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The Drenchwater deposit, Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn-Pb-Ag deposit

The Drenchwater shale-hosted Zn-Pb-Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ??? 4.3, Zn ??? 1400 ??g/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7-3.1) and very metal-rich waters (up to 2600 ??g/L Zn, ??? 260 ??g/L Cu and ???89 ??g/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Applied Geochemistry

Priority pollutants and associated constituents in untreated and treated discharges from coal mining or processing facilities in Pennsylvania, USA

Clean sampling and analysis procedures were used to quantify more than 70 inorganic constituents, including 35 potentially toxic or hazardous constituents, organic carbon, and other characteristics of untreated (influent) and treated (effluent) coal-mine discharges (CMD) at 38 permitted coal-mining or coal-processing facilities in the bituminous coalfield and 4 facilities in the anthracite coalfield of Pennsylvania. Of the 42 facilities sampled during 2011, 26 were surface mines, 11 were underground mines, and 5 were coal refuse disposal operations. Treatment of CMD with caustic soda (NaOH), lime (CaO or Ca(OH) 2 ), flocculent, or limestone was ongoing at 21%, 40%, 6%, and 4% of the facilities, respectively; no chemicals were added at the remaining facilities. All facilities with CMD treatment incorporated structures for active or passive aeration and settling of metal-rich precipitate. The untreated influent samples had wide ranges of pH (2.8&ndash;7.6), hot acidity (&minus;600 to 8000 mg/L as CaCO 3 ), specific conductance (SC; 253&ndash;13,000 &mu;S/cm), total dissolved solids (TDS; 168&ndash;18,100 mg/L), and associated dissolved (<0.45-&mu;m pore-size filter) constituents, including SO 4 (14.7&ndash;10,700 mg/L), Fe (<0.01 to 4100 mg/L), Mn (0.02&ndash;136 mg/L), Al (<0.01 to 128 mg/L), and Zn (<0.003 to 18.8 mg/L). Concentrations of Ag (<1 &mu;g/L), Hg (<1 &mu;g/L), Sn (<0.5 &mu;g/L), and CN (<0.01 mg/L) were below detection limits. Only one influent sample met permitted mine effluent (PME) limits plus dissolved-constituent criteria maximum concentration (CMC) thresholds for the protection of freshwater aquatic organisms. The pH of the treated effluent samples ranged from 5.5 to 11.9 and was greater than or equal to the pH of the corresponding influent at all sites. All the effluent samples met CMC levels for dissolved concentrations of Ag, As, Ba, Cd, Cl, Cr, Pb, Ni, Sb, Se, Tl, V, NH 3 , NO 2 , NO 3 , and CN; however, nine violated one or more of the PME limits for pH (<6, n = 1), net acidity (>0, n = 3), Fe (>7 mg/L, n = 1), or Mn (>5 mg/L, n = 8), plus one or more exceeded CMC levels for Al (>0.75 mg/L, n = 2), Co (>95 &mu;g/L, n = 5), Zn (>307 &mu;g/L, n = 1), Cu (>7.4 &mu;g/L, n = 1), or Se (>12.8 &mu;g/L, n = 3). Although CMC exceedances for Co and Zn were attributed to samples also violating the PME limit for pH or Mn, the samples that exceeded the CMC for Al, Cu, or Se met applicable PME limits for pH, Fe, and Mn. Furthermore, many of the pH-compliant effluents did not meet reference criteria for SO 4 and related measures of ionic strength, including TDS, SC, and osmotic pressure. The Wilcoxon matched-pair signed-ranks statistic was used to test if the overall difference between the effluent and influent pairs was equal to zero. Constituents that statistically were the same for effluent and influent ( p > 0.05) included flow rate, SC, osmotic pressure, hardness, alkalinity, total organic carbon (TOC), K, Cl, NO 3 , PO 4 , Sb, Sr, Br, Se, Mo, and V. Although temperature, dissolved oxygen, pH, Ca, and Na were greater in the effluent than the influent, most constituents decreased as a result of treatment, including TDS, acidity, SO 4 , Al, Fe, Mn, Mg, As, Ba, Be, Cd, Cr, Co, Cu, F, Pb, Ni, NH 3 , Tl, Ti, U, Zn, Zr, total phenols, total inorganic carbon (TIC), biological oxygen demand (BOD), and chemical oxygen demand (COD). Nevertheless, some constituents that decreased, such as SO 4 , still did not meet reference criteria. Findings from this study suggest that typical chemical or aerobic treatment of CMD to pH > 6 with removal of Fe to <7 mg/L and Mn to <5 mg/L may provide a reasonable measure of protection for aquatic life from priority pollutant metals and other toxic or hazardous constituents in effluent but may not be effective for achieving permissible or background levels for TDS, SC, osmotic pressure, or concentrations of SO 4 and some other pollutants, including Se, Br, and Cl, if present.

Pennsylvania

Estimating westslope cutthroat trout ( Oncorhynchus clarkii lewisi ) movements in a river network using strontium isoscapes

We used natural variation in the strontium concentration (Sr:Ca) and isotope composition ( 87 Sr: 86 Sr) of stream waters and corresponding values recorded in otoliths of westslope cutthroat trout ( Oncorhynchus clarkii lewisi ) to examine movements during their life history in a large river network. We found significant spatial differences in Sr:Ca and 87 Sr: 86 Sr values (strontium isoscapes) within and among numerous spawning and rearing streams that remained relatively constant seasonally. Both Sr:Ca and 87 Sr: 86 Sr values in the otoliths of juveniles collected from nine natal streams were highly correlated with those values in the ambient water. Strontium isoscapes measured along the axis of otolith growth revealed that almost half of the juveniles had moved at least some distance from their natal streams. Finally, otolith Sr profiles from three spawning adults confirmed homing to natal streams and use of nonoverlapping habitats over their migratory lifetimes. Our study demonstrates that otolith geochemistry records movements of cutthroat trout through Sr isoscapes and therefore provides a method that complements and extends the utility of conventional tagging techniques in understanding life history strategies and conservation needs of freshwater fishes in river networks.

Canadian Journal of Fisheries and Aquatic Sciences

Distribution of Cu, Co, As, and Fe in mine waste, sediment, soil, and water in and around mineral deposits and mines of the Idaho Cobalt Belt, USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.

Idaho

Geochemistry of Red Mountain Creek, Colorado, under low-flow conditions, August 2002

Red Mountain Creek, an acid mine drainage stream in southwestern Colorado, was the subject of a synoptic study conducted in August 2002. During the synoptic study, a solution containing lithium chloride was injected continuously to allow for the calculation of streamflow using the tracer-dilution method. Synoptic water-quality samples were collected from 48 stream sites and 29 inflow locations along a 5.4-kilometer study reach. Data from the study provide profiles of pH, concentration, and mass load with a high degree of spatial resolution. Despite the presence of 10 circumneutral inflows, pH remained below 3.4 at all stream sites. Concentration profiles indicate that dissolved concentrations of aluminum, cadmium, copper, lead, and zinc exceed chronic aquatic-life standards established by the State of Colorado along the entire study reach. Comparison of total recoverable and dissolved concentrations suggests that most constituents were transported conservatively. Exceptions to this pattern include arsenic, iron, molybdenum, and vanadium, four constituents that were subject to precipitation and(or) sorption reactions as the addition of a circumneutral tributary resulted in a slight increase in instream pH. Evaluation of data from the 29 inflow locations indicates a sharp contrast between the east and west sides of the watershed; inflows from the east side have high constituent concentrations and acidic pH, whereas inflows from the west side have lower concentrations and generally higher pH. Loading profiles, the product of streamflow and concentration, are used to rank potential sources of metals and acidity within the watershed. Four sources account for 83, 72, 70, 69, 64, and 61 percent of the aluminum, iron, arsenic, zinc, copper, and cadmium loading within the study reach, respectively. All four sources appear to be the result of surface inflows that have been affected by mining activities. The relatively small number of major sources and the fact that they are attributable to surface inflows are two factors that may facilitate effective remediation.

Colorado

Bacterial succession within an ephemeral hypereutrophic mojave desert playa lake

Ephemerally wet playas are conspicuous features of arid landscapes worldwide; however, they have not been well studied as habitats for microorganisms. We tracked the geochemistry and microbial community in Silver Lake playa, California, over one flooding/desiccation cycle following the unusually wet winter of 2004-2005. Over the course of the study, total dissolved solids increased by 10-fold and pH increased by nearly one unit. As the lake contracted and temperatures increased over the summer, a moderately dense planktonic population of 1 ?????106 cells ml-1 of culturable heterotrophs was replaced by a dense population of more than 1????????109 cells ml-1, which appears to be the highest concentration of culturable planktonic heterotrophs reported in any natural aquatic ecosystem. This correlated with a dramatic depletion of nitrate as well as changes in the microbial community, as assessed by small subunit ribosomal RNA gene sequencing of bacterial isolates and uncultivated clones. Isolates from the early-phase flooded playa were primarily Actinobacteria, Firmicutes, and Bacteroidetes, yet clone libraries were dominated by Betaproteobacteria and yet uncultivated Actinobacteria. Isolates from the late-flooded phase ecosystem were predominantly Proteobacteria, particularly alkalitolerant isolates of Rhodobaca, Porphyrobacter, Hydrogenophaga, Alishwenella, and relatives of Thauera; however, clone libraries were composed almost entirely of Synechococcus (Cyanobacteria). A sample taken after the playa surface was completely desiccated contained diverse culturable Actinobacteria typically isolated from soils. In total, 205 isolates and 166 clones represented 82 and 44 species-level groups, respectively, including a wide diversity of Proteobacteria, Bacteroidetes, Actinobacteria, Firmicutes, Gemmatimonadetes, Acidobacteria, and Cyanobacteria. ?? 2008 Springer Science+Business Media, LLC.

Microbial Ecology

The effect of acidic, metal-enriched drainage from the Wightman Fork and Alamosa River on the composition of selected wetlands in San Luis Valley, Colorado

The biogeochemistry of selected wetlands in the San Luis Valley, Colorado, was examined to assess the effect of acidic, metal-enriched water draining mineralized areas near and around the Summitville Mine. The sampling protocols, analytical methods, and chemical composition of water and stream bed sediment from the Wightman Fork and Alamosa River as well as water, surface sediment or cores, and rooted aquatic vegetation from wetland sites within and west of the Alamosa National Wildlife Refuge are presented. The data indicate that As, Co, Cr, Cu, Ni, and Zn are tracers of drainage from mineralized areas around the Summitville Mine. Sediments and aquatic plants in wetlands in the San Luis Valley that receive surface water from the Alamosa River tend to have larger concentrations of certain tracer elements (e.g., Co and Cu) than wetlands that receive water from other sources. Larger concentrations of Cu, Ni, and Zn in the sediments of wetlands receiving Alamosa River water appear to be related to the presence of larger amounts of Fe oxyhydroxides. However, there is little to no variation in the concentrations of tracer elements with depth in wetlands that receive Alamosa River water. This observation suggests that the geochemistry of these wetlands has not been significantly affected by recent mining activities at the Summitville Mine.

Colorado

Understanding contaminants associated with mineral deposits

Interdisciplinary studies by the U.S. Geological Survey (USGS) have resulted in substantial progress in understanding the processes that control the release of metals and acidic water from inactive mines and mineralized areas, the transport of metals and acidic water to streams, and the fate and effect of metals and acidity on downstream ecosystems. The potential environmental effects associated with abandoned and inactive mines, resulting from the complex interaction of a variety of chemical and physical processes, is an area of study that is important to the USGS Mineral Resources Program. Understanding the processes contributing to the environmental effects of abandoned and inactive mines is also of interest to a wide range of stakeholders, including both those responsible for managing lands with historically mined areas and those responsible for anticipating environmental consequences of future mining operations. The recently completed (2007) USGS project entitled 'Process Studies of Contaminants Associated with Mineral Deposits' focused on abandoned and inactive mines and mineralized areas in the Rocky Mountains of Montana, Colorado, New Mexico, Utah, and Arizona, where there are thousands of abandoned mines. Results from these studies provide new information that advances our understanding of the physical and biogeochemical processes causing the mobilization, transport, reaction, and fate of potentially toxic elements (including aluminum, arsenic, cadmium, copper, iron, lead, and zinc) in mineralized near-surface systems and their effects on aquatic and riparian habitat. These interdisciplinary studies provide the basis for scientific decisionmaking and remedial action by local, State, and Federal agencies charged with minimizing the effects of potentially toxic elements on the environment. Current (2007) USGS research highlights the need to understand (1) the geologic sources of metals and acidity and the geochemical reactions that release them from their sources, (2) the pathways that facilitate transport from those sources, and (3) the processes that control the fate of the elements once released from the sources. Experts in the fields of economic geology, structural geology, mineralogy, geophysics, geochemistry, hydrology, ground-water modeling, microbiology, and toxicology came together for a series of studies that address these relationships on scales ranging from the microscopic to the watershed. This Circular presents results and highlights from the detailed, interdisciplinary studies that include investigations in both mining-affected areas and mineralized but unmined areas. The first section of the Circular describes laboratory and site-scale field investigations that primarily focus on mineralogic and biologic controls on the source and release of metals and acidity from mine-waste rock and hydrothermally altered areas. The second section describes a set of basin- to watershed-scale studies that not only investigate the source and release of metals and acidity but also the transport of these constituents away from the source areas. The third section is a summary of results from postremediation ecosystem monitoring. For more information on these and other project-related studies, please visit the project Web site at http://minerals.cr.usgs.gov/projects/contaminants/index.html. The Web site includes a complete bibliography and detailed descriptions of each interdisciplinary study.

Circular

Methylation of Hg downstream from the Bonanza Hg mine, Oregon

Speciation of Hg and conversion to methyl-Hg were evaluated in stream sediment, stream water, and aquatic snails collected downstream from the Bonanza Hg mine, Oregon. Total production from the Bonanza mine was >1360t of Hg, during mining from the late 1800s to 1960, ranking it as an intermediate sized Hg mine on an international scale. The primary objective of this study was to evaluate the distribution, transport, and methylation of Hg downstream from a Hg mine in a coastal temperate climatic zone. Data shown here for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from this area. Stream sediment collected from Foster Creek flowing downstream from the Bonanza mine contained elevated Hg concentrations that ranged from 590 to 71,000ng/g, all of which (except the most distal sample) exceeded the probable effect concentration (PEC) of 1060ng/g, the Hg concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in stream sediment collected from Foster Creek varied from 11 to 62ng/g and were highly elevated compared to regional baseline concentrations (0.11-0.82ng/g) established in this study. Methyl-Hg concentrations in stream sediment collected in this study showed a significant correlation with total organic C (TOC, R 2 =0.62), generally indicating increased methyl-Hg formation with increasing TOC in sediment. Isotopic-tracer methods indicated that several samples of Foster Creek sediment exhibited high rates of Hg-methylation. Concentrations of Hg in water collected downstream from the mine varied from 17 to 270ng/L and were also elevated compared to baselines, but all were below the 770ng/L Hg standard recommended by the USEPA to protect against chronic effects to aquatic wildlife. Concentrations of methyl-Hg in the water collected from Foster Creek ranged from 0.17 to 1.8ng/L, which were elevated compared to regional baseline sites upstream and downstream from the mine that varied from <0.02 to 0.22ng/L. Aquatic snails collected downstream from the mine were elevated in Hg indicating significant bioavailability and uptake of Hg by these snails. Results for sediment and water indicated significant methyl-Hg formation in the ecosystem downstream from the Bonanza mine, which is enhanced by the temperate climate, high precipitation in the area, and high organic matter.

Oregon

Effect of ultramafic intrusions and associated mineralized rocks on the aqueous geochemistry of the Tangle Lakes Area, Alaska

Stream water was collected at 30 sites within the Tangle Lakes area of the Delta mineral belt in Alaska. Sampling focused on streams near the ultramafic rocks of the Fish Lake intrusive complex south of Eureka Creek and the Tangle Complex area east of Fourteen Mile Lake, as well as on those within the deformed metasedimentary, metavolcanic, and intrusive rocks of the Specimen Creek drainage and drainages east of Eureka Glacier. Major, minor, and trace elements were analyzed in aqueous samples for this reconnaissance aqueous geochemistry effort. The lithologic differences within the study area are reflected in the major-ion chemistry of the water. The dominant major cation in streams draining mafic and ultramafic rocks is Mg 2+ ; abundant Mg and low Ca in these streams reflect the abundance of Mg-rich minerals in these intrusions. Nickel and Cu are detected in 84 percent and 87 percent of the filtered samples, respectively. Nickel and Cu concentrations ranged from Ni <0.4 to 10.1 micrograms per liter (mg/L), with a median of 4.2 mg/L, and Cu <0.5 to 27 mg/L, with a median of 1.2 mg/L. Trace-element concentrations in water are generally low relative to U.S. Environmental Protection Agency freshwater aquatic-life criteria; however, Cu concentrations exceed the hardness-based criteria for both chronic and acute exposure at some sites. The entire rare earth element (REE) suite is found in samples from the Specimen Creek sites MH5, MH4, and MH6 and, with the exception of Tb and Tm, at site MH14. These samples were all collected within drainages containing or downstream from Tertiary gabbro, diabase, and metagabbro (Trgb) exposures. Chondrite and source rock fractionation profiles for the aqueous samples were light rare earth element depleted, with negative Ce and Eu anomalies, indicating fractionation of the REE during weathering. Fractionation patterns indicate that the REE are primarily in the dissolved, as opposed to colloidal, phase.

Alaska

Total mercury, methylmercury, and selected elements in soils of the Fishing Brook watershed, Hamilton County, New York, and the McTier Creek watershed, Aiken County, South Carolina, 2008

Mercury is an element of on-going concern for human and aquatic health. Mercury sequestered in upland and wetland soils represents a source that may contribute to mercury contamination in sensitive ecosystems. An improved understanding of mercury cycling in stream ecosystems requires identification and quantification of mercury speciation and transport dynamics in upland and wetland soils within a watershed. This report presents data for soils collected in 2008 from two small watersheds in New York and South Carolina. In New York, 163 samples were taken from multiple depths or soil horizons at 70 separate locations near Fishing Brook, located in Hamilton County. At McTier Creek, in Aiken County, South Carolina, 81 samples from various soil horizons or soil depths were collected from 24 locations. Sample locations within each watershed were selected to characterize soil geochemistry in distinct land-cover compartments. Soils were analyzed for total mercury, selenium, total and carbonate carbon, and 42 other elements. A subset of the samples was also analyzed for methylmercury.

Data Series

N-15 NMR spectra of naturally abundant nitrogen in soil and aquatic natural organic matter samples of the International Humic Substances Society

The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS 15 N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by 15 N NMR. Liquid state 15 N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection ( 1 H- 15 N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.

Organic Geochemistry

Geochemistry and occurrence of selenium: An overview

Selenium (Se) is both beneficial and toxic to animals, plants, and humans. Consequently, it is imperative to know its concentration in the environment and to understand the processes controlling its distribution. Determinations of Se concentrations in a variety of materials indicate that Se is widely distributed throughout the environment. The processes responsible for its distribution include volcanic activity, the burning of fossil fuels, the weathering of rocks and soils, groundwater transport, precipitation of minerals, adsorption, chemical or bacterial reduction and oxidation, and metabolic uptake and release by plants and animals. The importance of a particular process in controlling the distribution of Se is intimately linked to the speciation of Se, which is controlled by the pH and redox conditions of the environment. Selenium can exist as selenide (Se 2− ), elemental Se (Se 0 ), selenite (SeO 2− 3 ), and selenate (SeO 2− 4 ). Each oxidation state exhibits different chemical behavior. Selenide and elemental Se occur in acidic, reducing, and organic-rich environments. Metal selenides, Se-sulfides, and elemental Se are insoluble, and therefore biologically unavailable. For the pH and redox conditions of most soil and aquatic environments, SeO 2− 3 and SeO 2− 4 ; should be the dominant forms of Se. Selenite is immobilized by adsorption onto particles, particularly Fe oxyhydroxides. Selenate is highly mobile and biologically available because of the solubility of its salts and its weak adsorption by particles. Microbial action can change the speciation of Se through oxidation or reduction, or through the formation of organic Se compounds.

Book chapter

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

Geochemistry of mine waste and mill tailings, meadow deposits, streambed sediments, and the general hydrology and water quality for the Frohner Meadows area, upper Lump Gulch, Jefferson County, Montana

Frohner Meadows, an area of low-topographic gradient subalpine ponds and wetlands in glaciated terrane near the headwaters of Lump Gulch (a tributary of Prickly Pear Creek), is located about 15 miles west of the town of Clancy, Montana, in the Helena National Forest. Mining and ore treatment of lead-zinc-silver veins in granitic rocks of the Boulder batholith over the last 120 years from two sites (Frohner mine and the Nellie Grant mine) has resulted in accumulations of mine waste and mill tailings that have been distributed downslope and downstream by anthropogenic and natural processes. This report presents the results of an investigation of the geochemistry of the wetlands, streams, and unconsolidated-sediment deposits and the hydrology, hydrogeology, and water quality of the area affected by these sources of ore-related metals. Ground water sampled from most shallow wells in the meadow system contained high concentrations of arsenic, exceeding the Montana numeric water-quality standard for human health. Transport of cadmium and zinc in ground water is indicated at one site near Nellie Grant Creek based on water-quality data from one well near the creek. Mill tailings deposited in upper Frohner Meadow contribute large arsenic loads to Frohner Meadows Creek; Nellie Grant Creek contributes large arsenic, cadmium, and zinc loads to upper Frohner Meadows. Concentrations of total-recoverable cadmium, copper, lead, and zinc in most surface-water sites downstream from the Nellie Grant mine area exceeded Montana aquatic-life standards. Nearly all samples of surface water and ground water had neutral to slightly alkaline pH values. Concentrations of arsenic, cadmium, lead, and zinc in streambed sediment in the entire meadow below the mine waste and mill tailings accumulations are highly enriched relative to regional watershed-background concentrations and exceed consensus-based, probable-effects concentrations for streambed sediment at most sites. Cadmium, copper, and zinc typically are adsorbed to the surface coatings of streambed-sediment grains. Mine waste and mill tailings contain high concentrations of arsenic, cadmium, copper, lead, and zinc in a quartz-rich matrix. Most of the waste sites that were sampled had low acid-generating capacity, although one site (fine-grained mill tailings from the Nellie Grant mine deposited in the upper part of lower Frohner Meadows) had extremely high acid-generating potential because of abundant fine-grained pyrite. Two distinct sites were identified as metal sources based on streambed-sediment samples, cores in the meadow substrate, and mine and mill-tailings samples. The Frohner mine and mill site contribute material rich in arsenic and lead; similar material from the Nellie Grant mine and mill site is rich in cadmium and zinc.

Montana

Temporal variations of heavy metals in coral Porites lutea from Guangdong Province, China: Influences from industrial pollution, climate and economic factors

The eight heavy metals Cr, Mn, Co, Ni, Cu, Zn, Cd, and Pb have been determined in samples of coral Porites lutea collected from Dafangji Island waters (21&deg;21&prime;N, 111&deg;11&prime;E), Dianbai County, Guangdong Province, China, by the ICP-MS method. The samples represent the growth of coral in the period of 1982&ndash;2001. The results showed that the waters were polluted by the heavy metals Cu, Ni, Zn, and Pb in certain years, but not by other metals. The contamination may have come from industrial sources, including electroplating, metallurgy, mining, and aquatic industries in the coastal areas. The correlation coefficients among the metals and climatic and economic factors indicate that the metals Ni, Zn, and Cd behave similarly. Copper and Mn are positively correlated, and cobalt is negatively correlated with Cr, Ni, Zn, and Cd. Lead is not correlated with any other metals but is correlated with sea surface water temperature, air temperature, GDP and industrial-agricultural production in Dianbai County. Lead in corals is related to the enhanced pollution level of ocean waters as a result of increased industrial activities.

Chinese Journal of Geochemistry

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Organic Geochemistry

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

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

Science of the Total Environment