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Applied Geochemistry Special Issue on Environmental geochemistry of modern mining

Environmental geochemistry is an integral part of the mine-life cycle, particularly for modern mining. The critical importance of environmental geochemistry begins with pre-mining baseline characterization and the assessment of environmental risks related to mining, continues through active mining especially in water and waste management practices, and culminates in mine closure. The enhanced significance of environmental geochemistry to modern mining has arisen from an increased knowledge of the impacts that historical and active mining can have on the environment, and from new regulations meant to guard against these impacts. New regulations are commonly motivated by advances in the scientific understanding of the environmental impacts of past mining. The impacts can be physical, chemical, and biological in nature. The physical challenges typically fall within the purview of engineers, whereas the chemical and biological challenges typically require a multidisciplinary array of expertise including geologists, geochemists, hydrologists, microbiologists, and biologists. The modern mine-permitting process throughout most of the world now requires that potential risks be assessed prior to the start of mining. The strategies for this risk assessment include a thorough characterization of pre-mining baseline conditions and the identification of risks specifically related to the manner in which the ore will be mined and processed, how water and waste products will be managed, and what the final configuration of the post-mining landscape will be. In the Fall 2010, the Society of Economic Geologists held a short course in conjunction with the annual meeting of the Geological Society of America in Denver, Colorado (USA) to examine the environmental geochemistry of modern mining. The intent was to focus on issues that are pertinent to current and future mines, as opposed to abandoned mines, which have been the focus of numerous previous short courses. The geochemical challenges of current and future mines share similarities with abandoned mines, but differences also exist. Mining and ore processing techniques have changed; the environmental footprint of waste materials has changed; environmental protection has become a more integral part of the mine planning process; and most historical mining was done with limited regard for the environment. The 17 papers in this special issue evolved from the Society of Economic Geologists’ short course. The relevant geochemical processes encompass the source, transport, and fate of contaminants related to the life cycle of a mine. Contaminants include metals and other inorganic species derived from geologic sources such as ore and solid mine waste, and substances brought to the site for ore processing, such as cyanide to leach gold. Factors, such as mine-waste mineralogy, hydrologic setting, mine-drainage chemistry, and microbial activity, that affect the hydrochemical risks from mining are reviewed by Nordstrom et al. In another paper, Nordstrom discusses baseline characterization at mine sites in a regulatory framework, and emphasizes the influence of mineral deposits in producing naturally elevated concentrations of many trace elements in surface water and groundwater. Surface water quality in mineralized watersheds is influenced by a number of processes that act on daily (diel) cycles and can produce dramatic variations in trace element concentrations as described by Gammons et al. Pre-mining baseline characterization studies should strive to capture the magnitude of these diel variations. Desbarats et al., using a case study of mine drainage from a gold mine, illustrate how elements that commonly occur as negatively charged species (anions) in solution, such as arsenic as arsenate, behave in an opposite fashion than most metals, which occur as positively charged species (cations). Significant improvement in the understanding of factors that influence the toxicity of metals to aquatic organisms in surface water has highlighted the importance of aqueous chemistry, particularly dissolved organic carbon, as described by Smith et al. Stream sediment contamination is another important pathway for affecting aquatic organisms, as reviewed by Besser et al. Understanding and predicting environmental consequences from mining begins with knowing the mineralogy and mineral reactivity of the ore, the wastes, and of secondary minerals formed later. Jamieson et al. review the importance of mineralogical studies in mine planning and remediation. A number of types of site-specific studies are needed to identify environmental risks related to individual mines. Lapakko reviews the general framework of mine waste characterization studies that are integral to the mine planning process. Hageman et al. present a comparative study of several static tests commonly used to characterize mine waste. The mining and ore processing practices employed at a specific mine site will vary on the basis of the commodities being targeted, the geology of the deposit, the geometry of the deposit, and the mining and ore processing methods used. Thus, these factors, in addition to the waste management practices used, can result in a variety of end-member mine waste features, each of which has its own set of challenges. Open pit mines and underground mines require waste rock to be removed to access ore. Waste rock presents unique problems because the rock is commonly mineralized at sub-economic grades and has not been processed to remove potentially problematic minerals, such as pyrite. Amos et al. examine the salient aspects of the geochemistry of waste rock. Mill tailings – the waste material after ore minerals have been removed – are a volumetrically important solid waste at many mine sites. Their fine grain size and the options for their management make their behavior in the environment distinct from that of waste rock. Lindsay et al. describe some of these differences through three case-study examples. Subaqueous disposal of tailings is another option described by Moncur et al. Cyanide leaching for gold extraction is a common method throughout the world. Johnson describes environmental aspects of cyanidation. Uranium mining presents unique environmental challenges, particularly since in-situ recovery has seen widespread use. Campbell et al. review the environmental geochemistry of uranium mining and current research on bioremediation. Ore concentrates from many types of metal mining undergo a pyrometallurgical technique known as smelting to extract the metal. Slag is the result of smelting, and it may be an environmental liability or a valuable byproduct, as described by Piatak et al. Finally, the open pits that result from surface mining commonly reach below the water table. At the end of mining, these pits may fill to form lakes that become part of the legacy of the mine. Castendyk et al., in two papers, review theoretical aspects of the environmental limnology of pit lakes. They also describe approaches that have been used to model pit lake water balance, wall-rock contributions to pit lake chemistry, pit lake water quality, and limnological processes, such as vertical mixing, through the use of three case studies.

Applied Geochemistry↗

Crystalline gold in soil and the problem of supergene nugget formation: Freezing and exclusion as genetic mechanisms

Many of the world's richest gold placer deposits now occur in cold regions despite differences in their climatic history. It therefore seems possible that there may be some fundamental connection between freezing climates and the local chemical behavior of gold in the weathering cycle. This hypothesis, along with the problematical occurrence of gold as euhedral crystals in arctic gravel and soil placers, has led me to review low temperature phenomena that may bear on the geochemistry of gold. Several effects which may influence the weathering of natural gold-bearing rocks, the chemical complexation of gold, and its subsequent mobility and deposition appear to be strongly connected with freeze action. The exclusion of dissolved solutes, solute gases, and particles from ice, subjects rock and soil minerals to increased corrosion from thin, unfrozen, adsorbed water films which remain at particle surfaces throughout the freezing of rocks and soils. The preferential exclusion of cations (over anions) from growing ice crystals creates charge separations and measurable current flow across waterice phase boundaries in freezing soil — a phenomenon which leads to troublesome seasonal electrolytic corrosion of pipelines buried in soil; this phenomenon may also favor the dissolution of normally insoluble metals such as gold during geologic time periods. The ice-induced accumulation of clays, organic acids, bacteria, and other organic matter at mineral surfaces may also speed chemical attack by providing a nearby sink of alternate cation-binding sites and hence rapid removal of liberated cations from solution. The latter mechanism may be operative in both the dissolution and redeposition of gold. These physical, chemical, and electrical effects are favorable to the dissolution of rocks (in addition to frost shattering) and to the dissolution, mobilization, and redeposition of gold and other noble metals and must therefore contribute significantly to the behavior of gold at low temperatures. The occurrence of large numbers of gold placer deposits in northern Canada, Alaska, and Siberia may thus be due in part to the low temperatures common to these regions.

Precambrian Research↗

Trace-element budgets in the Ohio/Sunbury shales of Kentucky: Constraints on ocean circulation and primary productivity in the Devonian-Mississippian Appalachian Basin

The hydrography of the Appalachian Basin in late Devonian-early Mississippian time is modeled based on the geochemistry of black shales and constrained by others' paleogeographic reconstructions. The model supports a robust exchange of basin bottom water with the open ocean, with residence times of less than forty years during deposition of the Cleveland Shale Member of the Ohio Shale. This is counter to previous interpretations of these carbon-rich units having accumulated under a stratified and stagnant water column, i.e., with a strongly restricted bottom bottom-water circulation. A robust circulation of bottom waters is further consistent with the palaeoclimatology, whereby eastern trade-winds drove upwelling and arid conditions limited terrestrial inputs of siliciclastic sediment, fresh waters, and riverine nutrients. The model suggests that primary productivity was high (~ 2??g C m- 2 d- 1), although no higher than in select locations in the ocean today. The flux of organic carbon settling through the water column and its deposition on the sea floor was similar to fluxes found in modern marine environments. Calculations based on the average accumulation rate of the marine fraction of Ni suggest the flux of organic carbon settling out of the water column was approximately 9% of primary productivity, versus an accumulation rate (burial) of organic carbon of 0.5% of primary productivity. Trace-element ratios of V:Mo and Cr:Mo in the marine sediment fraction indicate that bottom waters shifted from predominantly anoxic (sulfate reducing) during deposition of the Huron Shale Member of the Ohio Shale to predominantly suboxic (nitrate reducing) during deposition of the Cleveland Shale Member and the Sunbury Shale, but with anoxic conditions occurring intermittently throughout this period. ?? 2008 Elsevier B.V.

Palaeogeography, Palaeoclimatology, Palaeoecology↗

Recent (2008-10) water quality in the Barton Springs segment of the Edwards aquifer and its contributing zone, central Texas, with emphasis on factors affecting nutrients and bacteria

The Barton Springs zone, which comprises the Barton Springs segment of the Edwards aquifer and the watersheds to the west that contribute to its recharge, is in south-central Texas, an area with rapid growth in population and increasing amounts of land area affected by development. During November 2008-March 2010, an investigation of factors affecting the fate and transport of nutrients and bacteria in the Barton Springs zone was conducted by the U.S. Geological Survey (USGS), in cooperation with the Texas Commission on Environmental Quality. The primary objectives of the study were to characterize occurrence of nutrients and bacteria in the Barton Springs zone under a range of flow conditions; to improve understanding of the interaction between surface-water quality and groundwater quality; and to evaluate how factors such as streamflow variability and dilution affect the fate and transport of nutrients and bacteria in the Barton Springs zone. The USGS collected and analyzed water samples from five streams (Barton, Williamson, Slaughter, Bear, and Onion Creeks), two groundwater wells (Marbridge and Buda), and the main orifice of Barton Springs in Austin, Texas. During the period of the study, during which the hydrologic conditions transitioned from exceptional drought to wetter than normal, water samples were collected routinely (every 3 to 4 weeks) from the streams, wells, and spring and, in response to storms, from the streams and spring. All samples were analyzed for major ions, nutrients, the bacterium Escherichia coli, and suspended sediment. During the dry period, the geochemistry of groundwater at the two wells and at Barton Springs was dominated by flow from the aquifer matrix and was relatively similar and unchanging at the three sites. At the onset of the wet period, when the streams began to flow, the geochemistry of groundwater samples from the Marbridge well and Barton Springs changed rapidly, and concentrations of most major ions and nutrients and densities of Escherichia coli became more similar to those of samples from the streams relative to concentrations and densities during the dry period. Geochemical modeling indicated that the proportion of Barton Springs discharge composed of stream recharge increased from about 0-8 percent during the dry period to about 80 percent during the wet period. The transition from exceptional drought to wetter-than-normal conditions resulted in a number of marked changes that highlight factors affecting the fate and transport of nutrients and bacteria and the strong influence of stream recharge on water quality in the Barton Springs segment of the Edwards aquifer and had a pronounced effect on the fate of nitrogen species. Organic nitrogen loaded to and stored in soils during the dry period was nitrified to nitrate when the soils were rewetted, resulting in elevated concentrations of nitrate plus nitrite in streams as these constituents were progressively leached during continued wet weather. Estimated mean monthly loads of organic nitrogen and nitrate plus nitrite in stream recharge and Barton Springs discharge, which were relatively low and constant during the dry period, increased during the wet period. Loads of organic nitrogen, on average, were about six times greater in stream recharge than in Barton Springs discharge, indicating that organic nitrogen likely was being converted to nitrate within the aquifer. Loads of total nitrogen (organic nitrogen plus ammonia and nitrate plus nitrite) in stream recharge (162 kilograms per day) and in Barton Springs discharge (157 kilograms per day) for the period of the investigation were not significantly different. Dilution was not an important factor affecting concentrations of nitrate plus nitrite in the streams or in Barton Springs during the period of this investigation: Concentrations of nitrate plus nitrite did not decrease in streams with increasing stream discharge, and nitrate plus nitrite concentrations measured at Barton

Scientific Investigations Report↗

Methane in aquifers used for public supply in the United States

In 2013 to 2015, 833 public supply wells in 15 Principal aquifers in the U.S. were sampled to identify which aquifers contained high methane concentrations (>1 mg/L) and determine the geologic, hydrologic, and geochemical conditions associated with high concentrations. This study represents the first national assessment of methane in aquifers used for public supply in the U.S. and, as such, advances the understanding of the occurrence and distribution of methane in groundwater nationally. Methane concentrations >1 and > 10 mg/L occurred in 6.7 and 1.1% of the samples, respectively. Most high concentrations occurred in aquifers in the Atlantic and Gulf Coastal Plain regions and upper Midwest. High methane concentrations were most commonly associated with Tertiary and younger aquifer sediments, old groundwater (>60 years), and concentrations of oxygen, nitrate-N, and sulfate <0.5 mg/L. Concentrations of methane were also positively correlated (p < 0.05) with dissolved organic carbon and ammonium. Case studies in Florida, Texas, and Iowa were used to explore how regional context from this data set could aid our understanding of local occurrences of methane in groundwater. Regional data for methane, Br/Cl ratios, sulfate, and other parameters helped identify mixing processes involving end members such as wastewater effluent-impacted groundwater, saline formation water, and pore water in glacial till that contributed methane to groundwater in some cases and supported methane oxidation in others.

Applied Geochemistry↗

Integrating magnetotellurics, soil gas geochemistry and structural analysis to identify hidden, high enthalpy, extensional geothermal systems

We applied magnetotellurics (MT), diagnostic structural affiliations, soil gas flux, and fluid geochemistry to assist in identifying hidden, high-enthalpy geothermal systems in extensional regimes of the U.S. Great Basin. We are specifically looking for high-angle, low-resistivity zones and dilatant geologic structures that can carry fluids from magmatic or high-grade metamorphic conditions in the deep crust upward to exploitable depths, and to verify the nature of the deep sources through soil gas and fluid compositions. The project was motivated by prior MT transect coverage of western and central Nevada centered upon the Dixie Valley producing geothermal system where such favorable indicators were first recognized. The high-angle MT structures are taken to be fluidized fault zones connecting deep magmatic/metamorphic activity with the geothermal system, but the concept required verification by testing at other systems. The project was set up with a two-phased organization. Phase I was carried out at the McGinness Hills system, central Nevada, where Ormat Inc flagship power facility is located and a considerable amount of pre-existing data were available. Resistivity models along MT transects also showed a strong low-resistivity upwelling originating from interpreted deep crustal magmatic underplating. Controlling structures on production as indicated by Ormat data and our new mapping were favorable to dilatancy, comprising an accommodation zone between major normal faults of opposing dip. A 3D MT survey and inversion confirmed the existence of the steep low-resistivity zone dipping ESE toward the deep crust and placed N-S bounds upon the feature. In cooperation with Ormat personnel, we sampled well fluids from production intervals for He isotope composition. Elevated 3He was verified through mass spectrometry analysis confirming a magmatic connection with the producing system. High CO2 soil gas flux including possibly metamorphic 13C and 14C component was measured over the area of dilatant structures. Hence, the triad of indicators posed above was confirmed in Phase I. Subsequently, Phase II of the project proceeded in the greenfield Kumiva-Blackrock Desert district of northwestern Nevada to see if a new system could be identified. Transect MT data also showed a low-resistivity upwelling originating from interpreted deep crustal magmatic underplating. An MT survey of 131 sites was imaged through 3D inversion using an in-house, DOE-supported finite element algorithm. Low resistivity upwellings that warranted follow up study occur under the flanks of the Seven Troughs Range, under Kumiva Playa immediately west of the Blue Wing Mountains, and under northern Granite Springs Valley. Structural assessment of the project area by Co-I J. Faulds at UNR provided numerous favorable Quaternary fault settings, which were correlated to the MT upwelling structures. Soil CO2 gas flux anomalies generally were not large but did show correlation with resistivity upwelling structure and favorable geological structures. Isotope analyses showed presence of possible inorganic/metamorphic 13C but 14C concentrations did not exceed background values. We view the initial concept of a confluence of low-resistivity upwelling, favorably dilatant 3D geological structure, and elevated soil gas flux including 13C component to be supported by the further evidence of this project although the indicators in the Phase II study were more diffuse. Mass balance calculations based upon 3He R/Ra values indicates that the proportion of magmatic fluids in a producing system is fairly low, 10-15% by volume. We suggest that the diagnostic MT geophysical structures denote zones of concentrated extensional deformation that increases permeability, potentially enabling a circulating upper crustal geothermal system, while at the same time connecting telltale deep component signatures to the upper crust. The northern Granite Springs Valley structure is receiving followup stu

Nevada↗

Temperature variations at diffuse and focused flow hydrothermal vent sites along the northern East Pacific Rise

In the decade following documented volcanic activity on the East Pacific Rise near 9°50′N, we monitored hydrothermal vent fluid temperature variations in conjunction with approximately yearly vent fluid sampling to better understand the processes and physical conditions that govern the evolution of seafloor hydrothermal systems. The temperature of both diffuse flow (low-temperature) and focused flow (high-temperature) vent fluids decreased significantly within several years of eruptions in 1991 and 1992. After mid-1994, focused flow vents generally exhibited periods of relatively stable, slowly varying temperatures, with occasional high- and low-temperature excursions lasting days to weeks. One such positive temperature excursion was associated with a crustal cracking event. Another with both positive and negative excursions demonstrated a subsurface connection between adjacent focused flow and diffuse flow vents. Diffuse flow vents exhibit much greater temperature variability than adjacent higher-temperature vents. On timescales of a week or less, temperatures at a given position within a diffuse flow field often varied by 5°–10°C, synchronous with near-bottom currents dominated by tidal and inertial forcing. On timescales of a week and longer, diffuse flow temperatures varied slowly and incoherently among different vent fields. At diffuse flow vent sites, the conceptual model of a thermal boundary layer immediately above the seafloor explains many of the temporal and spatial temperature variations observed within a single vent field. The thermal boundary layer is a lens of warm water injected from beneath the seafloor that is mixed and distended by lateral near-bottom currents. The volume of the boundary layer is delineated by the position of mature communities of sessile (e.g., tubeworms) and relatively slow-moving organisms (e.g., mussels). Vertical flow rates of hydrothermal fluids exiting the seafloor at diffuse vents are less than lateral flow rates of near-bottom currents (5–10 cm/s). The presence of a subsurface, shallow reservoir of warm hydrothermal fluids can explain differing temperature behaviors of adjacent diffuse flow and focused flow vents at 9°50′N. Different average temperatures and daily temperature ranges are explained by variable amounts of mixing of hydrothermal fluids with ambient seawater through subsurface conduits that have varying lateral permeability.

Geochemistry, Geophysics, and Geosystems↗

Geochemistry of sulfur in the Florida Everglades: 1994 through 1999

In this report, we present data on the geochemistry of sulfur in sediments and in surface water, groundwater, and rainwater in the Everglades region in south Florida. The results presented here are part of a larger study intended to determine the roles played by the cycling of carbon, nitrogen, phosphorus, and sulfur in the ecology of the south Florida wetlands. The geochemistry of sulfur in the region is particularly important because of its link to the production of toxic methylmercury through processes mediated by sulfate reducing bacteria. Sediment cores were collected from the Everglades Agricultural Area (EAA), Water Conservation Areas (WCAs) 1A and 2A, from Lake Okeechobee, and from Taylor Slough in the southern Everglades. Water collection was more widespread and includes surface water from WCAs 1A, 2A, 3A, 2B, the EAA, Taylor Slough, Lake Okeechobee, and the Kissimmee River. Groundwater was collected from The Everglades Nutrient Removal Area (ENR) and from WCA 2A. Rainwater was collected at two month intervals over a period of one year from the ENR and from WCA 2A. Water was analyzed for sulfate concentration and sulfate sulfur stable isotopic ratio (34S/32S). Sediment cores were analyzed for total sulfur concentration and/or for concentrations of sulfur species (sulfate, organic sulfur, disulfides, and acid volatile sulfides (AVS)) and for their stable sulfur isotopic ratio. Results show a decrease in total sulfur content (1.57 to 0.61 percent dry weight) with depth in two sediment cores collected in WCA 2A, indicating that there has been an increase in total sulfur content in recent times. A sediment core from the center of Lake Okeechobee shows a decrease in total sulfur content with depth (0.28 to 0.08 percent dry weight). A core from the periphery of the lake (South Bay) likewise shows a decrease in total sulfur content with depth (1.00 to 0.69 percent dry weight), however, the overall sulfur content is greater than that near the center at all depths. This suggests input of sulfur in recent times, especially near the lake margins. Sediments show a general decrease in sulfur concentration with depth, probably because of increases in sulfur input to the marshes in recent times. Regional differences in the concentrations and stable isotopic ratios of sulfate sulfur in surface water show that sulfur contamination to the northern Everglades likely originates from canals draining the EAA.

Florida↗

Release of 226Ra from uranium mill tailings by microbial Fe(III) reduction

Uranium mill tailings were anaerobically incubated in the presence of H 2 with Alteromonas putrefaciens , a bacterium known to couple the oxidation of H 2 and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved 226 Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of 226 Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved 226 Ra from uranium mill tailings.

Applied Geochemistry↗

Geophysics- and geochemistry-based assessment of the geochemical characteristics and groundwater-flow system of the U.S. part of the Mesilla Basin/Conejos-Médanos aquifer system in Doña Ana County, New Mexico, and El Paso County, Texas, 2010–12

One of the largest rechargeable groundwater systems by total available volume in the Rio Grande/Río Bravo Basin (hereinafter referred to as the “Rio Grande”) region of the United States and Mexico, the Mesilla Basin/Conejos-Médanos aquifer system, supplies water for irrigation as well as for cities of El Paso, Texas; Las Cruces, New Mexico; and Ciudad Juárez, Chihuahua, Mexico. The U.S. Geological Survey in cooperation with the Bureau of Reclamation assessed the groundwater resources in the Mesilla Basin and surrounding areas in Doña Ana County, N. Mex., and El Paso County, Tex., by using a combination of geophysical and geochemical methods. The study area consists of approximately 1,400 square miles in Doña Ana County, N. Mex., and 100 square miles in El Paso County, Tex. The Mesilla Basin composes most of the study area and can be divided into three parts: the Mesilla Valley, the West Mesa, and the East Bench. The Mesilla Valley is the part of the Mesilla Basin that was incised by the Rio Grande between Selden Canyon to the north and by a narrow valley (about 4 miles wide) to the southeast near El Paso, Tex., named the Paso del Norte, which is sometimes referred to in the literature as the “El Paso Narrows.” Previously published geophysical data for the study area were compiled and these data were augmented by collecting additional geophysical and geochemical data. Geophysical resistivity measurements from previously published helicopter frequency domain electromagnetic data, previously published direct-current resistivity soundings, and newly collected (2012) time-domain electromagnetic soundings were used in the study to detect spatial changes in the electrical properties of the subsurface, which reflect changes that occur within the hydrogeology. The geochemistry of the groundwater system was evaluated by analyzing groundwater samples collected in November 2010 for physicochemical properties, major ions, trace elements, nutrients, pesticides (reported but not used in the assessment), and environmental tracers. The data obtained from these samples (with the exception of the pesticide data) were used to gain insights into processes controlling the groundwater movement through the groundwater system in the study area. Results from the geophysical and geochemical assessments facilitated the interpretation of the geochemical characteristics of the groundwater sources and geochemical groups within the groundwater system. The groundwater-flow system in the study area consists primarily of the Mesilla Basin aquifer system, which can be divided into four hydrogeologic units by using an informal classification scheme based on basin-fill stratigraphy and sedimentology with an emphasis on aquifer characteristics. The four hydrogeologic units are (1) the Rio Grande alluvium, which is the shallow aquifer of the Mesilla Basin within the confines of the Mesilla Valley, and the three hydrogeologic units that compose the Santa Fe Group: (2) the lower part of the Santa Fe Group, which is the least productive zone, (3) the middle part of the Santa Fe Group, which is the primary water-bearing hydrogeologic unit in the basin and is generally saturated, and (4) the upper part of the Santa Fe Group, which is the most productive water-bearing unit within the Santa Fe Group but is only partially saturated in the north and largely unsaturated in the south and western parts of the Mesilla Basin. The helicopter frequency domain electromagnetic survey results indicated that approximately half of the resistivity values were less than 10 ohm-meters at depths of 50 and 100 feet with a transition where the resistivity values changed from relatively high values (greater than 20 ohm-meters) to relatively low resistivity values (less than 10 ohm-meters) near Vado, New Mexico. Slightly more than 25 percent of the gridded resistivity values from the three-dimensional grid of the combined inverse modeling results of the direct-current resistivity and time-domain electromagnetic soundings were equal to or less than 10 ohm-meters with large regions of low resistivity becoming apparent in the southernmost part of the study area near the Paso Del Norte where these low resistivity features are spatially the widest at or below the top of the bedrock. These low resistivity values might represent clayey deposits, sediments composed largely of sand and gravel saturated with saline water, or both. Historical dissolved-solids-concentration data within the surface geophysical subset area of the study area were compiled and compared to the inverse modeling results of the combined direct-current resistivity and time-domain soundings; this comparison was done to strengthen the interpretation made from the combined inverse modeling results that the low resistivity features were representative of sand and gravel deposits saturated with saline water and not clayey deposits. Water-level altitudes within the Rio Grande alluvium generally decreased from north to south, with a west to east decrease in water-level altitudes near Las Cruces, New Mexico, as a result of groundwater pumping. Groundwater flow within the Santa Fe Group is more complex than the groundwater flow within the Rio Grande alluvium because of the larger lateral and vertical extent of the Santa Fe Group compared to the Rio Grande alluvium. Groundwater from the Organ Mountains flows directly south towards the Paso del Norte. Groundwater from the Robledo Mountains, the Rough and Ready Hills, and the Sleeping Lady Hills generally flows to the southeast. Groundwater flowing near the north end of the midbasin uplift generally continues east towards the Rio Grande and then flows south on the east side of the midbasin uplift. Groundwater flowing near the west side of the midbasin uplift generally continues south parallel to the faults that make up the midbasin uplift and then flows east towards the Paso del Norte when it reaches the south end of the midbasin uplift. Groundwater from the Aden Hills and the East and West Potrillo Mountains flows to the south end of the midbasin uplift and then continues east towards the Paso del Norte. Throughout most of the Mesilla Valley, the vertical hydraulic gradient was downward because the water-level altitude in the Rio Grande alluvium was higher than it was in the Santa Fe Group, but in some areas (typically in the middle and southern parts of the Mesilla Valley), the vertical hydraulic gradient was substantially reduced or even reversed to an upward hydraulic gradient. The geochemistry data indicate that there was a complex system of multiple geochemical endmembers and mixing between these endmembers with recharge to the Rio Grande alluvium and Santa Fe Group composed mostly of seepage from the Rio Grande, inflows from deeper or neighboring water systems, and mountain-front recharge. Five distinct geochemical groups were identified in the Mesilla Basin study area: (1) ancestral Rio Grande (pre-Pleistocene) geochemical group, (2) modern Rio Grande (Pleistocene to present) geochemical group, (3) mountain-front geochemical group, (4) deep groundwater upwelling geochemical group, and (5) unknown freshwater geochemical group. The ancestral Rio Grande groundwater was water that recharged into the system as seepage losses from the ancestral Rio Grande; this groundwater generally flows from north to south-southeast towards the Paso del Norte. Groundwater on the west side of the midbasin uplift generally flows south until it reaches the southern part of the study area; from the southern part of the study area, the groundwater flows east towards the Paso del Norte. Groundwater on the east side of the midbasin uplift flows south-southeast towards the Paso del Norte where it mixes with groundwater from the modern Rio Grande, uplifted areas in the west, and the deep saline source. The water type of the modern Rio Grande geochemical group ranged from calcium-sulfate water type in the northern part of the study area to sodium-chloride-sulfate water type in the southern part of the study area; from north to south there was a substantial increase in specific conductance, strontium-87/strontium-86 ratio, potassium, and the trace metals of iron and lithium, changing the water chemistry such that it became similar to the water chemistry of the deep groundwater upwelling geochemical group. From age-dating results, water in the modern Rio Grande geochemical group was recharged to the Rio Grande alluvium within the past 10 years. The mountain-front geochemical group was generally old water (apparent age was greater than 10,000 carbon-14 years before present) that was somewhat mineralized and has relatively high concentrations of fluoride and silica, which might indicate longer exposure to volcanic and siliciclastic rocks or aluminosilicate minerals. There were five different locations of recharge determined from the groundwater geochemistry within the mountain-front geochemical group, all having a slightly different geochemical signature: (1) the Rough and Ready Hills, Robledo Mountains, and the Sleeping Lady Hills, (2) the Doña Ana Mountains, (3) the Aden Hills and West Potrillo Mountains, (4) the East Potrillo Mountains, and (5) the Sierra Juárez in Mexico. The groundwater from the Rough and Ready Hills, Robledo Mountains, the Sleeping Lady Hills, and the Doña Ana Mountains generally flows toward the Rio Grande and eventually mixes together and with the modern Rio Grande groundwater. The groundwater originating from the Aden Hills and East and West Potrillo Mountains generally flows east to southeast at a slow rate and eventually mixes and continues east, where it mixes with groundwater from the ancestral Rio Grande geochemical group and with the groundwater from the Sierra Juárez. The groundwater from the Sierra Juárez flows north and then east towards the Paso del Norte where it mixes with groundwater from the uplifted areas in the west, ancestral and modern Rio Grande groundwater, and the upwelling groundwater from a deep saline source. The deep groundwater upwelling geochemical group had the highest concentrations of bicarbonate, potassium, silica, aluminum, iron, and lithium within the study area, indicating that it had been in contact with carbonate and siliciclastic rocks for a much longer period of time and at higher temperatures compared to the other geochemical groups, and was most likely ancient marine groundwater originating from the Paleozoic and Cretaceous carbonate rocks which was upwelling into the Mesilla Basin aquifer system in the southeastern part of the study area through the extensive fault systems. Direct-current resistivity and time-domain electromagnetic soundings support the interpretation of ancient marine groundwater upwelling into the Mesilla Basin aquifer system, as do the analytical results from wells, and the helicopter frequency domain electromagnetic data collected along the Rio Grande. The hydrogen-2/hydrogen-1 ratio and oxygen-18/oxygen-16 ratio isotopic results for samples in the unknown freshwater geochemical group did not plot on the Rio Grande evaporation line, indicating this group did not have a Rio Grande signature (that is, there was no isotopic evidence of a component of Rio Grande water) and it also had the lowest mineralized content of any geochemical group in the study area.

New Mexico, Texas↗

The chemical evolution of Kurnub Group palcowater in the Sinai-Negev province - A mass balance approach

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO2, smectite and degasses CO2. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO2. Concomitantly, there is precipitation of calcite, smectite, SiO2 and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.

Applied Geochemistry↗

Sulfur isotope and porewater geochemistry of Florida escarpment seep sediments

Distributions of porewater constituents, SO 4 = , NH 4 + , Cl − , ∑CO 2 , and H 2 S, solid phase iron, and sulfur concentrations, and the sulfur isotopic composition of dissolved and solid phases were investigated in sediments from abyssal seeps at the base of the Florida escarpment. Despite the apparent similarity of seep sediment porewater chemistry to that of typical marine sediments undergoing early diagenesis, relationships between chemical distributions and isotopic measurements revealed that the distribution of pore fluid constituents was dominated by processes occurring within the platform rather than by in situ microbial processes. Ammonium and sulfate concentrations were linearly correlated with chloride concentrations, indicating that variations in porewater chemistry were controlled by the admixture of seawater and a sulfate depleted brine with a chlorinity of 27.5 ± 1.9%. and 2.2 ± 1.3 mM ammonium concentration. At sites dominated by seepage, dissolved sulfate isotopic composition remained near seawater values despite depletion in porewater concentrations. Porewater ∑CO 2 concentrations were found to be elevated relative to seawater, but not to the extent predicted from the observed sulfate depletion. Sediment solid phase sulfur was predominantly pyrite, at concentrations as high as 20% S by weight. In contrast to typical marine deposits, pyrite concentrations were not related to the quantity of sedimentary organic matter. Pyrite δ 34 S values ranged from −29%. to + 21%. (CDT). However, only positive δ 34 S values were observed at sites associated with high pyrite concentrations. Isotopically heavy pyrite was observed at sites with porewater sulfate of seawater-like isotopic composition. Isotopically light pyrite was associated with sites where porewater sulfate exhibited δ 34 S values greater than those in seawater, indicating the activity of in situ microbial sulfate reduction. Thus, dual sulfide sources are suggested to explain the range in sediment pyrite isotopic composition: a δ 34 S enriched (+10 to +20%.) source adverted from within the Florida platform, and a lighter 34 S depleted component generated in situ from microbial reduction of seawater sulfate. The degree of pyritization of seep sediments was as high as 0.9 and was controlled by pyrite concentrations, which varied over a wider range than did the non-pyrite solid phase iron concentrations. The highest non-sulfide solid phase iron concentrations were observed in sediments that are believed to be at the “front” of the advancing seep fluids (i.e., hemipelagic sediments newly exposed to the seep fluids), indicating that dissolution of hemipelagic background sediment may be the source of at least half of the iron to the highly pyritized seep sediments. Porewater sulfide concentrations were variable, reaching a maximum of 5.7 mM, and were not correlated with the degree of pyritization of the sediments, suggesting that iron was not particularly limiting to pyrite formation.

Geochimica et Cosmochimica Acta↗

Isolating detrital and diagenetic signals in magnetic susceptibility records from methane-bearing marine sediments

Volume-dependent magnetic susceptibility (κ) is commonly used for paleoenvironmental reconstructions in both terrestrial and marine sedimentary environments where it reflects a mixed signal between primary deposition and secondary diagenesis. In the marine environment, κ is strongly influenced by the abundance of ferrimagnetic minerals regulated by sediment transport processes. Post-depositional alteration by H 2 S, however, can dissolve titanomagnetite, releasing reactive Fe that promotes pyritization and subsequently decreases κ. Here, we provide a new approach for isolating the detrital signal in κ and identifying intervals of diagenetic alteration of κ driven by organoclastic sulfate reduction (OSR) and the anaerobic oxidation of methane (AOM) in methane-bearing marine sediments offshore India. Using the correlation of a heavy mineral proxy from X-ray fluorescence data (Zr/Rb) and κ in unaltered sediments, we predict the primary detrital κ signal and identify intervals of decreased κ, which correspond to increased total sulfur content. Our approach is a rapid, high-resolution method that can identify overprinted κ resulting from pyritization of titanomagnetite due to H 2 S production in marine sediments. In addition, total organic carbon, total sulfur, and authigenic carbonate δ 13 C measurements indicate that both OSR and AOM can drive the observed κ loss, but AOM drives the greatest decreases in κ. Overall, our approach can enhance paleoenvironmental reconstructions and provide insight into paleo-positions of the sulfate-methane transition zone, past enhancements of OSR or paleo-methane seepage, and the role of detrital iron oxide minerals on the marine sediment sulfur sink, with consequences influencing the development of chemosynthetic biological communities at methane seeps.

Geochemistry, Geophysics, Geosystems↗

Geochemistry of autochthonous and hypautochthonous siderite-dolomite coal-balls (Foord Seam, Bolsovian, Upper Carboniferous), Nova Scotia, Canada

The 11–13 m thick Foord Seam in the fault-bounded Stellarton Basin, Nova Scotia, is the thickest seam from the Euramerican floral province known to contain coal-balls. In addition to the first discovery of autochthonous coal-balls in the Foord Seam, Nova Scotia, its shale parting also contains hypautochthonous coal-balls with histologically preserved plant structures. The coal-ball discovery helps fill a stratigraphic gap in coal-ball occurrences in the upper Carboniferous (Bolsovian) of Euramerica. The autochthonous and hypautochthonous coal-balls have a similar mineralogical composition and are composed of siderite (81–100%), dolomite-ankerite (0–19%), minor quartz and illite, and trace amounts of `calcite'. Similar is also their permineralizing mineralogy, which consists of dolomite-ankerite and siderite. Their low pyrite content and carbonate mineralogy, and nonmarine origin, differentiates the Foord Seam coal-balls from other Euramerican coal-ball occurrences. A preliminary geochemical model, which is based on oxygen and carbon isotopic data, indicates that siderite in both the autochthonous and hypautochthonous coal-balls is of very early diagenetic (nonmarine) origin from 13 C-enriched bicarbonate derived from bacterial methanogenesis of organic matter.

International Journal of Coal Geology↗

Biodynamic modeling of PCB uptake by Macoma balthica and Corbicula fluminea from sediment amended with activated carbon

Activated carbon amendment was assessed in the laboratory as a remediation strategy for freshwater sediment contaminated with polychlorinated biphenyls (PCBs) from the Grasse River (near Massena, NY). Three end points were evaluated: aqueous equilibrium PCB concentration, uptake into semipermeable membrane devices (SPMDs), and 28-day bioaccumulation in the clam Corbicula fluminea. PCB uptake by water, SPMDs, and clams followed similar trends, with reductions increasing as a function of carbon dose. Average percent reductions in clam tissue PCBs were 67, 86, and 95% for activated carbon doses of 0.7, 1.3, and 2.5% dry wt, respectively. A biodynamic model that incorporates sediment geochemistry and dietary and aqueous uptake routes was found to agree well with observed uptake by C. fluminea in our laboratory test systems. Results from this study were compared to 28-day bioaccumulation experiments involving PCB-contaminated sediment from Hunters Point Naval Shipyard (San Francisco Bay, CA) and the clam Macoma balthica. Due to differences in feeding strategy, M. balthica deposit-feeds whereas C. fluminea filter-feeds, the relative importance of the aqueous uptake route is predicted to be much higher for C. fluminea than for M. balthica. Whereas M. balthica takes up approximately 90% of its body burden through sediment ingestion, C. fluminea only accumulates approximately 45% via this route. In both cases, results strongly suggest that it is the mass transfer of PCBs from native sediment to added carbon particles, not merely reductions in aqueous PCB concentrations, that effectively reduces PCB bioavailability and uptake by sediment-dwelling organisms. ?? 2008 American Chemical Society.

Environmental Science & Technology↗

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: II. Field application to Haiwee reservoir sediment

Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.

Environmental Science & Technology↗

A water-leach procedure for estimating bioaccessibility of elements in soils from transects across the United States and Canada

An objective of the North American Soil Geochemical Landscapes Project is to provide relevant data concerning bioaccessible concentrations of elements in soil to government and other institutions undertaking environmental studies. A protocol was developed that employs a 1-g soil sample agitated overnight with 40 mL of reverse-osmosis de-ionized water for 20 h, and determination of 63 elements following three steps of centrifugation by inductively coupled plasma&ndash;atomic emission spectrometry and inductively coupled plasma&ndash;mass spectrometry the following day. Statistical summaries are presented for those 48 elements (Ag, Al, As, B, Ba, Be, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Re, S, Sb, Si, Sm, Sn, Sr, Tb, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, and pH) for which <20% of their data were reported as below the detection limit. The resulting data set contains analyses for 161 A-horizon soils collected along two transects, one along the 38th parallel across the USA and the other from northern Manitoba to the USA&ndash;Mexico border. The spatial distribution of three selected elements (Ca, Cu, and Pb) along the two transects is discussed in this paper both as absolute amounts liberated by the leach and expressed as a percentage of the total, or near-total, amounts determined for the elements. The Ca data reflect broad trends in soil parent materials, their weathering, and subsequent soil development. Calcium concentrations are generally found to be lower in the older soils of the eastern USA. The Cu data are higher in the eastern half of the USA, correlating with soil organic C, with which it is sequestered. The Pb data exhibit little regional variability due to natural sources, but are influenced by anthropogenic sources. Based on the Pb results, the percentage water-extractable data demonstrate promise as a tool for identifying anthropogenic components. The soil&ndash;water partition (distribution) coefficients, K d s (L/kg), were determined and their relevance to estimating bioaccessible amounts of elements to soil fauna and flora is discussed. Finally, a possible link between W concentrations in human urine and water-extractable W levels in Nevada soils is discussed.

Applied Geochemistry↗

Evaluating drivers of environmental change in a lake sediment core: Insights from spectroscopic metrics of water-extractable organic matter and stable carbon isotopes

Freshwater lakes play a critical role in the global carbon cycle by storing and transforming organic matter (OM) from both terrestrial and aquatic sources. Small lakes in northern temperate regions, despite their limited surface area, disproportionately influence regional carbon budgets. Buried sediments integrate OM inputs over time and archive ecosystem responses to natural and anthropogenic disturbances. However, the direction and magnitude of recent environmental changes on sediment carbon (C) dynamics remain poorly understood. A 23-cm core was collected from a small temperate lake in northeastern USA to evaluate sediment OM content and composition over timescales relevant to historical land-use change, damming, and recovery from acid deposition. Patterns in OM burial and source contributions were revealed via elemental and isotopic analyses of bulk OM and ultraviolet-visible spectrophotometry of water-extractable organic matter (WEOM). The optical metrics expanded observations of likely OM sources beyond the information gained from bulk carbon metrics (total carbon, δ 13 C). The aromaticity of WEOM increased downcore, which is consistent with a shift from increased terrestrial inputs during early logging and damming activity (pre ∼1920) to more microbial-derived OM in recent surficial sediments. Future applications of WEOM optical properties as complements to traditional geochemical metrics can enhance interpretations of lake ecosystem responses recorded in lake sediments to environmental perturbations in temperate lakes.

New York↗