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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↗

Models, validation, and applied geochemistry: Issues in science, communication, and philosophy

Models have become so fashionable that many scientists and engineers cannot imagine working without them. The predominant use of computer codes to execute model calculations has blurred the distinction between code and model. The recent controversy regarding model validation has brought into question what we mean by a ‘model’ and by ‘validation.’ It has become apparent that the usual meaning of validation may be common in engineering practice and seems useful in legal practice but it is contrary to scientific practice and brings into question our understanding of science and how it can best be applied to such problems as hazardous waste characterization, remediation, and aqueous geochemistry in general. This review summarizes arguments against using the phrase model validation and examines efforts to validate models for high-level radioactive waste management and for permitting and monitoring open-pit mines. Part of the controversy comes from a misunderstanding of ‘prediction’ and the need to distinguish logical from temporal prediction. Another problem stems from the difference in the engineering approach contrasted with the scientific approach. The reductionist influence on the way we approach environmental investigations also limits our ability to model the interconnected nature of reality. Guidelines are proposed to improve our perceptions and proper utilization of models. Use of the word ‘validation’ is strongly discouraged when discussing model reliability.

Applied Geochemistry↗

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

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

Alaska↗

Applied geochemistry, geology and mineralogy of the northernmost Carlin trend, Nevada

Investigations in the northernmost Carlin trend were undertaken to advance understanding of the geochemical signatures and genesis of precious metal deposits in the trend . Two fundamental geologic relationships near the trend significantly affect regional geochemical distributions: a remarkably intact lower Paleozoic stratigraphic sequence of siliceous rocks in the upper plate of the middle Paleozoic Roberts Mountains thrust, and the widespread repetition of rocks high in the upper plate during late Paleozoic thrusting that thickens the cover above mineralized rock in the lower plate. A compilation of previously published chemical analyses of 440 stream sediment samples and 115 rocks from two 7 1/2-minute quadrangles, as well as new chemical analyses of approximately 1,000 drill core samples in a 1,514 m (4,970 ft) hole through the Rodeo Creek deposit were used to construct three-dimensional element distribution models that highlight metal zonation in the mineralized systems. The Rodeo Creek deposit comprises deep Ag base-metal ± Au-mineralized rock below the Roberts Mountains thrust and contains an unusually high Ag/Au ratio greater than 30. Stacked geochemical halos related to the deposit are confined to the lower plate of the Roberts Mountains thrust and include two horizons of Hg, Cu, and Zn anomalies-as much as 180 m above the deposit-that mostly result from mercurian sphalerite. Extremely subtle indications of mineralization in the upper plate of the Roberts Mountains thrust above the deposit include arsenopyrite overgrowths on small pyrite crystals in 50- to 75-μm-wide clay-carbonate veinlets that lack alteration halos, arsenical rims on small disseminated crystal of recrystallized diagenetic pyrite, and partial replacement of diagenetic pyrite by tennantite. Some of these minerals contain anomalously high Au. However, these As-(Au)-bearing rocks most likely represent another locus of largely untested mineralized rock rather than distal halos related to either the Rodeo Creek or the nearby Dee and Storm gold deposits. Application of micromineralogic techniques helped to identify mineral assemblages that are specific to mineralization and provided an empirical foundation for interpretations of geochemical halos in the Carlin trend . District-scale geochemical patterns of several elements in stream sediments and surface rocks coincide with the northernmost Carlin trend and can be used to explore for Carlin -type deposits. Concentrations of elevated As and Sb in stream sediments (as much as 54 ppm As) have northwest-elongate lobate patterns that clearly outline the trend across a width of approximately 4 km. Arsenic contents of exposed rocks (as much as 90 ppm As) strongly correlate with As contents of derivative stream sediments, and rock contents of Sb show a somewhat lesser but nonetheless strong and similar correspondence. Factor analysis of stream-sediment data shows that those factor scores that are correlated with As, Sb, Au, and Pb also are high along the trend and suggest that mineralized rocks may be present. Although As was not detected by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) studies in heavy mineral concentrates of high-As stream sediments in the Carlin trend , X-ray absorption near-edge spectra (XANES) of selected light fractions of stream sediment samples indicate that Al-bearing phases, such as gibbsite, amorphous Al oxyhydroxides, or aluminosilicate clay minerals host most of the As(V). The best fit, visually and in terms of the lowest residual, was obtained by a model compound of As(V) sorbed to gibbsite. Thus, most As in stream sediments derived from altered rock within the Carlin trend apparently is contained in light fractions. The geochemical character of young, unconsolidated, postmineral deposits that cover mineralized rocks on the Carlin trend partly results from mineralized sources along the trend . Concentration of As in the Miocene Carlin Formation shows an exceptionally well developed progressive increase to about 30 ppm As as altered rock surrounding the trend is approached. Mineralized and/or altered rock fragments probably have been shed directly into the sedimentary basin of the Carlin Formation, and migration of As, now fixed as As(V), also may have occurred in the supergene environment after material was recycled out of the Carlin Formation and into present-day gulleys.

Nevada↗

Developing integrated methods to address complex resource and environmental issues

Introduction This circular provides an overview of selected activities that were conducted within the U.S. Geological Survey (USGS) Integrated Methods Development Project, an interdisciplinary project designed to develop new tools and conduct innovative research requiring integration of geologic, geophysical, geochemical, and remote-sensing expertise. The project was supported by the USGS Mineral Resources Program, and its products and acquired capabilities have broad applications to missions throughout the USGS and beyond. In addressing challenges associated with understanding the location, quantity, and quality of mineral resources, and in investigating the potential environmental consequences of resource development, a number of field and laboratory capabilities and interpretative methodologies evolved from the project that have applications to traditional resource studies as well as to studies related to ecosystem health, human health, disaster and hazard assessment, and planetary science. New or improved tools and research findings developed within the project have been applied to other projects and activities. Specifically, geophysical equipment and techniques have been applied to a variety of traditional and nontraditional mineral- and energy-resource studies, military applications, environmental investigations, and applied research activities that involve climate change, mapping techniques, and monitoring capabilities. Diverse applied geochemistry activities provide a process-level understanding of the mobility, chemical speciation, and bioavailability of elements, particularly metals and metalloids, in a variety of environmental settings. Imaging spectroscopy capabilities maintained and developed within the project have been applied to traditional resource studies as well as to studies related to ecosystem health, human health, disaster assessment, and planetary science. Brief descriptions of capabilities and laboratory facilities and summaries of some applications of project products and research findings are included in this circular. The work helped support the USGS mission to “provide reliable scientific information to describe and understand the Earth; minimize loss of life and property from natural disasters; manage water, biological, energy, and mineral resources; and enhance and protect our quality of life.” Activities within the project include the following: Spanned scales from microscopic to planetary; Demonstrated broad applications across disciplines; Included life-cycle studies of mineral resources; Incorporated specialized areas of expertise in applied geochemistry including mineralogy, hydrogeology, analytical chemistry, aqueous geochemistry, biogeochemistry, microbiology, aquatic toxicology, and public health; and Incorporated specialized areas of expertise in geophysics including magnetics, gravity, radiometrics, electromagnetics, seismic, ground-penetrating radar, borehole radar, and imaging spectroscopy. This circular consists of eight sections that contain summaries of various activities under the project. The eight sections are listed below: Laboratory Facilities and Capabilities, which includes brief descriptions of the various types of laboratories and capabilities used for the project; Method and Software Development, which includes summaries of remote-sensing, geophysical, and mineralogical methods developed or enhanced by the project; Instrument Development, which includes descriptions of geophysical instruments developed under the project; Minerals, Energy, and Climate, which includes summaries of research that applies to mineral or energy resources, environmental processes and monitoring, and carbon sequestration by earth materials; Element Cycling, Toxicity, and Health, which includes summaries of several process-oriented geochemical and biogeochemical studies and health-related research activities; Hydrogeology and Water Quality, which includes descriptions of innovative geophysical, remote-sensing, and geochemical research pertaining to hydrogeology and water-quality applications; Hazards and Disaster Assessment, which includes summaries of research and method development that were applied to natural hazards, human-caused hazards, and disaster assessments; and Databases and Framework Studies, which includes descriptions of fundamental applications of geophysical studies and of the importance of archived data.

Circular↗

From extreme pH to extreme temperature: An issue in honor of the geochemical contributions of Kirk Nordstrom, USGS hydrogeochemist

This special issue of Applied Geochemistry honors Dr. D. Kirk Nordstrom, and his influential career spent primarily at the U.S. Geological Survey (USGS). This issue does not herald his retirement or other significant career milestone, but serves as a recognition of the impact his work has had on the field of geochemistry in general. This special issue grew from a symposium in Kirk’s honor (affectionately dubbed “Kirkfest”) at the Geological Society of America’s annual meeting in Denver, Colorado, USA, during October 2013. At GSA, 27 talks and 35 posters showed how Kirk’s work has influenced a wide range of current hydrogeochemical research, from geothermal processes to acid mine drainage to geochemical modeling. The breadth of his knowledge and his many contributions to the published literature have left an indelible mark on the field of geochemistry, and this special issue is a tribute to his experience and contributions.

Applied Geochemistry↗

Preface

Energy is the essential commodity that powers the expanding global economy. Starting in the 1950s, oil and natural gas became the main sources of primary energy for the rapidly increasing world population ( Edwards, 1997 ). In 2003, petroleum was the source for 62.1% of global energy, and projections by energy information administration (EIA) indicate that oil and gas will continue their dominance, supplying 59.5% of global energy in 2030 ( EIA, 2007 ). Unfortunately petroleum and coal consumption carry major detrimental environmental impacts that may be regional or global in scale, including air pollution, global climate change and oil spills. This special volume of Applied Geochemistry, devoted to “Environmental Issues Related to Oil and Gas Exploration and Production”, does not address these major impacts directly because air pollution and global climate change are issues related primarily to the burning of petroleum and coal, and major oil spills generally occur during ocean transport, such as the Exxon Valdez 1989 spill of 42,000 m 3 (260,000 bbl) oil into Prince William Sound, Alaska.

Applied Geochemistry↗

Top-down targeted network analysis of critical mineral commodities applied to international geochemistry database

The global demand for critical mineral commodities is rapidly increasing, making domestic production an important factor in supporting the economy and national security. Large scale, publicly available geochemical databases allow for the application of data informatics methods to interrogate critical mineral commodities data for correlations in deposit formation and distribution, particularly for identifying enrichment of multiple critical mineral commodities at the same deposit. In this study, we applied network analysis to the Critical Minerals Mapping Initiative (CMMI) ore geochemistry (Critical Minerals in Ores, CMiO) database to identify the high concentration (defined as 10× bulk crustal abundance) co-occurrence of different critical mineral commodities across a mineral system hierarchy from deposit environments to individual deposits. Identifying patterns or unique outliers in enrichment in network communities will allow for the location of secondary critical mineral commodity resources from under-utilized deposits. We find trends in the enrichment of critical mineral commodities in network-communities between the elements praseodymium (Pr), neodymium (Nd), terbium (Tb), and dysprosium (Dy) across multiple CMiO database deposit environments and groups down to specific deposit types and sites. A separate trend in network community deposition is observed as well between iridium (Ir) and platinum (Pt) in deposit environments, groups, types, and sites. Network analysis focused on critical minerals in magmatic-hydrothermal deposits identified multiple deposit sites from different deposit types within the CMiO database with concentrations of Dy, Nd, Tb, Pr, Ir, and Pt that are at least ten times greater than the crustal average. This approach can be applied to any target element(s) or deposit(s) of interest, allowing broad investigation of co-enriched critical mineral commodities.

Journal of Geochemical Exploration↗

Nuclear methods applied to uranium geochemistry

Stable and radioactive daughter products produced from nuclear disintegrations of uranium have proved useful in fundamental studies of the geochemistry of uranium in igneous rock and sedimentary environments and in ore deposits. Information gained from geochemical studies of uranium migration has been used to develop models for attempts to date archeological, geological, and oceanographic environments represented by samples of bone, wood, charcoal, continental and marine carbonates, marine sediments, and glacially derived soils. Recent improvements of nuclear instrumentation and techniques allowed accurate measurements of natural radioactive isotopes, and it is now believed that radioactive equilibrium between the long-lived isotopes of the two uranium decay series is more the exception than the rule in nature. It was assumed that the 234U and 238U isotopes were in equilibrium until Thurber confirmed that considerable separation between 234U daughter and 238U parent exists in nature. It now has been documented that the 234U content may range from 60% deficient to 500% in excess relative to 238U. An excess of 15% of 234U isotope in sea water is well documented. A summary of previous work has shown that geochemical fractionation of the radioactive nuclides in 238U and 235U decay series takes place in the hydrologic environment, resulting in depletion of 230Th and 231Pa with respect to their parents, 238U, 234U, and 235U, in water and a complementary enrichment of these daughter nuclides in some sediments. Subsequent assimilation of Uranium, essentially free of radioactive daughters, occurs in some specific types of deposits such as carbonates and phosphates.

IEEE Transactions on Nuclear Science↗

Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0

High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).

Applied Geochemistry↗

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

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

Applied Geochemistry↗

Effects of human-induced alteration of groundwater flow on concentrations of naturally-occurring trace elements at water-supply wells

The effects of human-induced alteration of groundwater flow patterns on concentrations of naturally-occurring trace elements were examined in five hydrologically distinct aquifer systems in the USA. Although naturally occurring, these trace elements can exceed concentrations that are considered harmful to human health. The results show that pumping-induced hydraulic gradient changes and artificial connection of aquifers by well screens can mix chemically distinct groundwater. Chemical reactions between these mixed groundwaters and solid aquifer materials can result in the mobilization of trace elements such as U, As and Ra, with subsequent transport to water-supply wells. For example, in the High Plains aquifer near York, Nebraska, mixing of shallow, oxygenated, lower-pH water from an unconfined aquifer with deeper, confined, anoxic, higher-pH water is facilitated by wells screened across both aquifers. The resulting higher-O2, lower-pH mixed groundwater facilitated the mobilization of U from solid aquifer materials, and dissolved U concentrations were observed to increase significantly in nearby supply wells. Similar instances of trace element mobilization due to human-induced mixing of groundwaters were documented in: (1) the Floridan aquifer system near Tampa, Florida (As and U), (2) Paleozoic sedimentary aquifers in eastern Wisconsin (As), (3) the basin-fill aquifer underlying the California Central Valley near Modesto (U), and (4) Coastal Plain aquifers of New Jersey (Ra). Adverse water-quality impacts attributed to human activities are commonly assumed to be related solely to the release of the various anthropogenic contaminants to the environment. The results show that human activities including various land uses, well drilling, and pumping rates and volumes can adversely impact the quality of water in supply wells, when associated with naturally-occurring trace elements in aquifer materials. This occurs by causing subtle but significant changes in geochemistry and associated trace element mobilization as well as enhancing advective transport processes.

Applied Geochemistry↗

Occurrence and geochemistry of radium in water from principal drinking-water aquifer systems of the United States

A total of 1270 raw-water samples (before treatment) were collected from 15 principal and other major aquifer systems (PAs) used for drinking water in 45 states in all major physiographic provinces of the USA and analyzed for concentrations of the Ra isotopes 224Ra, 226Ra and 228Ra establishing the framework for evaluating Ra occurrence. The US Environmental Protection Agency Maximum Contaminant Level (MCL) of 0.185Bq/L (5pCi/L) for combined Ra ( 226Ra plus 228Ra) for drinking water was exceeded in 4.02% (39 of 971) of samples for which both 226Ra and 228Ra were determined, or in 3.15% (40 of 1266) of the samples in which at least one isotope concentration ( 226Ra or 228Ra) was determined. The maximum concentration of combined Ra was 0.755Bq/L (20.4pCi/L) in water from the North Atlantic Coastal Plain quartzose sand aquifer system. All the exceedences of the MCL for combined Ra occurred in water samples from the following 7PAs (in order of decreasing relative frequency of occurrence): the Midcontinent and Ozark Plateau Cambro-Ordovician dolomites and sandstones, the North Atlantic Coastal Plain, the Floridan, the crystalline rocks (granitic, metamorphic) of New England, the Mesozoic basins of the Appalachian Piedmont, the Gulf Coastal Plain, and the glacial sands and gravels (highest concentrations in New England).The concentration of Ra was consistently controlled by geochemical properties of the aquifer systems, with the highest concentrations most likely to be present where, as a consequence of the geochemical environment, adsorption of the Ra was slightly decreased. The result is a slight relative increase in Ra mobility, especially notable in aquifers with poor sorptive capacity (Fe-oxide-poor quartzose sands and carbonates), even if Ra is not abundant in the aquifer solids. The most common occurrence of elevated Ra throughout the USA occurred in anoxic water (low dissolved-O 2) with high concentrations of Fe or Mn, and in places, high concentrations of the competing ions Ca, Mg, Ba and Sr, and occasionally of dissolved solids, K, SO 4 and HCO 3. The other water type to frequently contain elevated concentrations of the Ra radioisotopes was acidic (low pH), and had in places, high concentrations of NO 3 and other acid anions, and on occasion, of the competing divalent cations, Mn and Al. One or the other of these broad water types was commonly present in each of the PAs in which elevated concentrations of combined Ra occurred. Concentrations of 226Ra or 228Ra or combined Ra correlated significantly with those of the above listed water-quality constituents (on the basis of the non-parametric Spearman correlation technique) and loaded on principal components describing the above water types from the entire data set and for samples from the PAs with the highest combined Ra concentrations.Concentrations of 224Ra and 226Ra were significantly correlated to those of 228Ra (Spearman's rank correlation coefficient, +0.236 and +0.326, respectively). Activity ratios of 224Ra/ 228Ra in the water samples were mostly near 1 when concentrations of both isotopes were greater than or equal to 0.037Bq/L (1pCi/L), the level above which analytical results were most reliable. Co-occurrence among these highest concentrations of the Ra radionuclides was most likely in those PAs where chemical conditions are most conducive to Ra mobility (e.g. acidic North Atlantic Coastal Plain). The concentrations of 224Ra were occasionally greater than 0.037Bq/L and the ratios of 224Ra/ 228Ra were generally highest in the PAs composed of alluvial sands and Cretaceous/Tertiary sandstones from the western USA, likely because concentrations of 224Ra are enhanced in solution relative to those of 228Ra by alpha recoil from the aquifer matrix. Rapid adsorption of the two Ra isotopes (controlled by the alkaline and oxic aquifer geochemistry) combined with preferential faster recoil of 224Ra generates a 224Ra/ 228Ra ratio much greater than

Applied Geochemistry↗

Relationships between microbial communities and environmental parameters at sites impacted by mining of volcanogenic massive sulfide deposits, Prince William Sound, Alaska

The relations among geochemical parameters and sediment microbial communities were examined at three shoreline sites in the Prince William Sound, Alaska, which display varying degrees of impact by acid-rock drainage (ARD) associated with historic mining of volcanogenic massive sulfide deposits. Microbial communities were examined using total fatty acid methyl esters (FAMEs), a class of compounds derived from lipids produced by eukaryotes and prokaryotes (bacteria and Archaea); standard extraction techniques detect FAMEs from both living (viable) and dead (non-viable) biomass, but do not detect Archaeal FAMEs. Biomass and diversity (as estimated by FAMEs) varied strongly as a function of position in the tidal zone, not by study site; subtidal muds, Fe oxyhydroxide undergoing biogenic reductive dissolution, and peat-rich intertidal sediment had the highest values. These estimates were lowest in acid-generating, intertidal zone sediment; if valid, the estimates suggest that only one or two bacterial species predominate in these communities, and/or that Archeal species are important members of the microbial community in this sediment. All samples were dominated by bacterial FAMEs (median value >90%). Samples with the highest absolute abundance of eukaryotic FAMEs were biogenic Fe oxyhydroxides from shallow freshwater pools (fungi) and subtidal muds (diatoms). Eukaryotic FAMEs were practically absent from low-pH, sulfide-rich intertidal zone sediments. The relative abundance of general microbial functional groups such as aerobes/anaerobes and gram(+)/gram(-) was not estimated due to severe inconsistency among the results obtained using several metrics reported in the literature. Principal component analyses (PCAs) were performed to investigate the relationship among samples as separate functions of water, sediment, and FAMEs data. PCAs based on water chemistry and FAMEs data resulted in similar relations among samples, whereas the PCA based on sediment chemistry produced a very different sample arrangement. Specifically, the sediment parameter PCA grouped samples with high bulk trace metal concentration regardless of whether the metals were incorporated into secondary precipitates or primary sulfides. The water chemistry PCA and FAMEs PCA appear to be less prone to this type of artifact. Signature lipids in sulfide-rich sediments could indicate the presence of acid-tolerant and/or acidophilic members of the genus Thiobacillus or they could indicate the presence of SO4-reducing bacteria. The microbial community documented in subtidal and offshore sediments is rich in SRB and/or facultative anaerobes of the Cytophaga-Flavobacterium group; both could reasonably be expected in PWS coastal environments. The results of this study provide evidence for substantial feedback between local (meter to centimeter-scale) geochemical variations, and sediment microbial community composition, and show that microbial community signatures in the intertidal zone are significantly altered at sites where ARD drainage is present relative to sites where it is not, even if the sediment geochemistry indicates net accumulation of ARD-generated trace metals in the intertidal zone. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Strontium isotope geochemistry of groundwaters and streams affected by agriculture, Locust Grove, MD

The effects of agriculture on the isotope geochemistry of Sr were investigated in two small watersheds in the Atlantic coastal plain of Maryland. Stratified shallow oxic groundwaters in both watersheds contained a retrievable record of increasing recharge rates of chemicals including NO 3 − , Cl, Mg, Ca and Sr that were correlated with increasing fertilizer use between about 1940 and 1990. The component of Sr associated with recent agricultural recharge was relatively radiogenic ( 87 Sr/ 86 Sr=0.715) and it was overwhelming with respect to Sr acquired naturally by water–rock interactions in the oxidized, non-calcareous portion of the saturated zone. Agricultural groundwaters that penetrated relatively unoxidized calcareous glauconitic sediments at depth acquired an additional component of Sr from dissolution of early Tertiary marine CaCO 3 ( 87 Sr/ 86 Sr=0.708) while undergoing O 2 reduction and denitrification. Ground-water discharge contained mixtures of waters of various ages and redox states. Two streams draining the area are considered to have higher 87 Sr/ 86 Sr ratios and NO 3 − concentrations than they would in the absence of agriculture; however, the streams have consistently different 87 Sr/ 86 Sr ratios and NO 3 − concentrations because the average depth to calcareous reducing (denitrifying) sediments in the local groundwater flow system was different in the two watersheds. The results of this study indicate that agriculture can alter significantly the isotope geochemistry of Sr in aquifers and streams and that the effects could vary depending on the types, sources and amounts of fertilizers added, the history of fertilizer use and groundwater residence times.

Maryland↗

Isotopic analysis of radium geochemistry at discrete intervals in the Midwestern Cambrian-Ordovician aquifer system

Radium (Ra) is a geogenic radioactive contaminant that frequently occurs at elevated levels in the Midwestern Cambrian-Ordovician aquifer system (MCOAS). Geochemical indicators (e.g., redox conditions or total dissolved solids) can broadly characterize conditions associated with elevated Ra levels in groundwater, but do not consistently correlate to elevated Ra within specific stratigraphic horizons. A coupled geochemical and isotopic study of groundwater and aquifer solids for major and trace elements, Ra, and uranium (U) at discrete intervals in the MCOAS was used to elucidate processes that may be responsible for this disconnect, via analysis of groundwater as well as extracted and digested solid aquifer samples. We find that the potential for Ra mobilization varies by stratigraphic unit, as observed by whole-rock 226 Ra/ 238 U (dis)equilibrium. Overall, the examined aqueous geochemical characteristics (e.g., redox conditions, total dissolved solids) do not explain Ra concentrations within the system, suggesting that alternative factors, like solid-phase associations or the extent of alpha recoil damage, may be more important. A relation between aqueous 87 Sr/ 86 Sr and 226 Ra suggests that minerals with radiogenic 87 Sr/ 86 Sr are more likely to release 226 Ra to the aqueous system. Overall, the release of U and Ra due to water-rock interaction varies with discrete stratigraphy, depending on aqueous geochemistry and available mineral associations. Due to complex Ra-rock interactions and the heterogeneous geology of the MCOAS, aqueous geochemistry does not fully predict the mobilization and concentration of Ra in groundwater. As sources and sinks of Ra within the MCOAS vary across stratigraphy, knowledge of aqueous geochemistry, available solid-phase associations, and nuclide leachability all are important to consider for understanding elevated Ra occurrence in aquifer systems.

Wisconsin↗

Geochemistry of soils along a transect from Central Mexico to the Pacific Coast: a pilot study for continental-scale geochemical mapping

The Mexican Geological Survey (SGM), the National Institute of Statistics, Geography and Informatics (INEGI) and the Autonomous University of San Luis Potosi (UASLP) have established a multidisciplinary team with the objective of creating a national program of geochemical mapping of soils in Mexico. This is being done as part of the North American Soil Geochemical Landscapes Project in partnership with the US Geological Survey and the Geological Survey of Canada. As the first step, a pilot study was conducted over a transect that extends from the Mexico–US border near Ciudad Juarez in the north to the Pacific Ocean in the south. This pilot transect was conducted in two phases, and this paper presents results from the first phase, which sampled soils at about a 40-km spacing along a 730-km transect beginning in Central Mexico and ending at the Pacific Coast. Samples were collected from the A and C horizons at each site and 60 elements were analyzed. This pilot study demonstrates that geochemical mapping based on a 40-km spacing is adequate to identify broad-scale geochemical patterns. Geologic influence (i.e., soil parent material) was the most important factor influencing the distribution of elements along the transect, followed by the influence of regional mineralization. The study also showed that influence by human activities over the transect is minimal except possibly in large mining districts. A comparison of element abundance in the A horizon with the environmental soil guidelines in Mexico showed that the natural concentrations of the studied soils were lower than the established threshold for soil restoration with the exception of V and As. The former had a median value (75 mg/kg) approximately equal to the value established in Mexico for soil restoration in agricultural and residential lands (78 mg/kg), and the latter had three values higher than the 22 mg/kg threshold for soil restoration in agricultural and residential lands. These cases demonstrate the importance of knowing the national- and regional-scale geochemistry of Mexican soils as a support for the decision-making process, particularly for the proper formulation and application of soil guidelines designed to protect human and ecosystem health.

Applied Geochemistry↗

Regional patterns in the geochemistry of oil-field water, southern San Joaquin Valley, California, USA

Chemical and isotopic data for water co-extracted with hydrocarbons in oil and gas fields are commonly used to examine the source of the formation water and possible impacts on groundwater in areas of oil and gas development. Understanding the geochemical variability of oil-field water could help to evaluate its origin and delineate possible contamination of shallow aquifers in cases where oil-field water is released to the environment. Here we report geochemical and multiple isotope (H, C, O, Sr, Ra) data from 22 oil wells, three sources of produced water that are disposed of in injection wells, and two surface disposal ponds in four oil fields in the southern San Joaquin Valley, California (Fruitvale, Lost Hills, North and South Belridge). Correlations between Cl and δ 18 O, as well as other ions, and gradual increases in salinity with depth, indicate dilution of one or more saline end-members by meteoric water. The saline end-members, represented by deep samples (610 m–2621 m) in three oil-bearing zones, are characterized by Na Cl composition, near-seawater Cl concentrations (median 20,000 mg/L), enriched δ 18 O H 2 O (median 3.4‰), high ammonium(up to 460 mg-N/L), and relatively high radium activity ( 226 Ra+ 228 Ra = 12.3 Bq/L). The deepest sample has low Na/Cl (0.74), high Ca/Mg (5.0), and low 87 Sr/ 86 Sr (0.7063), whereas the shallower samples have higher Na/Cl (0.86–1.2), Ca/Mg near 1, and higher 87 Sr/ 86 Sr (∼0.7083). The data are consistent with an original seawater source being modified by various depth and lithology dependent diagenetic processes. Dilution by meteoric water occurs naturally on the east side of the valley, and in association with water-injectionactivities on the west side. Meteoric-water flushing, particularly on the east side, results in lower solute concentrations (minimum total dissolved solids 2730 mg/L) and total radium (minimum 0.27 Bq/L) in oil-field water, and promotes biodegradation of dissolved organic carbon and hydrocarbon gases like propane. Acetate concentrations and δ 13 C of dissolved inorganic carbon indicate biogenic methane production occurs in some shallow oil zones. Natural and human processes produce substantial variability in the geochemistry of oil-field water that should be considered when evaluating mixing between oil-field waters and groundwater. The variability could result in uncertainty as to detecting the potential source and impact of oil-field water on groundwater.

California↗