced, is addressed. Also, geochemical fingerprinting cannot always be used reliably in the nebulous region that is transitional between metamorphic and igneous environments. Ion exchange thermometers are typically useful to approximately 800 C in slowly cooled plutonic rocks unless one uses a reintegration technique on unmixed minerals, or unless a metastable mineral assemblage can be observed. It is argued that in most granulites, fossil temperatures are typically obliterated by reequilibration and/or deformation during slow cooling. Granulite metamorphism may be further complicated by the common association with igneous activity. The previously-used geochemical indicators such as high K/Rb ratios and LIL depletion may not be strictly the result of granulite facies metamorphic depletion, but also may result from igneous processes, which depend on bulk and mineral compositions and on the mineralogy of the protolith. Detailed geologic mapping will be the ultimate arbitrator of whether a given geochemical signature is the result of igneous or metamorphic processes.

Bioavailability of pollutants in bacterial communities of Rodrigo de Freitas Lagoon, Rio de Janeiro, Brazil

PubMed Central

da Fonseca, E.M.; Neto, J.A. Baptista; McAlister, J.J.; Smith, B.J.; Crapez, M.A.C.

2014-01-01

Processes involving heavy metals and other contaminants continue to present unsolved environmental questions. To advance the understanding of geochemical processes that involve the bioavailability of contaminants, cores where collected in the Rodrigo de Freitas lagoon, and analyzed for bacterial activity and metal concentrations. Results would suggest an extremely reducing environment where organic substances seem to be the predominant agents responsible for this geochemical process. Analytical data showed sulphate reduction to be the main agent driving this process, since this kind of bacteria was found to be active in all of the samples analyzed. Esterase enzyme production did not signal the influence of heavy metals and hydrocarbon concentrations and heavy metals were found to be unavailable for biota. However, correlation between results for bacterial biomass and the potentially mobile percentage of the total Ni concentrations would suggest a negative impact. PMID:25477931

The Altai Mountains environmental disaster (Eastern Kazakhstan)

NASA Astrophysics Data System (ADS)

Akhmadiyeva, Z. K.

2009-12-01

The space centre "Baikoniyr" (Kazakhstan) has had substantial affects on the environment. During the past several decades as a result of the launching of carrier rockets, such as "Proton" that use as fuel the asymmetrical dimethylhydrazine (ASDH), more well-known as "heptyl", the unique mountain landscapes in Eastern Kazakhstan have been subjected to pollution. In 2004, RSE "Kazakh research Institute of Ecology and Climate" carried out the complex geochemical and radiation researches in East Kazakhstan that is an impact area of second stages of carrier rockets. Such detailed examinations of this area were conducted for the first time because the Eastern Kazakhstan Mountains are difficult for human access. The landscape-geochemical research over the natural landscapes covered the ridge, low, and middle mountains with fir forests. The research results have shown the presence of heptyl in the samples of the soil, plants, and rivers’ bottom sediments. The findings of the influence of space activity on environment of the Kazakhstan part of the Altai Mountains confirm and complement the Russian scientific research results over the territory of the neighbouring Altai Krai. Though the heptyl pollution in the investigated region is of a local nature and highly spatially inhomogeneous, nevertheless, this anthropogenic effect intensifying from year to year increases the load on the natural ecosystems. In particular, it strengthens the desertification process of mountain regions of East Kazakhstan.

Microbiological and Geochemical Characterization of Fluvially Deposited Sulfidic Mine Tailings

PubMed Central

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

1999-01-01

The fluvial deposition of mine tailings generated from historic mining operations near Butte, Montana, has resulted in substantial surface and shallow groundwater contamination along Silver Bow Creek. Biogeochemical processes in the sediment and underlying hyporheic zone were studied in an attempt to characterize interactions consequential to heavy-metal contamination of shallow groundwater. Sediment cores were extracted and fractionated based on sediment stratification. Subsamples of each fraction were assayed for culturable heterotrophic microbiota, specific microbial guilds involved in metal redox transformations, and both aqueous- and solid-phase geochemistry. Populations of cultivable Fe(III)-reducing bacteria were most prominent in the anoxic, circumneutral pH regions associated with a ferricrete layer or in an oxic zone high in organic carbon and soluble iron. Sulfur- and iron-oxidizing bacteria were distributed in discrete zones throughout the tailings and were often recovered from sections at and below the anoxic groundwater interface. Sulfate-reducing bacteria were also widely distributed in the cores and often occurred in zones overlapping iron and sulfur oxidizers. Sulfate-reducing bacteria were consistently recovered from oxic zones that contained high concentrations of metals in the oxidizable fraction. Altogether, these results suggest a highly varied and complex microbial ecology within a very heterogeneous geochemical environment. Such physical and biological heterogeneity has often been overlooked when remediation strategies for metal contaminated environments are formulated. PMID:10103249

Modelling chemical degradation of concrete during leaching with rain and soil water types

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

Jacques, D., E-mail: djacques@sckcen.b; Wang, L.; Martens, E.

2010-08-15

Percolation of external water through concrete results in the degradation of cement and changes the concrete pore water and solid phase composition. The assessment of long-term degradation of concrete is possible by means of model simulation. This paper describes simulations of chemical degradation of cement for different types of rain and soil water at an ambient earth surface temperature (10 {sup o}C). Rain and soil water types were derived using generic equations and measurement of atmospheric boundary conditions representative for North-Belgium. An up-to-date and consistent thermodynamic model is used to calculate the geochemical changes during chemical degradation of the concrete.more » A general pattern of four degradation stages was simulated with the third stage being the geochemically most complex stage involving reactions with calcium-silicate hydrates, AFm and AFt phases. Whereas the sequence of the dissolution reactions was relatively insensitive to the composition of the percolating water, the duration of the different reactions depends strongly on the percolating water composition. Major identified factors influencing the velocity of cement degradation are the effect of dry deposition and biological activity increasing the partial pressure of CO{sub 2(g)} in the soil air phase (and thus increasing the inorganic carbon content in the percolating water). Soil weathering processes have only a minor impact, at least for the relatively inert sandy material considered in this study.« less

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.

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.

The role of rock moisture on regulating hydrologic and solute fluxes in the critical zone

NASA Astrophysics Data System (ADS)

Rempe, D. M.; Druhan, J. L.; Hahm, W. J.; Wang, J.; Murphy, C.; Cargill, S.; Dietrich, W. E.; Tune, A. K.

2017-12-01

In environments where the vadose zone extends below the soil layer into underlying weathered bedrock, the water held in the weathering -generated pores can be an important source of moisture to vegetation. The heterogeneous distribution of pore space in weathered bedrock, furthermore, controls the subsurface water flowpaths that dictate how water is partitioned in the critical zone (CZ) and evolves geochemically. Here, we present the results of direct monitoring of the fluxes of water and solutes through the deep CZ using a novel vadose zone monitoring system (VMS) as well as geophysical logging and sampling in a network of deep wells across a steep hillslope in Northern California. At our study site (Eel River CZO), multi-year monitoring reveals that a significant fraction of incoming rainfall (up to 30%) is seasonally stored in the fractures and matrix of the upper 12 m of weathered bedrock as rock moisture. Intensive geochemical and geophysical observations distributed from the surface to the depth of unweathered bedrock indicate that the seasonal addition and depletion of rock moisture has key implications for hydrologic and geochemical processes. First, rock moisture storage provides an annually consistent water storage reservoir for use by vegetation during the summer, which buffers transpiration fluxes against variability in seasonal precipitation. Second, because the timing and magnitude of groundwater recharge and streamflow are controlled by the annual filling and drainage of the rock moisture, rock moisture regulates the partitioning of hydrologic fluxes. Third, we find that rock moisture dynamics—which influence the myriad geochemical and microbial processes that weather bedrock—strongly correspond with the observed vertical weathering profile. As a result of the coupling between chemical weathering reactions and hydrologic fluxes, the geochemical composition of groundwater and streamflow is influenced by the temporal dynamics of rock moisture. Our findings highlight the strong influence of water transport and storage dynamics in the weathered bedrock beneath the soil layer on catchment-scale hydrologic and geochemical fluxes, and underscore the need for further exploration of the fractured bedrock vadose zones common to many upland landscapes.

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.

From mantle peridotites to hybrid troctolites: Textural, structural and geochemical evolution during multi-stage melt-rock interaction history

NASA Astrophysics Data System (ADS)

Basch, V.; Rampone, E.; Crispini, L.; Ferrando, C.; Ildefonse, B.; Godard, M.

2017-12-01

Recent studies investigate the replacive formation of hybrid troctolites from mantle peridotites after multiple stages of melt-rock reactions. However, none of these studies are conducted in a field-controlled geological setting displaying the clear evolution from peridotite to dunite to troctolite. We investigated the Mt.Maggiore and Erro Tobbio ophiolitic peridotites. They both preserve structural and chemical records of two distinct melt-rock interaction stages, from a reactive melt percolation at spinel facies to plagioclase-bearing melt impregnation at shallower lithospheric depths. We performed EBSD and in situ geochemical analyses to document the textural, structural and geochemical variations of the olivine matrix during melt-rock interactions and the associated evolution from peridotite to dunite to troctolite. The olivine-saturated reactive melt percolation leads to the dissolution of mantle pyroxenes in peridotite, and to the formation of replacive dunite. At shallower level, melt impregnation leads to the crystallization of plagioclase in the dunite, and to the formation of hybrid troctolite. The latter is characterized by textural, structural and geochemical features acquired during dunitization and impregnation processes. We documented a textural evolution of the olivine matrix (decrease in grain area, tortuosity and aspect ratio) during impregnation, with a progressive corrosion of mantle olivines by a reactive melt. As a result, olivine in the hybrid troctolites occurs both as coarse deformed relicts and disrupted undeformed grains. During melt-rock interactions, the variation in olivine Crystallographic Preferred Orientation is related to the local melt/rock ratio involved in the percolation process. At high melt/rock ratio, a change from axial-[100] to axial-[010] is observed, with the disaggregation of the solid matrix. REE-enriched compositions are observed in olivine of dunites and troctolites. A geochemical modeling of melt-rock interactions (Plate Model) fits the observed evolution of modal composition with the measured trace element composition variability. The combined field, structural, and geochemical investigation of the evolution from a mantle protolith to the product of the reactions truly supports the hybrid origin of an olivine-rich troctolite.

Regional Geochemistry - an Introduction

NASA Astrophysics Data System (ADS)

Reimann, Clemens

2017-04-01

Building on the pioneering ideas and work of V. Vernadsky (1883-1945) and V.M. Goldschmidt (1888-1947) the Geological Surveys of Europe have more than 60 years experience with geochemical mapping at a large variety of scales. Surveys using hundreds of samples per km2 for mineral exploration projects, 1 to 4 sites per km2 for mapping the urban environment, 1 site per 2 to 10 km2 in county or country-wide mapping projects to 1 site per 1000 to 5000 km2 for mapping at the continental scale have been successfully completed. Sample materials for these surveys include groundwater, surface water, stream sediments, floodplain sediments, different soil horizons (preferably soil O, A, B and C horizon) and plant materials from moss to trees. Surveys combining several sample materials from local to sub-continental scale in multi-media, multi-element geochemical investigations reflecting the interplay of chemical elements between the different compartments (lithosphere, pedosphere, biosphere and hydrosphere) of the ecosystem have also been carried out. These surveys provide ample empirical evidence that different geochemical processes become visible at different scales. Not all sample materials are suitable for all scales. A variety of scales in combination with a variety of different sample materials are needed to fully understand geochemical processes in the critical zone. Examples are shown that highlight the importance of a strategy to optimize sampling density and design for the chosen scale already during the planning stages of a project. Anthropogenic element sources are visible at a local scale and the major impact of geology, mineralogy and climate (as a driving force for weathering) dominates geochemical maps at the continental scale. Interestingly, mineralisation can generate features which are visible at a variety of scales. Some further issues that need attention when carrying out geochemical surveys at a variety of scales are (a) the need for an excellent and well documented analytical quality control, (b) the choice of the elements to be analysed (as many as possible) (c) the required detection limits (the lowest possible) and (d) the choice of extraction (several if feasible).

High-temperature life without photosynthesis as a model for Mars

NASA Technical Reports Server (NTRS)

Shock, E. L.

1997-01-01

Discoveries in biology and developments in geochemistry over the past two decades have lead to a radical revision of concepts relating to the upper temperature at which life thrives, the genetic relationships among all life on Earth, links between organic and inorganic compounds in geologic processes, and the geochemical supply of metabolic energy. It is now apparent that given a source of geochemical energy, in the form of a mixture of compounds that is far from thermodynamic equilibrium, microorganisms can take advantage of the energy and thrive without the need for photosynthesis as a means of primary productivity. This means that life can exist in the subsurface of a planet such as Mars without necessarily exhibiting a surface expression. Theoretical calculations quantify the geochemically provided metabolic energy available to hyperthermophilic organisms in submarine hydrothermal systems on the Earth, and help to explain the enormous biological productivity of these systems. Efforts to place these models in the context of the early Earth reveal that substantial geochemical energy would have been available and that organic synthesis would have been thermodynamically favored as hydrothermal fluids mix with seawater.

A kinetics database and scripts for PHREEQC

NASA Astrophysics Data System (ADS)

Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

2017-12-01

Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

FATE AND EFFECTS OF PHOSPHORUS ADDITIONS IN SOILS UNDER N2-FIXING RED ALDER

EPA Science Inventory

Soil phosphorus (P) dynamics are controlled by the interaction of geochemical, biochemical and biological processes, and changing species composition or management may alter the relative importance of these processes. We examined the role of these processes in two plantations of...

Constraints on the Locations of Volcanic Arcs (August Love Medal Lecture)

NASA Astrophysics Data System (ADS)

England, Philip

2010-05-01

Partial melting of the mantle in subduction zones is a leading mechanism of chemical differentiation of the Earth. Whereas the broad outlines of Earth's other major system of partial melting - the oceanic ridges - seem clear, the greater dynamic and thermodynamic complexities of subduction zones obscure fundamental aspects of the system, in particular the conditions under which melting initiates and the pathways by which the melt travels towards the Earth's surface. The vast majority of studies of these problems rest on interrogation of petrological and/or geochemical data on rocks erupted at the volcanic arcs, but this approach has resulted in the co-existence of mutually incompatible explanations for the locations of the volcanic arcs. An alternative to the complexity of petrological and geochemical argument is to focus on the geometrical simplicity of volcanic arcs. The observations (i) that the fronts to volcanic arcs fit small circles to within about 10 km and (ii) that the depth to the slab beneath the arc fronts correlates negatively with the descent speed of the slab provide a strong clue to the melting processes occurring at depth. Localized release of fluids by reactions taking place near the top of the slab are incapable of explaining this correlation. However, scaling analysis based on the physics of heat transfer in the wedge shows that such a correlation is predicted if the location of the arcs is controlled by a temperature-critical process taking place in the mantle wedge above the slab. Numerical experiments using realistic physical properties for the mantle in subduction zones support the scaling analysis and, when combined with the observed positions of the arcs, strongly imply that the arcs are localized above the places where the mantle wedge reaches a critical temperature of ~1250o-1300oC. Therefore, despite the importance of hydrous fluids for the overall magmatic budget in subduction zones, it is melting in the region above the anhydrous solidus that determines the location of the arcs. Heat carried by magma rising from this region is sufficient to modify the thermal structure of the wedge and determine the pathway through which both wet and dry melts reach the surface.

Magmatism at different crustal levels in the ancient North Cascades magmatic arc

NASA Astrophysics Data System (ADS)

Shea, E. K.; Bowring, S. A.; Miller, R. B.; Miller, J. S.

2013-12-01

The mechanisms of magma ascent and emplacement inferred from study of intrusive complexes have long been the subject of intense debate. Current models favor incremental construction based on integration of field, geochemical, geochronologic, and modeling studies. Much of this work has been focused on a single crustal level. However, study of magmatism throughout the crust is critical for understanding how magma ascends through and intrudes surrounding crustal material. Here, we present new geochronologic and geochemical work from intrusive complexes emplaced at a range of crustal depths in the Cretaceous North Cascades magmatic arc. These complexes were intruded between 92 and 87 Ma at depths of at ≤5 -10 km, ~20 km, and ~25 km during this time. U-Pb CA-TIMS geochronology in zircon can resolve <0.1% differences in zircon dates and when combined with detailed field relationships allow new insights into how magmatic systems are assembled. We can demonstrate highly variable rates of intrusion at different crustal levels: the shallow-crustal (5-10 km) Black Peak intrusive complex was assembled semi-continuously over ~5 My, while the deep-crustal (25-30 km) Tenpeak intrusive complex was assembled in brief, high-flux events over ~2.6 My. Between these bodies is the Seven-Fingered Jack-Entiat intrusive complex, a highly elongate amalgamation of intrusions recording two episodes of magmatism between~92-88 Ma and ~80-77 Ma. Each of these complexes provides a window into crustal processes that occur at different depths. Our data suggest assembly of the Black Peak intrusive complex occurred via a series of small (0.5-2 km2) magmatic increments from ~92 Ma to ~87 Ma. Field relations and zircon trace element geochemistry indicate each of these increments were emplaced and crystallized as closed systems-we find no evidence for mixing between magmas in the complex. However, zircon inheritance becomes more common in younger intrusions, indicating assimilation of older plutonic material, possibly during magma production or transport. The Seven-Fingered Jack intrusive complex, emplaced around 15-20 km, preserves a much more discontinuous record of intrusion than the Black Peak. Our data indicate major magmatism in the complex occurred between ~92.1-91.1 Ma. Inheritance in the Seven-Fingered Jack is common, particularly along contacts between intrusions. The Tenpeak intrusive complex, assembled between ~92 Ma and 89 Ma, represents one of the deepest exhumed complexes in the North Cascades. Our geochronology indicates that plutons comprising the complex were intruded rapidly (<200 ka) and followed by periods of magmatic quiescence. Contact relations between contemporaneous intrusions are often mixed, further supporting rapid assembly. Zircon systematics in the Tenpeak are relatively simple, showing no evidence for inheritance from the surrounding host rock or from earlier intrusions. However, zircon oxygen isotope data indicates many magmas contain significant crustal input. The Black Peak, Seven-Fingered Jack, and Tenpeak intrusions illustrate the complicated nature of magmatism at different crustal levels in the 92-87 Ma North Cascades magmatic arc. Our data support incremental assembly of these complexes, but show that many features, such as style of emplacement, zircon chemical and temporal systematics, and magma composition vary between these intrusions.

Ca cycling and isotopic fluxes in forested ecosystems in Hawaii

USGS Publications Warehouse

Wiegand, B.A.; Chadwick, O.A.; Vitousek, P.M.; Wooden, J.L.

2005-01-01

Biogeochemical processes fractionate Ca isotopes in plants and soils along a 4 million year developmental sequence in the Hawaiian Islands. We observed that plants preferentially take up 40Ca relative to 44Ca, and that biological fractionation and changes in the relative contributions from volcanic and marine sources produce a significant increase in 44Ca in soil exchangeable pools. Our results imply moderate fluxes enriched in 44Ca from strongly nutrient-depleted old soils, in contrast with high 40Ca fluxes in young and little weathered environments. In addition, biological fractionation controls divergent geochemical pathways of Ca and Sr in the plant-soil system. While Ca depletes progressively with increasing soil age, Sr/Ca ratios increase systematically. Sr isotope ratios provide a valuable tracer for provenance studies of alkaline earth elements in forested ecosystems, but its usefulness is limited when deciphering biogeochemical processes involved in the terrestrial Ca cycle. Ca isotopes in combination with Sr/ Ca ratios reveal more complex processes involved in the biogeochemistry of Ca and Sr. Copyright 2005 by the American Geophysical Union.

Chicxulub Impact Melts: Geochemical Signatures of Target Lithology Mixing and Post-Impact Hydrothermal Fluid Processes

NASA Technical Reports Server (NTRS)

Kring, David A.; Zurcher, Lukas; Horz, Freidrich; Mertzmann, Stanley A.

2004-01-01

Impact melts within complex impact craters are generally homogeneous, unless they differentiated, contain immiscible melt components, or were hydrothermally altered while cooling. The details of these processes, however, and their chemical consequences, are poorly understood. The best opportunity to unravel them may lie with the Chicxulub impact structure, because it is the world s most pristine (albeit buried) large impact crater. The Chicxulub Scientific Drilling Project recovered approx. 100 meters of impactites in a continuous core from the Yaxcopoil-1 (YAX-1) borehole. This dramatically increased the amount of melt available for analyses, which was previously limited to two small samples N17 and N19) recovered from the Yucatan-6 (Y-6) borehole and one sample (N10) recovered from the Chicxulub-1 (C-1) borehole. In this study, we describe the chemical compositions of six melt samples over an approx. 40 m section of the core and compare them to previous melt samples from the Y-6 and C-1 boreholes.

Coupled hydrological and geochemical process evolution at the Landscape Evolution Observatory

NASA Astrophysics Data System (ADS)

Troch, P. A. A.

2015-12-01

Predictions of hydrologic and biogeochemical responses to natural and anthropogenic forcing at the landscape scale are highly uncertain due to the effects of heterogeneity on the scaling of reaction, flow and transport phenomena. The physical, chemical and biological structures and processes controlling reaction, flow and transport in natural landscapes interact at multiple space and time scales and are difficult to quantify. The current paradigm of hydrological and geochemical theory is that process descriptions derived from observations at small scales in controlled systems can be applied to predict system response at much larger scales, as long as some 'equivalent' or 'effective' values of the scale-dependent parameters can be identified. Furthermore, natural systems evolve in time in a way that is hard to observe in short-run laboratory experiments or in natural landscapes with unknown initial conditions and time-variant forcing. The spatial structure of flow pathways along hillslopes determines the rate, extent and distribution of geochemical reactions (and biological colonization) that drive weathering, the transport and precipitation of solutes and sediments, and the further evolution of soil structure. The resulting evolution of structures and processes, in turn, produces spatiotemporal variability of hydrological states and flow pathways. There is thus a need for experimental research to improve our understanding of hydrology-biogeochemistry interactions and feedbacks at appropriate spatial scales larger than laboratory soil column experiments. Such research is complicated in real-world settings because of poorly constrained impacts of initial conditions, climate variability, ecosystems dynamics, and geomorphic evolution. The Landscape Evolution Observatory (LEO) at Biosphere 2 offers a unique research facility that allows real-time observations of incipient hydrologic and biogeochemical response under well-constrained initial conditions and climate forcing. The LEO allows to close the water, carbon and energy budgets at hillslope scales, thereby enabling elucidation of the tight coupling between the time water spends along subsurface flow paths and geochemical weathering reactions, including the feedbacks between flow and pedogenesis.

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.

Geobiochemistry: Placing Biochemistry in Its Geochemical Context

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Patterns and variability in geochemical signatures and microbial activity within and between diverse cold seep habitats along the lower continental slope, Northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Bowles, Marshall; Hunter, Kimberley S.; Samarkin, Vladimir; Joye, Samantha

2016-07-01

We collected 69 sediment cores from distinct ecological and geological settings along the deep slope in the Northern Gulf of Mexico to evaluate whether specific geochemical- or habitat-related factors correlated with rates of microbial processes and geochemical signatures. By collecting replicate cores from distinct habitats across multiple sites, we illustrate and quantify the heterogeneity of cold seep geochemistry and microbial activity. These data also document the factors driving unique aspects of the geochemistry of deep slope gas, oil and brine seeps. Surprisingly little variation was observed between replicate (n=2-5) cores within sites for most analytes (except methane), implying that the common practice of collecting one core for geochemical analysis can capture the signature of a habitat in most cases. Depth-integrated concentrations of methane, dissolved inorganic carbon (DIC), and calcium were the predominant geochemical factors that correlated with a site's ecological or geological settings. Pore fluid methane concentration was related to the phosphate and DIC concentration, as well as to rates of sulfate reduction. While distinctions between seep habitats were identified from geochemical signatures, habitat specific geochemistry varied little across sites. The relative concentration of dissolved inorganic nitrogen versus phosphorus suggests that phosphorus availability limits biomass production at cold seeps. Correlations between calcium, chloride, and phosphate concentrations were indicative of brine-associated phosphate transport, suggesting that in addition to the co-migration of methane, dissolved organic carbon, and ammonium with brine, phosphate delivery is also associated with brine advection.

Hydrothermal modification of host rock geochemistry within Mo-Cu porphyry deposits in the Galway Granite, western Ireland

NASA Astrophysics Data System (ADS)

Tolometti, Gavin; McCarthy, Will

2016-04-01

Hydrothermal alteration of host rock is a process inherent to the formation of porphyry deposits and the required geochemical modification of these rocks is regularly used to indicate proximity to an economic target. The study involves examining the changes in major, minor and trace elements to understand how the quartz vein structures have influenced the chemistry within the Murvey Granite that forms part of the 380-425Ma Galway Granite Complex in western Ireland. Molybdenite mineralisation within the Galway Granite Complex occurred in close association with protracted magmatism at 423Ma, 410Ma, 407Ma, 397Ma and 383Ma and this continues to be of interest to active exploration. The aim of the project is to characterize hydrothermal alteration associated with Mo-Cu mineralisation and identify geochemical indicators that can guide future exploration work. The Murvey Granite intrudes metagabbros and gneiss that form part of the Connemara Metamorphic complex. The intrusion is composed of albite-rich pink granite, garnetiferous granite and phenocrytic orthoclase granite. Minor doleritic dykes post-date the Murvey Granite, found commonly along its margins. Field mapping shows that the granite is truncated to the east by a regional NW-SE fault and that several small subparallel structures host Mo-Cu bearing quartz veins. Petrographic observations show heavily sericitized feldspars and plagioclase and biotite which have undergone kaolinization and chloritisation. Chalcopyrite minerals are fine grained, heavily fractured found crystallized along the margins of the feldspars and 2mm pyrite crystals. Molybdenite are also seen along the margins of the feldspars, crystallized whilst the Murvey Granite cooled. Field and petrographic observations indicate that mineralisation is structurally controlled by NW-SE faults from the selected mineralization zones and conjugate NE-SW cross cutting the Murvey Granite. Both fault orientations exhibit quartz and disseminated molybdenite mineralization. Extensive hydrothermal alteration is observed within 75 meters of veins that exhibit prominent disseminated mineralisation. To investigate associated geochemical alteration 24 samples were selected along two traverses that cross cut two distinct vein structures. XRF analysis results show that calcium decreases from 1.8 - 0.2 wt% and sulphur increases from 0.2 - 0.9 wt% moving away from the mineralized zones which is to be expected due to their mobile nature. Unexpectedly, minor element data shows no fluctuation in Cu concentrations moving away from either vein structures, despite chalcopyrite found greatest near the vein structures. XRF data analysis is underway to compare the non-mobile and mobile elements to investigate the extent of the decreasing and increasing trends moving proximal to the mineralization zones. The relative decrease in calcium may be caused by the exchange of ion end members between feldspars and this will be tested using a WDS electron micro-probe.

Geomechanical/Geochemical Modeling Studies Conducted within theInternational DECOVALEX Project

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

Birkholzer, J.T.; Rutqvist, J.; Sonnenthal, E.L.

2005-10-19

The DECOVALEX project is an international cooperative project initiated by SKI, the Swedish Nuclear Power Inspectorate, with participation of about 10 international organizations. The general goal of this project is to encourage multidisciplinary interactive and cooperative research on modeling coupled thermo-hydro-mechanical-chemical (THMC) processes in geologic formations in support of the performance assessment for underground storage of radioactive waste. One of the research tasks, initiated in 2004 by the U.S. Department of Energy (DOE), addresses the long-term impact of geomechanical and geochemical processes on the flow conditions near waste emplacement tunnels. Within this task, four international research teams conduct predictive analysismore » of the coupled processes in two generic repositories, using multiple approaches and different computer codes. Below, we give an overview of the research task and report its current status.« less

Geomechanical/ Geochemical Modeling Studies onducted Within the International DECOVALEX Project

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

J.T. Birkholzer; J. Rutqvist; E.L. Sonnenthal

2006-02-01

The DECOVALEX project is an international cooperative project initiated by SKI, the Swedish Nuclear Power Inspectorate, with participation of about 10 international organizations. The general goal of this project is to encourage multidisciplinary interactive and cooperative research on modeling coupled thermo-hydro-mechanical-chemical (THMC) processes in geologic formations in support of the performance assessment for underground storage of radioactive waste. One of the research tasks, initiated in 2004 by the U.S. Department of Energy (DOE), addresses the long-term impact of geomechanical and geochemical processes on the flow conditions near waste emplacement tunnels. Within this task, four international research teams conduct predictive analysismore » of the coupled processes in two generic repositories, using multiple approaches and different computer codes. Below, we give an overview of the research task and report its current status.« less

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)

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.

Mapping Microbial Populations Relative to Sites of Ongoing Serpentinization: Results from the Tablelands Ophiolite Complex, Canada

NASA Astrophysics Data System (ADS)

Schrenk, M. O.; Brazelton, W. J.; Woodruff, Q.; Szponar, N.; Morrill, P. L.

2010-12-01

The aqueous alteration of ultramafic rocks (serpentinization) has been suggested to be a favorable process for the habitability of astrobodies in our solar system including subsurface environments of Mars and Europa. Serpentinization produces copious quantities of hydrogen and small organic molecules, and leads to highly reducing, highly alkaline conditions (up to pH 12) and a lack of dissolved inorganic carbon, which both stimulates and challenges microbial activities. Several environments on Earth provide insight into the relationships between serpentinization and microbial life including slow-spreading mid-ocean ridges, subduction zones, and ophiolite materials emplaced along continental margins. The Tablelands, an ophiolite in western Newfoundland, Canada provides an opportunity to carefully document and map the relationships between geochemical energy, microbial growth, and physiology. Alkaline fluids at the Tablelands originate from 500-million year old oceanic crust and accumulate in shallow pools or seep from beneath serpentinized talus. Fluids, rocks, and gases were collected from the Tablelands during a series of field excursions in 2009 and 2010, and geochemical, microscopic, molecular, and cultivation-based approaches were used to study the serpentinite microbial ecosystem. These samples provide an opportunity to generate a comprehensive map of microbial communities and their activities in space and time. Data indicate that a low but detectable stock of microorganisms inhabit high pH pools associated with end-member serpentinite fluids. Enrichment cultures yielded brightly pigmented colonies related to Alphaproteobacteria, presumably carrying out anoxygenic photosynthesis, and Firmicutes, presumably catalyzing the fermentation of organic matter. Culture-independent analyses of SSU rRNA using T-RFLP indicated low diversity communities of Firmicutes and Archaea in standing alkaline pools, communities of Beta- and Gammaproteobacteria at high pH seeps, and assemblages consisting of diverse taxa at neutral pH background sites. Terrestrial serpentinite-hosted microbial ecosystems with their accessibility, their low phylogenetic diversity, and limited range of energetic resources provide an excellent opportunity to explore the interplay between geochemical energy and life and to elucidate the native serpentinite subsurface biosphere. From the perspective of Mars exploration, studies of serpentinite ecosystems provide the opportunity to pinpoint the organisms and physiological adaptations specifically associated with serpentinization and to directly measure their geochemical impacts. Both of these results will inform modeling and life detection efforts of the Martian subsurface environment.

Major hydrogeochemical processes in an acid mine drainage affected estuary.

PubMed

Asta, Maria P; Calleja, Maria Ll; Pérez-López, Rafael; Auqué, Luis F

2015-02-15

This study provides geochemical data with the aim of identifying and quantifying the main processes occurring in an Acid Mine Drainage (AMD) affected estuary. With that purpose, water samples of the Huelva estuary were collected during a tidal half-cycle and ion-ion plots and geochemical modeling were performed to obtain a general conceptual model. Modeling results indicated that the main processes responsible for the hydrochemical evolution of the waters are: (i) the mixing of acid fluvial water with alkaline ocean water; (ii) precipitation of Fe oxyhydroxysulfates (schwertmannite) and hydroxides (ferrihydrite); (iii) precipitation of Al hydroxysulfates (jurbanite) and hydroxides (amorphous Al(OH)3); (iv) dissolution of calcite; and (v) dissolution of gypsum. All these processes, thermodynamically feasible in the light of their calculated saturation states, were quantified by mass-balance calculations and validated by reaction-path calculations. In addition, sorption processes were deduced by the non-conservative behavior of some elements (e.g., Cu and Zn). Copyright © 2014 Elsevier Ltd. All rights reserved.

SilMush: A procedure for modeling of the geochemical evolution of silicic magmas and granitic rocks

NASA Astrophysics Data System (ADS)

Hertogen, Jan; Mareels, Joyce

2016-07-01

A boundary layer crystallization modeling program is presented that specifically addresses the chemical fractionation in silicic magma systems and the solidification of plutonic bodies. The model is a Langmuir (1989) type approach and does not invoke crystal settling in high-viscosity silicic melts. The primary aim is to model a granitic rock as a congealed crystal-liquid mush, and to integrate major element and trace element modeling. The procedure allows for some exploratory investigation of the exsolution of H2O-fluids and of the fluid/melt partitioning of trace elements. The procedure is implemented as a collection of subroutines for the MS Excel spreadsheet environment and is coded in the Visual Basic for Applications (VBA) language. To increase the flexibility of the modeling, the procedure is based on discrete numeric process simulation rather than on solution of continuous differential equations. The program is applied to a study of the geochemical variation within and among three granitic units (Senones, Natzwiller, Kagenfels) from the Variscan Northern Vosges Massif, France. The three units cover the compositional range from monzogranite, over syenogranite to alkali-feldspar granite. An extensive set of new major element and trace element data is presented. Special attention is paid to the essential role of accessory minerals in the fractionation of the Rare Earth Elements. The crystallization model is able to reproduce the essential major and trace element variation trends in the data sets of the three separate granitic plutons. The Kagenfels alkali-feldspar leucogranite couples very limited variation in major element composition to a considerable and complex variation of trace elements. The modeling results can serve as a guide for the reconstruction of the emplacement sequence of petrographically distinct units. Although the modeling procedure essentially deals with geochemical fractionation within a single pluton, the modeling results bring up a number of questions about the petrogenetic relationships among parental magmas of nearly coeval granitic units emplaced in close proximity.

Inverse geochemical modeling of groundwater evolution with emphasis on arsenic in the Mississippi River Valley alluvial aquifer, Arkansas (USA)

USGS Publications Warehouse

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

2008-01-01

Inverse geochemical modeling (PHREEQC) was used to identify the evolution of groundwater with emphasis on arsenic (As) release under reducing conditions in the shallow (25-30 m) Mississippi River Valley Alluvial aquifer, Arkansas, USA. The modeling was based on flow paths defined by high-precision (??2 cm) water level contour map; X-ray diffraction (XRD), scanning electron microscopic (SEM), and chemical analysis of boring-sediments for minerals; and detailed chemical analysis of groundwater along the flow paths. Potential phases were constrained using general trends in chemical analyses data of groundwater and sediments, and saturation indices data (MINTEQA2) of minerals in groundwater. Modeling results show that calcite, halite, fluorite, Fe oxyhydroxide, organic matter, H2S (gas) were dissolving with mole transfers of 1.40E - 03, 2.13E - 04, 4.15E - 06, 1.25E + 01, 3.11, and 9.34, respectively along the dominant flow line. Along the same flow line, FeS, siderite, and vivianite were precipitating with mole transfers of 9.34, 3.11, and 2.64E - 07, respectively. Cation exchange reactions of Ca2+ (4.93E - 04 mol) for Na+ (2.51E - 04 mol) on exchange sites occurred along the dominant flow line. Gypsum dissolution reactions were dominant over calcite dissolution in some of the flow lines due to the common ion effect. The concentration of As in groundwater ranged from <0.5 to 77 ??g/L. Twenty percent total As was complexed with Fe and Mn oxyhydroxides. The redox environment, chemical data of sediments and groundwater, and the results of inverse geochemical modeling indicate that reductive dissolution of Fe oxyhydroxide is the dominant process of As release in the groundwater. The relative rate of reduction of Fe oxyhydroxide over SO42 - with co-precipitation of As into sulfide is the limiting factor controlling dissolved As in groundwater. ?? 2007 Elsevier B.V. All rights reserved.

Integration of remote sensing, geochemical and field data in the Qena-Safaga shear zone: Implications for structural evolution of the Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

El-Din, Gamal Kamal; Abdelkareem, Mohamed

2018-05-01

The Qena-Safaga shear zone (QSSZ) represents a significant structural characteristic in the Eastern Desert of Egypt. Remote Sensing, field and geochemical data were utilized in the present study. The results revealed that the QSSZ dominated by metamorphic complex (MC) that intruded by syn-tectonic granitoids. The low angle thrust fault brings calc-alkaline metavolcanics to overlie MC and its association. Subsequently, the area is dissected by strike-slip faults and the small elongated basins of Hammamat sediments of Precambrian were accumulated. The MC intruded by late-to post-tectonic granites (LPG) and Dokhan Volcanics which comprise felsic varieties forming distinctive columnar joints. Remote sensing analysis and field data revealed that major sub-vertical conspicuous strike-slip faults (SSF) including sinistral NW-SE and dextral ca. E-W shaped the study area. Various shear zones that accompanying the SSF are running NW-SE, NE-SW, E-W, N-S and ENE-WSW. The obtained shear sense presented a multiphase of deformation on each trend. i.e., the predominant NW-SE strike-slip fault trend started with sinistral displacement and is reactivated during later events to be right (dextral) strike slip cutting with dextral displacement the E-W trending faults; while NE-SW movements are cut by both the N-S and NNW - SSE trends. Remote sensing data revealed that the NW-SE direction that dominated the area is associated with hydrothermal alteration processes. This allowed modifying the major and trace elements of the highly deformed rocks that showed depletion in SiO2 and enrichments in Fe2O3, MnO, Al2O3, TiO2, Na2O, K2O, Cu, Zn and Pb contents. The geochemical signatures of major and trace elements revealed two types of granites including I-type calc-alkaline granites (late-to post-tectonic) that formed during an extensional regime. However, syn-tectonic granitoids are related to subduction-related environment.

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.

The U.S. geological survey rass-statpac system for management and statistical reduction of geochemical data

USGS Publications Warehouse

VanTrump, G.; Miesch, A.T.

1977-01-01

RASS is an acronym for Rock Analysis Storage System and STATPAC, for Statistical Package. The RASS and STATPAC computer programs are integrated into the RASS-STATPAC system for the management and statistical reduction of geochemical data. The system, in its present form, has been in use for more than 9 yr by scores of U.S. Geological Survey geologists, geochemists, and other scientists engaged in a broad range of geologic and geochemical investigations. The principal advantage of the system is the flexibility afforded the user both in data searches and retrievals and in the manner of statistical treatment of data. The statistical programs provide for most types of statistical reduction normally used in geochemistry and petrology, but also contain bridges to other program systems for statistical processing and automatic plotting. ?? 1977.

Particle Fluxes and Bulk Geochemical Characterization of the Cabo Frio Upwelling System in Southeastern Brazil: Sediment Trap Experiments between Spring 2010 and Summer 2012.

PubMed

Albuquerque, Ana Luiza S; Belém, André L; Zuluaga, Francisco J B; Cordeiro, Livia G M; Mendoza, Ursula; Knoppers, Bastiaan A; Gurgel, Marcio H C; Meyers, Philip A; Capilla, Ramsés

2014-05-14

Physical and biogeochemical processes in continental shelves act synergistically in both transporting and transforming suspended material, and ocean dynamics control the dispersion of particles by the coastal zone and their subsequent mixing and dilution within the shelf area constrained by oceanic boundary currents, followed by their gradual settling in a complex sedimentary scenario. One of these regions is the Cabo Frio Upwelling System located in a significantly productive area of Southeastern Brazil, under the control of the nutrient-poor western boundary Brazil Current but also with a wind-driven coastal upwelling zone, inducing cold-water intrusions of South Atlantic Central Water on the shelf. To understand these synergic interactions among physical and biogeochemical processes in the Cabo Frio shelf, a series of four experiments with a total of 98 discrete samples using sediment traps was performed from November 2010 to March 2012, located on the 145 m isobath on the edge of the continental shelf. The results showed that lateral transport might be relevant in some cases, especially in deep layers, although no clear seasonal cycle was detected. Two main physical-geochemical coupling scenarios were identified: singular downwelling events that can enhance particles fluxes and are potentially related to the Brazil Current oscillations; and events of significant fluxes related to the intrusion of the 18°C isotherm in the euphotic zone. The particulate matter settling in the Cabo Frio shelf area seems to belong to multiple marine and terrestrial sources, in which both Paraiba do Sul River and Guanabara Bay could be potential land-sources, although the particulate material might subject intense transformation (diagenesis) during its trajectory to the shelf edge.

Altered volcanic ash layers of the Late Cretaceous San Felipe Formation, Sierra Madre Oriental (Northeastern Mexico): Usbnd Pb geochronology, provenance and tectonic setting

NASA Astrophysics Data System (ADS)

Velasco-Tapia, Fernando; Martínez-Paco, Margarita; Iriondo, Alexander; Ocampo-Díaz, Yam Zul Ernesto; Cruz-Gámez, Esther María; Ramos-Ledezma, Andrés; Andaverde, Jorge Alberto; Ostrooumov, Mikhail; Masuch, Dirk

2016-10-01

A detailed petrographic, geochemical, and Usbnd Pb geochronological study of altered volcanic ash layers, collected in eight outcrops of the Late Cretaceous San Felipe Formation (Sierra Madre Oriental, Northeastern Mexico), has been carried out. The main objectives have been: (1) to establish a deposit period, and (2) to propose a reliable provenance-transport-deposit-diagenetic model. These volcano-sedimentary strata represent the altered remains of vitreous-crystalline ash (main grains: quartz + K-feldspar (sanidine) + Na-plagioclase + zircon + biotite; groundmass: glass + calcite + clinochlore + illite) deposited and preserved in a shallow, relatively large in area, open platform environment. Major and trace element geochemistry indicate that parent volcanism was mainly rhyodacitic to rhyolitic in composition. Discrimination diagrams suggest a link to continental arc transitional to extension tectonic setting. Usbnd Pb geochronology in zircon has revealed that the volcanic ash was released from their sources approximately during the range 84.6 ± 0.8 to 73.7 ± 0.3 Ma, being transported to the depocenters. Burial diagenesis process was marked by: (a) a limited recycling, (b) the partial loss of original components (mainly K-feldspar, plagioclase, biotite and glass), and (c) the addition of quartz, calcite, illite and clinochlore. The location of the source area remains uncertain, although the lack of enrichment in Zr/Sc ratio suggests that ashes were subjected to relatively fast and short-distance transport process. El Peñuelo intrusive complex, at 130-170 km west of the depocenters, is the nearest known zone of active magmatism during the Upper Cretaceous. This intermediate to felsic pluton, characterized by a geochemical affinity to post-orogenic tectonic setting, could be linked to the volcanic sources.

DECADE web portal: toward the integration of MaGa, EarthChem and VOTW data systems to further the knowledge on Earth degassing

NASA Astrophysics Data System (ADS)

Cardellini, Carlo; Frigeri, Alessandro; Lehnert, Kerstin; Ash, Jason; McCormick, Brendan; Chiodini, Giovanni; Fischer, Tobias; Cottrell, Elizabeth

2015-04-01

The release of volatiles from the Earth's interior takes place in both volcanic and non-volcanic areas of the planet. The comprehension of such complex process and the improvement of the current estimates of global carbon emissions, will greatly benefit from the integration of geochemical, petrological and volcanological data. At present, major online data repositories relevant to studies of degassing are not linked and interoperable. In the framework of the Deep Earth Carbon Degassing (DECADE) initiative of the Deep Carbon Observatory (DCO), we are developing interoperability between three data systems that will make their data accessible via the DECADE portal: (1) the Smithsonian Institutionian's Global Volcanism Program database (VOTW) of volcanic activity data, (2) EarthChem databases for geochemical and geochronological data of rocks and melt inclusions, and (3) the MaGa database (Mapping Gas emissions) which contains compositional and flux data of gases released at volcanic and non-volcanic degassing sites. The DECADE web portal will create a powerful search engine of these databases from a single entry point and will return comprehensive multi-component datasets. A user will be able, for example, to obtain data relating to compositions of emitted gases, compositions and age of the erupted products and coincident activity, of a specific volcano. This level of capability requires a complete synergy between the databases, including availability of standard-based web services (WMS, WFS) at all data systems. Data and metadata can thus be extracted from each system without interfering with each database's local schema or being replicated to achieve integration at the DECADE web portal. The DECADE portal will enable new synoptic perspectives on the Earth degassing process allowing to explore Earth degassing related datasets over previously unexplored spatial or temporal ranges.

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.

Lead Isotope Compositions of Acid Residues from Olivine-Phyric Shergottite Tissint: Implications for Heterogeneous Shergottite Source Reservoirs

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Yokoyama, T.; Simon, J. I.; Jones, J. H.

2015-01-01

Geochemical studies of shergottites suggest that their parental magmas reflect mixtures between at least two distinct geochemical source reservoirs, producing correlations between radiogenic isotope compositions and trace element abundances. These correlations have been interpreted as indicating the presence of a reduced, incompatible element- depleted reservoir and an oxidized, incompatible- element-enriched reservoir. The former is clearly a depleted mantle source, but there is ongoing debate regarding the origin of the enriched reservoir. Two contrasting models have been proposed regarding the location and mixing process of the two geochemical source reservoirs: (1) assimilation of oxidized crust by mantle derived, reduced magmas, or (2) mixing of two distinct mantle reservoirs during melting. The former requires the ancient Martian crust to be the enriched source (crustal assimilation), whereas the latter requires isolation of a long-lived enriched mantle domain that probably originated from residual melts formed during solidification of a magma ocean (heterogeneous mantle model). This study conducts Pb isotope and trace element concentration analyses of sequential acid-leaching fractions (leachates and the final residues) from the geochemically depleted olivine-phyric shergottite Tissint. The results suggest that the Tissint magma is not isotopically uniform and sampled at least two geochemical source reservoirs, implying that either crustal assimilation or magma mixing would have played a role in the Tissint petrogenesis.

A batch sliding window method for local singularity mapping and its application for geochemical anomaly identification

NASA Astrophysics Data System (ADS)

Xiao, Fan; Chen, Zhijun; Chen, Jianguo; Zhou, Yongzhang

2016-05-01

In this study, a novel batch sliding window (BSW) based singularity mapping approach was proposed. Compared to the traditional sliding window (SW) technique with disadvantages of the empirical predetermination of a fixed maximum window size and outliers sensitivity of least-squares (LS) linear regression method, the BSW based singularity mapping approach can automatically determine the optimal size of the largest window for each estimated position, and utilizes robust linear regression (RLR) which is insensitive to outlier values. In the case study, tin geochemical data in Gejiu, Yunnan, have been processed by BSW based singularity mapping approach. The results show that the BSW approach can improve the accuracy of the calculation of singularity exponent values due to the determination of the optimal maximum window size. The utilization of RLR method in the BSW approach can smoothen the distribution of singularity index values with few or even without much high fluctuate values looking like noise points that usually make a singularity map much roughly and discontinuously. Furthermore, the student's t-statistic diagram indicates a strong spatial correlation between high geochemical anomaly and known tin polymetallic deposits. The target areas within high tin geochemical anomaly could probably have much higher potential for the exploration of new tin polymetallic deposits than other areas, particularly for the areas that show strong tin geochemical anomalies whereas no tin polymetallic deposits have been found in them.

Is there a geochemical link between volcanic and plutonic rocks in the Organ Mountains caldera?

NASA Astrophysics Data System (ADS)

Memeti, V.; Davidson, J.

2013-12-01

Results from separate volcanic and plutonic studies have led to inconsistent conclusions regarding the origins and thus links between volcanic and plutonic systems in continental arcs and the magmatic processes and time scales responsible for their compositional variations. Some have suggested that there is a geochemical and geochronological disconnect between volcanic and plutonic rocks and hence have questioned the existence of magma mush columns beneath active volcanoes. Investigating contemporary volcanic and plutonic rocks that are spatially connected is thus critical in exploring these issues. The ca. 36 Ma Organ Mountains caldera in New Mexico, USA, represents such a system exposing contemporaneous volcanic and plutonic rocks juxtaposed at the surface due to tilting during extensional tectonics along the Rio Grande Rift. Detailed geologic and structural mapping [1] and 40Ar/39Ar ages of both volcanics and plutons [2] demonstrate the spatial and temporal connection of both rock types with active magmatism over >2.5 myr. Three caldera-forming ignimbrites erupted within 600 kyr [2] from this system with a total erupted volume of 500-1,000 km3 as well as less voluminous pre- and post-caldera trachyte and andesite lavas. The ignimbrite sequence ranges from a crystal-poor, high-SiO2 rhyolite at the base to a more crystal-rich, low-SiO2 rhyolite at the top. Compositional zoning with quartz-monzonite at the base grading to syenite and alaskite at the top is also found in the Organ Needle pluton, the main intrusion, which is interpreted to be the source for the ignimbrites [1]. Other contemporaneous and slightly younger plutons have dioritic to leucogranitic compositions. We examined both volcanic and plutonic rocks with petrography and their textural variations with color cathodoluminescence, and used whole rock element and Sr, Nd and Pb isotope geochemistry to constrain magma compositions and origins. Electron microprobe analyses on feldspars have been completed to determine within-crystal geochemical variations. Our current conclusions and working hypotheses are: 1) All igneous rocks from the Organ Mountains are crustal-mantle melt mixtures indicating two component mixing; 2) the caldera-forming ignimbrites are likely derived from a fractionating Organ Needle pluton; 3) pre- and post-caldera lavas are isotopically similar to the post-caldera Sugarloaf Peak quartz-monzonite; 4) K-feldspar cumulate textures in the structurally top 0.5-1 km of the Organ Needle pluton indicate that interstitial melt was lost from the magma mush, which likely fed the ignimbrite eruptions. 5) Plutonic feldspar textures are complex compared to rather simple zoned volcanic feldspars including K-feldspar rimmed plagioclase, plagioclase rimmed K-feldspar and unrimmed feldspars occurring over a range of grain sizes at thin section scale. Some volcanic feldspar phenocrysts have any previous zonation erased due to late stage albitization. Although the single mineral studies are still work in progress and details need resolving, our data so far suggest a geochemical link between volcanic and plutonic rocks of the Organ Mountains caldera, albeit a complex one; and greater complexity in plutonic versus volcanic minerals. [1] Seager (1980), NM Bureau of Mines and Min. Res. Memoir 36, 97 p. [2] Zimmerer & McIntosh (2013) Journal of Geophysical Research, v. 93, p. 4421-4433

Geochemistry of the Birch Creek Drainage Basin, Idaho

USGS Publications Warehouse

Swanson, Shawn A.; Rosentreter, Jeffrey J.; Bartholomay, Roy C.; Knobel, LeRoy L.

2003-01-01

The U.S. Survey and Idaho State University, in cooperation with the U.S. Department of Energy, are conducting studies to describe the chemical character of ground water that moves as underflow from drainage basins into the eastern Snake River Plain aquifer (ESRPA) system at and near the Idaho National Engineering and Environmental Laboratory (INEEL) and the effects of these recharge waters on the geochemistry of the ESRPA system. Each of these recharge waters has a hydrochemical character related to geochemical processes, especially water-rock interactions, that occur during migration to the ESRPA. Results of these studies will benefit ongoing and planned geochemical modeling of the ESRPA at the INEEL by providing model input on the hydrochemical character of water from each drainage basin. During 2000, water samples were collected from five wells and one surface-water site in the Birch Creek drainage basin and analyzed for selected inorganic constituents, nutrients, dissolved organic carbon, tritium, measurements of gross alpha and beta radioactivity, and stable isotopes. Four duplicate samples also were collected for quality assurance. Results, which include analyses of samples previously collected from four other sites, in the basin, show that most water from the Birch Creek drainage basin has a calcium-magnesium bicarbonate character. The Birch Creek Valley can be divided roughly into three hydrologic areas. In the northern part, ground water is forced to the surface by a basalt barrier and the sampling sites were either surface water or shallow wells. Water chemistry in this area was characterized by simple evaporation models, simple calcite-carbon dioxide models, or complex models involving carbonate and silicate minerals. The central part of the valley is filled by sedimentary material and the sampling sites were wells that are deeper than those in the northern part. Water chemistry in this area was characterized by simple calcite-dolomite-carbon dioxide models. In the southern part, ground water enters the ESRPA. In this area, the sampling sites were wells with depths and water levels much deeper than those in the northern and central parts of the valley. The calcium and carbon water chemistry in this area was characterized by a simple calcite-carbon dioxide model, but complex calcite-silicate models more accurately accounted for mass transfer in these areas. Throughout the geochemical system, calcite precipitated if it was an active phase in the models. Carbon dioxide either precipitated (outgassed) or dissolved depending on the partial pressure of carbon dioxide in water from the modeled sites. Dolomite was an active phase only in models from the central part of the system. Generally the entire geochemical system could be modeled with either evaporative models, carbonate models, or carbonate-silicate models. In both of the latter types of models, a significant amount of calcite precipitated relative to the mass transfer to and from the other active phases. The amount of calcite precipitated in the more complex models was consistent with the amount of calcite precipitated in the simpler models. This consistency suggests that, although the simpler models can predict calcium and carbon concentrations in Birch Creek Valley ground and surface water, silicate-mineral-based models are required to account for the other constituents. The amount of mass transfer to and from the silicate mineral phases was generally small compared with that in the carbonate phases. It appears that the water chemistry of well USGS 126B represents the chemistry of water recharging the ESRPA by means of underflow from the Birch Creek Valley.

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

An illustration of the complexity of continent formation

NASA Technical Reports Server (NTRS)

Burke, Kevin

1988-01-01

It was pointed out that a consensus may be emerging in crustal growth models, considering the clustering of most growth curves and their uncertainties. Curves most distant from this clustering represent models involving extensive recycling of continental material back into the mantle, but the author wondered if geochemical signatures for this would be recognizable considering the lack of evidence from seismic tomography for discrete mantle reservoirs, and the likelihood of core-mantle interaction based on recent high pressure experiments. Unreactivated Archean rocks represent only 2 percent of present continental area, and the author was uncomfortable about basing inferences on what the early Earth was like on such a small amount of information. He feels that the hypothesis of continental assembly that needs testing is that of banging together of island arcs, such as in Indonesia today. As an example of how complex this process can be, the author described the geology of the Caribbean arc system, which shows evidence for reversals of subduction polarity, numerous collisional events, and substantial strike-slip movements. It seemed unlikely to the author that Archean examples would have been less complicated.

Geochemical Specific Characters of the Oil and the Origin of the Oil and Gas Fields

NASA Astrophysics Data System (ADS)

Gottikh, Rimma; Pisotskiy, Bogdan; Plotnikova, Irina

2010-05-01

It is generally assumed that the fluid regime of the basement of ancient platforms is not associated with that of the sedimentary cover. This assumption is mainly due to the substantial time gap between the formation of the crystalline and sedimentary rocks as well as the evolutionary differences between the thermal regime of the interior and the redox potentials of fluid systems. The presence of loosely aggregated zones filled with salt-water solutions, oil or gas in the upper basement is explained by downward fluid flows from sedimentary rocks through tectonic faults into the disintegrated crystalline rocks. The formation of such zones is believed to be due to the crustal stratification due to Earth's pulsation, periodic variations of its rotational rate, hydrogenic deconsolidation, burial of the post-Early Proterozoic disintegration zones, etc. This pattern suggests that the matter and energy exchange between the Earth's spheres in the late stages of the platform development could only take place with the help of magmatic melts and the associated fluids during the tectonomagmatic cycles of the Earth's crust transformation. Gas and liquid hydrocarbon components mainly occur in crystalline basement rocks of ancient platforms penetrated to a depth of more than 3000 m due to deep degassing processes. The traces of the upward migration of fluids are sealed in the geological sequence, including the sedimentary cover, within secondary inclusions of rocks and minerals. The fluids are complex, reduced, multicomponent systems that transport lithophilous, chalcophilous and siderophilous elements. The presence of microelements in the bituminous phase of inclusions indicates that metals mainly occur in the complexes containing organic ligands. During the evolution of the fluid systems under new pressure and temperature conditions, low-solubility substances were separated out of the fluid to form hard bitumen, and the lighter components migrated into the overlying fractured and porous rocks. The high metal content of carbonaceous substances and their compositional variations governed by homogenisation temperatures of the inclusions suggest that they are not the products of the decomposition of oil fields. The constant presence of uranium in the fluid and its differentiation products allows the tracing of the systems' migration ways from the crystalline basement to oil-saturated reservoir zones of the sedimentary cover The known geochemical properties of bitumen and oil - high platinum content, specific distributions of rare earth elements, that are not characteristic of the upper crust formations, as well as 143Nd/144Nd and 87Sr/86Sr isotopic compounds, which are out of balance with the organic matter of sedimentary rocks - suggest that hydrocarbons are accumulated in the presence of cooling high-alkalinity mafite-ultramafite intrusions. This logically corresponds to the distribution of seismic anomalies and magnetic and gravity fields in the consolidated crust below the various petroleum fields (for example, South Tatarstan and Nepsky arches of the Romashkino and Verkhne-Chonskoye oil fields). The acquired geochemical and thermodynamic characteristics of the reduced fluids and their differentiation products from the crystalline basement and the sedimentary cover of the southern Siberian and eastern East European platforms indicate that these were formed outside of the sedimentary cover and that the migration was directed upwards. The analysis of the magmatic evolution on platforms reveals its alkaline trend due to the impeded degassing of magmatic sources at depth and the inflow of new doses of alkaline fluids or melts into them. Further evolution of the zones of partial melting of the substratum led, in the authors' view, to the generation of oil-forming fluids and their transportation into the Earth's upper crust. Their interaction with the surrounding rocks in turn led to the formation of oil accumulations. Thus, oil is the product of the interaction of deep, reduced fluids. Oil, graphite of the Archaean crystalline complexes and hard bitumens are interrelated elements of the evolution of deep, high-enthalpy systems. These large-scale reduced palaeofluid phenomena are obviously related to geodynamic and tectonomagmatic processes. The source of these fluid systems, their impact on the geological environment and its consequences can be determined through additional integrated geochemical studies using the isotopes of heavy elements and through the correlation of the observed potential fields with the structure of the consolidated crust and the sedimentary cover for the identification of geodynamic processes in geophysically inhomogeneous zones of the geological medium.

Enrichment of trace elements in garnet amphibolites from a paleo-subduction zone: Catalina Schist, southern California

USGS Publications Warehouse

Sorensen, Sorena S.; Grossman, J.N.

1989-01-01

The abundance, P-T stability, solubility, and element-partitioning behavior of minerals such as rutile, garnet, sphene, apatite, zircon, zoisite, and allanite are critical variables in models for mass transfer from the slab to the mantle wedge in deep regions of subduction zones. The influence of these minerals on the composition of subduction-related magmas has been inferred (and disputed) from inverse modelling of the geochemistry of island-arc basalt, or by experiment. Although direct samples of the dehydration + partial-melting region of a mature subduction zone have not been reported from subduction complexes, garnet amphibolites from melanges of circumpacific and Caribbean blueschist terranes reflect high T (>600??C) conditions in shallower regions. Such rocks record geochemical processes that affected deep-seated, high-T portions of paleo-subduction zones. In the Catalina Schist, a subduction-zone metamorphic terrane of southern California, metasomatized and migmatitic garnet amphibolites occur as blocks in a matrix of meta-ultramafic rocks. This mafic and ultramafic complex may represent either slab-derived material accreted to the mantle wedge of a nascent subduction zone or a portion of a shear zone closely related to the slab-mantle wedge contact, or both. The trace-element geochemistry of the complex and the distribution of trace elements among the minerals of garnet amphibolites were studied by INAA, XRF, electron microprobe, and SEM. In order of increasing alteration from a probable metabasalt protolith, three common types of garnet amphibolite blocks in the Catalina Schist are: (1) non-migmatitic, clinopyroxene-bearing blocks, which are compositionally similar to MORB that has lost an albite component; (2) garnet-amphibolite blocks, which have rinds that reflect local interaction between metabasite, metaperidotite, and fluid; and (3) migmatites that are extremely enriched in Th, HFSE, LREE, and other trace elements. These trace-element enrichments are mineralogically controlled by rutile, garnet, sphene, apatite, zircon, zoisite, and allanite. Alkali and alkaline earth elements are much less enriched in the solid assemblage, and thus appear to be decoupled from the other elements in the inferred metasomatic process(es). The compositions of migmatitic garnet amphibolite blocks seem to complement that of "average" island-arc tholeiite. Trace-element metasomatism reflects fluid-solid, rather than melt-solid, interaction. The metasomatic effects indicate that H2O-rich fluid, perhaps with a significant component of Na-Al silicate and alkalis, carried Th, U, Sr, REE, and HFSE. Fractionations of LREE in migmatites resemble those of migmatitic metasedimentary rocks underlying the mafic and ultramafic complex. "Exotic" LREE deposited in allanite in migmatites could have been derived from fluids in equilibrium with subducted sediment. If the paleo-subduction zone represented by the mafic and ultramafic complex of the Catalina Schist had continued its thermal and fluid evolution, a selvage of similarly enriched rocks might have been generated along the slab-mantle wedge contact between ~30 and 85 km depth. Rocks affected by "subduction-zone metasomatism," although rarely recognized at the surface, could be volumetrically significant products of the initiation of subduction and may prove to be geochemical probes of convergent margins that approach the significance of xenoliths in the study of other magmatic environments. ?? 1989.

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.

Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments

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

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.

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

Effects of common groundwater ions on chromate removal by magnetite: Importance of chromate adsorption

DOE PAGES

Meena, Amanda H.; Arai, Yuji

2016-04-29

Reductive precipitation of hexavalent chromium (Cr(VI)) with magnetite is a well-known Cr(VI) remediation method to improve water quality. The rapid (< a few hr) reduction of soluble Cr(VI) to insoluble Cr(III) species by Fe(II) in magnetite has been the primary focus of the Cr(VI) removal process in the past. However, the contribution of simultaneous Cr(VI) adsorption processes in aged magnetite has been largely ignored, leaving uncertainties in evaluating the application of in situ Cr remediation technologies for aqueous systems. In this study, effects of common groundwater ions (i.e., nitrate and sulfate) on Cr(VI) sorption to magnetite were investigated using batchmore » geochemical experiments in conjunction with X-ray absorption spectroscopy. As a result, in both nitrate and sulfate electrolytes, batch sorption experiments showed that Cr(VI) sorption decreases with increasing pH from 4 to 8. In this pH range, Cr(VI) sorption decreased with increasing ionic strength of sulfate from 0.01 to 0.1 M whereas nitrate concentrations did not alter the Cr(VI) sorption behavior. This indicates the background electrolyte specific Cr(VI) sorption process in magnetite. Under the same ionic strength, Cr(VI) removal in sulfate containing solutions was greater than that in nitrate solutions. This is because the oxidation of Fe(II) by nitrate is more thermodynamically favorable than by sulfate, leaving less reduction capacity of magnetite to reduce Cr(VI) in the nitrate media. X-ray absorption spectroscopy analysis supports the macroscopic evidence that more than 75 % of total Cr on the magnetite surfaces was adsorbed Cr(VI) species after 48 h. In conclusion, this experimental geochemical study showed that the adsorption process of Cr(VI) anions was as important as the reductive precipitation of Cr(III) in describing the removal of Cr(VI) by magnetite, and these interfacial adsorption processes could be impacted by common groundwater ions like sulfate and nitrate. The results of this study highlight new information about the large quantity of adsorbed Cr(VI) surface complexes at the magnetite-water interface. It has implications for predicting the long-term stability of Cr at the magnetite-water interface.« less

Discriminating sediment archives and sedimentary processes in the arid endorheic Ejina Basin, NW China using a robust geochemical approach

NASA Astrophysics Data System (ADS)

Yu, Kaifeng; Hartmann, Kai; Nottebaum, Veit; Stauch, Georg; Lu, Huayu; Zeeden, Christian; Yi, Shuangwen; Wünnemann, Bernd; Lehmkuhl, Frank

2016-04-01

Geochemical characteristics have been intensively used to assign sediment properties to paleoclimate and provenance. Nonetheless, in particular concerning the arid context, bulk geochemistry of different sediment archives and corresponding process interpretations are hitherto elusive. The Ejina Basin, with its suite of different sediment archives, is known as one of the main sources for the loess accumulation on the Chinese Loess Plateau. In order to understand mechanisms along this supra-regional sediment cascade, it is crucial to decipher the archive characteristics and formation processes. To address these issues, five profiles in different geomorphological contexts were selected. Analyses of X-ray fluorescence and diffraction, grain size, optically stimulated luminescence and radiocarbon dating were performed. Robust factor analysis was applied to reduce the attribute space to the process space of sedimentation history. Five sediment archives from three lithologic units exhibit geochemical characteristics as follows: (i) aeolian sands have high contents of Zr and Hf, whereas only Hf can be regarded as a valuable indicator to discriminate the coarse sand proportion; (ii) sandy loess has high Ca and Sr contents which both exhibit broad correlations with the medium to coarse silt proportions; (iii) lacustrine clays have high contents of felsic, ferromagnesian and mica source elements e.g., K, Fe, Ti, V, and Ni; (iv) fluvial sands have high contents of Mg, Cl and Na which may be enriched in evaporite minerals; (v) alluvial gravels have high contents of Cr which may originate from nearby Cr-rich bedrock. Temporal variations can be illustrated by four robust factors: weathering intensity, silicate-bearing mineral abundance, saline/alkaline magnitude and quasi-constant aeolian input. In summary, the bulk-composition of the late Quaternary sediments in this arid context is governed by the nature of the source terrain, weak chemical weathering, authigenic minerals, aeolian sand input, whereas pedogenesis and diagenesis exert only limited influences. Hence, this study demonstrates a practical geochemical strategy supplemented by grain size and mineralogical data, to discriminate sediment archives and thereafter enhance our ability to offer more intriguing information about the sedimentary processes in the arid central Asia.

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.

iTOUGH2: A multiphysics simulation-optimization framework for analyzing subsurface systems

NASA Astrophysics Data System (ADS)

Finsterle, S.; Commer, M.; Edmiston, J. K.; Jung, Y.; Kowalsky, M. B.; Pau, G. S. H.; Wainwright, H. M.; Zhang, Y.

2017-11-01

iTOUGH2 is a simulation-optimization framework for the TOUGH suite of nonisothermal multiphase flow models and related simulators of geophysical, geochemical, and geomechanical processes. After appropriate parameterization of subsurface structures and their properties, iTOUGH2 runs simulations for multiple parameter sets and analyzes the resulting output for parameter estimation through automatic model calibration, local and global sensitivity analyses, data-worth analyses, and uncertainty propagation analyses. Development of iTOUGH2 is driven by scientific challenges and user needs, with new capabilities continually added to both the forward simulator and the optimization framework. This review article provides a summary description of methods and features implemented in iTOUGH2, and discusses the usefulness and limitations of an integrated simulation-optimization workflow in support of the characterization and analysis of complex multiphysics subsurface systems.

Exploration computer applications to primary dispersion halos: Kougarok tin prospect, Seward Peninsula, Alaska, USA

USGS Publications Warehouse

Reid, Jeffrey C.

1989-01-01

Computer processing and high resolution graphics display of geochemical data were used to quickly, accurately, and efficiently obtain important decision-making information for tin (cassiterite) exploration, Seward Peninsula, Alaska (USA). Primary geochemical dispersion patterns were determined for tin-bearing intrusive granite phases of Late Cretaceous age with exploration bedrock lithogeochemistry at the Kougarok tin prospect. Expensive diamond drilling footage was required to reach exploration objectives. Recognition of element distribution and dispersion patterns was useful in subsurface interpretation and correlation, and to aid location of other holes.

A Centimeter-Scale Investigation of Geochemical Hotspots in a Soil Lysimeter

NASA Astrophysics Data System (ADS)

Umanzor, M.; Wang, Y.; Dontsova, K.; Chorover, J.; Troch, P. A. A.

2016-12-01

Studying the co-evolution of hydrological and biogeochemical processes in the subsurface of natural landscapes can enhance the understanding of coupled Earth-system processes. Such knowledge is imperative for improving predictions of hydro-biogeochemical cycles, especially under climate change scenarios. Hotspots may form in porous media that is undergoing biogeochemical weathering at locations where reactants accumulate to threshold values along hydrologic flow paths. This is expected to occur in weatherable silicate media, like granular basalt. To examine such processes during incipient soil formation, we constructed a sloping weighing lysimeter 2-m in length, 0.5-m in width and 1-m in depth. Mini-LEO was filled with crushed granular basalt rock with a known initial chemical composition. After 18 months of irrigation and intensive hydrological study, the model "landscape" was divided into a 3D matrix of 324 voxels and excavated. Collected samples were subjected to detailed hydro-bio-geochemical analysis to assess the formation of geochemical heterogeneity. A five-step sequential extraction was employed to characterize incongruent mineral weathering, and its relation to the spatial distribution of microbial composition (in a related study). The changes in Fe and Mn concentration and speciation along the lysimeter length and depth (as measured by each step of the sequential extraction) was quantified to characterize spatial distribution of weathering processes. Results are being used to assist in understanding not only spatial and temporal distribution of basalt weathering on the slope, but also, connections between hydrological and biogeochemical cycles that lead to formation of hotspots.

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.

Evidence and age estimation of mass wasting at the distal lobe of the Congo deep-sea fan

NASA Astrophysics Data System (ADS)

Croguennec, Claire; Ruffine, Livio; Dennielou, Bernard; Baudin, François; Caprais, Jean-Claude; Guyader, Vivien; Bayon, Germain; Brandily, Christophe; Le Bruchec, Julie; Bollinger, Claire; Germain, Yoan; Droz, Laurence; Babonneau, Nathalie; Rabouille, Christophe

2017-08-01

On continental margins, sulfate reduction occurs within the sedimentary column. It is coupled with the degradation of organic matter and the anaerobic oxidation of methane. These processes may be significantly disturbed by sedimentary events, leading to transient state profiles for the involved chemical species. Yet, little is known about the impact of turbidity currents and mass wasting on the migration of chemical species and the redox reactions in which they are involved. Due to its connection to the River, the Congo deep-sea fan continuously receives huge amount of organic matter-rich sediments primarily transported by turbidity currents, which impact on the development of the associated ecosystems (Rabouille et al., 2017). Thus, it is well suited to better understand causal relationships between sedimentary events and fluid flow path, with consequences on the zonation of early diagenesis sequences. Here, we combined sedimentological observations with geochemical analyses of pore-water and sediment samples to explore how sedimentary instabilities affected the migration of methane and the distribution of organic matter within the sedimentary column. The results unveiled mass wasting processes affecting recent turbiditic and pelagic deposits, and are interpreted as being slides/ slumps and debrites. Two slides were responsible for the exhumation of an organic matter-rich sedimentary block of more than 5 m thick and the movement of a methane-rich sedimentary block, while turbidity currents enable the intercalation of sandy intervals within a pelagic clay layer. The youngest slide promoted the development of two Sulfate Methane Transition Zones (SMTZ), and may have possibly triggered a lateral migration of methane. Numerical simulation of the sulfate profile indicates that the youngest sedimentary event has occurred around a century ago. Our study emphasizes that turbidity currents and sedimentary instabilities can significantly affect the transport paths and the distribution of both methane and organic matter in the terminal lobe complex, with consequences on geochemical zonation of the sequential early diagenetic processes within the sedimentary column.

Effects of Land-Use Change and Managed Aquifer Recharge on Geochemical Reactions with Implications for Groundwater Quantity and Quality in Atoll Island Aquifers, Roi-Namur, Republic of the Marshall Islands

NASA Astrophysics Data System (ADS)

Hejazian, M.; Swarzenski, P. W.; Gurdak, J. J.; Odigie, K. O.; Storlazzi, C. D.

2015-12-01

This study compares the hydrogeochemistry of two contrasting atoll groundwater systems in Roi-Namur, Republic of the Marshall Islands. Roi-Namur houses a U.S. Department of Defense military installation and presents an ideal study location where a human impacted aquifer is co-located next to a natural aquifer as part of two artificially conjoined atoll islands. The hydrogeology and geochemistry of carbonate atoll aquifers has been well studied, particularly because of its small, well-defined hydrologic system that allows for relatively precise modeling. However, it is unknown how changes in land-use/land cover and managed aquifer recharge (MAR) alters natural geochemical processes in atoll aquifers. A better understanding of this has implications on groundwater quantity and quality, carbonate dissolution, and best aquifer management practices in the context of rising sea level and saltwater intrusion. Roi has been heavily modified to house military and civilian operations; here, lack of vegetation and managed recharge has increased the volume of potable groundwater and affected the geochemical processes in the freshwater lens and saltwater transition zone. Namur is heavily vegetated and the hydrogeology is indicative of a natural atoll island. A suite of monitoring wells were sampled across both island settings for major ions, nutrients, trace elements, DOC/DIC, δ13C and δ18O/2H isotopes. By modeling geochemical reactions using a conservative mixing approach, we measure deviations from expected reactions and compare the two contrasting settings using derived geochemical profiles through a wide salinity spectrum. Results indicate that groundwater on Namur is more heavily depleted in δ13C and has greater dissolved inorganic carbon, suggesting higher microbial oxidation and greater dissolution within the carbonate aquifer. This suggests MAR and reduction of vegetation makes the groundwater supply on atoll islands more resilient to sea level rise.

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.

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.

Use of dissolved H2 concentrations to determine distribution of microbially catalyzed redox reactions in anoxic groundwater

USGS Publications Warehouse

Lovley, D.R.; Chapelle, F.H.; Woodward, J.C.

1994-01-01

The potential for using concentrations of dissolved H2 to determine the distribution of redox processes in anoxic groundwaters was evaluated. In pristine aquifers in which standard geochemical measurements indicated that Fe-(III) reduction, sulfate reduction, or methanogenesis was the terminal electron accepting process (TEAP), the H2 concentrations were similar to the H2 concentrations that have previously been reported for aquatic sediments with the same TEAPs. In two aquifers contaminated with petroleum products, it was impossible with standard geochemical analyses to determine which TEAPs predominated in specific locations. However, the TEAPs predicted from measurements of dissolved H2 were the same as those determined directly through measurements of microbial processes in incubated aquifer material. These results suggest that H2 concentrations may be a useful tool for analyzing the redox chemistry of nonequilibrium groundwaters.

Geochemical distinctions between igneous carbonate, calcite cements, and limestone xenoliths (Polino carbonatite, Italy): spatially resolved LAICPMS analyses

NASA Astrophysics Data System (ADS)

Rosatelli, G.; Wall, F.; Stoppa, F.; Brilli, M.

2010-11-01

Petrography-controlled laser ablation inductively coupled plasma mass spectrometry (LAICPMS) analyses of carbonate in fresh shallow level sub-volcanic Polino monticellite calcio-carbonatite tuffisite have been performed to assess the geochemical differences between fresh igneous, epigenetic carbonates and sedimentary accidental fragments. Igneous calcite has consistently high LREE/HREE ratios (La/Yb N , 15-130) due to high LREE (ΣLREE, 425-1,269 ppm). Secondary calcite cements are characterized by progressively lower and more variable trace element contents, with lower LREE/HREE ratios. A distinguishing geochemical feature is progressively increasing negative Ce anomalies observed through coarse secondary calcite that can be related to the surface environment processes. The limestone accidental fragments in the tuffisite have trace element contents almost two orders of magnitude lower than igneous carbonate and low LREE (ΣLREE < 9.5 ppm) with low LREE/HREE fractionation (La/Yb N ratios < 18). The stable isotope composition of different carbonate types is consistent with their formation in different environments. The tuffisitization processes during diatreme formation under high CO2-OH fugacity conditions may account for the differences noted in the igneous carbonates.

Fluid geochemistry of Fault zone hydrothermal system in the Yidun-Litang area, eastern Tibetan Plateau geothermal belt

NASA Astrophysics Data System (ADS)

Shi, Z.; Wang, G.

2017-12-01

Understanding the geochemical and geothermal characteristic of the hydrothermal systems provide useful information in appropriate evaluating the geothermal potential in this area. In this paper, we investigate the chemical and isotopic composition of thermal water in an underexploited geothermal belt, Yidun-Litang area, in eastern Tibetan Plateau geothermal belt. 24 hot springs from the Yidun and Litang area were collected and analyzed. The chemical facies of the hot springs are mainly Na-HCO3 type water. Water-rock interaction, cation exchange are the dominant hydrogeochemical processes in the hydrothermal evolution. All the hot springs show long-time water-rock interaction and significant 18O shift occurred in the Yindun area. Tritium data indicate the long-time water-rock interaction time in the hydrothermal system. According to the isotope and geochemical data, the hydrothermal systems in Yidun and Litang area may share a common deep parent geothermal liquid but receive different sources of meteoric precipitation and undergone different geochemical processes. The Yidun area have relative high reservoir equilibrium temperature (up to 230 °C) while the reservoir temperature at Litang area is relative low (up to 128 °C).

Multivariate analysis of the geochemistry and mineralogy of soils along two continental-scale transects in North America

USGS Publications Warehouse

Drew, L.J.; Grunsky, E.C.; Sutphin, D.M.; Woodruff, L.G.

2010-01-01

Soils collected in 2004 along two North American continental-scale transects were subjected to geochemical and mineralogical analyses. In previous interpretations of these analyses, data were expressed in weight percent and parts per million, and thus were subject to the effect of the constant-sum phenomenon. In a new approach to the data, this effect was removed by using centered log-ratio transformations to 'open' the mineralogical and geochemical arrays. Multivariate analyses, including principal component and linear discriminant analyses, of the centered log-ratio data reveal the effects of soil-forming processes, including soil parent material, weathering, and soil age, at the continental-scale of the data arrays that were not readily apparent in the more conventionally presented data. Linear discriminant analysis of the data arrays indicates that the majority of the soil samples collected along the transects can be more successfully classified with Level 1 ecological regional-scale classification by the soil geochemistry than soil mineralogy. A primary objective of this study is to discover and describe, in a parsimonious way, geochemical processes that are both independent and inter-dependent and manifested through compositional data including estimates of the elements and corresponding mineralogy. ?? 2010.

Lithologic Controls on Critical Zone Processes in a Variably Metamorphosed Shale-Hosted Watershed

NASA Astrophysics Data System (ADS)

Eldam Pommer, R.; Navarre-Sitchler, A.

2017-12-01

Local and regional shifts in thermal maturity within sedimentary shale systems impart significant variation in chemical and physical rock properties, such as pore-network morphology, mineralogy, organic carbon content, and solute release potential. Even slight variations in these properties on a watershed scale can strongly impact surface and shallow subsurface processes that drive soil formation, landscape evolution, and bioavailability of nutrients. Our ability to map and quantify the effects of this heterogeneity on critical zone processes is hindered by the complex coupling of the multi-scale nature of rock properties, geochemical signatures, and hydrological processes. This study addresses each of these complexities by synthesizing chemical and physical characteristics of variably metamorphosed shales in order to link rock heterogeneity with modern earth surface and shallow subsurface processes. More than 80 samples of variably metamorphosed Mancos Shale were collected in the East River Valley, Colorado, a headwater catchment of the Upper Colorado River Basin. Chemical and physical analyses of the samples show that metamorphism decreases overall rock porosity, pore anisotropy, and surface area, and introduces unique chemical signatures. All of these changes result in lower overall solute release from the Mancos Shale in laboratory dissolution experiments and a change in rock-derived solute chemistry with decreasing organic carbon and cation exchange capacity (Ca, Na, Mg, and K). The increase in rock competency and decrease in reactivity of the more thermally mature shales appear to subsequently control river morphology, with lower channel sinuosity associated with areas of the catchment underlain by metamorphosed Mancos Shale. This work illustrates the formative role of the geologic template on critical zone processes and landscape development within and across watersheds.

30 CFR 551.11 - Submission, inspection, and selection of geological data and information collected under a permit...

Code of Federal Regulations, 2014 CFR

2014-07-01

..., or interpretation of any geological data and information. Initial analysis and processing are the stages of analysis or processing where the data and information first become available for in-house... geochemical) data and information describing each operation of analysis, processing, and interpretation; (2...

30 CFR 551.11 - Submission, inspection, and selection of geological data and information collected under a permit...

Code of Federal Regulations, 2012 CFR

2012-07-01

..., or interpretation of any geological data and information. Initial analysis and processing are the stages of analysis or processing where the data and information first become available for in-house... geochemical) data and information describing each operation of analysis, processing, and interpretation; (2...

30 CFR 551.11 - Submission, inspection, and selection of geological data and information collected under a permit...

Code of Federal Regulations, 2013 CFR

2013-07-01

..., or interpretation of any geological data and information. Initial analysis and processing are the stages of analysis or processing where the data and information first become available for in-house... geochemical) data and information describing each operation of analysis, processing, and interpretation; (2...

Geology is the Key to Explain Igneous Activity in the Mediterranean Area

NASA Astrophysics Data System (ADS)

Lustrino, M.

2014-12-01

Igneous activity in tectonically complex areas can be interpreted in many different ways, producing completely different petrogenetic models. Processes such as oceanic and continental subduction, lithospheric delamination, changes in subduction polarity, slab break-off and mantle plumes have all been advocated as causes for changes in plate boundaries and magma production, including rate and temporal distribution, in the circum-Mediterranean area. This region thus provides a natural laboratory to investigate a range of geodynamic and magmatic processes. Although many petrologic and tectonic models have been proposed, a number of highly controversial questions still remain. No consensus has yet been reached about the capacity of plate-tectonic processes to explain the origin and style of the magmatism. Similarly, there is still not consensus on the ability of geochemical and petrological arguments to reveal the geodynamic evolution of the area. The wide range of chemical and mineralogical magma compositions produced within and around the Mediterranean, from carbonatites to strongly silica-undersaturated silico-carbonatites and melilitites to strongly silica-oversaturated rhyolites, complicate models and usually require a large number of unconstrained assumptions. Can the calcalkaline-sodic alkaline transition be related to any common petrogenetic point? Is igneous activity plate-tectonic- (top-down) or deep-mantle-controlled (bottom-up)? Do the rare carbonatites and carbonate-rich igneous rocks derive from the deep mantle or a normal, CO2-bearing upper mantle? Do ultrapotassic compositions require continental subduction? Understanding chemically complex magmas emplaced in tectonically complex areas require open minds, and avoiding dogma and assumptions. Studying the geology and shallow dynamics, not speculating about the deep lower mantle, is the key to understanding the igneous activity.

Reactive transport modeling in fractured rock: A state-of-the-science review

NASA Astrophysics Data System (ADS)

MacQuarrie, Kerry T. B.; Mayer, K. Ulrich

2005-10-01

The field of reactive transport modeling has expanded significantly in the past two decades and has assisted in resolving many issues in Earth Sciences. Numerical models allow for detailed examination of coupled transport and reactions, or more general investigation of controlling processes over geologic time scales. Reactive transport models serve to provide guidance in field data collection and, in particular, enable researchers to link modeling and hydrogeochemical studies. In this state-of-science review, the key objectives were to examine the applicability of reactive transport codes for exploring issues of redox stability to depths of several hundreds of meters in sparsely fractured crystalline rock, with a focus on the Canadian Shield setting. A conceptual model of oxygen ingress and redox buffering, within a Shield environment at time and space scales relevant to nuclear waste repository performance, is developed through a review of previous research. This conceptual model describes geochemical and biological processes and mechanisms materially important to understanding redox buffering capacity and radionuclide mobility in the far-field. Consistent with this model, reactive transport codes should ideally be capable of simulating the effects of changing recharge water compositions as a result of long-term climate change, and fracture-matrix interactions that may govern water-rock interaction. Other aspects influencing the suitability of reactive transport codes include the treatment of various reaction and transport time scales, the ability to apply equilibrium or kinetic formulations simultaneously, the need to capture feedback between water-rock interactions and porosity-permeability changes, and the representation of fractured crystalline rock environments as discrete fracture or dual continuum media. A review of modern multicomponent reactive transport codes indicates a relatively high-level of maturity. Within the Yucca Mountain nuclear waste disposal program, reactive transport codes of varying complexity have been applied to investigate the migration of radionuclides and the geochemical evolution of host rock around the planned disposal facility. Through appropriate near- and far-field application of dual continuum codes, this example demonstrates how reactive transport models have been applied to assist in constraining historic water infiltration rates, interpreting the sealing of flow paths due to mineral precipitation, and investigating post-closure geochemical monitoring strategies. Natural analogue modeling studies, although few in number, are also of key importance as they allow the comparison of model results with hydrogeochemical and paleohydrogeological data over geologic time scales.

Biogeochemical controls on mercury methylation in the Allequash Creek wetland.

PubMed

Creswell, Joel E; Shafer, Martin M; Babiarz, Christopher L; Tan, Sue-Zanne; Musinsky, Abbey L; Schott, Trevor H; Roden, Eric E; Armstrong, David E

2017-06-01

We measured mercury methylation potentials and a suite of related biogeochemical parameters in sediment cores and porewater from two geochemically distinct sites in the Allequash Creek wetland, northern Wisconsin, USA. We found a high degree of spatial variability in the methylation rate potentials but no significant differences between the two sites. We identified the primary geochemical factors controlling net methylmercury production at this site to be acid-volatile sulfide, dissolved organic carbon, total dissolved iron, and porewater iron(II). Season and demethylation rates also appear to regulate net methylmercury production. Our equilibrium speciation modeling demonstrated that sulfide likely regulated methylation rates by controlling the speciation of inorganic mercury and therefore its bioavailability to methylating bacteria. We found that no individual geochemical parameter could explain a significant amount of the observed variability in mercury methylation rates, but we found significant multivariate relationships, supporting the widely held understanding that net methylmercury production is balance of several simultaneously occurring processes.

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.

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.

Geochemical processes controlling water salinization in an irrigated basin in Spain: identification of natural and anthropogenic influence.

PubMed

Merchán, D; Auqué, L F; Acero, P; Gimeno, M J; Causapé, J

2015-01-01

Salinization of water bodies represents a significant risk in water systems. The salinization of waters in a small irrigated hydrological basin is studied herein through an integrated hydrogeochemical study including multivariate statistical analyses and geochemical modeling. The study zone has two well differentiated geologic materials: (i) Quaternary sediments of low salinity and high permeability and (ii) Tertiary sediments of high salinity and very low permeability. In this work, soil samples were collected and leaching experiments conducted on them in the laboratory. In addition, water samples were collected from precipitation, irrigation, groundwater, spring and surface waters. The waters show an increase in salinity from precipitation and irrigation water to ground- and, finally, surface water. The enrichment in salinity is related to the dissolution of soluble mineral present mainly in the Tertiary materials. Cation exchange, precipitation of calcite and, probably, incongruent dissolution of dolomite, have been inferred from the hydrochemical data set. Multivariate statistical analysis provided information about the structure of the data, differentiating the group of surface waters from the groundwaters and the salinization from the nitrate pollution processes. The available information was included in geochemical models in which hypothesis of consistency and thermodynamic feasibility were checked. The assessment of the collected information pointed to a natural control on salinization processes in the Lerma Basin with minimal influence of anthropogenic factors. Copyright © 2014 Elsevier B.V. All rights reserved.

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

Manual hierarchical clustering of regional geochemical data using a Bayesian finite mixture model

USGS Publications Warehouse

Ellefsen, Karl J.; Smith, David

2016-01-01

Interpretation of regional scale, multivariate geochemical data is aided by a statistical technique called “clustering.” We investigate a particular clustering procedure by applying it to geochemical data collected in the State of Colorado, United States of America. The clustering procedure partitions the field samples for the entire survey area into two clusters. The field samples in each cluster are partitioned again to create two subclusters, and so on. This manual procedure generates a hierarchy of clusters, and the different levels of the hierarchy show geochemical and geological processes occurring at different spatial scales. Although there are many different clustering methods, we use Bayesian finite mixture modeling with two probability distributions, which yields two clusters. The model parameters are estimated with Hamiltonian Monte Carlo sampling of the posterior probability density function, which usually has multiple modes. Each mode has its own set of model parameters; each set is checked to ensure that it is consistent both with the data and with independent geologic knowledge. The set of model parameters that is most consistent with the independent geologic knowledge is selected for detailed interpretation and partitioning of the field samples.

Biogenic Manganese-Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi-Copper Oxidase, MnxEFG.

PubMed

Tao, Lizhi; Simonov, Alexandr N; Romano, Christine A; Butterfield, Cristina N; Fekete, Monika; Tebo, Bradley M; Bond, Alan M; Spiccia, Leone; Martin, Lisandra L; Casey, William H

2017-01-26

In a natural geochemical cycle, manganese-oxide minerals (MnO x ) are principally formed through a microbial process, where a putative multicopper oxidase MnxG plays an essential role. Recent success in isolating the approximately 230 kDa, enzymatically active MnxEFG protein complex, has advanced our understanding of biogenic MnO x mineralization. Here, the kinetics of MnO x formation catalyzed by MnxEFG are examined using a quartz crystal microbalance (QCM), and the first electrochemical characterization of the MnxEFG complex is reported using Fourier transformed alternating current voltammetry. The voltammetric studies undertaken using near-neutral solutions (pH 7.8) establish the apparent reversible potentials for the Type 2 Cu sites in MnxEFG immobilized on a carboxy-terminated monolayer to be in the range 0.36-0.40 V versus a normal hydrogen electrode. Oxidative priming of the MnxEFG protein complex substantially enhances the enzymatic activity, as found by in situ electrochemical QCM analysis. The biogeochemical significance of this enzyme is clear, although the role of an oxidative priming of catalytic activity might be either an evolutionary advantage or an ancient relic of primordial existence. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the ecocline at shallow coasts of the Baltic Sea

NASA Astrophysics Data System (ADS)

Lenartz, B.; Jurasinski, G.; Voss, M.; Janssen, M.

2017-12-01

We report on results of the Research Training Group Baltic TRANSCOAST. The overall aim of Baltic TRANSCOAST is to enhance our knowledge of the shallow coast ecocline. How is the marine coastal zone influenced by terrestrial processes? How is the terrestrial coastal zone influenced by marine processes? These questions lead our research within the three research fields covering hydro-dynamic, (bio)geochemical and biological processes. Regarding the hydro-dynamics we assess how the peatland's water balance, the current dynamics and hydraulic properties of the marine sediments and the subsoil influence sea water intrusions into the peatland and/or submarine groundwater discharge into the Baltic Sea. With respect to (bio)geochemical processes we address how (bio)geochemical transformation processes both in the marine and the terrestrial part of the coast are influenced by water and matter inputs from the respective other coastal domain. Finally, reagrding the biological processes, we are interested in revealing how the primary production and the composition of the micro- and macro-phytobenthos in the shallow Baltic Sea influence matter transformation processes. The integrative approach of Baltic TRANSCOAST allows us to get to grips with questions that are otherwise hard to tackle. For instance, we address how the pore water constituents drive microbial processes and the deposition of nutrients and and how they are impacted by sediment resuspension and translocation. We investigate how the hydrology of the peat layers interferes with the generation of trace gases and investigate the role of the nearby Warnow river and its plume and how this changes under the impact of wind direction and wind strength. For the latter we rely on data and models. Further, as a common basis for all topics addressed in Baltic TRANSCOAST we established the geology of the study area and learned that regional variability may play a major role in shaping the processes under study.

Amanzi: An Open-Source Multi-process Simulator for Environmental Applications

NASA Astrophysics Data System (ADS)

Moulton, J. D.; Molins, S.; Johnson, J. N.; Coon, E.; Lipnikov, K.; Day, M.; Barker, E.

2014-12-01

The Advanced Simulation Capabililty for Environmental Management (ASCEM) program is developing an approach and open-source tool suite for standardized risk and performance assessments at legacy nuclear waste sites. These assessments begin with simplified models, and add geometric and geologic complexity as understanding is gained. The Platform toolsets (Akuna) generates these conceptual models and Amanzi provides the computational engine to perform the simulations, returning the results for analysis and visualization. In this presentation we highlight key elements of the design, algorithms and implementations used in Amanzi. In particular, the hierarchical and modular design is aligned with the coupled processes being sumulated, and naturally supports a wide range of model complexity. This design leverages a dynamic data manager and the synergy of two graphs (one from the high-level perspective of the models the other from the dependencies of the variables in the model) to enable this flexible model configuration at run time. Moreover, to model sites with complex hydrostratigraphy, as well as engineered systems, we are developing a dual unstructured/structured capability. Recently, these capabilities have been collected in a framework named Arcos, and efforts have begun to improve interoperability between the unstructured and structured AMR approaches in Amanzi. To leverage a range of biogeochemistry capability from the community (e.g., CrunchFlow, PFLOTRAN, etc.), a biogeochemistry interface library was developed called Alquimia. To ensure that Amanzi is truly an open-source community code we require a completely open-source tool chain for our development. We will comment on elements of this tool chain, including the testing and documentation development tools such as docutils, and Sphinx. Finally, we will show simulation results from our phased demonstrations, including the geochemically complex Savannah River F-Area seepage basins.

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.

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

Assessing the Biological Contribution to Mineralized Cap Formation in the Little Hot Creek Hot Spring System

NASA Astrophysics Data System (ADS)

Floyd, J. G.; Beeler, S. R.; Mors, R. A.; Kraus, E. A.; 2016, G.; Piazza, O.; Frantz, C. M.; Loyd, S. J.; Berelson, W.; Stevenson, B. S.; Marenco, P. J.; Spear, J. R.; Corsetti, F. A.

2016-12-01

Hot spring environments exhibit unique redox/physical gradients that may create favorable conditions for the presence of life and commonly contain mineral precipitates that could provide a geologic archive of such ecosystems on Earth and potentially other planets. However, it is critical to discern biologic from abiotic formation mechanisms if hot spring-associated minerals are to be used as biosignatures. The study of modern hot spring environments where mineral formation can be directly observed is necessary to better interpret the biogenicity of ancient/extraterrestrial examples. Little Hot Creek (LHC), a hot spring located in the Long Valley Caldera, California, contains mineral precipitates composed of a carbonate base covered with amorphous silica and minor carbonate in close association with microbial mats/biofilms. Geological, geochemical, and microbiological techniques were integrated to investigate the role of biology in mineral formation at LHC. Geochemical measurements indicate that the waters of the spring are near equilibrium with respect to carbonate and undersaturated with respect to silica, implying additional processes are necessary to initiate cap formation. Geochemical modeling, integrating elemental and isotopic data from hot spring water and mineral precipitates, indicate that the abiotic processes of degassing and evaporation drive mineral formation at LHC, without microbial involvement. However, petrographic analysis of LHC caps revealed microbial microfabrics within silica mineral phases, despite the fact that microbial metabolism was not required for mineral precipitation. Our results show that microorganisms in hot spring environments can shape mineral precipitates even in the absence of a control on authigenesis, highlighting the need for structural as well as geochemical investigation in similar systems.

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.

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.

Geochemical evolution processes and water-quality observations based on results of the National Water-Quality Assessment Program in the San Antonio segment of the Edwards aquifer, 1996-2006

USGS Publications Warehouse

Musgrove, MaryLynn; Fahlquist, Lynne; Houston, Natalie A.; Lindgren, Richard J.; Ging, Patricia B.

2010-01-01

As part of the National Water-Quality Assessment Program, the U.S. Geological Survey collected and analyzed groundwater samples during 1996-2006 from the San Antonio segment of the Edwards aquifer of central Texas, a productive karst aquifer developed in Cretaceous-age carbonate rocks. These National Water-Quality Assessment Program studies provide an extensive dataset of groundwater geochemistry and water quality, consisting of 249 groundwater samples collected from 136 sites (wells and springs), including (1) wells completed in the shallow, unconfined, and urbanized part of the aquifer in the vicinity of San Antonio (shallow/urban unconfined category), (2) wells completed in the unconfined (outcrop area) part of the regional aquifer (unconfined category), and (3) wells completed in and springs discharging from the confined part of the regional aquifer (confined category). This report evaluates these data to assess geochemical evolution processes, including local- and regional-scale processes controlling groundwater geochemistry, and to make water-quality observations pertaining to sources and distribution of natural constituents and anthropogenic contaminants, the relation between geochemistry and hydrologic conditions, and groundwater age tracers and travel time. Implications for monitoring water-quality trends in karst are also discussed. Geochemical and isotopic data are useful tracers of recharge, groundwater flow, fluid mixing, and water-rock interaction processes that affect water quality. Sources of dissolved constituents to Edwards aquifer groundwater include dissolution of and geochemical interaction with overlying soils and calcite and dolomite minerals that compose the aquifer. Geochemical tracers such as magnesium to calcium and strontium to calcium ratios and strontium isotope compositions are used to evaluate and constrain progressive fluid-evolution processes. Molar ratios of magnesium to calcium and strontium to calcium in groundwater typically increase along flow paths; results for samples of Edwards aquifer groundwater show an increase from shallow/urban unconfined, to unconfined, to confined groundwater categories. These differences are consistent with longer residence times and greater extents of water-rock interaction controlling fluid compositions as groundwater evolves from shallow unconfined groundwater to deeper confined groundwater. Results for stable isotopes of hydrogen and oxygen indicate specific geochemical processes affect some groundwater samples, including mixing with downdip saline water, mixing with recent recharge associated with tropical cyclonic storms, or mixing with recharge water than has undergone evaporation. The composition of surface water recharging the aquifer, as well as mixing with downdip water from the Trinity aquifer or the saline zone, also might affect water quality. A time-series record (1938-2006) of discharge at Comal Springs, one of the major aquifer discharge points, indicates an upward trend for nitrate and chloride concentrations, which likely reflects anthropogenic activities. A small number of organic contaminants were routinely or frequently detected in Edwards aquifer groundwater samples. These were the pesticides atrazine, its degradate deethylatrazine, and simazine; the drinking-water disinfection byproduct chloroform; and the solvent tetrachloroethene. Detection of these contaminants was most frequent in samples of the shallow/urban unconfined groundwater category and least frequent in samples of the unconfined groundwater category. Results indicate that the shallow/urban unconfined part of the aquifer is most affected by anthropogenic contaminants and the unconfined part of the aquifer is the least affected. The high frequency of detection for these anthropogenic contaminants aquifer-wide and in samples of deep, confined groundwater indicates that the entire aquifer is susceptible to water-quality changes as a result of anthropogenic activities. L

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.

Cerium and Neodymium Isotope Fractionation in Geochemical Samples

NASA Astrophysics Data System (ADS)

Ohno, T.; Ishibashi, T.

2014-12-01

The study of naturally occurring isotopic variations of rare earth elements (REE) has a potentially significant influence in geochemical research fields with other traditional studies of REE. One of the key features of REE are their chemical similarities and gradual changes of ionic radius, which may make the isotopic variation of REE a potential tool to understand the mechanisms of isotopic fractionation in nature. Among the REE, geochemical and physicochemical features of Ce could be anomalous, because Ce could be present as the tetravalent (+IV) state as well as the common trivalent (+III) state of other REE. Since the oxidation state of Ce can change by reflecting the redox conditions of the environment, the measured differences in the degree of isotopic fractionation between Ce and other REE can provide unique information about the redox conditions. In this study, we developed a new analytical method to determine the mass-dependent isotopic fractionations of Ce and Nd in geochemical samples. The reproducibility of the isotopic ratio measurements on 142Ce/140Ce, 146Nd/144Nd and 148Nd/144Nd were 0.08‰ (2SD, n=25), 0.06‰ (2SD, n=39) and 0.12‰ (2SD, n=39), respectively. The present technique was applied to determine the variations of the Ce and Nd isotopic ratios for five geochemical reference materials (igneous rocks, JB-1a and JA-2; sedimentary rocks, JMn-1, JCh-1 and JDo-1). The resulting ratios for two igneous rocks (JB-1a and JA-2) and two sedimentary rocks (JMn-1 and JCh-1) did not vary significantly among the samples, whereas the Ce and Nd isotope ratios for the carbonate samples (JDo-1) were significantly higher than those for igneous and sedimentary rock samples. The 1:1 simple correlation between δ142Ce and δ146Nd indicates that there were no significant difference in the degree of isotopic fractionation between the Ce and Nd. This suggests that the isotopic fractionation for Ce found in the JDo-1 could be induced by physicochemical processes without changing the oxidation status of Ce, since the redox-reaction can produce larger isotopic fractionation than the reactions without changing the oxidation state. The variations in the Ce and Nd isotope ratios for geochemical samples could provide new information concerning the physico-chemical processes of the sample formation.

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

USGS Publications Warehouse

Apps, J.A.; Zheng, Lingyun; Spycher, N.; Birkholzer, J.T.; Kharaka, Y.; Thordsen, J.; Kakouros, E.; Trautz, R.

2011-01-01

Food-grade CO2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1-2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca+2-driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO2 dissolution appears to compete for sorption with anionic species such as HAsO4-2, potentially increasing dissolved As levels in groundwater. ?? 2011 Published by Elsevier Ltd.

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.

NATURAL ARSENIC CONTAMINATION OF HOLOCENE ALLUVIAL AQUIFERS BY LINKED TECTONIC, WEATHERING, AND MICROBIAL PROCESSES

EPA Science Inventory

Linked tectonic, geochemical, and biologic processes lead to natural arsenic contamination of groundwater in Holocene alluvial aquifers, which are the main threat to human health around the world. These groundwaters are commonly found a long distance from their ultimate source of...

Contrasted crustal sources as defined by whole-rock and Sr-Nd-Pb isotope geochemistry of neoproterozoic early post-collisional granitic magmatism within the Southern Brazilian Shear Belt, Camboriú, Brazil

NASA Astrophysics Data System (ADS)

Florisbal, Luana Moreira; de Assis Janasi, Valdecir; de Fátima Bitencourt, Maria; Stoll Nardi, Lauro Valentim; Heaman, Larry M.

2012-11-01

The early phase of post-collisional granitic magmatism in the Camboriú region, south Brazil, is represented by the porphyritic biotite ± hornblende Rio Pequeno Granite (RPG; 630-620 Ma) and the younger (˜610 Ma), equigranular, biotite ± muscovite Serra dos Macacos Granite (SMG). The two granite types share some geochemical characteristics, but the more felsic SMG constitutes a distinctive group not related to RPG by simple fractionation processes, as indicated by its lower FeOt, TiO2, K2O/Na2O and higher Zr Al2O3, Na2O, Ba and Sr when compared to RPG of similar SiO2 range. Sr-Nd-Pb isotopes require different sources. The SMG derives from old crustal sources, possibly related to the Paleoproterozoic protoliths of the Camboriú Complex, as indicated by strongly negative ɛNdt (-23 to -24) and unradiogenic Pb (e.g., 206Pb/204Pb = 16.0-16.3; 207Pb/204Pb = 15.3-15.4) and confirmed by previous LA-MC-ICPMS data showing dominant zircon inheritance of Archean to Paleoproterozoic age. In contrast, the RPG shows less negative ɛNdt (-12 to -15) and a distinctive zircon inheritance pattern with no traces of post-1.6 Ga sources. This is indicative of younger sources whose significance in the regional context is still unclear; some contribution of mantle-derived magmas is indicated by coeval mafic dykes and may account for some of the geochemical and isotopic characteristics of the least differentiated varieties of the RPG. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas despite their emplacement within a low-strain zone. It may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of Paleoproterozoic orthogneisses from the Camboriú Complex.

Microbial Metabolic Roles in Bedrock Degradation and the Genesis of Biomineral and Biopattern Biosignatures in Caves and Mines

NASA Astrophysics Data System (ADS)

Boston, P. J.

2016-12-01

In subsurface environments like natural or anthropogenic caves (aka mines), microorganisms facilitate considerable bedrock degradation under a variety of circumstances. Mobilization of materials from these processes frequently produces distinctive biominerals, identifiable biotextures, and unique biopatterns. Microbial activities can even determine the form of speleothems (secondary mineral cave decorations), thus providing highly conspicuous macroscopic biosignatures. It is critical to understand microbial-mineral interactions, recognizing that while the lithology controls important aspects of the environment, in turn, the geochemistry is greatly affected by the biology. Microbial communities can contribute to the actual formation of cavities (speleogenesis), and subsequent enlargement of caves and vugs and the mineral deposits that enrich many subterranean spaces. A major challenge is to quantify such influences. Genetic analysis is revealing a vast but highly partitioned biodiversity in the overall rock fracture habitat of Earth's crust especially in caves and mines where the three phases of matter (solid rock, fluids, and gases) typically interact producing high niche richness. Lessons learned from the microbial/geochemical systems that we have studied include: 1) significant similarities in metabolic functions between different geochemical systems, 2) ubiquity of metal oxidation for energy, 3) ubiquity of biofilms, some highly mineralized, 4) highly interdependent, multi-species communities that can only transform materials in consortia, 5) complex ecological succession including characteristic pioneer species, 6) often very slow growth rates in culture, 7) prevalence of very small cell sizes, ( 100 - 500 nm diam.), 8) mineral reprecipitation of mobilized materials, often dependent on the presence of live microbial communities to produce initial amorphous compounds followed by gradual crystallization, and 9) resultant in situ self-fossilization. Microbial metabolism occurs against a complex backdrop of hydrology, geochemistry, and geological structures of subsurface environments. These are not static but change in response to both short term and much longer geological time scales thus presenting significant challenges in interpretation.

Zinc isotope investigation of surface and pore waters in a mountain watershed impacted by acid rock drainage.

PubMed

Aranda, Suzan; Borrok, David M; Wanty, Richard B; Balistrieri, Laurie S

2012-03-15

The pollution of natural waters with metals derived from the oxidation of sulfide minerals like pyrite is a global environmental problem. However, the metal loading pathways and transport mechanisms associated with acid rock drainage reactions are often difficult to characterize using bulk chemical data alone. In this study, we evaluated the use of zinc (Zn) isotopes to complement traditional geochemical tools in the investigation of contaminated waters at the former Waldorf mining site in the Rocky Mountains, Colorado, U.S.A. Geochemical signatures and statistical analysis helped in identifying two primary metal loading pathways at the Waldorf site. The first was characterized by a circumneutral pH, high alkalinity, and high Zn/Cd ratios. The second was characterized by acidic pHs and low Zn/Cd ratios. Zinc isotope signatures in surface water samples collected across the site were remarkably similar (the δ(66)Zn, relative to JMC 3-0749-L, for most samples ranged from 0.20 to 0.30‰±0.09‰ 2σ). This probably suggests that the ultimate source of Zn is consistent across the Waldorf site, regardless of the metal loading pathway. The δ(66)Zn of pore water samples collected within a nearby metal-impacted wetland area, however, were more variable, ranging from 0.20 to 0.80‰±0.09‰ 2σ. Here the Zn isotopes seemed to reflect differences in groundwater flow pathways. However, a host of secondary processes might also have impacted Zn isotopes, including adsorption of Zn onto soil components, complexation of Zn with dissolved organic matter, uptake of Zn into plants, and the precipitation of Zn during the formation of reduced sulfur species. Zinc isotope analysis proved useful in this study; however, the utility of this isotopic tool would improve considerably with the addition of a comprehensive experimental foundation for interpreting the complex isotopic relationships found in soil pore waters. Copyright © 2012 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

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.

Stable isotope monitoring of ionic trapping of CO2 in deep brines

NASA Astrophysics Data System (ADS)

Myrttinen, A.; Barth, J. A. C.; Becker, V.; Blum, P.; Grathwohl, P.

2009-04-01

CO2 injection into a depleted gas-reservoir is used as a combined method for Enhanced Gas Recovery (EGR) and CO2 storage. In order to safeguard this process, monitoring the degree of dissolution and potential further precipitation and mineral interactions are a necessity. Here a method is introduced, in which stable isotope and geochemical data can be used as a monitoring technique to quantify ionic trapping of injected CO2. Isotope and geochemical data of dissolved inorganic carbon (DIC) can be used to distinguish between already present and to be injected inorganic carbon. Injected CO2, for instance, is formed during combustion of former plant material and is expected to have a different isotope ratio (δ13C value) than the baseline data of the aquifer. This is because combusted CO2 originates from organic material, such as coal and oil with a predominant C3 plant signature. Mixing the injected CO2 with groundwater is therefore expected to change the isotope, as well as the geochemical composition of the groundwater. Mass balance calculations with stable isotope ratios can serve to quantify ionic trapping of CO2 as DIC in groundwater. However, depending on the composition of the aquifer, weathering of carbonate or silicates may occur. Enhanced weathering processes due to CO2 injection can also further influence the isotopic composition. Such interactions between dissolved CO2 and minerals depend on the temperature and pressure regimes applied. Field data, as well as laboratory experiments are planned to quantify isotope ratios of dissolved inorganic carbon as well as oxygen isotope ratios of the water. These are indicative of geochemical processes before, during and after EGR. The isotope method should therefore provide a new tool to quantify the efficiency of ionic trapping under various temperatures and pressures. Keywords: Enhanced Gas Recovery, monitoring of CO2 dissolution, stable isotopes

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.

Geochemical results from stream-water and stream-sediment samples collected in Colorado and New Mexico

USGS Publications Warehouse

Hageman, Philip L.; Todd, Andrew S.; Smith, Kathleen S.; DeWitt, Ed; Zeigler, Mathew P.

2013-01-01

Scientists from the U.S. Geological Survey are studying the relationship between watershed lithology and stream-water chemistry. As part of this effort, 60 stream-water samples and 43 corresponding stream-sediment samples were collected in 2010 and 2011 from locations in Colorado and New Mexico. Sample sites were selected from small to midsize watersheds composed of a high percentage of one rock type or geologic unit. Stream-water and stream-sediment samples were collected, processed, preserved, and analyzed in a consistent manner. This report releases geochemical data for this phase of the study.

Archean cherts: field, petrographic and geochemical criteria to determine their origin

NASA Astrophysics Data System (ADS)

Ledevin, Morgane; Arndt, Nicholas T.; Simionovici, Alexandre

2013-04-01

Archean cherts provide valuable information about conditions on the sea floor during the early history of Earth. We conducted field, petrological and geochemical studies on examples from different environments in the Barberton Greenstone Belt (3.2-3.5 Ga), South Africa, with the aim of improving our understanding of these enigmatic rocks. We distinguish three different origins for cherts: direct precipitation from seawater (C-cherts); precipitation in fractures from silica-rich fluids (F-cherts); and replacement of preexisting rocks (silicification) either at or near the surface (S-cherts). The three types were distinguished using a combination of sedimentary and deformation structures, petrological observations (RAMAN, electron microprobe, X-Ray microfluorescence, cathodoluminescence) and geochemical data. C-cherts best record the composition and physical conditions in primitive oceans and the depositional environment because they precipitated from seawater. Based on sedimentary structures, we show that the silica was deposited as a siliceous ooze or amorphous gel on the seafloor, with variable precipitation rates that depend on the amount and nature of co-precipitated phases (called here the "contaminant"), such as detrital grains, carbonates, carbonaceous matter and oxides. We observe a complex rheology of C-cherts, which show both ductile to brittle deformation structures, sometimes in the same layer. We infer that the cherts underwent extremely rapid diagenetic induration at or near the surface, a process that proceeded faster when contaminants are lacking. Geochemical data (ICP-MS/ICP-AES) indicate that whole rock chemistries are dominated by the contaminant phases. Detrital grains with continental signatures dominate the compositions of cherts in the turbidite sequence of the Komati River whereas carbonates preserving modern, seawater-like compositions control the compositions of cherts of Fig Tree Fm in the Barite Valley. The silica minerals do not contribute significantly to the trace-element composition, but acts as a diluent. Buck Reef cherts have extremely low contents of most trace elements due to low contents of detrital minerals and carbonates. S-cherts result from the silicification of preexisting rocks: under the action of circulating fluids, primary minerals are replaced by silica minerals and the porosity of the protolith is significantly reduced. Such process occurs even at the surface and persist downward the sedimentary units until after the rocks are indurated. F-cherts were observed in the Barite Valley, where chert dykes cross-cut surrounding units at high angle. The fractures often display jigsaw-puzzle textures, suggesting hydraulic fracturation, and their near-vertical orientation points to emplacement at shallow levels in the sediment pile. The dykes are filled with a black chert that contains variable amounts of host rock fragments that vary in shape (angular to rounded) and size (dm to µm). They control the whole-rock chemistry of cherts, and obscure the chemical composition of the primary, precipitating fluid. We believe that this fluid had a thixotropic behavior, i.e. it was fluid enough during the intrusion to fill very fine <1mm fractures but viscous enough when the velocity decreased to suspend decimetric host rock fragments. Based on our observations, we conclude that (1) field and petrological studies are more reliable than geochemical analyses for the recognition of various chert types; (2) the composition of cherts strongly depends on the type and amount of mineral phases other than silica, especially clays and carbonates; (3) C-cherts might be more abundant than previously thought and deposited as an amorphous, siliceous gel onto the seafloor before being rapidly indurated.

Processes controlling trace element geochemistry of Arabian Sea sediments during the last 25,000 years

NASA Astrophysics Data System (ADS)

Sirocko, Frank; Garbe-Schönberg, Dieter; Devey, Colin

2000-11-01

Thirty seven deep-sea sediment cores from the Arabian Sea were studied geochemically (49 major and trace elements) for four time slices during the Holocene and the last glacial, and in one high sedimentation rate core (century scale resolution) to detect tracers of past variations in the intensity of the atmospheric monsoon circulation and its hydrographic expression in the ocean surface. This geochemical multi-tracer approach, coupled with additional information on the grain size composition of the clastic fraction, the bulk carbonate and biogenic opal contents makes it possible to characterize the sedimentological regime in detail. Sediments characterized by a specific elemental composition (enrichment) originated from the following sources: river suspensions from the Tapti and Narbada, draining the Indian Deccan traps (Ti, Sr); Indus sediments and dust from Rajasthan and Pakistan (Rb, Cs); dust from Iran and the Persian Gulf (Al, Cr); dust from central Arabia (Mg); dust from East Africa and the Red Sea (Zr/Hf, Ti/Al). C org, Cd, Zn, Ba, Pb, U, and the HREE are associated with the intensity of upwelling in the western Arabian Sea, but only those patterns that are consistently reproduced by all of these elements can be directly linked with the intensity of the southwest monsoon. Relying on information from a single element can be misleading, as each element is affected by various other processes than upwelling intensity and nutrient content of surface water alone. The application of the geochemical multi-tracer approach indicates that the intensity of the southwest monsoon was low during the LGM, declined to a minimum from 15,000-13,000 14C year BP, intensified slightly at the end of this interval, was almost stable during the Bölling, Alleröd and the Younger Dryas, but then intensified in two abrupt successions at the end of the Younger Dryas (9900 14C year BP) and especially in a second event during the early Holocene (8800 14C year BP). Dust discharge by northwesterly winds from Arabia exhibited a similar evolution, but followed an opposite course: high during the LGM with two primary sources—the central Arabian desert and the dry Persian Gulf region. Dust discharge from both regions reached a pronounced maximum at 15,000-13,000 14C year. At the end of this interval, however, the dust plumes from the Persian Gulf area ceased dramatically, whereas dust discharge from central Arabia decreased only slightly. Dust discharge from East Africa and the Red Sea increased synchronously with the two major events of southwest monsoon intensification as recorded in the nutrient content of surface waters. In addition to the tracers of past dust flux and surface water nutrient content, the geochemical multi-tracer approach provides information on the history of deep sea ventilation (Mo, S), which was much lower during the last glacial maximum than during the Holocene. The multi-tracer approach—i.e. a few sedimentological parameters plus a set of geochemical tracers widely available from various multi-element analysis techniques—is a highly applicable technique for studying the complex sedimentation patterns of an ocean basin, and, specifically in the case of the Arabian Sea, can even reveal the seasonal structure of climate change.

Sulfur and carbon geochemistry of the Santa Elena peridotites: Comparing oceanic and continental processes during peridotite alteration

NASA Astrophysics Data System (ADS)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Gazel, Esteban; Madrigal, Pilar

2016-05-01

Ultramafic rocks exposed on the continent serve as a window into oceanic and continental processes of water-peridotite interaction, so called serpentinization. In both environments there are active carbon and sulfur cycles that contain abiogenic and biogenic processes, which are eventually imprinted in the geochemical signatures of the basement rocks and the calcite and magnesite deposits associated with fluids that issue from these systems. Here, we present the carbon and sulfur geochemistry of ultramafic rocks and carbonate deposits from the Santa Elena ophiolite in Costa Rica. The aim of this study is to leverage the geochemistry of the ultramafic sequence and associated deposits to distinguish between processes that were dominant during ocean floor alteration and those dominant during low-temperature, continental water-peridotite interaction. The peridotites are variably serpentinized with total sulfur concentrations up to 877 ppm that is typically dominated by sulfide over sulfate. With the exception of one sample the ultramafic rocks are characterized by positive δ34Ssulfide (up to + 23.1‰) and δ34Ssulfate values (up to + 35.0‰). Carbon contents in the peridotites are low and are isotopically distinct from typical oceanic serpentinites. In particular, δ13C of the inorganic carbon suggests that the carbon is not derived from seawater, but rather the product of the interaction of meteoric water with the ultramafic rocks. In contrast, the sulfur isotope data from sulfide minerals in the peridotites preserve evidence for interaction with a hydrothermal fluid. Specifically, they indicate closed system abiogenic sulfate reduction suggesting that oceanic serpentinization occurred with limited input of seawater. Overall, the geochemical signatures preserve evidence for both oceanic and continental water-rock interaction with the majority of carbon (and possibly sulfate) being incorporated during continental water-rock interaction. Furthermore, there is evidence for microbial activity that was possibly stimulated by carbon sourced from water-rock interaction with adjacent sediments or fluid inclusions. This study provides detailed insight into the complex hydrothermal history of continental serpentinization systems and adds to our understanding of the carbon and sulfur cycling within peridotite-hosted hydrothermal systems.

Geoinformation modeling system for analysis of atmosphere pollution impact on vegetable biosystems using space images

NASA Astrophysics Data System (ADS)

Polichtchouk, Yuri; Ryukhko, Viatcheslav; Tokareva, Olga; Alexeeva, Mary

2002-02-01

Geoinformation modeling system structure for assessment of the environmental impact of atmospheric pollution on forest- swamp ecosystems of West Siberia is considered. Complex approach to the assessment of man-caused impact based on the combination of sanitary-hygienic and landscape-geochemical approaches is reported. Methodical problems of analysis of atmosphere pollution impact on vegetable biosystems using geoinformation systems and remote sensing data are developed. Landscape structure of oil production territories in southern part of West Siberia are determined on base of processing of space images from spaceborn Resource-O. Particularities of atmosphere pollution zones modeling caused by gas burning in torches in territories of oil fields are considered. For instance, a pollution zones were revealed modeling of contaminants dispersal in atmosphere by standard model. Polluted landscapes areas are calculated depending on oil production volume. It is shown calculated data is well approximated by polynomial models.

[Recent advances in analysis of petroleum geological samples by comprehensive two-dimensional gas chromatography].

PubMed

Gao, Xuanbo; Chang, Zhenyang; Dai, Wei; Tong, Ting; Zhang, Wanfeng; He, Sheng; Zhu, Shukui

2014-10-01

Abundant geochemical information can be acquired by analyzing the chemical compositions of petroleum geological samples. The information obtained from the analysis provides scientifical evidences for petroleum exploration. However, these samples are complicated and can be easily influenced by physical (e. g. evaporation, emulsification, natural dispersion, dissolution and sorption), chemical (photodegradation) and biological (mainly microbial degradation) weathering processes. Therefore, it is very difficult to analyze the petroleum geological samples and they cannot be effectively separated by traditional gas chromatography/mass spectrometry. A newly developed separation technique, comprehensive two-dimensional gas chromatography (GC x GC), has unique advantages in complex sample analysis, and recently it has been applied to petroleum geological samples. This article mainly reviews the research progres- ses in the last five years, the main problems and the future research about GC x GC applied in the area of petroleum geology.

Nonlinear metallogeny and the depths of the earth

NASA Astrophysics Data System (ADS)

Shcheglov, A. D.; Govorov, I. N.

This book is concerned with the basic relations regarding a new approach in the field of knowledge of metallogenesis, taking into account the complex character of the mutual dependence between ore deposits, the structure of the earth's crust, and depth relations. The principles of nonlinear metallogeny are examined, giving attention to the development of the metallogenic science during the past few years, the formation of the concept 'nonlinear metallogeny', the main aspects of nonlinear metallogeny, the origin of the ore deposits and the characteristics of ore formations in the mantle, the parallel manifestation of ore-forming processes in the crust, sedimentary-hydrothermal ore formations and their place in nonlinear metallogeny, and various types of rock and ore formations. The structure, composition, and metalliferous characteristics found at various depth zones of the tectonosphere are discussed along with the geochemical and metallogenic heterogeneity in the mantle. General questions of nonlinear metallogeny are also investigated.

Evidence for life on Earth before 3,800 million years ago.

PubMed

Mojzsis, S J; Arrhenius, G; McKeegan, K D; Harrison, T M; Nutman, A P; Friend, C R

1996-11-07

It is unknown when life first appeared on Earth. The earliest known microfossils (approximately 3,500 Myr before present) are structurally complex, and if it is assumed that the associated organisms required a long time to develop this degree of complexity, then the existence of life much earlier than this can be argued. But the known examples of crustal rocks older than 3,500 Myr have experienced intense metamorphism, which would have obliterated any fragile microfossils contained therein. It is therefore necessary to search for geochemical evidence of past biotic activity that has been preserved within minerals that are resistant to metamorphism. Here we report ion-microprobe measurements of the carbon-isotope composition of carbonaceous inclusions within grains of apatite (basic calcium phosphate) from the oldest known sediment sequences--a approximately 3,800-Myr-old banded iron formation from the Isua supracrustal belt, West Greenland, and a similar formation from the nearby Akilia island that is possibly older than 3,850 Myr. The carbon in the carbonaceous inclusions is isotopically light, indicative of biological activity; no known abiotic process can explain the data. Unless some unknown abiotic process exists which is able both to create such isotopically light carbon and then selectively incorporate it into apatite grains, our results provide evidence for the emergence of life on Earth by at least 3,800 Myr before present.

Evidence for Life on Earth before 3,800 Million Years Ago

NASA Technical Reports Server (NTRS)

Mojzsis, S. J.; Arrhenius, G.; McKeegan, K. D.; Harrison, T. M.; Nutman, A. P.; Friend, C. R. L.

1996-01-01

It is unknown when life first appeared on Earth. The earliest known microfossils (approx. 3,500 Myr before present) are structurally complex, and if it is assumed that the associated organisms required a long time to develop this degree of complexity, then the existence of life much earlier than this can be argued. But the known examples of crustal rocks older than approx. 3,500 Myr have experienced intense metamorphism, which would have obliterated any fragile microfossils contained therein. It is therefore necessary to search for geochemical evidence of past biotic activity that has been preserved within minerals that are resistant to metamorphism. Here we report ion-microprobe measurements of the carbon-isotope composition of carbonaceous inclusions within grains of apatite (basic calcium phosphate) from the oldest known sediment sequences a approx. 3,800 Myr-old banded iron formation from the Isua supracrustal belt, West Greenland, and a similar formation from the nearby Akilia island that is possibly older than 3,850 Myr. The carbon in the carbonaceous inclusions is isotopically light, indicative of biological activity; no known abiotic process can explain the data. Unless some unknown abiotic process exists which is able both to create such isotopically light carbon and then selectively incorporate it into apatite grains, our results provide evidence for the emergence of life on Earth by at least 3,800 Myr before present.

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.

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.

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.

Natural inactivation of Escherichia coli in anoxic and reduced groundwater

USGS Publications Warehouse

Lisle, John T.

2016-01-01

Aquifer recharge zones with geochemical characteristics observed in this study complement above ground engineered processes (e.g., filtration, disinfection), while increasing the overall indicator microorganism log-reduction rate of a facility.

Geochemical markers of sedimentary organic matter in Todos os Santos Bay, Bahia - Brazil. Indicators of sources and preservation.

PubMed

de Souza, José Roberto Bispo; do Rosário Zucchi, Maria; Costa, Alexandre Barreto; de Azevedo, Antonio Expedito Gomes; Spano, Saulo

2017-06-30

Natural stable isotopes, such as carbon (C) and nitrogen (N), are modern tools to assess geochemical processes. C and N in organic matter can carry fingerprints of their hydrologic flows and sedimentary processes, including any anthropogenic modification on the natural system. This study focuses on the determination of aliphatic and polycyclic aromatic hydrocarbons and isotopic ratio in the sediment of Todos os Santos Bay (TSB). The isotopic results of the total organic matter indicate varied contribution marine and terrigenous. Typical rates of PAHs mainly indicate a pyrogenic source and mixture between pyrogenic and petrogenic sources. Typical ratios for the n-alkanes indicate the presence of petroleum hydrocarbons. The isotopic composition of n-alkanes suggests a mixture of sources, with the possible contribution of petrogenic. Copyright © 2017. Published by Elsevier Ltd.

Multivariate analysis of the heterogeneous geochemical processes controlling arsenic enrichment in a shallow groundwater system.

PubMed

Huang, Shuangbing; Liu, Changrong; Wang, Yanxin; Zhan, Hongbin

2014-01-01

The effects of various geochemical processes on arsenic enrichment in a high-arsenic aquifer at Jianghan Plain in Central China were investigated using multivariate models developed from combined adaptive neuro-fuzzy inference system (ANFIS) and multiple linear regression (MLR). The results indicated that the optimum variable group for the AFNIS model consisted of bicarbonate, ammonium, phosphorus, iron, manganese, fluorescence index, pH, and siderite saturation. These data suggest that reductive dissolution of iron/manganese oxides, phosphate-competitive adsorption, pH-dependent desorption, and siderite precipitation could integrally affect arsenic concentration. Analysis of the MLR models indicated that reductive dissolution of iron(III) was primarily responsible for arsenic mobilization in groundwaters with low arsenic concentration. By contrast, for groundwaters with high arsenic concentration (i.e., > 170 μg/L), reductive dissolution of iron oxides approached a dynamic equilibrium. The desorption effects from phosphate-competitive adsorption and the increase in pH exhibited arsenic enrichment superior to that caused by iron(III) reductive dissolution as the groundwater chemistry evolved. The inhibition effect of siderite precipitation on arsenic mobilization was expected to exist in groundwater that was highly saturated with siderite. The results suggest an evolutionary dominance of specific geochemical process over other factors controlling arsenic concentration, which presented a heterogeneous distribution in aquifers. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of Environmental Science and Health, Part A, to view the supplemental file.

Evolution of geothermal fluids deduced from chemistry plots: Yellowstone National Park (U.S.A.)

USGS Publications Warehouse

Mazor, E.; Thompson, J.M.

1982-01-01

Large amounts of chemical data, obtained in geothermal fields, may readily be sorted-out by the aid of a simple set of graphs that provide a clear over-all picture and facilitate the understanding of geochemical processes taking place. As a case study, data from several hundred samples of the thermal springs at the well-known Yellowstone National Park are discussed. The pattern obtained seems to indicate: (1) geochemical similarity between the spring groups of Heart Lake, Shoshone, Upper, Midway, Lower and Norris Geyser Basins, i.e., a geochemical uniformity of major spring groups located over 40 km apart; (2) these groups may be described as originating from a common fluid, most resembling the composition of Norris waters, accompanied by CO2, and other volatiles, that react with igneous rocks, forming local variations; (3) the secondary reactions occur at (medium) depth, before the ascent to the surface; (4) extensive concentration-dilution processes occur during the ascent to the surface. The water of the Mammoth group may be described as originating from the same Norris-like fluid that has been diluted (low Na and Cl contents) and intensively reacted with carbonaceous rocks, thus gaining in Ca, Mg, SO4, and HCO3. ?? 1982.

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.

Using Tidal Fluctuation-Induced Dynamics of Radium Isotopes (224Ra, 223Ra, and 228Ra) to Trace the Hydrodynamics and Geochemical Reactions in a Coastal Groundwater Mixing Zone

NASA Astrophysics Data System (ADS)

Liu, Yi; Jiao, Jiu Jimmy; Liang, Wenzhao; Luo, Xin

2018-04-01

The reactive transport of radium isotopes (224Ra, 223Ra, and 228Ra) in coastal groundwater mixing zones (CGMZs) is sensitive to shifts of redox conditions and geochemical reactions induced by tidal fluctuation. This study presents a spatial distribution and temporal variation of radium isotopes in the CGMZ for the first time. Results show that the activity of radium isotopes in the upper saline plume (USP) is comparatively low due to a short residence time and mixing loss induced by the infiltration of low radium seawater whereas the activity of radium isotopes in the salt wedge (SW) is comparatively high due to a long residence time in the aquifer. The spatial distribution of radium isotopes is determined by the partitioning of radium isotopes, groundwater residence time, and relative ingrowth rates of radium isotopes. In addition, the variation of radium isotopes in the USP lags slightly (˜0 h) whereas the fluctuation of radium isotopes in the SW lags significantly (˜12 h) behind sea level oscillation. Tidal fluctuation affects the partitioning of radium isotopes through controlling seawater infiltration and subsequently influences the dynamics of radium isotopes in the USP. Concurrently, seawater infiltration significantly affects geochemical processes such as the production of nutrients and total alkalinity. Therefore, radium dynamics in the USP have implications for these geochemical processes. The variation of radium isotopes in the USP also has potential implications for transformation of trace metals such as iron and manganese because of the close affinity of radium isotopes to manganese and iron oxides.

A strong enrichment of potentially toxic elements (PTEs) in Nord-Trøndelag (central Norway) forest soil.

PubMed

Reimann, C; Fabian, K; Schilling, J; Roberts, D; Englmaier, P

2015-12-01

Analysis of soil C and O horizon samples in a recent regional geochemical survey of Nord-Trøndelag, central Norway (752 sample sites covering 25,000 km2), identified a strong enrichment of several potentially toxic elements (PTEs) in the O horizon. Of 53 elements analysed in both materials, Cd concentrations are, on average, 17 times higher in the O horizon than in the C horizon and other PTEs such as Ag (11-fold), Hg (10-fold), Sb (8-fold), Pb (4-fold) and Sn (2-fold) are all strongly enriched relative to the C horizon. Geochemical maps of the survey area do not reflect an impact from local or distant anthropogenic contamination sources in the data for O horizon soil samples. The higher concentrations of PTEs in the O horizon are the result of the interaction of the underlying geology, the vegetation zone and type, and climatic effects. Based on the general accordance with existing data from earlier surveys in other parts of northern Europe, the presence of a location-independent, superordinate natural trend towards enrichment of these elements in the O horizon relative to the C horizon soil is indicated. The results imply that the O and C horizons of soils are different geochemical entities and that their respective compositions are controlled by different processes. Local mineral soil analyses (or published data for the chemical composition of the average continental crust) cannot be used to provide a geochemical background for surface soil. At the regional scale used here surface soil chemistry is still dominated by natural sources and processes. Copyright © 2015 Elsevier B.V. All rights reserved.

Nanostructures and radionuclide transport in clay formations (Invited)

NASA Astrophysics Data System (ADS)

Wang, Y.

2010-12-01

Nanostructures are widely present in geologic materials and are expected to directly affect the interactions of these materials with geologic fluids. The study of mineral-water interface chemistry as controlled by nanostructures is a necessary step to bridge the existing gap between the molecular level understanding of a geochemical process and the macro-scale laboratory and field observations. In this presentation, I will review the recent progresses in nanoscience and provide a perspective on how these progresses can potentially impact geochemical studies. My presentation will be focused the following areas: (1) the characterization of nanostructures in natural systems, (2) the study of water and chemical species in nanoconfinement, (3) the effects of nanopores on geochemical reaction and mass transfers, and (4) the use nanostructured materials for environmental remediation and cleanup. Specifically, I will demonstrate that the nanopore confinement can significantly modify geochemical reactions in porous geologic media. As the pore size is reduced to a few nanometers, the difference between surface acidity constants (pK2 - pK1) decreases, giving rise to a higher surface charge density on a nanopore surface than that on an unconfined mineral-water interface. The change in surface acidity constants results in a shift of ion sorption edges and enhances ion sorption on nanopore surfaces. This effect causes preferential enrichment of trace elements in nanopores and therefore directly impacts the bioavailability of these elements. The implication of these processes to radionuclide transport in clay formations will be discussed. This work was performed at Sandia National Laboratories, which is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the DOE under contract DE-AC04-94AL8500.

Late Paleozoic-Early Mesozoic tectonic evolution of the Paleo-Asian Ocean: geochronological and geochemical evidence from granitoids in the northern margin of Alxa, Western China

NASA Astrophysics Data System (ADS)

Sha, Xin; Wang, Jinrong; Chen, Wanfeng; Liu, Zheng; Zhai, Xinwei; Ma, Jinlong; Wang, Shuhua

2018-03-01

The Paleo-Asian Ocean (Southern Mongolian Ocean) ophiolitic belts and massive granitoids are exposed in the Alxa block, in response to oceanic subduction processes. In this work, we report petrographic, geochemical, and zircon U-Pb age data of some granitoid intrusions from the northern Alxa. Zircon U-Pb dating for the quartz diorite, tonalite, monzogranite, and biotite granite yielded weighted mean 206Pb/238U ages of 302±9.2 Ma, 246.5±4.6 Ma, 235±4.4 Ma, and 229.5±5.6 Ma, respectively. The quartz diorites ( 302 Ma) exhibit geochemical similarities to adakites, likely derived from partial melting of the initially subducted Chaganchulu back-arc oceanic slab. The tonalites ( 246.5 Ma) display geochemical affinities of I-type granites. They were probably derived by fractional crystallization of the modified lithospheric mantle-derived basaltic magmas in a volcanic arc setting. The monzogranites ( 235 Ma) are characterized by low Al2O3, but high Y and Yb with notably negative Eu anomalies. In contrast, the biotite granites ( 229.5 Ma) show high Al2O3 but low Y and Yb with steep HREE patterns and the absence of negative Eu anomalies. Elemental data suggested that the biotite granites were likely derived from a thickened lower crust, but the monzogranites originated from a thin crust. Our data suggested that the initial subduction of the Chaganchulu oceanic slab towards the Alxa block occurred at 302 Ma. This subduction process continued to the Early Triassic ( 246 Ma) and the basin was finally closed before the Middle Triassic ( 235 Ma). Subsequently, the break-off of the subducted slab triggered asthenosphere upwelling (240-230 Ma).

A compilation of rate parameters of water-mineral interaction kinetics for application to geochemical modeling

USGS Publications Warehouse

Palandri, James L.; Kharaka, Yousif K.

2004-01-01

Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. The compiled dissolution rate constants range from -0.21 log moles m-2 s-1 for halite, to -17.44 log moles m-2 s-1 for kyanite, for conditions far from equilibrium, at 25 ?C, and pH near neutral. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

Investigating ebullition in a sand column using dissolved gas analysis and reactive transport modeling

USGS Publications Warehouse

Amos, Richard T.; Mayer, K. Ulrich

2006-01-01

Ebullition of gas bubbles through saturated sediments can enhance the migration of gases through the subsurface, affect the rate of biogeochemical processes, and potentially enhance the emission of important greenhouse gases to the atmosphere. To better understand the parameters controlling ebullition, methanogenic conditions were produced in a column experiment and ebullition through the column was monitored and quantified through dissolved gas analysis and reactive transport modeling. Dissolved gas analysis showed rapid transport of CH4 vertically through the column at rates several times faster than the bromide tracer and the more soluble gas CO2, indicating that ebullition was the main transport mechanism for CH4. An empirically derived formulation describing ebullition was integrated into the reactive transport code MIN3P allowing this process to be investigated on the REV scale in a complex geochemical framework. The simulations provided insights into the parameters controlling ebullition and show that, over the duration of the experiment, 36% of the CH4 and 19% of the CO2 produced were transported to the top of the column through ebullition.

Process-based reactive transport model to quantify arsenic mobility during aquifer storage and recovery of potable water.

PubMed

Wallis, Ilka; Prommer, Henning; Pichler, Thomas; Post, Vincent; Norton, Stuart B; Annable, Michael D; Simmons, Craig T

2011-08-15

Aquifer storage and recovery (ASR) is an aquifer recharge technique in which water is injected in an aquifer during periods of surplus and withdrawn from the same well during periods of deficit. It is a critical component of the long-term water supply plan in various regions, including Florida, USA. Here, the viability of ASR as a safe and cost-effective water resource is currently being tested at a number of sites due to elevated arsenic concentrations detected during groundwater recovery. In this study, we developed a process-based reactive transport model of the coupled physical and geochemical mechanisms controlling the fate of arsenic during ASR. We analyzed multicycle hydrochemical data from a well-documented affected southwest Floridan site and evaluated a conceptual/numerical model in which (i) arsenic is initially released during pyrite oxidation triggered by the injection of oxygenated water (ii) then largely complexes to neo-formed hydrous ferric oxides before (iii) being remobilized during recovery as a result of both dissolution of hydrous ferric oxides and displacement from sorption sites by competing anions.

PHAST--a program for simulating ground-water flow, solute transport, and multicomponent geochemical reactions

USGS Publications Warehouse

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

2004-01-01

The computer program PHAST simulates multi-component, reactive solute transport in three-dimensional saturated ground-water flow systems. PHAST is a versatile ground-water flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. PHAST is applicable to the study of natural and contaminated ground-water systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock-water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, density-dependent flow, or waters with high ionic strengths. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux, and leaky conditions, as well as the special cases of rivers and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, gases, surface complexation sites, ion exchange sites, and solid solutions; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, gases, exchangers, surfaces, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a format suitable for exporting to spreadsheets and post-processing programs; or in Hierarchical Data Format (HDF), which is a compressed binary format. Data in the HDF file can be visualized on Windows computers with the program Model Viewer and extracted with the utility program PHASTHDF; both programs are distributed with PHAST. Operator splitting of the flow, transport, and geochemical equations is used to separate the three processes into three sequential calculations. No iterations between transport and reaction calculations are implemented. A three-dimensional Cartesian coordinate system and finite-difference techniques are used for the spatial and temporal discretization of the flow and transport equations. The non-linear chemical equilibrium equations are solved by a Newton-Raphson method, and the kinetic reaction equations are solved by a Runge-Kutta or an implicit method for integrating ordinary differential equations. The PHAST simulator may require large amounts of memory and long Central Processing Unit (CPU) times. To reduce the long CPU times, a parallel version of PHAST has been developed that runs on a multiprocessor computer or on a collection of computers that are networked. The parallel version requires Message Passing Interface, which is currently (2004) freely available. The parallel version is effective in reducing simulation times. This report documents the use of the PHAST simulator, including running the simulator, preparing the input files, selecting the output files, and visualizing the results. It also presents four examples that verify the numerical method and demonstrate the capabilities of the simulator. PHAST requires three input files. Only the flow and transport file is described in detail in this report. The other two files, the chemistry data file and the database file, are identical to PHREEQC files and the detailed description of these files is found in the PHREEQC documentation.

Improved Algorithms for Accurate Retrieval of UV - Visible Diffuse Attenuation Coefficients in Optically Complex, Inshore Waters

NASA Technical Reports Server (NTRS)

Cao, Fang; Fichot, Cedric G.; Hooker, Stanford B.; Miller, William L.

2014-01-01

Photochemical processes driven by high-energy ultraviolet radiation (UVR) in inshore, estuarine, and coastal waters play an important role in global bio geochemical cycles and biological systems. A key to modeling photochemical processes in these optically complex waters is an accurate description of the vertical distribution of UVR in the water column which can be obtained using the diffuse attenuation coefficients of down welling irradiance (Kd()). The Sea UV Sea UVc algorithms (Fichot et al., 2008) can accurately retrieve Kd ( 320, 340, 380,412, 443 and 490 nm) in oceanic and coastal waters using multispectral remote sensing reflectances (Rrs(), Sea WiFS bands). However, SeaUVSeaUVc algorithms are currently not optimized for use in optically complex, inshore waters, where they tend to severely underestimate Kd(). Here, a new training data set of optical properties collected in optically complex, inshore waters was used to re-parameterize the published SeaUVSeaUVc algorithms, resulting in improved Kd() retrievals for turbid, estuarine waters. Although the updated SeaUVSeaUVc algorithms perform best in optically complex waters, the published SeaUVSeaUVc models still perform well in most coastal and oceanic waters. Therefore, we propose a composite set of SeaUVSeaUVc algorithms, optimized for Kd() retrieval in almost all marine systems, ranging from oceanic to inshore waters. The composite algorithm set can retrieve Kd from ocean color with good accuracy across this wide range of water types (e.g., within 13 mean relative error for Kd(340)). A validation step using three independent, in situ data sets indicates that the composite SeaUVSeaUVc can generate accurate Kd values from 320 490 nm using satellite imagery on a global scale. Taking advantage of the inherent benefits of our statistical methods, we pooled the validation data with the training set, obtaining an optimized composite model for estimating Kd() in UV wavelengths for almost all marine waters. This optimized composite set of SeaUVSeaUVc algorithms will provide the optical community with improved ability to quantify the role of solar UV radiation in photochemical and photobiological processes in the ocean.

Compilation of new and previously published geochemical and modal data for Mesoproterozoic igneous rocks of the St. Francois Mountains, southeast Missouri

USGS Publications Warehouse

du Bray, Edward A.; Day, Warren C.; Meighan, Corey J.

2018-04-16

The purpose of this report is to present recently acquired as well as previously published geochemical and modal petrographic data for igneous rocks in the St. Francois Mountains, southeast Missouri, as part of an ongoing effort to understand the regional geology and ore deposits of the Mesoproterozoic basement rocks of southeast Missouri, USA. The report includes geochemical data that is (1) newly acquired by the U.S. Geological Survey and (2) compiled from numerous sources published during the last fifty-five years. These data are required for ongoing petrogenetic investigations of these rocks. Voluminous Mesoproterozoic igneous rocks in the St. Francois Mountains of southeast Missouri constitute the basement buried beneath Paleozoic sedimentary rock that is over 600 meters thick in places. The Mesoproterozoic rocks of southeast Missouri represent a significant component of approximately 1.4 billion-year-old (Ga) igneous rocks that crop out extensively in North America along the southeast margin of Laurentia and subsequent researchers suggested that iron oxide-copper deposits in the St. Francois Mountains are genetically associated with ca. 1.4 Ga magmatism in this region. The geochemical and modal data sets described herein were compiled to support investigations concerning the tectonic setting and petrologic processes responsible for the associated magmatism.

Instrumenting caves to collect hydrologic and geochemical data: case study from James Cave, Virginia

USGS Publications Warehouse

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

2015-01-01

Karst aquifers are productive groundwater systems, supplying approximately 25 % of the world’s drinking water. Sustainable use of this critical water supply requires information about rates of recharge to karst aquifers. The overall goal of this project is to collect long-term, high-resolution hydrologic and geochemical datasets at James Cave, Virginia, to evaluate the quantity and quality of recharge to the karst system. To achieve this goal, the cave has been instrumented for continuous (10-min interval) measurement of the (1) temperature and rate of precipitation; (2) temperature, specific conductance, and rate of epikarst dripwater; (3) temperature of the cave air; and (4) temperature, conductivity, and discharge of the cave stream. Instrumentation has also been installed to collect both composite and grab samples of precipitation, soil water, the cave stream, and dripwater for geochemical analysis. This chapter provides detailed information about the instrumentation, data processing, and data management; shows examples of collected datasets; and discusses recommendations for other researchers interested in hydrologic and geochemical monitoring of cave systems. Results from the research, briefly described here and discussed in more detail in other publications, document a strong seasonality of the start of the recharge season, the extent of the recharge season, and the geochemistry of recharge.

The Origin of 87Sr/86Sr in Cold Springs and Travertines of the Franciscan Complex near Cazadero, California

NASA Astrophysics Data System (ADS)

Marks, N.; Schiffman, P.; Yin, Q.; Zierenberg, R.

2005-12-01

Ultrabasic springs within the Franciscan Complex of the California Coast Range have been intensely investigated by geochemists and geobiologists. Springs located in Sonoma County in an area historically known as The Cedars are of particular interest to scientists exploring Martian analogues (Johnson et al. 2004) or investigating serpentinization processes (Barnes and O'Neil, 1969; Barnes et al. 1972). Laser ablation and solution phase multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) were used to obtain 87Sr/86Sr isotope ratios in fluid, travertine and serpentinite samples collected at the Cedars. 87Sr/86Sr isotopic ratios in the serpentinizing springs range from 0.70926 to 0.70955; the Mg2+-HCO3- type stream water has an isotopic ratio of 0.70848. The 87Sr/86Sr ratio in the travertines ranges from 0.70931 to 0.70966. The mean 87Sr/86Sr ratio of the travertine (0.7094) is far more radiogenic than typical mantle values of 0.703 to 0.705, indicating that the peridotite is an unlikely source of the radiogenic Sr. Similarly, the measured ratio is much higher than the expected Sr isotope ratio of seawater that might be trapped in Jurassic Franciscan Sediments or oceanic crust. Strontium leached from Franciscan sediments themselves should reflect a Sierran or Klamath source with expected values in the range of 0.705 to 0.706. Indeed the measured isotope ratios even exceed modern seawater values. The observed radiogenic values suggest the presence of older, potassium (and rubidium)-rich rocks within the fluid flow path. Alternatively, the presence of clay minerals that readily substitute Sr for Ca may well account for the radiogenic strontium signal. It is possible that the serpentinization observed at The Cedars initiated along a ridge flank and the Sr isotopic chemistry reflects the site of initiation. The radiogenic strontium in these springs may result from fluid interaction with seafloor sediments deposited along the flank of a slow spreading ridge. If this is the case, it may be possible to use 87Sr/86Sr to determine the location of serpentinization initiation (Gruau et al, 1998). Such a revelation might provide insight into the geochemical processes associated with mid-ocean ridge flank serpentinization at sites like Lost City (Kelley et al., 2005). The implications of this correlation could provide information about the preservation of geochemical systems through obduction of ophiolitic sequences and provide insights into ridge flank hydrothermal and serpentinizing processes.

Statistical geochemistry reveals disruption in secular lithospheric evolution about 2.5 Gyr ago.

PubMed

Keller, C Brenhin; Schoene, Blair

2012-05-23

The Earth has cooled over the past 4.5 billion years (Gyr) as a result of surface heat loss and declining radiogenic heat production. Igneous geochemistry has been used to understand how changing heat flux influenced Archaean geodynamics, but records of systematic geochemical evolution are complicated by heterogeneity of the rock record and uncertainties regarding selection and preservation bias. Here we apply statistical sampling techniques to a geochemical database of about 70,000 samples from the continental igneous rock record to produce a comprehensive record of secular geochemical evolution throughout Earth history. Consistent with secular mantle cooling, compatible and incompatible elements in basalts record gradually decreasing mantle melt fraction through time. Superimposed on this gradual evolution is a pervasive geochemical discontinuity occurring about 2.5 Gyr ago, involving substantial decreases in mantle melt fraction in basalts, and in indicators of deep crustal melting and fractionation, such as Na/K, Eu/Eu* (europium anomaly) and La/Yb ratios in felsic rocks. Along with an increase in preserved crustal thickness across the Archaean/Proterozoic boundary, these data are consistent with a model in which high-degree Archaean mantle melting produced a thick, mafic lower crust and consequent deep crustal delamination and melting--leading to abundant tonalite-trondhjemite-granodiorite magmatism and a thin preserved Archaean crust. The coincidence of the observed changes in geochemistry and crustal thickness with stepwise atmospheric oxidation at the end of the Archaean eon provides a significant temporal link between deep Earth geochemical processes and the rise of atmospheric oxygen on the Earth.

GEMAS: The Fennoscandian perspective

NASA Astrophysics Data System (ADS)

Katarzyna Ladenberger, Anna; Uhlbäck, Jo; Andersson, Madelen; Reimann, Clemens; Tarvainen, Timo; Sadeghi, Martiya; Morris, George; Eklund, Mikael

2014-05-01

The GEMAS Project (Geochemical Mapping of Agricultural and Grazing Land Soil in Europe) resulted in a large coherent data set displaying baseline levels of elements in agricultural and grazing land soil, on both a European and a regional scale. The geochemical mapping of agricultural and grazing land soil in Norway, Sweden and Finland revealed regional features, noticeably different from the general geochemical pattern in the rest of Europe. When looking at the European data set as a whole, Norway, Sweden and Finland stand out as geochemically distinct, mainly due to the old bedrock and the extent of the last glaciations. They were thus considered valuable for a study as a separate entity. The interpretation of element maps and statistics identified several factors responsible for the observed trends in the geochemical patterns in Norway, Sweden and Finland, with the most important factors being bedrock geology, the presence of ore deposits, the soil type and its properties, and climate. The soil of the Fennoscandian Shield is very young and the composition of parent material has a crucial influence on the soil chemical signature. On the other hand the occurrence of organic peaty soil and clayey varieties plays an important role in enrichment processes leading to enhanced levels of many elements. Anthropogenic impact on soils appears to have a minor influence on the soil geochemistry of both agricultural and grazing land. In mining regions, with the natural signal from the mineralisation, it is often difficult to discriminate between the original anomaly and any additional anthropogenic contamination. The results of this survey are available to the public and can be used by both local authorities and research groups.

Beyond the obvious limits of ore deposits: The use of mineralogical, geochemical, and biological features for the remote detection of mineralization

USGS Publications Warehouse

Kelley, D.L.; Kelley, K.D.; Coker, W.B.; Caughlin, B.; Doherty, M.E.

2006-01-01

Far field features of ore deposits include mineralogical, geochemical, or biological attributes that can be recognized beyond the obvious limits of the deposits. They can be primary, if formed in association with mineralization or alteration processes, or secondary, if formed from the interaction of ore deposits with the hydrosphere and biosphere. This paper examines a variety of far field features of different ore deposit types and considers novel applications to exploration and discovery. Primary far field features include mineral and rock chemistry, isotopic or element halos, fluid pathways and thermal anomalies in host-rock sequences. Examples include the use of apatite chemistry to distinguish intrusive rocks permissive for iron oxide copper gold (IOCG) and porphyry deposits; resistate mineral (e.g., rutile, tourmaline) chemistry in exploration for volcanogenic massive sulfide (VMS), orogenic gold, and porphyry deposits; and pyrite chemistry to vector toward sedimentary exhalative (sedex) deposits. Distinctive whole-rock geochemical signatures also can be recognized as a far field feature of porphyry deposits. For example, unique Sr/Y ratios in whole-rock samples, used to distinguish barren versus fertile magmas for Cu mineralization, result from the differentiation of oxidized hydrous melts. Anomalous concentrations of halogen elements (Cl, Br, and I) have been found for distances of up to 200 m away from some mineralized centers. Variations in isotopic composition between ore-bearing and barren intrusions and/or systematic vertical and lateral zonation in sulfur, carbon, or oxygen isotope values have been documented for some deposit types. Owing to the thermal aureole that extends beyond the area of mineralization for some deposits, detection of paleothermal effects through methods such as conodont alteration indices, vitrinite or bitumen reflectance, illite crystallinity, and apatite or zircon thermochronology studies also can be valuable, particularly for deposits with a low-temperature thermal history. A number of newly investigated secondary far field features include the development of reduced columns by electrochemical processes in transported overburden, geochemical dispersion related to the expulsion of groundwater from tectonic and seismic compression, dispersion of vapor above ore deposits, and geochemical dispersion related to biological processes. Redox gradients have been found between underlying reduced and overlying oxidized environments associated with sulfide bodies, which result in mass transfer through electro-chemical dispersion. Recent studies have characterized the pH, oxidation-reduction potential (ORP), and self potential (SP) in overburden overlying sulfide-hosted gold and VMS deposits. Lateral migration of metals in groundwater is well understood from normal groundwater flow, but the processes responsible for vertical mass transfer of groundwater and its dissolved components have been recognized only recently. One process, termed cyclical dilatancy pumping, expels groundwater during and after earthquake events, which can cause the redistribution of metals around deposits in some environments. Soil gases are of interest owing to their high degree of mobility through the vadose zone in transported overburden. Numerous soil gas species (CO2, O2, Hg, Rn, He, sulfur compounds, and light hydrocarbons) have been measured and interpreted as diagnostic of some buried mineral deposits, and some evidence suggests a possible link between vapor dispersion and metal enrichment in soil. Geochemical enrichment in plant material and soils through successive growth-death cycles is well established, but the important role of microorganisms is now increasingly evident. Microorganisms significantly enhance the kinetics of sulfide oxidation and influence the distribution of metals around ore deposits. The presence of metal-resistant bacteria and enhanced concentrations of sulfate-reducing bacteria in exotic overburd

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.