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India National Gas Hydrate Program Expedition-02: Operational and technical summary

The India National Gas Hydrate Program is being steered by the government of India's Ministry of Petroleum and Natural Gas (MoPNG) with participation of Directorate General of Hydrocarbons (DGH), Oil and Natural Gas Corporation Limited (ONGC), and the National Oil Companies and Research Institutes of India. The India National Gas Hydrate Program Expedition 01 (NGHP-01) established the presence of gas hydrate in the Krishna Godavari (KG) and Mahanadi Basins and in the offshore area of the Andaman Sea Basin. However, the gas hydrates discovered during NGHP-01 were mainly distributed as fracture-filling material in fine-grained clay-rich sediments. The India National Gas Hydrate Program Expedition 02 (NGHP-02) was carried out with an objective to discover gas hydrate in sand-rich sediment along the eastern offshore margin of India. ONGC planned and executed NGHP-02 on the behalf of the MoPNG. NGHP-02 started on March 3, 2015 and was completed on July 28, 2015 (total 147 days) using the Japanese scientific Drilling Vessel Chikyu (D/V Chikyu). During NGHP-02, 42 holes at 25 sites were drilled, cored, and/or surveyed with downhole logging tools. These sites were located in four areas along the eastern margin of India and formally named Area A (Mahanadi Basin, three sites), Area B (northern part of the KG-Basin, twelve sites), Area C (central part of the KG-Basin, six sites), and Area E (southern part to the KG-Basin, four sites). All 25 sites established during NGHP-02 were first drilled and logged with logging-while-drilling (LWD) tools and an additional 17 holes were then drilled and/or cored with conventional coring tools (HPCS/ESCS) or pressure coring tools (PCTB). Wireline logging was conducted in 10 holes and formation tests using a dual packer Modular Formation Dynamics Tester (MDT) tool were carried out in two holes. The onboard science team used the laboratory facilities on the D/V Chikyu to examine and analyse the physical properties, geochemistry, and sedimentology of all the cores collected during the expedition. Core samples were also analysed in additional post-expedition shore-based studies conducted in numerous domestic and international gas hydrate research laboratories. The NGHP-02 sediment cores were archived at the National Gas Hydrate Core Repository in Mumbai (India), which is associated with the ONGC Gas Hydrate Research and Technology Centre (GHRTC). The necessary data for characterizing the occurrence of gas hydrate, such as interstitial water chlorinities, core-derived gas chemistry, physical and sedimentological properties, thermal images of the recovered cores, pressure core and downhole measured logging data (LWD and/or conventional wireline log data), were obtained from most of the drill sites established during NGHP-02. Almost all the drill sites yielded evidence for the occurrence of gas hydrate; however, the inferred in situ concentration of gas hydrate varied substantially from site to site. For the most part, the interpretation of downhole logging data, core thermal images, interstitial water analyses, and pressure core images from the sites established during NGHP-02 indicate that the occurrence of concentrated gas hydrate is mostly associated with coarser grained (sand-rich) sediments. This paper presents the operational and technical summary of NGHP-02. NGHP-02 started on March 3, 2015 and was completed on July 28, 2015 (total 147 days) using the Japanese scientific Drilling Vessel Chikyu (D/V Chikyu). During NGHP-02, 42 holes at 25 sites were drilled, cored, and/or surveyed with downhole logging tools. These sites were located in four areas along the eastern margin of India and formally named Area A (Mahanadi Basin, three sites), Area B (northern part of the KG-Basin, twelve sites), Area C (central part of the KG-Basin, six sites), and Area E (southern part to the KG-Basin, four sites). All 25 sites established during NGHP-02 were first drilled and logged with logging-while-drilling (LWD) to

Journal of Marine and Petroleum Geology

Health risks of gold miners: a synoptic review

Health problems of gold miners who worked underground include decreased life expectancy; increased frequency of cancer of the trachea, bronchus, lung, stomach, and liver; increased frequency of pulmonary tuberculosis (PTB), silicosis, and pleural diseases; increased frequency of insect-borne diseases, such as malaria and dengue fever; noise-induced hearing loss; increased prevalence of certain bacterial and viral diseases; and diseases of the blood, skin, and musculoskeletal system. These problems are briefly documented in gold miners from Australia, North America, South America, and Africa. In general, HIV infection or excessive alcohol and tobacco consumption tended to exacerbate existing health problems. Miners who used elemental mercury to amalgamate and extract gold were heavily contaminated with mercury. Among individuals exposed occupationally, concentrations of mercury in their air, fish diet, hair, urine, blood, and other tissues significantly exceeded all criteria proposed by various national and international regulatory agencies for protection of human health. However, large-scale epidemiological evidence of severe mercury-associated health problems in this cohort was not demonstrable.

Environmental Geochemistry and Health

Inputs and internal cycling of nitrogen to a causeway influenced, hypersaline lake, Great Salt Lake, Utah, USA

Nitrogen inputs to Great Salt Lake (GSL), located in the western USA, were quantified relative to the resident nitrogen mass in order to better determine numeric nutrient criteria that may be considered at some point in the future. Total dissolved nitrogen inputs from four surface-water sources entering GSL were modeled during the 5-year study period (2010–2014) and ranged from 1.90 × 10 6 to 5.56 × 10 6 kg/year. The railroad causeway breach was a significant conduit for the export of dissolved nitrogen from Gilbert to Gunnison Bay, and in 2011 and 2012, net losses of total nitrogen mass from Gilbert Bay via the Causeway breach were 9.59 × 10 5 and 1.51 × 10 6 kg. Atmospheric deposition (wet + dry) was a significant source of nitrogen to Gilbert Bay, exceeding the dissolved nitrogen load contributed via the Farmington Bay causeway surface-water input by >100,000 kg during 2 years of the study. Closure of two railroad causeway culverts in 2012 and 2013 likely initiated a decreasing trend in the volume of the higher density Deep Brine Layer and associated declines in total dissolved nitrogen mass contained in this layer. The large dissolved nitrogen pool in Gilbert Bay relative to the amount of nitrogen contributed by surface-water inflow sources is consistent with the terminal nature of GSL and the predominance of internal nutrient cycling. The opening of the new railroad causeway breach in 2016 will likely facilitate more efficient bidirectional flow between Gilbert and Gunnison Bays, resulting in potentially substantial changes in nutrient pools within GSL.

Utah

A preliminary assessment of the spatial sources of contemporary suspended sediment in the Ohio River basin, United States, using water quality data from the NASQAN programme in a source tracing procedure

Reliable information on catchment scale suspended sediment sources is required to inform the design of management strategies for helping abate the numerous environmental issues associated with enhanced sediment mobilization and off‐site loadings. Since sediment fingerprinting techniques avoid many of the logistical constraints associated with using more traditional indirect measurement methods at catchment scale, such approaches have been increasingly reported in the international literature and typically use data sets collected specifically for sediment source apportionment purposes. There remains scope for investigating the potential for using geochemical data sets assembled by routine monitoring programmes to fingerprint sediment provenance. In the United States, routine water quality samples are collected as part of the US Geological Survey's revised National Stream Quality Accounting Network programme. Accordingly, the geochemistry data generated from these samples over a 10‐year period (1996–2006) were used as the basis for a fingerprinting exercise to assess the key tributary sub‐catchment spatial sources of contemporary suspended sediment transported by the Ohio River. Uncertainty associated with the spatial source estimates was quantified using a Monte Carlo approach in conjunction with mass balance modelling. Relative frequency weighted means were used as an alternative way of summarizing the spatial source contributions, thereby avoiding the need to use confidence limits. The results should be interpreted in the context of the routine, but infrequent nature, of the suspended sediment samples used to assemble geochemistry as a basis for the sourcing exercise. Nonetheless, the study demonstrates how routine monitoring samples can be used to provide some preliminary information on sediment provenance in large drainage basins.

Tennessee, Ohio, West Virginia, Pennsylvania, Indi

Reference samples for the earth sciences

A revised list of reference samples of interest to geoscientists has been extended to include samples for the agronomist, the archaeologist and the environmentalist. In addition to the source from which standard samples may be obtained, references or pertinent notes for some samples are included. The number of rock reference samples is now almost adequate, and the variety of ore samples will soon be sufficient. There are very few samples for microprobe work. Oil shales will become more important because of the outlook for world petroleum resources. The dryland equivalent of a submarine basalt might be useful in studies of sea-floor spreading and of the geochemistry of basalts. The Na- and K-feldspars of BCS (British Chemical Standards—Bureau of Analysed Samples), NBS (National Bureau of Standards), and ANRT (Association Kationale de la Recherche Technique) could serve as trace-element standards if such data were available. Similarly, the present NBS flint and plastic clays, as well as their predecessors, might be useful for archaeological pottery studies. The International Decade for Ocean Exploration may stimulate the preparation of ocean-water standards for trace elements or pollutants and a standard for manganese nodules.

Geochimica et Cosmochimica Acta

Enhanced microbial coalbed methane generation: A review of research, commercial activity, and remaining challenges

Coalbed methane (CBM) makes up a significant portion of the world’s natural gas resources. The discovery that approximately 20% of natural gas is microbial in origin has led to interest in microbially enhanced CBM (MECoM), which involves stimulating microorganisms to produce additional CBM from existing production wells. This paper reviews current laboratory and field research on understanding processes and reservoir conditions which are essential for microbial CBM generation, the progress of efforts to stimulate microbial methane generation in coal beds, and key remaining knowledge gaps. Research has been primarily focused on identifying microbial communities present in areas of CBM generation and attempting to determine their function, in-situ reservoir conditions that are most favorable for microbial CBM generation, and geochemical indicators of metabolic pathways of methanogenesis (i.e., acetoclastic or hydrogenotrophic methanogenesis). Meanwhile, researchers at universities, government agencies, and companies have focused on four primary MECoM strategies: 1) microbial stimulation (i.e., addition of nutrients to stimulate native microbes); 2) microbial augmentation (i.e., addition of microbes not native to or abundant in the reservoir of interest); 3) physically increasing microbial access to coal and distribution of amendments; and 4) chemically increasing the bioavailability of coal organics. Most companies interested in MECoM have pursued microbial stimulation: Luca Technologies, Inc., successfully completed a pilot scale field test of their stimulation strategy, while two others, Ciris Energy and Next Fuel, Inc., have undertaken smaller scale field tests. Several key knowledge gaps remain that need to be addressed before MECoM strategies can be implemented commercially. Little is known about the bacterial community responsible for coal biodegradation and how these microorganisms may be stimulated to enhance microbial methanogenesis. In addition, research is needed to understand what fraction of coal is available for biodegradation, and methods need to be developed to determine the extent of in-situ coal biodegradation by MECoM processes for monitoring changes to coal quality. Questions also remain about how well field-scale pilot tests will scale to commercial production, how often amendments will need to be added to maintain new methane generation, and how well MECoM strategies transfer between coal basins with different formation water geochemistries and coal ranks. Addressing these knowledge gaps will be key in determining the feasibility and commercial viability of MECoM technology.

International Journal of Coal Geology

Volcanic tremor masks its seismogenic source: Results from a study of noneruptive tremor recorded at Mount St. Helens, Washington

On 2 October 2004, a significant noneruptive tremor episode occurred during the buildup to the 2004–2008 eruption of Mount St. Helens (Washington). This episode was remarkable both because no explosion followed, and because seismicity abruptly stopped following the episode. This sequence motivated us to consider a model for volcanic tremor that does not involve energetic gas release from magma but does involve movement of conduit magma through extension on its way toward the surface. We found that the tremor signal was composed entirely of Love and Rayleigh waves and that its spectral bandwidth increased and decreased with signal amplitude, with broader bandwidth signals containing both higher and lower frequencies. Our modeling results demonstrate that the forces giving rise to this tremor were largely normal to conduit walls, generating hybrid head waves along conduit walls that are coupled to internally reflected waves. Together these form a crucial part of conduit resonance, giving tremor wavefields that are largely a function of waveguide geometry and velocity. We find that the mechanism of tremor generation fundamentally masks the nature of the seismogenic source giving rise to resonance. Thus multiple models can be invoked to explain volcanic tremor, requiring that information from other sources (such as visual observations, geodesy, geology, and gas geochemistry) be used to constrain source models. With concurrent GPS and field data supporting rapid rise of magma, we infer that tremor resulted from drag of nearly solid magma along rough conduit walls as magma was forced toward the surface.

Washington

Quality assurance and quality control of geochemical data—A primer for the research scientist

Geochemistry is a constantly expanding science. More and more, scientists are employing geochemical tools to help answer questions about the Earth and earth system processes. Scientists may assume that the responsibility of examining and assessing the quality of the geochemical data they generate is not theirs but rather that of the analytical laboratories to which their samples have been submitted. This assumption may be partially based on knowledge about internal and external quality assurance and quality control (QA/QC) programs in which analytical laboratories typically participate. Or there may be a perceived lack of time or resources to adequately examine data quality. Regardless of the reason, the lack of QA/QC protocols can lead to the generation and publication of erroneous data. Because the interpretations drawn from the data are primary products to U.S. Geological Survey (USGS) stakeholders, the consequences of publishing erroneous results can be significant. The principal investigator of a scientific study ultimately is responsible for the quality and interpretation of the project's findings, and thus must also play a role in the understanding, implementation, and presentation of QA/QC information about the data. Although occasionally ignored, QA/QC protocols apply not only to procedures in the laboratory but also in the initial planning of a research study and throughout the life of the project. Many of the tenets of developing a sound QA/QC program or protocols also parallel the core concepts of developing a good study: What is the main objective of the study? Will the methods selected provide data of enough resolution to answer the hypothesis? How should samples be collected? Are there known or unknown artifacts or contamination sources in the sampling and analysis methods? Assessing data quality requires communication between the scientists responsible for designing the study and those collecting samples, analyzing samples, treating data, and interpreting results. This primer has been developed to provide basic information and guidance about developing QA/QC protocols for geochemical studies. It is not intended to be a comprehensive guide but rather an introduction to key concepts tied to a list of relevant references for further reading. The guidelines are presented in stepwise order beginning with presampling considerations and continuing through final data interpretation. The goal of this primer is to outline basic QA/QC practices that scientists can use before, during, and after chemical analysis to ensure the validity of the data they collect with the goal of providing defendable results and conclusions.

Open-File Report

Organic geochemistry applied to environmental assessments of Prince William Sound, Alaska, after the Exxon Valdez oil spill—a review

Organic geochemistry played a major role in the environmental assessments conducted following the Exxon Valdez oil spill, which occurred on March 24, 1989, and released about 258,000 bbls (41 million liters) of Alaska North Slope crude oil into Prince William Sound. Geochemical analyses of more than 15,000 sediment, tar, and biological samples and about 5000 water samples provide the largest database yet collected on oil-spill chemistry, and we review the results here. The marine environment of the Sound has a complex background of petrogenic, pyrogenic, and biogenic hydrocarbons from natural and anthropogenic sources. Geochemical evaluation of the fate and effects of the spilled oil required that this oil and its residues be distinguished from the background. A variety of molecular and isotopic techniques were employed to identify various hydrocarbon sources and to distinguish quantitatively among mixed sources in the samples. Although the specific criteria used to distinguish multiple sources in the region affected by the Exxon Valdez spill are not necessarily applicable to all spill situations, the principles that governed their selection are. Distributions of polycyclic aromatic hydrocarbons (PAH) and dibenzothiophenes distinguish Exxon Valdez oil and its weathered residues from background hydrocarbons in benthic sediments. Ratios of C 2 -dibenzothiophene C 2 -phenanthrene "> C 2 -dibenzothiopheneC 2 -phenanthrene and C 3 -dibenzothiophene C 3 -phenanthrene "> C 3 -dibenzothiopheneC 3 -phenanthrene were particularly useful. Carbon isotopes and terpane distributions distinguished Exxon Valdez residues found on shorelines from tars from other sources. Diesel and diesel soot were identified by the absence of alkylated chrysenes and a narrow distribution of n -alkanes, whereas pyrogenic products were distinguished by the dominance of 4- to 6-ring PAH over 2- to 3-ring PAH and by the dominance of non-alkylated over alkylated homologues of each PAH series. The presence of 18α(H)-oleanane in benthic sediments, coupled with its absence in Exxon Valdez oil and its residues, confirm another petrogenic source. Results of geochemical studies suggest that the petrogenic component in the background of benthic sediments is derived from oil seeps in the eastern Gulf of Alaska. In 1990 and 1991, Exxon Valdez residues, generally forming a small increment to the pre-spill background, were found to be only sporadically distributed in some shallow, near shore sediments adjacent to shorelines that had been heavily oiled in 1989. In 1994, occurrences of Exxon Valdez tars on shoreline surfaces were rare, although residues could be found buried in shoreline sediments at some isolated locations along the spill path where they were protected from wave action. Spilled oil residues collected 16 months after the spill were degraded, on average, by nearly 50%. Shoreline residues from sources other than the spill were also identified and are widespread throughout the Sound. These residues include (1) geochemically distinct tars and oils imported from California oil fields to Alaska for fuel and construction purposes prior to the discovery of the Cook Inlet and North Slope oil fields, (2) diesel and diesel soot, and (3) more highly refined products. Of the more than 2700 chemical analyses of biological samples of higher life forms (fish, birds, and mammals) about 150 (6%) indicate recognizable residues of Exxon Valdez oil, which were identified by their distribution of polycyclic aromatic hydrocarbons (PAH). Most of these samples (138) were collected in 1989 and most were associated with external surfaces or the gastrointestinal tract. Rarely do internal tissues or fluids contain recognizable fingerprints of spilled oil. This observation includes samples from marine mammals that were visibly oiled externally. Other hydrocarbon sources, including diesel and a non-petroleum artifact that occurs when concentrations of individual PAH are at or near their method detection limit, are also identified in biological samples.

Alaska

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 2. Modeling carbon sources, sinks, and δ13C evolution

Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO 2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO 2 to respiration CO 2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO 2 to respiration CO 2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.

South Carolina

Trace element geochemistry of altered volcanic ash layers (tonsteins) in late Permian coal-bearing formations of eastern Yunnan and western Guizhou Provinces, China

Trace element compositions were determined (by instrumental neutron activation analysis; INAA) in 30 samples of synsedimentary volcanic ash-derived tonsteins and detrital claystones from coal seams within the late Permian coal-bearing formation of eastern Yunnan and western Guizhou Provinces, China. The characteristics of trace-element geochemistry in the tonsteins can be distinguished from those of detrital claystones because of the former's unique volcanic-ash origin. The detrital claystones are characterized by their relatively high content of V, Ti, Sc, Cr, Co and Ni, relatively low content of Th and U, Th/U ratio, and small negative Eu anomaly (Eu/Eu* 0.63-0.93). Overall, these trace element characteristics are consistent with a mafic source similar to the composition of basalt rocks in the erosional region on the western edge of the study area. In contrast, the tonsteins are low in V, Ti, Sc, Cr, Co and Ni contents and have a high Th/U ratio with a distinct negative Eu anomaly (Eu/Eu* normally in the range of 0.2-0.4), consistent with a silicic magmatic source. Within the group of tonsteins, those from the lower section (P2.1) of the coal-bearing formation are relatively high in Ti, Zr, Hf, Nb, Ta and rare earth elements (REE), as compared to those from the middle and upper sections (P2.2+3). In trace-element discrimination diagrams (scatter plots) of Hf-Ta, Ti-Ta, Ti-V, Hf-Sc, Lu-Hf and Lu-Th, tonsteins from the P2.1 horizon always fall in isolated distribution areas, separate from the tonsteins of the P2.2+3 horizon. These results suggest that the source materials of tonsteins from the two separate horizons were probably derived from volcanic ash falls of two distinctly different natures. Based on a comparison of the concentrations and assemblages of trace elements between various magmatic rocks, the source materials of tonsteins from P2.1 horizon were mostly composed of calc-alkalic, silica-poor volcanic ash (similar to rhyodacitic magma), whereas those from P2.+3 were apparently more siliceous and K-rich (rhyolitic magma). Thus, tonsteins from the two different horizons are characterized by unique geochemical properties, which remain constant over a wide lateral extent. Integration of trace-elemental compositions with mineralogical and textural observations makes possible the establishment of tonstein stratigraphy, thus, facilitating more precise and reliable coal-seam correlations. (C) 2000 Elsevier Science B.V. All rights reserved.Trace element compositions were determined in 30 samples of synsedimentary volcanic ash-derived tonsteins and detrital claystones from coal seams within the late Permian coal-bearing formation of eastern Yunnan and western Guizhou Provinces, China. The characteristics of trace-element geochemistry in the tonsteins can be distinguished from those of detrital claystones because of the former's unique volcanic-ash origin. The detrital claystones are characterized by their relatively high content of V, Ti, Sc, CR, Co and Ni, relatively low content of Th and U, Th/U ratio, and small negative Eu anomaly.

International Journal of Coal Geology

Host-rock controlled epigenetic, hydrothermal metasomatic origin of the Bayan Obo REEFe-Nb ore deposit, Inner Mongolia, P.R.C.

Bayan Obo, a complex rare earth element (REE) Fe Nb ore deposit, located in Inner Mongolia, P.R.C. is the world's largest known REE deposit. The deposit is chiefly in a marble unit (H8), but extends into an overlying unit of black shale, slate and schist unit (H9), both of which are in the upper part of the Middle Proterozoic Bayan Obo Group. Based on sedimentary structures, the presence of detrital quartz and algal fossil remains, and the 16-km long geographic extent, the H8 marble is a sedimentary deposit, and not a carbonatite of magmatic origin, as proposed by some previous investigators. The unit was weakly regionally metamorphosed (most probably the lower part of the green schist facies) into marble and quartzite prior to mineralization. Tectonically, the deposit is located on the northern flank of the Sino-Korean craton. Many hypotheses have been proposed for the origin of the Bayan Obo deposit; the studies reported here support an epigenetic, hydrothermal, metasomatic origin. Such an origin is supported by field and laboratory textural evidence; 232 Th/ 208 Pb internal isochron mineral ages of selected monazite and bastnaesite samples; 40 Ar/ 39 Ar incremental heating minimum mineral ages of selected alkali amphiboles; chemical compositions of different generations of both REE ore minerals and alkali amphiboles; and evidence of host-rock influence on the various types of Bayan Obo ores. The internal isochron ages of the REE minerals indicate Caledonian ages for various episodes of REE and Fe mineralization. No evidence was found to indicate a genetic relation between the extensive biotite granitic rocks of Hercynian age in the mine region and the Bayan Obo are deposit, as suggested by previous workers.

Applied Geochemistry

The U.S.Geological Survey Energy Resources Program

Energy resources are an essential component of modern society. Adequate, reliable, and affordable energy supplies obtained using environmentally sustainable practices underpin economic prosperity, environmental quality and human health, and political stability. National and global demands for all forms of energy are forecast to increase significantly over the next several decades. Throughout its history, our Nation has faced important, often controversial, decisions regarding the competing uses of public lands, the supply of energy to sustain development and enable growth, and environmental stewardship. The U.S. Geological Survey (USGS) Energy Resources Program (ERP) provides information to address these challenges by supporting scientific investigations of energy resources, such as research on the geology, geochemistry, and geophysics of oil, gas, coal, heavy oil and natural bitumen, oil shale, uranium, and geothermal resources, emerging resources such as gas hydrates, and research on the effects associated with energy resource occurrence, production, and (or) utilization. The results from these investigations provide impartial, robust scientific information about energy resources and support the U.S. Department of the Interior's (DOI's) mission of protecting and responsibly managing the Nation's natural resources. Primary consumers of ERP information and products include the DOI land- and resource-management Bureaus; other Federal, State, and local agencies; the U.S. Congress and the Administration; nongovernmental organizations; the energy industry; academia; international organizations; and the general public.

Fact Sheet

Germanium redistribution during weathering of Zn mine wastes: Implications for environmental mobility and recovery of a critical mineral

Germanium (Ge) is a metal used in emerging energy technologies, communications, and defense, and has been deemed critical by the United States due to its essential applications and scarce supply. Germanium is recovered as a byproduct of zinc (Zn) sulfides, and mining and processing of these materials lead to waste that could act both as a source of extractable Ge and a source for exposure to humans and ecosystems. Yet the distribution, speciation, and mineral hosts of Ge in mining-impacted areas are poorly understood. The Tar Creek Superfund Site, a former Zn mining area and Ge producer, is a natural laboratory to understand the environmental behavior and economic implications of Ge in mine wastes. We studied the distribution and behavior of Ge in solid wastes at the Tar Creek Superfund Site using bulk and microanalytical techniques. In wastes at this site we find that Ge has been redistributed from its original host, sphalerite (ZnS), to the fine-grained weathering product hemimorphite (Zn4Si2O7(OH)2·H2O), which impacts germanium's mobility, bioaccessibility, and potential for recovery. We provide chemical and mineralogical evidence of this redistribution, along with an evaluation of the oxidation state and molecular-scale substitution of Ge into sphalerite, hemimorphite, and quartz. Geochemical modeling shows that hemimorphite is more stable than sphalerite in waste piles and provides a stable secondary repository for Ge. However, hemimorphite is fine-grained, and if ingested or inhaled is readily soluble, with the potential to release Ge. Lastly, we discuss other sites internationally where similar behavior may be important. This study shows that weathering can have a significant impact on the distribution, speciation, and mineral hosts of Ge in mine wastes; directly influence mobilization from waste piles and subsequent availability to humans and ecosystems; and dictate metallurgical strategies to target Ge for recovery.

Oklahoma

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group--Determination of dissolved isoxaflutole and its sequential degradation products, diketonitrile and benzoic acid, in water using solid-phase extraction and liquid chromatography/tandem mass spectrometry

An analytical method for the determination of isoxaflutole and its sequential degradation products, diketonitrile and a benzoic acid analogue, in filtered water with varying matrices was developed by the U.S. Geological Survey Organic Geochemistry Research Group in Lawrence, Kansas. Four different water-sample matrices fortified at 0.02 and 0.10 ug/L (micrograms per liter) are extracted by vacuum manifold solid-phase extraction and analyzed by liquid chromatography/tandem mass spectrometry using electrospray ionization in negative-ion mode with multiple-reaction monitoring (MRM). Analytical conditions for mass spectrometry detection are optimized, and quantitation is carried out using the following MRM molecular-hydrogen (precursor) ion and product (p) ion transition pairs: 357.9 (precursor), 78.9 (p), and 277.6 (p) for isoxaflutole and diketonitrile, and 267.0 (precursor), 159.0 (p), and 223.1 (p) for benzoic acid. 2,4-dichlorophenoxyacetic acid-d3 is used as the internal standard, and alachlor ethanesulfonic acid-d5 is used as the surrogate standard. Compound detection limits and reporting levels are calculated using U.S. Environmental Protection Agency procedures. The mean solid-phase extraction recovery values ranged from 104 to 108 percent with relative standard deviation percentages ranging from 4.0 to 10.6 percent. The combined mean percentage concentration normalized to the theoretical spiked concentration of four water matrices analyzed eight times at 0.02 and 0.10 ug/L (seven times for the reagent-water matrix at 0.02 ug/L) ranged from approximately 75 to 101 percent with relative standard deviation percentages ranging from approximately 3 to 26 percent for isoxaflutole, diketonitrile, and benzoic acid. The method detection limit (MDL) for isoxaflutole and diketonitrile is 0.003 ug/L and 0.004 ug/L for benzoic acid. Method reporting levels (MRLs) are 0.011, 0.010, and 0.012 ug/L for isoxaflutole, diketonitrile, and benzoic acid, respectively. On the basis of the calculated MRLs and MDLs and evaluation of the signal-to-noise ratios for each compound, the MRLs and MDLs are set at 0.010 and 0.003 ug/L, respectively, for all three compounds.

Techniques and Methods

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group—Determination of glyphosate, aminomethylphosphonic acid, and glufonsinate in water using online solid-phase extraction and high-performance liquid chromatography/mass spectrometry

An analytical method for the determination of glyphosate, its principal degradation compound, aminomethylphosphonic acid (AMPA), and glufosinate in water with varying matrices has been developed. Four different sample matrices fortified at 0.2 and 2.0 μg/L (micrograms per liter) were analyzed using precolumn derivatization with 9-fluorenylmethylchloroformate (FMOC). After derivatization, cleanup and concentration were accomplished using automated online solid-phase extraction followed by elution with the mobile phase allowing for direct injection into a liquid chromatograph/mass spectrometer (LC/MS). Analytical conditions for MS detection were optimized, and quantitation was carried out using the following representative ions: 390 and 168 for glyphosate; 332, 110, and 136 for AMPA; and 402, 180, and 206 for glufosinate. Matrix effects were minimized by utilizing standard addition for quantification and an isotope-labeled glyphosate (2- 13 C, 15 N) as the internal standard. Method detection limits (MDLs) were 0.084 μg/L for glyphosate, 0.078 μg/L for AMPA, and 0.057 μg/L for glufosinate. The method reporting limits (MRLs) were set at 0.1 μg/L for all three compounds. The mean recovery values ranged from 88.0 to 128.7 percent, and relative standard deviation values ranged from 5.6 to 32.6 percent.

Open-File Report

Holocene sedimentary architecture and paleoclimate variability at Mono Lake, California

Mono Lake occupies an internally drained basin on the eastern flank of the Sierra Nevada, and it is sensitive to climatic changes affecting precipitation in the mountains (largely delivered in the form of snowpack). Efforts to recover cores from the lake have been impeded by coarse tephra erupted from the Mono Craters, and by disruption of the lake floor due to the uplift of Paoha Island ~300 yr ago. In this study, we describe the stratigraphy of cores from three recent campaigns, in 2007, 2009, and 2010, and the extents and depths of the tephras and disturbed sediments. In the most successful of these cores, BINGO-MONO10-4A-1N (BINGO/10-4A, 2.8 m water depth), we used core stratigraphy, geochemistry, radiocarbon dates, and tephrostratigraphy to show that the core records nearly all of the Holocene in varying proportions of detrital, volcanic, and authigenic sediment. Both the South Mono tephra of ca. 1350 cal yr B.P. (calibrated years before A.D. 1950) and the 600-yr-old North Mono–Inyo tephra are present in the BINGO/10-4A core, as are several older, as-yet-unidentified tephras. Laminated muds are inferred to indicate a relatively deep lake (³10 m over the core site) during the Early Holocene, similar to many records across the region during that period. The Middle and Late Holocene units are more coarsely bedded, and coarser grain size and greater and more variable amounts of authigenic carbonate detritus in this interval are taken to suggest lower lake levels, possibly due to lower effective wetness. A very low lake level, likely related to extreme drought, is inferred to have occurred sometime between 3500 and 2100 cal yr B.P. This interval likely corresponds to the previously documented Marina Low Stand and the regional Late Holocene Dry Period. The BINGO/10-4A core does not preserve a complete record of the period encompassing the Medieval Climate Anomaly, the Little Ice Age, and the historical period, probably due to erosion because of its nearshore position.

Califiornia

Standard reference water samples for rare earth element determinations

Standard reference water samples (SRWS) were collected from two mine sites, one near Ophir, CO, USA and the other near Redding, CA, USA. The samples were filtered, preserved, and analyzed for rare earth element (REE) concentrations (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) by inductively coupled plasma-mass spectrometry (ICP-MS). These two samples were acid mine waters with elevated concentrations of REEs (0.45–161 μg/l). Seventeen international laboratories participated in a ‘round-robin’ chemical analysis program, which made it possible to evaluate the data by robust statistical procedures that are insensitive to outliers. The resulting most probable values are reported. Ten to 15 of the participants also reported values for Ba, Y, and Sc. Field parameters, major ion, and other trace element concentrations, not subject to statistical evaluation, are provided.

Applied Geochemistry