High-frequency sensor data capture short-term variability in Fe and Mn concentrations due to hypolimnetic oxygenation and seasonal dynamics in a drinking water reservoir.

The biogeochemical cycles of iron (Fe) and manganese (Mn) in lakes and reservoirs have predictable seasonal trends, largely governed by stratification dynamics and redox conditions in the hypolimnion. However, short-term (i.e., sub-weekly) trends in Fe and Mn cycling are less well-understood, as most monitoring efforts focus on longer-term (i.e., monthly to yearly) time scales. The potential for elevated Fe and Mn to degrade water quality and impact ecosystem functioning, coupled with increasing evidence for high spatiotemporal variability in other biogeochemical cycles, necessitates a closer evaluation of the short-term Fe and Mn dynamics in lakes and reservoirs. We adapted a UV-visible spectrophotometer coupled with a multiplexor pumping system and partial least squares regression (PLSR) modeling to generate high spatiotemporal resolution predictions of Fe and Mn concentrations in a drinking water reservoir (Falling Creek Reservoir, Vinton, VA, USA) equipped with a hypolimnetic oxygenation (HOx) system. We quantified hourly Fe and Mn concentrations during two transitional periods: reservoir turnover (Fall 2020) and HOx initiation (Summer 2021). Our sensor system successfully predicted mean Fe and Mn concentrations and trends, ground-truthed by grab sampling and laboratory analysis. During fall turnover, hypolimnetic Fe and Mn concentrations began to decrease more than two weeks before complete mixing of the reservoir, with rapid equalization of epilimnetic and hypolimnetic Fe and Mn concentrations in less than 48 h after full water column mixing. During the initiation of HOx in Summer 2021, Fe and Mn displayed distinctly different responses to oxygenation, as indicated by the rapid oxidation of soluble Fe but not soluble Mn. This study demonstrates that Fe and Mn concentrations are sensitive to changes in redox conditions induced by stratification and oxygenation, although their responses to these changes differ. We also show that high spatio-temporal resolution predictions of Fe and Mn can improve drinking water monitoring programs and reservoir management practices.

Anoxia decreases the magnitude of the carbon, nitrogen, and phosphorus sink in freshwaters.

Oxygen availability is decreasing in many lakes and reservoirs worldwide, raising the urgency for understanding how anoxia (low oxygen) affects coupled biogeochemical cycling, which has major implications for water quality, food webs, and ecosystem functioning. Although the increasing magnitude and prevalence of anoxia has been documented in freshwaters globally, the challenges of disentangling oxygen and temperature responses have hindered assessment of the effects of anoxia on carbon, nitrogen, and phosphorus concentrations, stoichiometry (chemical ratios), and retention in freshwaters. The consequences of anoxia are likely severe and may be irreversible, necessitating ecosystem-scale experimental investigation of decreasing freshwater oxygen availability. To address this gap, we devised and conducted REDOX (the Reservoir Ecosystem Dynamic Oxygenation eXperiment), an unprecedented, 7-year experiment in which we manipulated and modeled bottom-water (hypolimnetic) oxygen availability at the whole-ecosystem scale in a eutrophic reservoir. Seven years of data reveal that anoxia significantly increased hypolimnetic carbon, nitrogen, and phosphorus concentrations and altered elemental stoichiometry by factors of 2-5× relative to oxic periods. Importantly, prolonged summer anoxia increased nitrogen export from the reservoir by six-fold and changed the reservoir from a net sink to a net source of phosphorus and organic carbon downstream. While low oxygen in freshwaters is thought of as a response to land use and climate change, results from REDOX demonstrate that low oxygen can also be a driver of major changes to freshwater biogeochemical cycling, which may serve as an intensifying feedback that increases anoxia in downstream waterbodies. Consequently, as climate and land use change continue to increase the prevalence of anoxia in lakes and reservoirs globally, it is likely that anoxia will have major effects on freshwater carbon, nitrogen, and phosphorus budgets as well as water quality and ecosystem functioning.

Arsenic release to the environment from hydrocarbon production, storage, transportation, use and waste management.

Arsenic (As) is a toxic trace element with many sources, including hydrocarbons such as oil, natural gas, oil sands, and oil- and gas-bearing shales. Arsenic from these hydrocarbon sources can be released to the environment through human activities of hydrocarbon production, storage, transportation and use. In addition, accidental release of hydrocarbons to aquifers with naturally occurring (geogenic) As can induce mobilization of As to groundwater through biogeochemical reactions triggered by hydrocarbon biodegradation. In this paper, we review the occurrence of As in different hydrocarbons and the release of As from these sources into the environment. We also examine the occurrence of As in wastes from hydrocarbon production, including produced water and sludge. Last, we discuss the potential for As release related to waste management, including accidental or intentional releases, and recycling and reuse of these wastes.

Iron and manganese fluxes across the sediment-water interface in a drinking water reservoir.

The development of low dissolved oxygen (DO) concentrations in the hypolimnion of drinking water reservoirs during thermal stratification can lead to the reduction of oxidized, insoluble iron (Fe) and manganese (Mn) in sediments to soluble forms, which are then released into the water column. As metals degrade drinking water quality, robust measurements of metal fluxes under changing oxygen conditions are critical for optimizing water treatment. In this study, we conducted benthic flux chamber experiments in summer 2018 to directly quantify Fe and Mn fluxes at the sediment-water interface under different DO and redox conditions of a eutrophic drinking water reservoir with an oxygenation system (Falling Creek Reservoir, Vinton, VA, USA). Throughout the experiments, we monitored DO, oxidation-reduction potential (ORP), water temperature, and pH in the chambers and compared the metal fluxes in the chambers with time-series of fluxes calculated using a hypolimnetic mass balance method. Our results showed that metal fluxes were highly variable during the monitoring period and were sensitive to redox conditions in the water column at the sediment-water interface. The time-series changes in fluxes and relationship to redox conditions are suggestive of "hot moments", short time periods of intense biogeochemical cycling. Although the metal concentrations and fluxes are specific to this site, the approaches for examining relationships between metals, oxygen concentrations and overall redox conditions can be applied by water utilities to improve water quality management of Fe and Mn.

Metalimnetic oxygen minima alter the vertical profiles of carbon dioxide and methane in a managed freshwater reservoir.

Metalimnetic oxygen minimum zones (MOMs) commonly develop during the summer stratified period in freshwater reservoirs because of both natural processes and water quality management. While several previous studies have examined the causes of MOMs, much less is known about their effects, especially on reservoir biogeochemistry. MOMs create distinct redox gradients in the water column which may alter the magnitude and vertical distribution of dissolved methane (CH4) and carbon dioxide (CO2). The vertical distribution and diffusive efflux of CH4 and CO2 was monitored for two consecutive open-water seasons in a eutrophic reservoir that develops MOMs as a result of the operation of water quality engineering systems. During both summers, elevated concentrations of CH4 accumulated within the anoxic MOM, reaching a maximum of 120 µM, and elevated concentrations of CO2 accumulated in the oxic hypolimnion, reaching a maximum of 780 µM. Interestingly, the largest observed diffusive CH4 effluxes occurred before fall turnover in both years, while peak diffusive CO2 effluxes occurred both before and during turnover. Our data indicate that MOMs can substantially change the vertical distribution of CH4 and CO2 in the water column in reservoirs, resulting in the accumulation of CH4 in the metalimnion (vs. at the sediments) and CO2 in the hypolimnion.

A mass balance approach to investigate arsenic cycling in a petroleum plume.

Natural attenuation of organic contaminants in groundwater can give rise to a series of complex biogeochemical reactions that release secondary contaminants to groundwater. In a crude oil contaminated aquifer, biodegradation of petroleum hydrocarbons is coupled with the reduction of ferric iron (Fe(III)) hydroxides in aquifer sediments. As a result, naturally occurring arsenic (As) adsorbed to Fe(III) hydroxides in the aquifer sediment is mobilized from sediment into groundwater. However, Fe(III) in sediment of other zones of the aquifer has the capacity to attenuate dissolved As via resorption. In order to better evaluate how long-term biodegradation coupled with Fe-reduction and As mobilization can redistribute As mass in contaminated aquifer, we quantified mass partitioning of Fe and As in the aquifer based on field observation data. Results show that Fe and As are spatially correlated in both groundwater and aquifer sediments. Mass partitioning calculations demonstrate that 99.9% of Fe and 99.5% of As are associated with aquifer sediment. The sediments act as both sources and sinks for As, depending on the redox conditions in the aquifer. Calculations reveal that at least 78% of the original As in sediment near the oil has been mobilized into groundwater over the 35-year lifespan of the plume. However, the calculations also show that only a small percentage of As (∼0.5%) remains in groundwater, due to resorption onto sediment. At the leading edge of the plume, where groundwater is suboxic, sediments sequester Fe and As, causing As to accumulate to concentrations 5.6 times greater than background concentrations. Current As sinks can serve as future sources of As as the plume evolves over time. The mass balance approach used in this study can be applied to As cycling in other aquifers where groundwater As results from biodegradation of an organic carbon point source coupled with Fe reduction.

The role of alluvial aquifer sediments in attenuating a dissolved arsenic plume.

In a crude-oil-contaminated sandy aquifer at the Bemidji site in northern Minnesota, biodegradation of petroleum hydrocarbons has resulted in release of naturally occurring As to groundwater under Fe-reducing conditions. This study used chemical extractions of aquifer sediments collected in 1993 and 2011-2014 to evaluate the relationship between Fe and As in different redox zones (oxic, methanogenic, Fe-reducing, anoxic-suboxic transition) of the contaminated aquifer over a twenty-year period. Results show that 1) the aquifer has the capacity to naturally attenuate the plume of dissolved As, primarily through sorption; 2) Fe and As are linearly correlated in sediment across all redox zones, and a regression analysis between Fe and As reasonably predicted As concentrations in sediment from 1993 using only Fe concentrations; 3) an As-rich "iron curtain," associated with the anoxic-suboxic transition zone, migrated 30m downgradient between 1993 and 2013 as a result of the hydrocarbon plume evolution; and 4) silt lenses in the aquifer preferentially sequester dissolved As, though As is remobilized into groundwater from sediment after reducing conditions are established. Using results of this study coupled with historical data, we develop a conceptual model which summarizes the natural attenuation of As and Fe over time and space that can be applied to other sites that experience As mobilization due to an influx of bioavailable organic matter.

Using column experiments to examine transport of As and other trace elements released from poultry litter: Implications for trace element mobility in agricultural watersheds.

Trace elements are added to poultry feed to control infection and improve weight gain. However, the fate of these trace elements in poultry litter is poorly understood. Because poultry litter is applied as fertilizer in many agricultural regions, evaluation of the environmental processes that influence the mobility of litter-derived trace elements is critical for predicting if trace elements are retained in soil or released to water. This study examined the effect of dissolved organic carbon (DOC) in poultry litter leachate on the fate and transport of litter-derived elements (As, Cu, P and Zn) using laboratory column experiments with soil collected from the Delmarva Peninsula (Mid-Atlantic, USA), a region of intense poultry production. Results of the experiments showed that DOC enhanced the mobility of all of the studied elements. However, despite the increased mobility, 60-70% of Zn, As and P mass was retained within the soil. In contrast, almost all of the Cu was mobilized in the litter leachate experiments, with very little retention in soil. Overall, our results demonstrate that the mobility of As, Cu, Zn and P in soils which receive poultry litter application is strongly influenced by both litter leachate composition, specifically organic acids, and adsorption to soil. Results have implications for understanding fate and transport of trace elements released from litter application to soil water and groundwater, which can affect both human health and the environment.

Effectiveness of hypolimnetic oxygenation for preventing accumulation of Fe and Mn in a drinking water reservoir.

The accumulation of Fe and Mn in seasonally stratified drinking water reservoirs adversely impacts water quality. To control issues with Fe and Mn at the source, some drinking water utilities have deployed hypolimnetic oxygenation systems to create well-oxygenated conditions in the water column that are favorable for the oxidation, and thus removal, of Fe and Mn. However, in addition to being controlled by dissolved oxygen (DO), Fe and Mn concentrations are also influenced by pH and metal-oxidizing microorganisms. We studied the response of Fe and Mn concentrations to hypolimnetic oxygenation in a shallow drinking water reservoir in Vinton, Virginia, USA by sequentially activating and deactivating an oxygenation system over two summers. We found that maintaining well-oxygenated conditions effectively prevented the accumulation of soluble Fe in the hypolimnion. However, while the rate of Mn oxidation increased under well-oxygenated conditions, soluble Mn still accumulated in the slightly acidic to neutral (pH 5.6 to 7.5) hypolimnion. In parallel, we conducted laboratory incubation experiments, which showed that the presence of Mn-oxidizing microorganisms increased the rate of Mn oxidation in comparison with rates under oxic, abiotic conditions. Combined, our field and laboratory results demonstrate that increasing DO concentrations in the water column is important for stimulating the oxidation of Fe and Mn, but that the successful management of Mn is also tied to the activity of Mn-oxidizing organisms in the water column and favorable (neutral to alkaline) pH.

Arsenic Cycling in Hydrocarbon Plumes: Secondary Effects of Natural Attenuation.

Monitored natural attenuation is widely applied as a remediation strategy at hydrocarbon spill sites. Natural attenuation relies on biodegradation of hydrocarbons coupled with reduction of electron acceptors, including solid phase ferric iron (Fe(III)). Because arsenic (As) adsorbs to Fe-hydroxides, a potential secondary effect of natural attenuation of hydrocarbons coupled with Fe(III) reduction is a release of naturally occurring As to groundwater. At a crude-oil-contaminated aquifer near Bemidji, Minnesota, anaerobic biodegradation of hydrocarbons coupled to Fe(III) reduction has been well documented. We collected groundwater samples at the site annually from 2009 to 2013 to examine if As is released to groundwater and, if so, to document relationships between As and Fe inside and outside of the dissolved hydrocarbon plume. Arsenic concentrations in groundwater in the plume reached 230 µg/L, whereas groundwater outside the plume contained less than 5 µg/L As. Combined with previous data from the Bemidji site, our results suggest that (1) naturally occurring As is associated with Fe-hydroxides present in the glacially derived aquifer sediments; (2) introduction of hydrocarbons results in reduction of Fe-hydroxides, releasing As and Fe to groundwater; (3) at the leading edge of the plume, As and Fe are removed from groundwater and retained on sediments; and (4) downgradient from the plume, patterns of As and Fe in groundwater are similar to background. We develop a conceptual model of secondary As release due to natural attenuation of hydrocarbons that can be applied to other sites where an influx of biodegradable organic carbon promotes Fe(III) reduction.

The impact of poultry litter application on sediment chemistry of the Broadkill River estuary system, Delaware.

This project examined the impact of long-term poultry litter application on the chemical signatures of As, Cu, Zn, and P in stream sediments of the Broadkill River watershed within the Delmarva Peninsula, a region of intense poultry production. Thirty-seven sediment samples were collected from Broadkill River drainage systems and analyzed for litter-derived elements (As, Cu, Zn, P) and basic soil parameters such as particle size distribution, organic matter, and soluble salts. Results showed that concentrations of elements in stream sediments are approximately log-normally distributed. Spatial variability in concentrations of elements was evident, with most elements increasing in concentration and enrichment from upgradient headwaters to downgradient reaches draining predominantly agricultural areas. Results of correlation analyses showed positive significant correlation among elements; elements were also positively correlated with percent clay and silt in the sediment. Using GIS maps with overlays of hydrology and land use activities, statistical correlations between As, Cu, Zn, and P enrichment factors and land use were examined. Results showed statistically significant relationships between As, Mn, and Zn enrichment factors and residential areas within the watershed, but did not show a statistically significant relationship between element enrichment factors and agricultural land use. Factors that complicate this type of landscape-scale study include the presence of poultry processing plants, impoundments, changes in land use over time, and the influence of tides, all of which can have direct and indirect influences on element mobility.

Arsenic release from arsenopyrite weathering: insights from sequential extraction and microscopic studies.

At a former As mine site, arsenopyrite oxidation has resulted in formation of scorodite and As-bearing iron hydroxide, both in host rock and mine tailings. Electron microprobe analysis documents that arsenopyrite weathers along two pathways: one that involves formation of sulfur, and one that does not. In both pathways, arsenopyrite oxidizes to form scorodite, which dissolves incongruently to form As-bearing iron hydroxides. From a mass balance perspective, arsenopyrite oxidation to scorodite conserves As, but as scorodite dissolves incongruently to iron hydroxides, As is released to solution, resulting in elevated As concentrations in the headwater stream adjacent to the site. The As-bearing iron hydroxide is the dominant solid phase reservoir of As in mine tailings and stream sediment, as suggested by sequential extraction. This As-bearing iron hydroxide is stable under the aerobic and pH 4-6 conditions at the site; however, changes in biogeochemical conditions resulting from sediment burial or future remedial efforts, which could promote As release from this reservoir due to reductive dissolution, should be avoided.

Using watershed characteristics, sediment, and tissue of resident mollusks to identify potential sources of trace elements to streams in a complex agricultural landscape.

Trace elements used in animal feed additives can be introduced to aquatic environments through application of manures from animal feeding operations to agricultural land as fertilizer. The use of poultry feed additives containing arsenic (As) is of particular concern in the Shenandoah River watershed (Virginia, USA), an agricultural landscape with a high density of poultry operations. This study investigated the relationship between watershed characteristics of Shenandoah River tributaries and trace element concentrations in streambed sediment and tissue of resident mollusks, including: Asian clams (Corbicula fluminea), which are commonly used biomonitors, and pleurocerid snails (Leptoxis carinata), which are generally understudied. Results failed to support the primary hypothesis of a predictive relationship between watershed densities of poultry operations and As concentrations in sediment and mollusk tissue. However, there were statistical relationships between land use in tributary watersheds and other trace elements in sediment (Cu, Mn, Pb, Zn) and tissue (Cd, Hg, Pb). Principal components analysis of the sediment data suggested a possible geologic source of As at some sites. Tissue concentrations of As were significantly higher in snails than in clams, but clams accumulated higher concentrations of other trace elements (Cd, Cr, Hg, Pb, Se). Snails may be useful biomonitors of environmental As, but appear to be less suitable than clams for studies of landscape sources of other trace elements.

Quantifying potential recharge in mantled sinkholes using ERT.

Potential recharge through thick soils in mantled sinkholes was quantified using differential electrical resistivity tomography (ERT). Conversion of time series two-dimensional (2D) ERT profiles into 2D volumetric water content profiles using a numerically optimized form of Archie's law allowed us to monitor temporal changes in water content in soil profiles up to 9 m in depth. Combining Penman-Monteith daily potential evapotranspiration (PET) and daily precipitation data with potential recharge calculations for three sinkhole transects indicates that potential recharge occurred only during brief intervals over the study period and ranged from 19% to 31% of cumulative precipitation. Spatial analysis of ERT-derived water content showed that infiltration occurred both on sinkhole flanks and in sinkhole bottoms. Results also demonstrate that mantled sinkholes can act as regions of both rapid and slow recharge. Rapid recharge is likely the result of flow through macropores (such as root casts and thin gravel layers), while slow recharge is the result of unsaturated flow through fine-grained sediments. In addition to developing a new method for quantifying potential recharge at the field scale in unsaturated conditions, we show that mantled sinkholes are an important component of storage in a karst system.

Scorodite dissolution kinetics: implications for arsenic release.

We have measured the rate of scorodite (FeAsO4.2H2O) dissolution over an environmentally relevant range of pH and temperature conditions. Dissolution rates, calculated using arsenic (As) as the reaction progress variable, were slowest at pH 3 and increased with both decreasing and increasing pH. Comparison of the pH-dependence of the dissolution rates with a scorodite stability diagram suggests that our measurements of dissolution rate at pH 2 reflect congruent dissolution, and those at and above pH 3 reflect incongruent dissolution. Because As was used as the reaction progress variable, and recognizing that As may adsorb to iron hydroxides during incongruent dissolution of scorodite, the derived rates may be underestimated. The pH and temperature dependence of scorodite dissolution rates determined in these experiments have implications for the stability of scorodite at field sites and also for the potential use of scorodite to sequester As. Although scorodite dissolution is slow, it can be enhanced by up to a half order of magnitude by increases in pH and temperature.

Bioassessment of an Appalachian headwater stream influenced by an abandoned arsenic mine.

Recent debate concerning the modification of safe drinking water standards for arsenic (As) has led to increased awareness of the risks As poses to both humans and the environment. However, few studies have examined the effects of As on the diversity and composition of aquatic assemblages in streams. Benthic macroinvertebrate surveys, chemical analysis of water column and sediment, and laboratory toxicity tests were conducted to assess effects of an abandoned As mine on a headwater stream, and to determine the primary component of toxicity. The average 48-hr LC50 value for Daphnia magna was 4316 microg As/L, and the average 96-hr LC50 value for Lepidostoma spp. was 2138 microg As/L. Reproduction was significantly reduced for D. magna at concentrations > or =312 microg As/L in water column laboratory bioassays, and for treatments in bioassays with sediments containing elevated As (> or =2630 mg/kg). These results support the findings of the in-stream benthic macroinvertebrate survey as the density and percent Ephemeroptera + Plecoptera, + Trichoptera (EPT) were substantially lower at sites downstream of the mine compared to upstream reference sites. Results of bioassays comparing the toxicity of As-contaminated site water and upstream reference water spiked with As salts suggest that As is the primary component of toxicity impacting the stream. Measured As concentrations at downstream sites were above the recommended Criterion Maximum Concentration of 340 microg As/L and Criterion Continuous Concentration of 150 microg As/L for protection of aquatic life published by the United States Environmental Protection Agency. At the study site, elevated As concentrations likely prevent recruitment of benthic macroinvertebrates and recovery of the perturbed headwater stream.

Arsenic mobilization through microbially mediated deflocculation of ferrihydrite.

This study examined the potential impact of microbially mediated reduction of Fe in the Fe(III)-(hydr)oxide mineral ferrihydrite on the mobility of As in natural waters. In microcosm experiments, the obligately anaerobic bacterium Geobacter metallireducens reduced on average 10% of the Fe(III) in ferrihydrite with varying sorbed As(V) surface coverages, which resulted in deflocculation of initially micron-sized As-bearing ferrihydrite aggregates to nanometersized colloids. No reduction of As(V) to As(III) was observed in microcosm samples. Measurement of Fe and As within operationally defined particulate, colloidal, and dissolved fractions of microcosm slurry samples revealed that little Fe or As was released from ferrihydrite as dissolved species. Microbially induced deflocculation of ferrihydrite in the presence of G. metallireducens was correlated with more negative zeta potential of ferrihydrite nanoparticles suggesting that G. metallireducens mediated As mobilization through alteration of ferrihydrite surface charge. TEM analysis and solution chemistry conditions suggested formation of a magnetite surface layer through topotactic recrystallization of ferrihydrite (2LFH) driven by sorbed Fe(II). The formation of nanometer-sized As-bearing colloids through microbially mediated reduction of Fe-(hydr)oxides has the potential to increase human As exposure by enhancing As mobility in natural waters and hindering As removal during subsequent drinking water treatment.

Freshwater mussel shells as environmental chronicles: geochemical and taphonomic signatures of mercury-related extirpations in the North Fork Holston River, Virginia.

This study utilized freshwater mussel shells to assess mercury (Hg) contamination in the North Fork Holston River that extirpated (caused local extinctions of) a diverse mussel fauna. Shells (n = 366) were collected from five sites situated upstream (two sites), just below (one site), and downstream (two sites) of the town of Saltville, Virginia, where Hg was used to produce chlorine and caustic soda from 1950 to 1972. Shell samples were used to test the (1) utility of geochemical signatures of shells for assessing the spatial variation in Hg levels in the river relative to the contamination source and (2) value of taphonomy (post-mortem shell alteration) for distinguishing sites that differ in extirpation histories. Geochemical signatures of 40 shells, analyzed using atomic absorption spectroscopy, indicated a strong longitudinal pattern. All shells from the two upstream sites had low Hg concentrations (<5-31 microg/kg), shells directly below Saltville had variable, but dramatically higher concentrations (23-4637 microg/kg), and shells from the two downstream sites displayed intermediate Hg levels (<5-115 microg/kg) that declined with distance from Saltville. Two pre-industrial shells, collected at Saltville in 1917, yielded very low Hg estimates (5-6 microg/kg). Hg signatures were consistent among mussel species, suggesting that Hg concentrations were invariant to species type; most likely, highly variable Hg levels, both across sites and through time, overwhelmed any interspecific differences in Hg acquisition. Also, a notable postmortem incorporation of Hg in mussel shells seemed unlikely, as the Hg content was not correlated with shell taphonomy (r= 0.18; p = 0.28). The taphonomic analysis (n = 366) showed that the degree of shell alteration reliably distinguished sites with different extirpation histories. At Saltville, where live mussels have been absent for at least 30 years, shells were most heavily altered and fragmented. Conversely, fresh-looking shells abounded upstream, where reproducing mussel populations are still present. In summary, relic shells offered valuable spatio-temporal data on Hg concentrations in a polluted ecosystem, and shell taphonomic signatures discriminated sites with different extirpation histories. The shell-based strategies exemplified here do not require sampling live specimens and may augment more standard strategies applied to environmental monitoring. The approach should prove especially useful in areas with unknown extirpation and pollution histories.

Effects of water use on arsenic release to well water in a confined aquifer.

Field-based experiments were designed to investigate the release of naturally occurring, low to moderate (< 50 microg/L) arsenic concentrations to well water in a confined sandstone aquifer in northeastern Wisconsin. Geologic, geochemical, and hydrogeologic data collected from a 115 m2 site demonstrate that arsenic concentrations in ground water are heterogeneous at the scale of the field site, and that the distribution of arsenic in ground water correlates to solid-phase arsenic in aquifer materials. Arsenic concentrations in a test well varied from 1.8 to 22 microg/L during experiments conducted under no, low, and high pumping rates. The quality of ground water consumed from wells under typical domestic water use patterns differs from that of ground water in the aquifer because of reactions that occur within the well. Redox conditions in the well can change rapidly in response to ground water withdrawals. The well borehole is an environment conducive to microbiological growth, and biogeochemical reactions also affect borehole chemistry. While oxidation of sulfide minerals appears to release arsenic to ground water in zones within the aquifer, reduction of arsenic-bearing iron (hydr)oxides is a likely mechanism of arsenic release to water having a long residence time in the well borehole.