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Continental-scale patterns in soil geochemistry and mineralogy: results from two transects across the United States and Canada

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada (GSC) initiated a pilot study that involved collection of more than 1500 soil samples from 221 sites along two continental transects across Canada and the United States. The pilot study was designed to test and refine protocols for a soil geochemical survey of North America. The two transects crossed a wide array of soil parent materials, soil ages, climatic conditions, landforms, land covers and land uses. Sample sites were selected randomly at approximately 40-km intervals from a population defined as all soils of the continent. At each site, soils representing 0 to 5 cm depth, and the O, A, and C horizons, if present, were collected and analyzed for their near-total content of over 40 major and trace elements. Soils from 0–5 cm depth were also collected for analysis of organic compounds. Results from the transects confirm that soil samples collected at a 40-km spacing reveal coherent, continental- to subcontinental-scale geochemical and mineralogical patterns that can be correlated to aspects of underlying soil parent material, soil age and climate influence. The geochemical data also demonstrate that at the continental-scale the dominance of any of these major factors that control soil geochemistry can change across the landscape. Along both transects, soil mineralogy and geochemistry change abruptly with changes in soil parent materials. However, the chemical influence of a soil’s parent material can be obscured by changing climatic conditions. For the transects, increasing precipitation from west to east and increasing temperature from north to south affect both soil mineralogy and geochemistry because of climate effects on soil weathering and leaching, and plant productivity. Regional anomalous metal concentrations can be linked to natural variations in soil parent materials, such as high Ni and Cr in soils developed on ultramafic rocks in California or high P in soils formed on weathered Ordovician limestones in central Kentucky. On local scales, anomalous metal concentrations recognized in soil profiles, such as high P in soils from animal confinement sites, are consistent with local anthropogenic disturbances. At a larger scale, the distribution of Hg across the west to east transect demonstrates that it can be difficult to distinguish between natural or anthropogenic contributions and that many factors can contribute to an element’s spatial distribution. Only three samples in a subset of seventy-three 0–5 cm depth soil samples from the north to south transect had organochlorine pesticides values above the method detection limit, apparently related to historic usage of the pesticides DDT and dieldrin.

Applied Geochemistry↗

Crude oil in a shallow sand and gravel aquifer—I. Hydrogeology and inorganic geochemistry

Changes in the distribution of inorganic solutes in a shallow ground water contaminated by crude oil document a series of geochemical reactions initiated by biodegradation of the oil. Upgradient of an oil body floating on the water table, oxidation of oil to carbonic acid dissolves carbonate minerals in the aquifer matrix. In this oxidized zone pH is depressed ∼1 pH unit, and the concentrations of Ca, Mg and HCO 3 − increase to more than twice that of the native ground water. In the anoxic zone beneath the oil body concentrations of dissolved SiO 2 , Sr, K, Fe and Mn increase significantly. Here, Fe is mobilized by microbial reduction, pH is buffered by the carbonate system, and silicates weather via hydrolysis and organic-acid-enhanced dissolution. Farther down-gradient the ground water is reoxygenated and Fe precipitates from solution, possibly as iron hydroxide or iron carbonates, while SiO 2 precipitates as amorphous silica. Other solutes, such as Mg, are transported more conservatively down-gradient where contaminated and native ground water mix. The observed changes in inorganic aqueous chemistry document changes in water-mineral interactions caused by the presence of an organic contaminant. These organic-initiated interactions are likely present in many contaminated aquifers and may be analogous to interactions occurring in other organic-rich natural waters.

Minnesota↗

Geochemistry of rock units at the potential repository level, Yucca Mountain, Nevada

The compositional variability of the phenocryst-poor member of the 12.8 Ma Topopah Spring Tuff at the potential repository level was assessed by duplicate analysis of 20 core samples from the cross drift at Yucca Mountain, Nevada. Previous analyses of outcrop and core samples of the Topopah Spring Tuff showed that the phenocryst-poor rhyolite, which includes both lithophysal and nonlithophysal zones, is relatively uniform in composition. Analyses of rock samples from the cross drift, the first from the actual potential repository block, also indicate the chemical homogeneity of this unit excluding localized deposits of vapor-phase minerals and low-temperature calcite and opal in fractures, cavities, and faults. The possible influence of vapor-phase minerals and calcite and opal coatings on rock composition at a scale sufficiently large to incorporate these heterogeneously distributed deposits was evaluated and is considered to be relatively minor. Therefore, the composition of the phenocryst-poor member of the Topopah Spring Tuff is considered to be adequately represented by the analyses of samples from the cross drift. The mean composition as represented by the 10 most abundant oxides in wt. % or g/100 g is: SiO2, 76.29; Al2O3, 12.55; FeO, 0.14; Fe2O3, 0.97; MgO, 0.13; CaO, 0.50; Na2O, 3.52; K2O, 4.83; TiO2, 0.11; and MnO, 0.07. ?? 2002 Published by Elsevier Science Ltd.

Applied Geochemistry↗

Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

Applied Geochemistry↗

Environmental geochemistry of shale-hosted Ag-Pb-Zn massive sulfide deposits in northwest Alaska: Natural background concentrations of metals in water from mineralized areas

Red Dog, Lik and Drenchwater are shale-hosted stratiform Ag-Pb-Zn massive sulfide deposits in the northwestern Brooks Range. Natural background concentrations of metals in waters from the undisturbed (unmined) Drenchwater prospect and Lik deposit were compared to pre-mining baseline studies conducted at Red Dog. The primary factors affecting water chemistry are the extent of exposure of the deposits, the grade of mineralization, the presence of carbonate reeks in the section, and the proportion of Fe-sulfide in the ore. Surface water samples from the Drenchwater prospect, which has pyrite-dominant mineralization exposed in outcrop, have pH values as low as 2.8 and high dissolved concentrations of metals including as much as 95 mg 1-1 Al, 270 mg 1-1 Fe, 8 ??1-1 Cd, 10 ??1-1 Pb, and 2600 ??1-1 Zn, with As up to 26 ??g1-1. Surface waters from the Red Dog deposit prior to mining were also acidic and metal-rich, however, dissolved metal concentrations in Red Dog waters were many times greater. The higher metal concentrations in Red Dog waters reflect the high Zn grades and the abundant sphalerite, pyrite, and galena that were present in outcrop prior to mining. In contrast, despite significant mineralization at the Lik deposit, carbonate rocks in the section buffer the system, resulting in less acidic, mostly near-neutral pH values with low concentrations of most metals except Zn.

Applied Geochemistry↗

Strontium isotope geochemistry of groundwater in the central part of the Dakota (Great Plains) aquifer, USA

The Dakota aquifer of the central and eastern Great Plains of the United States is an important source of water for municipal supplies, irrigation and industrial use. Although the regional flow system can be characterized generally as east to northeasterly from the Rocky Mountains towards the Missouri River, locally the flow systems are hydrologically complex. This study uses Sr isotopic data from groundwater and leached aquifer samples to document the complex subsystems within the Dakota aquifer in Nebraska and Kansas. The interaction of groundwater with the geologic material through which it flows has created spatial patterns in the isotopic measurements that are related to: long-term water-rock interaction, during which varying degrees of isotopic equilibrium between water and rock has been achieved; and the alteration of NaCl fluids by water-rock interaction. Specifically, Sr isotopic data distinguish brines from Kansas and western Nebraska from those in eastern Nebraska: the former are interpreted to reflect interaction with Permian rocks, whereas the latter record interaction with Pennsylvanian rocks. The Sr isotopic composition of groundwater from other parts of Nebraska and Kansas are a function of the dynamic interaction between groundwater and unlithified sediments (e.g., glacial till and loess), followed by interaction with oxidized and unoxidized sediments within the Dakota Formation. This study illustrates the power of combining Sr chemistry with more conventional geochemical data to obtain a more complete understanding of groundwater flow systems within regional aquifer systems where extensive monitoring networks do not exist. ?? 2003 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Crude oil in a shallow sand and gravel aquifer-II. Organic geochemistry

Crude oil spilled from a pipeline break in a remote area of north-central Minnesota has contaminated a shallow glacial outwash aquifer. Part of the oil was sprayed over a large area to the west of the pipeline and part of it accumulated in an oil body that floats at the water table to the east of the point of discharge. Total dissolved organic carbon (TDOC) concentrations in shallow groundwater collected in the oil spray area reach 16 mg/l. This is nearly an order of magnitude higher than the TDOC concentrations of native groundwater (∼2–3mg/l). The additional TDOC derives from the partial degradation of petroleum residues deposited at the land surface and transported to the aquifer by vertical recharge. In the vicinity of the oil body, TDOC concentrations in groundwater are 48 mg/l, 58% of the TDOC being composed of non-volatile organic C. The majority of the volatile DOC (63%) is a mixture of low-molecular-weight saturated, aromatic and alicyclic hydrocarbons derived from the oil. Downgradient from the oil body along the direction of groundwater flow, concentrations of all measured constituents of the TDOC pool decrease. Concentrations begin to decline most rapidly, however, in the zone where dissolved O 2 concentrations begin to increase, ∼50m downgradient from the leading edge of the oil. Within the anoxic zone near the oil body, removal rates of isometric monoaromatic hydrocarbons vary widely. This indicates that the removal processes are mediated mainly by microbiological activity. Molecular and spectroscopic characterization of the TDOC and its spatial and temporal variation provide evidence of the importance of biogeochemical processes in attenuating petroleum contaminants in this perturbed subsurface environment.

Applied Geochemistry↗

The geochemistry of groundwater resources in the Jordan Valley: The impact of the Rift Valley brines

The chemical composition of groundwater in the Jordan Valley, along the section between the Sea of Galilee and the Dead Sea, is investigated in order to evaluate the origin of the groundwater resources and, in particular, to elucidate the role of deep brines on the chemical composition of the regional groundwater resources in the Jordan Valley. Samples were collected from shallow groundwater in research boreholes on two sites in the northern and southern parts of the Jordan Valley, adjacent to the Jordan River. Data is also compiled from previous published studies. Geochemical data (e.g., Br/Cl, Na/Cl and SO 4 /Cl ratios) and B, O, Sr and S isotopic compositions are used to define groundwater groups, to map their distribution in the Jordan valley, and to evaluate their origin. The combined geochemical tools enabled the delineation of three major sources of solutes that differentially affect the quality of groundwater in the Jordan Valley: (1) flow and mixing with hypersaline brines with high Br/Cl (>2 × 10 −3 ) and low Na/Cl (<0.8) ratios; (2) dissolution of highly soluble salts (e.g., halite, gypsum) in the host sediments resulting in typically lower Br/Cl signal (<2 × 10 −3 ); and (3) recharge of anthropogenic effluents, primarily derived from evaporated agricultural return flow that has interacted (e.g., base-exchange reactions) with the overlying soil. It is shown that shallow saline groundwaters influenced by brine mixing exhibit a north–south variation in their Br/Cl and Na/Cl ratios. This chemical trend was observed also in hypersaline brines in the Jordan valley, which suggests a local mixing process between the water bodies.

Applied Geochemistry↗

Geochemistry of fluid phases and sediments: Relevance to hydrothermal circulation in Middle Valley, ODP Legs 139 and 169

Geochemical and isotopic studies of pore fluids and solid phases recovered from the Dead Dog and Bent Hill hydrothermal sites in Middle Valley (Ocean Drilling Program Leg 169) have been compared with similar data obtained previously from these sites during Ocean Drilling Program Leg 139. Although generally the hydrothermal systems reflect non-steady state conditions, the data allow an assessment of the history of the hydrothermal processes. Sediment K/A1 ratios as well as the distribution of anhydrite in the sediments suggest that the Dead Dog hydrothermal field has been, and still is, active. In contrast, similar data in the Bent Hill hydrothermal field indicate a waning of hydrothermal activity. Pore fluid and hydrothermal vent data in the Dead Dog hydrothermal field are similar in nature to the data collected during ODP Leg 139. In the area of the Bent Hill sulfide deposit, however, the pore water data indicate that recent wholesale flushing of the sediment column with relatively unaltered seawater has obliterated a previous record of hydrothermal activity in the pore fluids. Data from the deepest part of Hole 1035A in the Bent Hill locality show the presence of hydrothermal fluids at greater depths in this area. This suggests the origin of the hydrothermal fluids found to be emanating from Hole 1035F, which constitutes one of the first man made hydrothermal vents in the Middle Valley hydrothermal system. Similarly, CORKed Hole 858G, because of seal failures, has acted as a hydrothermal vent, with sulfide deposits forming inside the CORK. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗

Geochemistry of surface water in alpine catchments in central Colorado, USA: Resolving host-rock effects at different spatial scales

The US Geological Survey is conducting a study of surface-water quality in the Rocky Mountains of central Colorado, an area of approximately 55,000 km 2 . Using new and existing geologic maps, the more than 200 rock formations represented in the area were arranged into 17 groups based on lithologic similarity. The dominant regional geologic feature affecting water quality in central Colorado is the Colorado mineral belt (CMB), a NE-trending zone hosting many polymetallic vein or replacement deposits, and porphyry Mo deposits, many of which have been mined historically. The influence of the CMB is seen in lower surface-water pH (<5), and higher concentrations of SO 4 2 - (>100 mg/L) and chalcophile metals such as Cu (>10 ??g/L), Zn (>100 ??g/L), and Cd (>1 ??g/L) relative to surface water outside the CMB. Not all streams within the CMB have been affected by mineralization, as there are numerous catchments within the CMB that have no mineralization or alteration exposed at the surface. At the regional-scale, and away from sites affected by mineralization, hydrothermal alteration, or mining, the effects of lithology on water quality can be distinguished using geochemical reaction modeling and principal components analysis. At local scales (100 s of km 2 ), effects of individual rock units on water chemistry are subtle but discernible, as shown by variations in concentrations of major lithophile elements or ratios between them. These results demonstrate the usefulness of regional geochemical sampling of surface waters and process-based interpretations incorporating geologic and geochemical understanding to establish geochemical baselines.

Applied Geochemistry↗

Cr(VI) occurrence and geochemistry in water from public-supply wells in California

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment-Priority Basin Project (GAMA-PBP) ranged from less than the study reporting limit of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of wells. Cr(VI) data collected for regulatory purposes overestimated Cr(VI) occurrence compared to spatially-distributed GAMA-PBP data. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and at higher concentrations in alkaline (pH ≥ 8), oxic water; and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that can mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.

California↗

Soil chemistry in lithologically diverse datasets: the quartz dilution effect

National- and continental-scale soil geochemical datasets are likely to move our understanding of broad soil geochemistry patterns forward significantly. Patterns of chemistry and mineralogy delineated from these datasets are strongly influenced by the composition of the soil parent material, which itself is largely a function of lithology and particle size sorting. Such controls present a challenge by obscuring subtler patterns arising from subsequent pedogenic processes. Here the effect of quartz concentration is examined in moist-climate soils from a pilot dataset of the North American Soil Geochemical Landscapes Project. Due to variable and high quartz contents (6.2&ndash;81.7 wt.%), and its residual and inert nature in soil, quartz is demonstrated to influence broad patterns in soil chemistry. A dilution effect is observed whereby concentrations of various elements are significantly and strongly negatively correlated with quartz. Quartz content drives artificial positive correlations between concentrations of some elements and obscures negative correlations between others. Unadjusted soil data show the highly mobile base cations Ca, Mg, and Na to be often strongly positively correlated with intermediately mobile Al or Fe, and generally uncorrelated with the relatively immobile high-field-strength elements (HFS) Ti and Nb. Both patterns are contrary to broad expectations for soils being weathered and leached. After transforming bulk soil chemistry to a quartz-free basis, the base cations are generally uncorrelated with Al and Fe, and negative correlations generally emerge with the HFS elements. Quartz-free element data may be a useful tool for elucidating patterns of weathering or parent-material chemistry in large soil datasets.

Applied Geochemistry↗

A regional soil and sediment geochemical study in northern California

Regional-scale variations in soil geochemistry were investigated in a 20,000-km 2 study area in northern California that includes the western slope of the Sierra Nevada, the southern Sacramento Valley and the northern Coast Ranges. Over 1300 archival soil samples collected from the late 1970s to 1980 in El Dorado, Placer, Sutter, Sacramento, Yolo and Solano counties were analyzed for 42 elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry following a near-total dissolution. These data were supplemented by analysis of more than 500 stream-sediment samples from higher elevations in the Sierra Nevada from the same study site. The relatively high-density data (1 sample per 15 km 2 for much of the study area) allows the delineation of regional geochemical patterns and the identification of processes that produced these patterns. The geochemical results segregate broadly into distinct element groupings whose distribution reflects the interplay of geologic, hydrologic, geomorphic and anthropogenic factors. One such group includes elements associated with mafic and ultramafic rocks including Cr, Ni, V, Co, Cu and Mg. Using Cr as an example, elevated concentrations occur in soils overlying ultramafic rocks in the foothills of the Sierra Nevada (median Cr = 160 mg/kg) as well as in the northern Coast Ranges. Low concentrations of these elements occur in soils located further upslope in the Sierra Nevada overlying Tertiary volcanic, metasedimentary and plutonic rocks (granodiorite and diorite). Eastern Sacramento Valley soil samples, defined as those located east of the Sacramento River, are lower in Cr (median Cr = 84 mg/kg), and are systematically lower in this suite compared to soils from the west side of the Sacramento Valley (median Cr = 130 mg/kg). A second group of elements showing a coherent pattern, including Ca, K, Sr and REE, is derived from relatively silicic rocks types. This group occurs at elevated concentrations in soils overlying volcanic and plutonic rocks at higher elevations in the Sierras (e.g. median La = 28 mg/kg) and the east side of the Sacramento Valley (median 20 mg/kg) compared to soils overlying ultramafic rocks in the Sierra Nevada foothills (median 15 mg/kg) and the western Sacramento Valley (median 14 mg/kg). The segregation of soil geochemistry into distinctive groupings across the Sacramento River arises from the former presence of a natural levee (now replaced by an artificial one) along the banks of the river. This levee has been a barrier to sediment transport. Sediment transport to the Valley by glacial outwash from higher elevations in the Sierra Nevada and, more recently, debris from placer Au mining has dominated sediment transport to the eastern Valley. High content of mafic elements (and low content of silicic elements) in surface soil in the west side of the valley is due to a combination of lack of silicic source rocks, transport of ultramafic rock material from the Coast Ranges, and input of sediment from the late Mesozoic Great Valley Group, which is itself enriched in mafic elements. A third group of elements (Zn, Cd, As and Cu) reflect the impact of mining activity. Soil with elevated content of these elements occurs along the Sacramento River in both levee and adjacent flood basin settings. It is interpreted that transport of sediment down the Sacramento River from massive sulfide mines in the Klamath Mountains to the north has caused this pattern. The Pb, and to some extent Zn, distribution patterns are strongly impacted by anthropogenic inputs. Elevated Pb content is localized in major cites and along major highways due to inputs from leaded gasoline. Zinc has a similar distribution pattern but the source is tire wear.

Applied Geochemistry↗

Geochemistry of shallow ground water in coastal plain environments in the southeastern United States: Implications for aquifer susceptibility

Ground-water chemistry data from coastal plain environments have been examined to determine the geochemical conditions and processes that occur in these areas and assess their implications for aquifer susceptibility. Two distinct geochemical environments were studied to represent a range of conditions: an inner coastal plain setting having more well-drained soils and lower organic carbon (C) content and an outer coastal plain environment that has more poorly drained soils and high organic C content. Higher concentrations of most major ions and dissolved inorganic and organic C in the outer coastal plain setting indicate a greater degree of mineral dissolution and organic matter oxidation. Accordingly, outer coastal plain waters are more reducing than inner coastal plain waters. Low dissolved oxygen (O2) and nitrate (NO 3-) concentrations and high iron (Fe) concentrations indicate that ferric iron (Fe (III)) is an important electron acceptor in this setting, while dissolved O2 is the most common terminal electron acceptor in the inner coastal plain setting. The presence of a wide range of redox conditions in the shallow aquifer system examined here underscores the importance of providing a detailed geochemical characterization of ground water when assessing the intrinsic susceptibility of coastal plain settings. The greater prevalence of aerobic conditions in the inner coastal plain setting makes this region more susceptible to contamination by constituents that are more stable under these conditions and is consistent with the significantly (p<0.05) higher concentrations of NO3- found in this setting. Herbicides and their transformation products were frequently detected (36% of wells sampled), however concentrations were typically low (<0.1 ??g/L). Shallow water table depths often found in coastal plain settings may result in an increased risk of the detection of pesticides (e.g., alachlor) that degrade rapidly in the unsaturated zone.

Applied Geochemistry↗

Geochemistry, radiocarbon ages, and paleorecharge conditions along a transect in the central High Plains aquifer, southwestern Kansas, USA

Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N 2 , Ar, O 2 , CH 4 ) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O 2 reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka ( 14 C) B.P. near the water table to 12.8 ± 0.9 ka ( 14 C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO 3 in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO 3 in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N 2 derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10 −3 μmol N L −1 a −1 ), indicating this process would require >10 ka to reduce the average NO 3 concentration in recent recharge to the Holocene background concentration.

Kansas↗

Airborne gamma-ray and magnetic anomaly signatures of serpentinite in relation to soil geochemistry, northern California

Serpentinized ultramafic rocks and associated soils in northern California are characterized by high concentrations of Cr and Ni, low levels of radioelements (K, Th, and U) and high amounts of ferrimagnetic minerals (primarily magnetite). Geophysical attributes over ultramafic rocks, which include airborne gamma-ray and magnetic anomaly data, are quantified and provide indirect measurements on the relative abundance of radioelements and magnetic minerals, respectively. Attributes are defined through a statistical modeling approach and the results are portrayed as probabilities in chart and map form. Two predictive models are presented, including one derived from the aeromagnetic anomaly data and one from a combination of the airborne K, Th and U gamma-ray data. Both models distinguish preferential values within the aerogeophysical data that coincide with mapped and potentially unmapped ultramafic rocks. The magnetic predictive model shows positive probabilities associated with magnetic anomaly highs and, to a lesser degree, anomaly lows, which accurately locate many known ultramafic outcrops, but more interestingly, locate potentially unmapped ultramafic rocks, possible extensions of ultramafic bodies that dip into the shallow subsurface, as well as prospective buried ultramafic rocks. The airborne radiometric model shows positive probabilities in association with anomalously low gamma radiation measurements over ultramafic rock, which is similar to that produced by gabbro, metavolcanic rock, and water bodies. All of these features share the characteristic of being depleted in K, Th and U. Gabbro is the only rock type in the study area that shares similar magnetic properties with the ultramafic rock. The aerogeophysical model results are compared to the distribution of ultramafic outcrops and to Cr, Ni, K, Th and U concentrations and magnetic susceptibility measurements from soil samples. Analysis of the soil data indicates high positive correlation between magnetic susceptibilities and concentration of Cr and Ni. Although the study focused on characterizing the geophysical properties of ultramafic rocks and associated soils, it has also yielded information on other rock types in addition to ultramafic rocks, which can also locally host naturally-occurring asbestos; specifically, gabbro and metavolcanic rocks.

Applied Geochemistry↗

Land-use interactions, Oil-Field infrastructure, and natural processes control hydrocarbon and arsenic concentrations in groundwater, Poso Creek Oil Field, California, USA

Like many hydrocarbon production areas in the U.S., the Poso Creek Oil Field in California includes and is adjacent to other land uses (agricultural and other developed lands) that affect the hydrology and geochemistry of the aquifer overlying and adjacent to oil development. We hypothesize that the distributions of hydrocarbons and arsenic in groundwater in such areas will be controlled by complex interactions between mixed land uses, oil-field infrastructure, and natural processes. In 2020–2021, samples of groundwater and surface water were collected and analyzed for a large suite of inorganic and organic chemicals and isotope and gas tracers to test this hypothesis. Those data are supplemented with ancillary data on historical geochemistry, hydrology, geology, and oil-field infrastructure. Hydrocarbons in groundwater (e.g., methane through pentane gases and benzene) are associated with natural processes (e.g., fault offsets or transition in sediment depositional environment) and oil-field infrastructure (e.g., fluid-migration pathways associated with uncemented annulus in oil wells or unlined pits). Arsenic concentrations >10 μg per liter (μg/L; maximum concentration 12.9 μg/L) are associated with natural processes in old, high-pH groundwater, and more recent recharge of water from natural and/or engineered recharge processes. Along the southwest margin of the oil field, pumping for drinking-water and irrigation supplies in combination with engineered groundwater recharge produce a depression in groundwater elevations where groundwater with elevated sulfate concentrations from agricultural areas and groundwater with hydrocarbons from the oil field mix to produce a zone of sulfate reduction that removes hydrocarbons and arsenic from groundwater but produces elevated sulfide (S 2- ) concentrations (maximum concentration 29 mg per liter, mg/L). In this study, multiple approaches were required to resolve the overlapping effects of land uses, oil-field infrastructure, and natural processes on the distributions of hydrocarbons and arsenic in groundwater. The combined use of geographic, historical, physical, chemical, isotopic, and other information to constrain processes could be a useful approach for studies in other hydrocarbon-production areas. This is particularly important where land uses affect aquifer hydrology to an extent that causes mixing of groundwaters with different chemical compositions.

California↗

Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.

Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70–120°C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are Na Ca Cl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H 2 S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H 2 S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl 4 2− and ZnCl 4 2− , respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters.

Applied Geochemistry↗