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USGS2011

Processes affecting geochemistry and contaminant movement in the middle Claiborne aquifer of the Mississippi embayment aquifer system

Groundwater chemistry and tracer-based age data were used to assess contaminant movement and geochemical processes in the middle Claiborne aquifer (MCA) of the Mississippi embayment aquifer system. Water samples were collected from 30 drinking-water wells (mostly domestic and public supply) and analyzed for nutrients, major ions, pesticides, volatile organic compounds (VOCs), and transient age tracers (chlorofluorocarbons, tritium and helium-3, and sulfur hexafluoride). Redox conditions are highly variable throughout the MCA. However, mostly oxic groundwater with low dissolved solids is more vulnerable to nitrate contamination in the outcrop areas east of the Mississippi River in Mississippi and west Tennessee than in mostly anoxic groundwater in downgradient areas in western parts of the study area. Groundwater in the outcrop area was relatively young (apparent age of less than 40 years) with significantly ( p < 0.05) higher dissolved oxygen and nitrate–N concentrations and higher detections of pesticides and VOCs compared to water samples from wells in downgradient areas. Oxygen reduction and denitrification rates were low compared to other aquifers in the United States (zero order rate constants for oxygen reduction and denitrification were 4.7 and 5–10 μmol/L/year, respectively). Elevated concentrations of nitrate–N, and detections of pesticides and VOCs in some deep public supply wells (>50 m depth) indicated contaminant movement from shallow parts of the aquifer into deeper oxic zones. Given the persistence of nitrate in young oxic groundwater that was recharged several decades ago, and the lack of a confining unit, the downward movement of young contaminated water may result in higher nitrate concentrations over time in deeper parts of the aquifer containing older oxic water.

Claiborne Aquifer;Mississippi Embayment↗

USGS2001

Evidence and characteristics of hydrolytic disproportionation of organic matter during metasomatic processes

Petroleum-geochemical analyses of carbonaceous regionally metamorphosed rocks, carbonaceous rocks from ore deposits, and alkalic plutonic rocks from diverse settings, demonstrated the presence of very low to moderately low concentrations of solvent-extractable organic matter, this observation in spite of the fact that some of these rocks were exposed to extremely high metamorphic temperatures. Biomarker and ??13C analyses established that the extractable organic matter originated as sedimentary-derived hydrocarbons. However, the chemistry of the extractable bitumen has been fundamentally transformed from that found in sediment bitumen and oils. Asphaltenes and resins, as defined in the normal petroleum-geochemical sense, are completely missing. The principal aromatic hydrocarbons present in oils and sediment bitumens (especially the methylated naphthalenes) are either in highly reduced concentrations or are missing altogether, Instead, aromatic hydrocarbons typical of sediment bitumens and oils are very minor, and a number of unidentified compounds and oxygen-bearing compounds are dominant. Relatively high concentrations of alkylated benzenes are typical. The polar "resin" fraction, eluted during column chromatography, is the principal compound group, by weight, being composed of six to eight dominant peaks present in all samples, despite the great geologic diversity of the samples. These, and other, observations suggest that a strong drive towards equilibrium exists in the "bitumen." Gas chromatograms of the saturated hydrocarbons commonly have a pronounced hump in both the n-paraffins and naphthenes, centered near the C19 to C26 carbon numbers, and a ubiquitos minimum in the n-paraffin distribution near n-C12 to n-C14. Multiple considerations dictate that the bitumen in the samples is indigenous and did not originate from either surficial field contamination or from laboratory procedures. Our observations are consistent with the hydrolytic disproportion of organic matter (HDOM), in which water and organic matter, including hydrocarbons, easily exchange hydrogen or oxygen with one another under certain conditions (Helgeson et al., 1993). The process appears to take place via well-known organic-chemical redox reaction pathways and is most evident in open-fluid systems. The conclusion that HDOM took place in the analyzed samples, thus producing the chemistry of the extractable bitumen, is supported by numerous previously published organic-geochemical studies of metamorphic, volcanic, plutonic, and ore-deposit-related rocks by other investigators. HDOM is suggested as an unrecognized geologic agent of fundamental importance. The process appears to control major chemical reactions in diverse geologic environments including, but not limited to, petroleum geology and geochemistry, regional metamorphism, and base- and precious-metal ore deposition. Copyright ?? 2001 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

USGS2017

Abundant carbon substrates drive extremely high sulfate reduction rates and methane fluxes in Prairie Pothole Wetlands

Inland waters are increasingly recognized as critical sites of methane emissions to the atmosphere, but the biogeochemical reactions driving such fluxes are less well understood. The Prairie Pothole Region (PPR) of North America is one of the largest wetland complexes in the world, containing millions of small, shallow wetlands. The sediment pore waters of PPR wetlands contain some of the highest concentrations of dissolved organic carbon (DOC) and sulfur species ever recorded in terrestrial aquatic environments. Using a suite of geochemical and microbiological analyses, we measured the impact of sedimentary carbon and sulfur transformations in these wetlands on methane fluxes to the atmosphere. This research represents the first study of coupled geochemistry and microbiology within the PPR and demonstrates how the conversion of abundant labile DOC pools into methane results in some of the highest fluxes of this greenhouse gas to the atmosphere ever reported. Abundant DOC and sulfate additionally supported some of the highest sulfate reduction rates ever measured in terrestrial aquatic environments, which we infer to account for a large fraction of carbon mineralization in this system. Methane accumulations in zones of active sulfate reduction may be due to either the transport of free methane gas from deeper locations or the co-occurrence of methanogenesis and sulfate reduction. If both respiratory processes are concurrent, any competitive inhibition of methanogenesis by sulfate-reducing bacteria may be lessened by the presence of large labile DOC pools that yield noncompetitive substrates such as methanol. Our results reveal some of the underlying mechanisms that make PPR wetlands biogeochemical hotspots, which ultimately leads to their critical, but poorly recognized role in regional greenhouse gas emissions.

North Dakota↗

USGS2003

Geochemistry of Permian rocks from the margins of the Phosphoria Basin: Lakeridge core, western Wyoming

The Permian Phosphoria Formation and interbedded units of the Park City Formation and Shedhorn Sandstone in western Wyoming represent deposition along a carbonate ramp at the eastern margin of the Phosphoria Basin, with portions of the Phosphoria units reflecting periods of upwelling and widespread phosphogenesis. Thickness-weighted slab-samples of these units were collected at a maximum interval of 3 m along an 80+ m-length of unweathered core and analyzed for major-, minor-, and trace-element contents. Interpretations of geochemistry were made within the confines of a previously recognized sequence stratigraphy framework. Major shifts in element ratios characteristic of terrigenous debris that occur at sequence boundaries at the base of the Meade Peak and Retort Members of the Phosphoria Formation are attributed to changing sediment sources. Inter-element relationships in the marine fraction indicate that bottom waters of the Phosphoria Basin were predominantly denitrifying during deposition of the Ervay, Grandeur, and Phosphoria sediments, although sulfate-reducing conditions may have existed during deposition of the lower Meade Peak sediments. Oxic conditions were prevalent during deposition of a large part of the Franson Member, which represents sedimentation in a shallow, inner- to back-ramp setting. Variations in sediment facies and organic matter and trace element contents largely reflect changes in Permian sea level. Changes in sea level in basin-margin areas, such as represented by the study section, may have affected the oxidation of settling organic matter, the foci of intersection of upwelling bottom waters with the photic zone, the rate of terrigenous sedimentation, and, ultimately, the overall environment of deposition. Our study suggests that phosphogenesis can occur under lowstand, transgressive, and highstand conditions in marginal areas, assuming water depths sufficient for upwelling to occur. Formation of phosphorite layers under upwelling conditions appears to have been most dependent on a lack of dilution by terrigenous sedimentation and carbonate shoaling. Differences in the geochemistry between two similar environments represented by the upper and lower Phosphoria units are largely attributed to higher rates of diluting terrigenous sediment during deposition of the upper unit. This is consistent with prior interpretations of a more shoreward setting for the upper Phosphoria.

Wyoming↗

USGS1991

Geochemistry of halogens in the Milk River aquifer, Alberta, Canada

Analytical data are presented for Cl, Br and I on a regional scale for the Milk River aquifer. The three halides show strikingly similar spatial distributions and are highly correlated. Concentrations are low in the freshwater portions of the aquifer but increase by as much as two orders of magnitude along the margins. However, halide ratios reach nearly constant values moving down-gradient, suggesting the dominance of a common subsurface source for these ions. Ratios of Cl/I and Cl/Br are less than those of seawater and fit an origin derived from the diagenesis of organic matter in the sediments. Halide ratios rule out leakage and/or diffusion from the underlying Colorado Group as a major influence on the chemistry; the favored hypothesis is altered connate seawater diffusing from low-permeability units within the Milk River Formation as the primary source of salts. This hypothesis of an internal source has important implications for solute sources in other aquifers affected by saline waters because it does not require the importation of a distant fluid.

Alberta↗

USGS1988

Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.-1: Buffering capacity of dissolved organic carbon in soil solutions

Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai − , derived from DOC at sample pH and the concentration of organic anion, Ax − at the equivalence point were calculated using car☐yl contents from isolated and purified humic material from soil solutions. Subtracting Ax − from Ai − yields the contribution of humic substances to the buffering capacity (A equiv. − ). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado.

Colorado↗

USGS2009

Feldspar dissolution rates in the Topopah Spring Tuff, Yucca Mountain, Nevada

Two different field-based methods are used here to calculate feldspar dissolution rates in the Topopah Spring Tuff, the host rock for the proposed nuclear waste repository at Yucca Mountain, Nevada. The center of the tuff is a high silica rhyolite, consisting largely of alkali feldspar (∼60 wt%) and quartz polymorphs (∼35 wt%) that formed by devitrification of rhyolitic glass as the tuff cooled. First, the abundance of secondary aluminosilicates is used to estimate the cumulative amount of feldspar dissolution over the history of the tuff, and an ambient dissolution rate is calculated by using the estimated thermal history. Second, the feldspar dissolution rate is calculated by using measured Sr isotope compositions for the pore water and rock. Pore waters display systematic changes in Sr isotopic composition with depth that are caused by feldspar dissolution. The range in dissolution rates determined from secondary mineral abundances varies from 10 −16 to 10 −17 mol s −1 kg tuff −1 with the largest uncertainty being the effect of the early thermal history of the tuff. Dissolution rates based on pore water Sr isotopic data were calculated by treating percolation flux parametrically, and vary from 10 −15 to 10 −16 mol s −1 kg tuff −1 for percolation fluxes of 15 mm a −1 and 1 mm a −1 , respectively. Reconciling the rates from the two methods requires that percolation fluxes at the sampled locations be a few mm a −1 or less. The calculated feldspar dissolution rates are low relative to other measured field-based feldspar dissolution rates, possibly due to the age (12.8 Ma) of the unsaturated system at Yucca Mountain; because oxidizing and organic-poor conditions limit biological activity; and/or because elevated silica concentrations in the pore waters (∼50 mg L −1 ) may inhibit feldspar dissolution.

Nevada↗

USGS1992

Relationship between inferred redox potential of the depositional environment and geochemistry of the Upper Pennsylvanian (Missourian) Stark Shale Member of the Dennis Limestone, Wabaunsee County, Kansas, U.S.A.

Analyses of 21 samples collected from a core of the 52.8-cm-thick Stark Shale Member of the Dennis Limestone in Wabaunsee County, Kansas, demonstrate four cycles with two-orders-of-magnitude variations in contents of Cd, Mo, P, V and Zn, and order-of-magnitude variations in contents of organic carbon, Cr, Ni, Se and U. The observed variability in amounts and/or ratios of many metals and amounts and compositions of the organic matter appear related to the cause and degree of water-column stratification and the resulting absence/presence of dissolved O2 or H2S. High Cd, Mo, U, V, Zn and S contents, a high degree of pyritization (DOP) (0.75-0.88), and high high V (V + Ni) (0.84-0.89) indicate the presence of H2S in a strongly stratified water column. Intermediate contents of metals and S, intermediate DOP (0.67-0.75) and intermediate V (V + Ni) (054-0.82) indicate a less strongly stratified anoxic water column. Whereas, low metal contents and low V (V + Ni) (0.46-0.60) indicate a weakly stratified, dysoxic water column. High P contents at the top of the organic-matter-rich intervals within the Stark Shale Member indicate that phosphate precipitation was enhanced near the boundary between anoxic and dysoxic water compositions. Relatively abundant terrestrial organic matter in intervals deposited from the more strongly stratified H2S-bearing water column indicates a combined halocline-thermocline with the fresher near-surface water the transport mode for the terrestrial organic matter. The predominance of algal organic matter in intervals deposited from a less strongly stratified water column indicates the absence of the halocline and the presence of the more generally established thermocline. Relatively low amounts of degraded, hydrogen-poor organic matter characterize intervals deposited in a weakly stratified, dysoxic water column. The inferred variability in chemistry of the depositional environments may be related to climate variations and/or minor changes in sea level during the general phase of deeper water deposition responsible for this widespread shale member. ?? 1992.

Chemical Geology↗

USGS2020

Endocrine disrupting activities and geochemistry of water resources associated with unconventional oil and gas activity

The rise of hydraulic fracturing and unconventional oil and gas (UOG) exploration in the United States has increased public concerns for water contamination induced from hydraulic fracturing fluids and associated wastewater spills. Herein, we collected surface and groundwater samples across Garfield County, Colorado, a drilling-dense region, and measured endocrine bioactivities, geochemical tracers of UOG wastewater, UOG-related organic contaminants in surface water, and evaluated UOG drilling production (weighted well scores, nearby well count, reported spills) surrounding sites. Elevated antagonist activities for the estrogen, androgen, progesterone, and glucocorticoid receptors were detected in surface water and associated with nearby shale gas well counts and density. The elevated endocrine activities were observed in surface water associated with medium and high UOG production (weighted UOG well score-based groups). These bioactivities were generally not associated with reported spills nearby, and often did not exhibit geochemical profiles associated with UOG wastewater from this region. Our results suggest the potential for releases of low-saline hydraulic fracturing fluids or chemicals used in other aspects of UOG production, similar to the chemistry of the local water, and dissimilar from defined spills of post-injection wastewater. Notably, water collected from certain medium and high UOG production sites exhibited bioactivities well above the levels known to impact the health of aquatic organisms, suggesting that further research to assess potential endocrine activities of UOG operations is warranted.

Science of the Total Environment↗

USGS1993

Understanding our fragile environment; Lessons from geochemical studies

An understanding of our fragile environment can begin with a recognition of the importance of certain elements, commonly called "minerals substances" (such as iron and zinc), in the lives of humans and animals and in the soils that support plants. This recognition is well deserved because these elements are essential for the life or optimum health of an organism. Some elements such as carbon, hydrogen, oxygen, magnesium, potassium, and phosphorus are required in relatively large amounts by organisms. However, others are required in smaller quantities; these are referred to as trace elements. Diseases have been related to the deficiency of about 20 elements in animals and humans and to the deficiency of approximately 13 elements in plants. At the same time, if these and other elements occur in quantities great enough, toxicity can result. An element, or any substance, that occurs in the environment and contains concentrations above what are considered to be background levels may be considered a contaminant. When contaminants occur at levels that are potentially harmful to organisms, they are labeled as hazards. Often the quantitative difference between essential amounts and toxic concentrations of these elements is very small. For example, the trace element selenium is required at a level of no less than 0.4 ppm in the diet of cattle but can be toxic at levels greater than approximately 4ppm. Elements that are required for survival by animals and plants are termed essential, while those not required are nonessential. Trace essential elements such as fluorine, copper, selenium, molybdenum, and others listed in the table on page 1 can be hazardous to life forms if present at high levels. Nonessential heavy metals such as arsenic, lead, mercury, cadmium, and chromium are usually toxic to organisms at much lower levels than trace essential elements. Depending on the association that these nonessential elements may form with natural geologic materials such as organic matter, other elements or minerals, and adsorbers (such as clays), these elements can range from being safe to being extremely toxic. The elemental composition of plants, animals, and humans correlates with the geologic makeup of the Earth, and life has evolved reflecting these natural occurrences. The science of environmental geochemistry examines the interrelationship of life with the physical and chemical Earth.

Circular↗

USGS2011

Responses of soil and water chemistry to mountain pine beetle induced tree mortality in Grand County, Colorado, USA

Pine forest in northern Colorado and southern Wyoming, USA, are experiencing the most severe mountain pine beetle epidemic in recorded history, and possible degradation of drinking-water quality is a major concern. The objective of this study was to investigate possible changes in soil and water chemistry in Grand County, Colorado in response to the epidemic, and to identify major controlling influences on stream-water nutrients and C in areas affected by the mountain pine beetle. Soil moisture and soil N increased in soils beneath trees killed by the mountain pine beetle, reflecting reduced evapotranspiration and litter accumulation and decay. No significant changes in stream-water NO 3 - "> NO 3 - or dissolved organic C were observed; however, total N and total P increased, possibly due to litter breakdown or increased productivity related to warming air temperatures. Multiple-regression analyses indicated that % of basin affected by mountain pine beetles had minimal influence on stream-water NO 3 - "> NO 3 - and dissolved organic C; instead, other basin characteristics, such as percent of the basin classified as forest, were much more important.

Colorado↗

USGS2011

Chromium(VI) generation in vadose zone soils and alluvial sediments of the southwestern Sacramento Valley, California: a potential source of geogenic Cr(VI) to groundwater

Concentrations of geogenic Cr(VI) in groundwater that exceed the World Health Organization’s maximum contaminant level for drinking water (50 μg L −1 ) occur in several locations globally. The major mechanism for mobilization of this Cr(VI) at these sites is the weathering of Cr(III) from ultramafic rocks and its subsequent oxidation on Mn oxides. This process may be occurring in the southern Sacramento Valley of California where Cr(VI) concentrations in groundwater can approach or exceed 50 μg L −1 . To characterize Cr geochemistry in the area, samples from several soil auger cores (approximately 4 m deep) and drill cores (approximately 25 m deep) were analyzed for total concentrations of 44 major, minor and trace elements, Cr associated with labile Mn and Fe oxides, and Cr(VI). Total concentrations of Cr in these samples ranged from 140 to 2220 mg per kg soil. Between 9 and 70 mg per kg soil was released by selective extractions that target Fe oxides, but essentially no Cr was associated with the abundant reactive Mn oxides (up to ~1000 mg hydroxylamine-reducible Mn per kg soil was present). Both borehole magnetic susceptibility surveys performed at some of the drill core sites and relative differences between Cr released in a 4-acid digestion versus total Cr (lithium metaborate fusion digestion) suggest that the majority of total Cr in the samples is present in refractory chromite minerals transported from ultramafic exposures in the Coast Range Mountains. Chromium(VI) in the samples studied ranged from 0 to 42 μg kg −1 , representing a minute fraction of total Cr. Chromium(VI) content was typically below detection in surface soils (top 10 cm) where soil organic matter was high, and increased with increasing depth in the soil auger cores as organic matter decreased. Maximum concentrations of Cr(VI) were up to 3 times greater in the deeper drill core samples than the shallow auger cores. Although Cr(VI) in these vadose zone soils and sediments was only a very small fraction of the total solid phase Cr, they are a potentially important source for Cr(VI) to groundwater. Enhanced groundwater recharge through the vadose zone due to irrigation could carry Cr(VI) from the vadose zone to the groundwater and may be the mechanism responsible for the correlation observed between elevated Cr(VI) and NO 3 - source concentrations in previously published data for valley groundwaters. Incubation of a valley subsoil showed a Cr(VI) production rate of 24 μg kg −1 a −1 suggesting that field Cr(VI) concentrations could be regenerated annually. Increased Cr(VI) production rates in H + -amended soil incubations indicate that soil acidification processes such as nitrification of ammonium in fertilizers could potentially increase the occurrence of geogenic Cr(VI) in groundwater. Thus, despite the natural origin of the Cr, Cr(VI) generation in the Sacramento Valley soils and sediments has the potential to be influenced by human activities.

California↗

USGS2012

Selected water-quality data from the Cedar River and Cedar Rapids well fields, Cedar Rapids, Iowa, 2006-10

The Cedar River alluvial aquifer is the primary source of municipal water in the Cedar Rapids, Iowa area. Municipal wells are completed in the alluvial aquifer approximately 40 to 80 feet below land surface. The City of Cedar Rapids and the U.S. Geological Survey have been conducting a cooperative study of the groundwater-flow system and water quality of the aquifer since 1992. Cooperative reports between the City of Cedar Rapids and the U.S. Geological Survey have documented hydrologic and water-quality data, geochemistry, and groundwater models. Water-quality samples were collected for studies involving well field monitoring, trends, source-water protection, groundwater geochemistry, surface-water-groundwater interaction, and pesticides in groundwater and surface water. Water-quality analyses were conducted for major ions (boron, bromide, calcium, chloride, fluoride, iron, magnesium, manganese, potassium, silica, sodium, and sulfate), nutrients (ammonia as nitrogen, nitrite as nitrogen, nitrite plus nitrate as nitrogen, and orthophosphate as phosphorus), dissolved organic carbon, and selected pesticides including two degradates of the herbicide atrazine. Physical characteristics (alkalinity, dissolved oxygen, pH, specific conductance and water temperature) were measured in the field and recorded for each water sample collected. This report presents the results of routine water-quality data-collection activities from January 2006 through December 2010. Methods of data collection, quality-assurance, and water-quality analyses are presented. Data include the results of water-quality analyses from quarterly sampling from monitoring wells, municipal wells, and the Cedar River.

Iowa↗

USGS2020

Hydrogeology and shallow groundwater quality in the tidal Anacostia River watershed, Washington, D.C.

Groundwater hydrology and geochemistry within the tidal Anacostia River watershed of Washington, D.C. are related to natural and human influences. The U.S. Geological Survey, in cooperation with the District Department of Energy & Environment, began investigating the hydrogeology and groundwater quality of the watershed in 2002. Lithologic coring, groundwater-level and tidal monitoring, and water-quality sampling have been conducted to improve understanding of the groundwater-flow system, geochemistry, water quality, and the likely interaction between groundwater and the tidal Anacostia River. The flow and interaction of shallow groundwater with the tidal Anacostia River and other area streams are affected by diversions, pumping, land reclamation, and other human activities in this highly urbanized watershed. The tidal Anacostia River watershed is underlain by a wedge of unconsolidated sediments that is part of the Atlantic Coastal Plain Physiographic Province. These sediments form a system of confined and unconfined aquifers. The coarse sediments of the Potomac Group sand-dominated lithofacies form the Patuxent aquifer. The Patuxent aquifer crops out and subcrops in the northwestern part of the study area, but is confined to the southeast by the overlying Potomac Group clay-dominated lithofacies. Overlying the Potomac Group is a series of interbedded sands and clays that form an unconfined surficial aquifer system. Regional correlation in the unconfined surficial aquifer system is complicated by local heterogeneity in aquifer sediments. Local perched and semi-confined conditions occur in some areas. Recharge of the confined Patuxent aquifer occurs primarily in the outcrop and subcrop area, although some recharge may also occur through overlying confining units. Recharge to the unconfined surficial aquifer system occurs through infiltration of precipitation and possible artificial recharge from structures such as underground water or sewer pipes. In the Patuxent aquifer, hydraulic gradients indicate downward movement in the outcrop area, whereas hydraulic heads beneath the Anacostia River are higher than land surface, indicating an upward hydraulic gradient. In the unconfined surficial aquifer system, groundwater generally flows from upland recharge areas towards discharge areas near the Anacostia River and its tributaries. Groundwater from the confined part of the Patuxent aquifer also may discharge to the Anacostia River in locations where the overlying clay-dominated lithofacies of the Potomac Group is absent as a result of past geologic and (or) alluvial processes. Geochemistry and groundwater quality are affected by hydrologic conditions as well as anthropogenic influences. Local variability in groundwater quality reflects local variability in hydrogeologic conditions and sources of chemicals. Groundwater ranges from anoxic and iron- or calcium-bicarbonate type, to oxic with elevated nitrate. The occurrence and distribution of pesticides, volatile organic compounds, and other selected chemical compounds in groundwater reflect the multitude of sources common to urban areas, as well as variable hydrogeologic and geochemical conditions that affect their fate and transport in the environment. Overall, concentrations of only a few of the over 200 chemical constituents included in laboratory analyses exceeded regulatory standards or guidance values. These include tetrachloroethene and arsenic, which were each detected one time in different wells. There were also several detections of iron and manganese that exceeded regulatory standards or guidance values that are associated with reducing conditions in aquifer sediments.

Washington, D.C.↗

USGS1993

Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils

Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300??C for 2348 h. The high-oxygen oil was also heated at 200??C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum. The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10-30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils. ?? 1993.

Applied Geochemistry↗

USGS2004

The geochemistry of Seine River Basin particulate matter: Distribution of an integrated metal pollution index

Spatial analysis (1994-2001) and temporal trends (1980-2000) for particulate-associated metals at key stations in the Seine River Basin have been determined using a new metal pollution index (MPI). The MPI is based on the concentrations of Cd, Cu, Hg, Pb and Zn, normalized to calculated background levels estimated for each particulate matter samples for four fractions (clays and other aluminosilicates, carbonates, organic matter, and quartz). Background levels ascribed to each fraction were determined from a specific set of samples collected from relatively pristine areas in the upper Seine basin and validated on prehistoric samples. The unitless MPI is designed to vary between 0 for pristine samples to 100 for the ones extremely impacted by human activities and to assess the trends of general metal contamination and its mapping. Throughout the Seine basin, MPI currently range from 1 to 40, but values exceeding 100 have been found in periurban streams and the Eure tributary. Based on the MPI spatial distribution, the Seine River Basin displays a wide range of anthropogenic impacts linked to variations in population density, stream order, wastewater discharges and industrial activities. Correlations between the MPI and other trace elements indicate that anthropogenic impacts also strongly affect the concentrations of Ag, Sb, and P, marginally affect the concentrations of Ba, Ni, and Cr, and appear to have little effect on the concentrations of Li, Be, V, Co, and the major elements. Temporal MPI trends can also be reconstituted from past regulatory surveys. In the early 1980s, MPI were 2-5 times higher than nowadays at most locations, particularly downstream of Greater Paris where it reached levels as high as 250 (now 40), a value characteristic of present Paris urban sewage. The exceptional contamination of the Seine basin is gradually improving over the last 20 years but remains very high. ?? 2004 Elsevier B.V. All rights reserved.

Science of the Total Environment↗

USGS1955

Geochemistry and mineralogy of a uraniferous sub bituminous coal

A sample of subbituminous uraniferous coal from the Red Desert, Sweetwater County, Wyo., has been studied mineralogically. The coal contains gypsum (6 percent), kaolinite (1 percent), quartz (0.3 percent), calcite (trace), and limonite (trace). This suite of minerals and the absence of pyrite show that the coal has been subjected to weathering and oxidation. No uranium minerals have been found; mechanical fractionation has indicated that the uranium is associated with the organic constituents of the coal. The minerals that have been isolated contain 0.0006 percent uranium, a content that is to be expected for nonuraniferous sedimentary rocks. The organic components of the coal contain approximately 0.002 percent uranium. On the basis of material-balance calculations, the organic components carry 98 percent of the uranium in the coal. Batch extraction of the Wyoming coal with 6 N hydrochloric acid leads to the solution of almost 90 percent of its uranium. Recovery of uranium is independent of the particle size of the coal between - 4 and - 20 mesh, and is accompanied by the solution of approximately 70 percent of the inorganic constituents (ash) of the coal. The extract contains, together with uranium, a concentration of several elements such as manganese, cerium, and vanadium that are present in the coal. Fischer assays of this weathered coal from the Red Desert indicate a yield of 16.7 gallons of tar per ton. Yields of both tar and char are about 15 percent lower if the coal is first treated with 6 N hydrochloric acid to extract the uranium. It is suggested that uranium was introduced into the coal by means of ground water carrying soluble alkaline or alkaline-earth uranyl carbonate complexes. The mineral schroeckingerite-a similar complex-is found near this subbituminous coal in the Red Desert of Wyoming. These complexes, which are unstable in acid medium, release the uranyl ion (U02++), which may then react with organic constituents of the coal to form ionic uranyl-organic compounds that are insoluble above a pH of about 2.2. Preliminary data indicate that the uranium is associated with various humic components of the coal. The distribution of uranium among the components of the subbituminous coal from Wyoming is similar to the distribution in a lignite from South Dakota. There is no indication that uranium was introduced into or retained by the two coals by appreciably different geochemical processes. © 1955 Society of Economic Geologists, Inc.

Wyoming↗

USGS2000

Alunite-jarosite crystallography, thermodynamics, and geochronology

The alunite supergroup consists of more than 40 mineral species that have in common the general formula DG 3 ( T O 4 ) 2 (OH,H 2 O) 6 . The D sites are occupied by monovalent (e.g. K, Na, NH 4 , Ag, Tl, H 3 O), divalent (e.g. Ca, Sr, Ba, Pb), trivalent (e.g. Bi, REE) or more rarely quadrivalent (Th) ions; G is Al or Fe 3+ or rarely Ga or V; T is S 6+ , As 5+ , or P 5+ , and may include subordinate amounts of Cr 6+ or Si 4+ . Many of the minerals in this supergroup are exotic, having been described from relatively few localities worldwide, generally in association with ore deposits. Rarely are end-member compositions attained in these natural occurrences, and extensive solid solution is typical for one or more of the D , G , and T sites. In this chapter, the two solid-solution series considered in detail are alunite-natroalunite [KAl 3 (SO 4 ) 2 (OH) 6 – NaAl 3 (SO 4 ) 2 (OH) 6 ] and jarosite-natrojarosite [KFe 3 (SO 4 ) 2 (OH) 6 – NaFe 3 (SO 4 ) 2 (OH) 6 ]. These minerals are by far the most abundant naturally occurring species of the alunite supergroup. Minerals with the generalized formula cited above can be variously grouped, but the simplest initial subdivision is on the basis of Fe > Al versus Al > Fe. Further subdivision is generally made on the basis of the predominant cation within the two T O 4 sites. Thus, within the supergroup, the alunite group consists of minerals in which both of the T sites are occupied by sulfur. This leads to a total negative charge of four on the T O 4 sites. In the ideal formulas of some members of the supergroup [e.g. woodhouseite, CaAl 3 (PO 4 )(SO 4 )(OH) 6 ], half of the T sites are occupied by sulfur, and the other half by arsenic or phosphorus, which produces a total negative charge of five on the T O 4 sites. In still other end-members of the supergroup [e.g. crandallite, CaAl 3 (PO 4 ) 2 (OH) 5 (H 2 O), and arsenocrandallite, CaAl 3 (AsO 4 ) 2 (OH) 5 (H 2 O)], both of the T sites are occupied solely by phosphorus or arsenic, thus producing a total negative charge of six on the T O 4 sites (see Table 1 1 of Dutrizac and Jambor, this volume). In this chapter, however, the primary concern is with those minerals for which T O 4 is represented by SO 4 2− (Table 1 1 ). Precipitates with compositions near those of the end-members in the system alunite-natroalunite and jarosite-natrojarosite are readily prepared using sulfate salts. The products, however, almost invariably have a slight to appreciable deficiency in G 3+ , and have an apparent non-stoichiometry for D . The latter may reflect incorporation a H 3 O + , a solid solution that is difficult to prove because H 3 O + cannot be determined directly by wet-chemistry or microprobe methods. Nevertheless, the existence of two minerals in the alunite supergroup is dependent solely on their D -site predominance of H 3 O + , namely, hydronium jarosite [(H 3 O)Fe 3 (SO 4 ) 2 (OH) 6 ] and schlossmacherite [(H 3 O,Ca)Al 3 (SO 4 ) 2 (OH,H 2 O) 6 ]. This chapter is organized into four sections. In the first section, crystallographic data for alunite-natroalunite and jarosite-natrojarosite are presented and discussed. The second section describes available thermodynamic data for these two solid-solution series, in terms of properties of the end-members and mixing properties for intermediate compositions. The third section discusses the geochemistry and occurrences of alunite and jarosite, and the last section summarizes the published literature on the use of alunite and jarosite in geochronology.

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