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A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2???. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Illegal dumping of oil and gas wastewater alters arid soil microbial communities

The Permian Basin, underlying southeast New Mexico and west Texas, is one of the most productive oil and gas (OG) provinces in the United States. Oil and gas production yields large volumes of wastewater with complex chemistries, and the environmental health risks posed by these OG wastewaters on sensitive desert ecosystems are poorly understood. Starting in November 2017, 39 illegal dumps, as defined by federal and state regulations, of OG wastewater were identified in southeastern New Mexico, releasing ~600,000 L of fluid onto dryland soils. To evaluate the impacts of these releases, we analyzed changes in soil geochemistry and microbial community composition by comparing soils from within OG wastewater dump-affected samples to unaffected zones. We observed significant changes in soil geochemistry for all dump-affected compared with control samples, reflecting the residual salts and hydrocarbons from the OG-wastewater release (e.g., enriched in sodium, chloride, and bromide). Microbial community structure significantly ( P < 0.01) differed between dump and control zones, with soils from dump areas having significantly ( P < 0.01) lower alpha diversity and differences in phylogenetic composition. Dump-affected soil samples showed an increase in halophilic and halotolerant taxa, including members of the Marinobacteraceae, Halomonadaceae, and Halobacteroidaceae, suggesting that the high salinity of the dumped OG wastewater was exerting a strong selective pressure on microbial community structure. Taxa with high similarity to known hydrocarbon-degrading organisms were also detected in the dump-affected soil samples. Overall, this study demonstrates the potential for OG wastewater exposure to change the geochemistry and microbial community dynamics of arid soils.

Applied and Environmental Microbiology↗

Plan of study for the regional aquifer systems analysis of the Michigan Basin

Quaternary glacial deposits and Pennsylvanian and Mississippian sandstones, -the Saginaw Formation and Marshall Sandstone- are the major aquifers in the Michigan basin. These aquifers supply approximately 188 million gal/day to municipalities in the 29 ,000 sq mi study area. The most significant problems related to groundwater supplies are the identification of potable sources of groundwater in large quantities and the migration of saline groundwater toward pumping centers. Saline water underlies the entire lower Peninsula of Michigan at indeterminate depth in the deeper parts of the Saginaw Formation and Marshall Sandstone in the center of the Michigan basin. In places, saline water is present in glacial deposits. Overdraft has resulted in severe drawdown in the Lansing area and the abandonment of wells near Flint because of saline water encroachment. Increased demand on the groundwater resources of the study area are expected to cause further problems. In 1985, the U.S. Geological Survey began a 5-yr study to define the geohydrologic framework, describe the geochemistry of groundwater in the glacial and bedrock aquifers, and analyze regional groundwater flow patterns. The scope, plan of study, organization and work elements are described in this report.

Michigan↗

Geochemistry of the Cretaceous Mowry Shale in the Wind River Basin, Wyoming

The siliceous nature of the Mowry Shale distinguishes it from many of the well-studied organic-rich mudstones of the Cretaceous Western Interior Seaway. Available models of organic enrichment in mudstones rarely incorporate detailed biomarker, bulk organic, inorganic, and mineralogy data. Here, we used these data to evaluate how variations in organic matter source, productivity, dilution, and preservation modulated organic matter accumulation during the deposition of the Mowry Shale, while also demonstrating the benefits of this integrated approach. An organic stable carbon isotope vertical profile for the Mowry Shale is presented to test whether the Mowry Shale was deposited during oceanic anoxic event 1d (OAE 1d), thereby contributing to organic enrichment in the Mowry Shale.

Wyoming↗

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

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

Applied Geochemistry↗

Heavy metals and manganese oxides in the genesee watershed, New York state: Effects of geology and land use

Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic matter.

New York↗

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↗

Arsenic Geochemistry and Hydrostratigraphy in Midwestern U.S. Glacial Deposits

Arsenic concentrations exceeding the U.S. EPA's 10 ??g/L standard are common in glacial aquifers in the midwestern United States. Previous studies have indicated that arsenic occurs naturally in these aquifers in association with metal-(hydr)oxides and is released to groundwater under reducing conditions generated by microbial oxidation of organic matter. Despite this delineation of the arsenic source and mechanism of arsenic mobilization, identification of arsenic-impacted aquifers is hindered by the heterogeneous and discontinuous nature of glacial sediments. In much of the Midwest, the hydrostratigraphy of glacial deposits is not sufficiently characterized to predict where elevated arsenic concentrations are likely to occur. This case study from southeast Wisconsin presents a detailed characterization of local stratigraphy, hydrostratigraphy, and geochemistry of the Pleistocene glacial deposits and underlying Silurian dolomite. Analyses of a single core, water chemistry data, and well construction reports enabled identification of two aquifers separated by an organic-rich aquitard. The upper, unconfined aquifer provides potable water, whereas arsenic generally exceeds 10 ??g/L in the deeper aquifer. Although coring and detailed hydrostratigraphic characterization are often considered impractical, our results demonstrate that a single core improved interpretation of the complex lithology and hydrostratigraphy. This detailed characterization of hydrostratigraphy facilitated development of well construction guidelines and lays the ground work for further studies of the complex interactions among aquifer sediments, hydrogeology, water chemistry, and microbiology that lead to elevated arsenic in groundwater. Copyright ?? 2009 The Author(s). Journal compilation ?? 2009 National Ground Water Association.

Ground Water↗

Sedimentary geochemistry of deepwater slope deposits in southern Lake Tanganyika (East Africa): Effects of upwelling and minor lake level oscillations

Lake Tanganyika ranks among the most valuable modern analogs for understanding depositional processes of carbonaceous sediments in ancient tropical rifts. Prior research on Lake Tanganyika has emphasized the importance of bottom-water anoxia, depositional processes (hemipelagic settling versus gravity flows), and large-scale (100s of meters) lake level change on the quality of sedimentary organic matter content. Here, facies analysis and numerous organic geochemical tools (elemental, carbon isotope, and programmed pyrolysis) were applied to a radiocarbon-dated core from southern Lake Tanganyika to investigate the accumulation of carbonaceous sediments in a deepwater slope environment influenced by high-frequency climatic fluctuations accompanied by only minor (10s of meters) lake level changes. Considerable variability in lithofacies and geochemistry characterizes the ∼ 1030-year-long core record, chiefly driven by climate-mediated changes to the lake's upwelling system. Laminated diatom oozes and sapropels with mean total organic carbon (TOC) concentrations and hydrogen indices of 6.9 wt.% and 385 mg hydrocarbon/g TOC, respectively, characterize sediments deposited during periods of strong upwelling and variable water levels. Silty sediments deposited via gravity-flow processes were likewise rich in organic matter, likely due to preservation-enhancing bottom-water anoxia. Dilution by reworked tephra was the chief constraint on organic enrichment at the study site. Data from this study reveal that oscillations in atmospheric and limnological processes in the absence of major shoreline movements can result in geochemically diverse deepwater slope sediments, which have implications for improving depositional models of petroliferous continental rift basins.

Journal of Sedimentary Research↗

Redox chemistry and natural organic matter (NOM): Geochemists' dream, analytical chemists' nightmare

Natural organic matter (NOM) is an inherently complex mixture of polyfunctional organic molecules. Because of their universality and chemical reversibility, oxidation/reductions (redox) reactions of NOM have an especially interesting and important role in geochemistry. Variabilities in NOM composition and chemistry make studies of its redox chemistry particularly challenging, and details of NOM-mediated redox reactions are only partially understood. This is in large part due to the analytical difficulties associated with NOM characterization and the wide range of reagents and experimental systems used to study NOM redox reactions. This chapter provides a summary of the ongoing efforts to provide a coherent comprehension of aqueous redox chemistry involving NOM and of techniques for chemical characterization of NOM. It also describes some attempts to confirm the roles of different structural moieties in redox reactions. In addition, we discuss some of the operational parameters used to describe NOM redox capacities and redox states, and describe nomenclature of NOM redox chemistry. Several relatively facile experimental methods applicable to predictions of the NOM redox activity and redox states of NOM samples are discussed, with special attention to the proposed use of fluorescence spectroscopy to predict relevant redox characteristics of NOM samples.

ACS Symposium Series↗

A 1500-year record of climatic and environmental change in Elk Lake, Clearwater County, Minnesota II: Geochemistry, mineralogy, and stable isotopes

Most of the sediment components that have accumulated in Elk Lake, Clearwater County, northwestern Minnesota, over the past 1500 years are authigenic or biogenic (CaCO3, biogenic SiO2, organic matter, iron and manganese oxyhydroxides, and iron phosphate) and are delivered to the sediment-water interface on a seasonal schedule where they are preserved as distinct annual laminae (varves). The annual biogeochemical cycles of these components are causally linked through the 'carbon pump', and are recapitulated in longer-term cycles, most prominently with a periodicity of about 400 years. Organic carbon is fixed in the epilimnion by photosynthetic removal of CO2, which also increases the pH, triggering the precipitation of CaCO3. The respiration and degradation of fixed organic carbon in the hypolimnion consumes dissolved oxygen, produces CO2, and lowers the pH so that the hypolimnion becomes anoxic and undersaturated with respect to CaCO3 during the summer. Some of the CaCO3 produced in the epilimnion is dissolved in the anoxic, lower pH hypolimnion and sediments. The amount of CaCO3 that is ultimately incorporated into the sediments is a function of how much is produced in the epilimnion and how much is consumed in the hypolimnion and the sediments. Iron, manganese, and phosphate accumulate in the anoxic hypolimnion throughout the summer. Sediment-trap studies show that at fall overturn, when iron-, manganese-, and phosphate-rich bottom waters mix with carbonate- and oxygen-rich surface waters, precipitation of iron and manganese oxyhydroxides, iron phosphate, and manganese carbonate begins and continues into the winter months. Detrital clastic material in the sediments of Elk Lake deposited over the last 1500 years is a minor component (<10% by weight) that is mostly wind-borne (eolian). Detailed analyses of the last 1500 years of the Elk Lake sediment record show distinct cycles in eolian clastic variables (e.g. aluminum, sodium, potassium, titanium, and quartz), with a periodicity of about 400 years. The 400-yr cycle in eolian clastic material does not correspond to the 400-yr cycles in redox-sensitive authigenic components, suggesting that the clastic component is responding to external forcing (wind) whereas the authigenic components are responding to internal forcing (productivity), although both may ultimately be forced by climate change. Variations in the oxygen and carbon isotopic composition of CaCO3 are small but appear to reflect small variations in ground water influx that are also driven by external forcing.

Journal of Paleolimnology↗

Organic geochemical analysis of sedimentary organic matter associated with uranium

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO 2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO 2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO 2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO 2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples.

Applied Geochemistry↗

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9-7.5 nm size range relative to the 10-250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter. ?? 2009 Elsevier Ltd.

Applied Geochemistry↗

Biogeochemistry at a wetland sediment-alluvial aquifer interface in a landfill leachate plume

The biogeochemistry at the interface between sediments in a seasonally ponded wetland (slough) and an alluvial aquifer contaminated with landfill leachate was investigated to evaluate factors that can effect natural attenuation of landfill leachate contaminants in areas of groundwater/surface-water interaction. The biogeochemistry at the wetland-alluvial aquifer interface differed greatly between dry and wet conditions. During dry conditions (low water table), vertically upward discharge was focused at the center of the slough from the fringe of a landfill-derived ammonium plume in the underlying aquifer, resulting in transport of relatively low concentrations of ammonium to the slough sediments with dilution and dispersion as the primary attenuation mechanism. In contrast, during wet conditions (high water table), leachate-contaminated groundwater discharged upward near the upgradient slough bank, where ammonium concentrations in the aquifer where high. Relatively high concentrations of ammonium and other leachate constituents also were transported laterally through the slough porewater to the downgradient bank in wet conditions. Concentrations of the leachate-associated constituents chloride, ammonium, non-volatile dissolved organic carbon, alkalinity, and ferrous iron more than doubled in the slough porewater on the upgradient bank during wet conditions. Chloride, non-volatile dissolved organic carbon (DOC), and bicarbonate acted conservatively during lateral transport in the aquifer and slough porewater, whereas ammonium and potassium were strongly attenuated. Nitrogen isotope variations in ammonium and the distribution of ammonium compared to other cations indicated that sorption was the primary attenuation mechanism for ammonium during lateral transport in the aquifer and the slough porewater. Ammonium attenuation was less efficient, however, in the slough porewater than in the aquifer and possibly occurred by a different sorption mechanism. A stoichiometrically balanced increase in magnesium concentration with decreasing ammonium and potassium concentrations indicated that cation exchange was the sorption mechanism in the slough porewater. Only a partial mass balance could be determined for cations exchanged for ammonium and potassium in the aquifer, indicating that some irreversible sorption may be occurring. Although wetlands commonly are expected to decrease fluxes of contaminants in riparian environments, enhanced attenuation of the leachate contaminants in the slough sediment porewater compared to the aquifer was not observed in this study. The lack of enhanced attenuation can be attributed to the fact that the anoxic plume, comprised largely of recalcitrant DOC and reduced inorganic constituents, interacted with anoxic slough sediments and porewaters, rather than encountering a change in redox conditions that could cause transformation reactions. Nevertheless, the attenuation processes in the narrow zone of groundwater/surface-water interaction were effective in reducing ammonium concentrations by a factor of about 3 during lateral transport across the slough and by a factor of 2 to 10 before release to the surface water. Slough porewater geochemistry also indicated that the slough could be a source of sulfate in dry conditions, potentially providing a terminal electron acceptor for natural attenuation of organic compounds in the leachate plume.

Journal of Contaminant Hydrology↗

Topics in coal geochemistry—Short course

This short course was prepared at the request of Servicio Geológico Colombiano (SGC) as a module for staff training. Prior to the short course, the SGC expressed interest in receiving training in (1) geochemistry and quality of coal; (2) geochemistry of trace elements in coal; (3) mercury and halogens in coal; (4) characterization and cycling of atmospheric mercury; (5) mercury, trace elements, and organic constituents in atmospheric fine particulate matter; (6) mercury in coal and the effect of coal quality on mercury emissions from combustion systems; (7) environmental and health effects related to coal use; and (8) related topics in coal combustion processes. A five-session short course was prepared that addressed all but the engineering aspects of coal use. In the sections that follow, topic overviews are given for the material that was presented. Brief descriptions of each slide are given in appendix 1, and the actual short course material, presented as a series of PowerPoint slides, is included in Portable Document Format (PDF) as appendix 2.

Open-File Report↗

Integrated investigations of environmental effects of historical mining in the Basin and Boulder Mining Districts, Boulder River watershed, Jefferson County, Montana

The Boulder River watershed is one of many watersheds in the western United States where historical mining has left a legacy of acid mine drainage and elevated concentrations of potentially toxic trace elements. Abandoned mine lands commonly are located on or affect Federal land. Cleaning up these Federal lands will require substantial investment of resources. As part of a cooperative effort with Federal land-management agencies, the U.S. Geological Survey implemented an Abandoned Mine Lands Initiative in 1997. The goal of the initiative was to use the watershed approach to develop a strategy for gathering and communicating the scientific information needed to formulate effective and cost-efficient remediation of affected lands in a watershed. The watershed approach is based on the premise that contaminated sites that have the most profound effect on water and ecosystem quality within an entire watershed should be identified, characterized, and ranked for remediation. The watershed approach provides an effective means to evaluate the overall status of affected resources and helps to focus remediation at sites where the most benefit will be gained in the watershed. Such a large-scale approach can result in the collection of extensive information on the geology and geochemistry of rocks and sediment, the hydrology and water chemistry of streams and ground water, and the diversity and health of aquatic and terrestrial organisms. During the assessment of the Boulder River watershed, we inventoried historical mines, defined geological conditions, assessed fish habitat, collected and chemically analyzed hundreds of water and sediment samples, conducted toxicity tests, analyzed fish tissue and indicators of physiological malfunction, examined invertebrates and biofilm, and defined hydrological regimes. Land- and resource-management agencies are faced with evaluating risks associated with thousands of potentially harmful mine sites, and this level of effort is not always feasible for every affected watershed. The detailed work described in this report can help Federal land-management agencies decide which characterization efforts would be most useful in characterization of other affected watersheds.

Montana↗

Relationships between ambient geochemistry, watershed land-use and trace metal concentrations in aquatic invertebrates living in stormwater treatment ponds

Stormwater treatment ponds receive elevated levels of metals from urban runoff, but the effects of these pollutants on organisms residing in the ponds are unknown. We investigated the accumulation of Cu, Zn, and Pb by macroinvertebrates collected from stormwater treatment ponds in Maryland serving commercial, highway, residential and open-space watersheds, and determined whether watershed land-use classification influences metal concentrations in macroinvertebrates, sediments, and water. Three types of invertebrate samples were analyzed for molluscs, odonates, and composite. Zn concentrations in odonates from ponds draining watersheds with commercial development (mean=113.82 ug/g) were significantly higher than concentrations in the other land-use categories. Similarly, Cu levels in odonates from commercial ponds (mean=27.12 ug/g) were significantly higher than from highway (mean=20.23 ug/g) and open space (mean=17.79 ug/g) ponds. However, metal concentrations in sediments and water did not differ significantly among land-uses. The results suggest that despite the high variation in ambient metal concentrations within each land-use category, macroinvertebrates in ponds serving commercial watersheds accumulate higher levels of Cu and Zn. The levels of Cu, Zn, and Pb in invertebrates from all ponds were less than dietary concentrations considered toxic to fish.

Environmental Pollution↗

Changes in the isotopic and chemical composition of ground water resulting from a recharge pulse from a sinking stream

The Little River, an ephemeral stream that drains a watershed of approximately 88 km2 in northern Florida, disappears into a series of sinkholes along the Cody Scarp and flows directly into the carbonate Upper Floridan aquifer, the source of water supply in northern Florida. The changes in the geochemistry of ground water caused by a major recharge pulse from the sinking stream were investigated using chemical and isotopic tracers and mass-balance modeling techniques. Nine monitoring wells were installed open to the uppermost part of the aquifer in areas near the sinks where numerous subterranean karst solution features were identified using ground penetrating radar. During high-flow conditions in the Little River, the chemistry of water in some of the monitoring wells changed, reflecting the mixing of river water with ground water. Rapid recharge of river water into some parts of the aquifer during high-flow conditions was indicated by enriched values of delta 18O and delta deuterium (-1.67 to -3.17 per mil and -9.2 to -15.6 per mil, respectively), elevated concentrations of tannic acid, higher (more radiogenic) 87Sr/86Sr ratios, and lower concentrations of 222Rn, silica, and alkalinity compared to low-flow conditions. The proportion of river water that mixed with ground water ranged from 0.10 to 0.67 based on binary mixing models using the tracers 18O, deuterium, tannic acid, silica, 222Rn, and 87Sr/86Sr. On the basis of mass-balance modeling during steady-state flow conditions, the dominant processes controlling carbon cycling in ground water are the dissolution of calcite and dolomite in aquifer material, and aerobic degradation of organic matter.The Little River of northern Florida disappears into a series of sinkholes along the Cody Scarp and flows directly into the carbonate Upper Floridan aquifer. The changes in the geochemistry of ground water caused by a major recharge pulse from the sinking stream were investigated using chemical and isotopic tracers and mass-balance modeling techniques. Nine monitoring wells were installed open to the uppermost part of the aquifer. During high-flow conditions in the Little River, the chemistry of water in some of the monitoring wells changed, reflecting the mixing of river water with ground water. Based on mass-balance modeling during steady-state flow conditions, it was found that the dominant processes controlling carbon cycling in ground water are the dissolution of calcite and dolomite in aquifer material, and aerobic degradation of organic matter.

Journal of Hydrology↗