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Geology topics

Mark C. Marvin-DiPasquale

Publications and source records attributed to Mark C. Marvin-DiPasquale.

At least 37 records · Page 2Linked to original sources

Mercury cycling in the Hells Canyon Complex of the Snake River, Idaho and Oregon

Introduction The Hells Canyon Complex (HCC) is a hydroelectric project built and operated by the Idaho Power Company (IPC) that consists of three dams on the Snake River along the Oregon and Idaho border (fig. 1). The dams have resulted in the creation of Brownlee, Oxbow, and Hells Canyon Reservoirs, which have a combined storage capacity of more than 1.5 million acre-feet and span about 90 miles of the Snake River. The Snake River upstream of and through the HCC historically has been impaired by water-quality issues related to excessive contributions of nutrients, algae, sediment, and other pollutants. In addition, historical data collected since the 1960s from the Snake River and tributaries near the HCC have documented high concentrations of mercury in fish tissue and sediment (Harris and Beals, 2013). Data collected from more recent investigations within the HCC continue to indicate elevated concentrations of mercury and methylmercury in the water column, bottom sediments, and biota (Clark and Maret, 1998; Essig, 2010; Fosness and others, 2013). As a result, Brownlee and Hells Canyon Reservoirs are listed as impaired for mercury by the State of Idaho, and the Snake River from the Oregon and Idaho border through the HCC downstream to the Oregon and Washington border is listed as impaired for mercury by the State of Oregon.

Idaho, Oregon

Isotopic composition of inorganic mercury and methylmercury downstream of a historical gold mining region

We measured total mercury (THg) and monomethyl mercury (MMHg) concentrations and mercury (Hg) isotopic compositions in sediment and aquatic organisms from the Yuba River (California, USA) to identify Hg sources and biogeochemical transformations downstream of a historical gold mining region. Sediment THg concentrations and δ 202 Hg decreased from the upper Yuba Fan to the lower Yuba Fan and the Feather River. These results are consistent with the release of Hg during gold mining followed by downstream mixing and dilution. The Hg isotopic composition of Yuba Fan sediment (δ 202 Hg = −0.38 ± 0.17‰ and Δ 199 Hg = 0.04 ± 0.03‰; mean ± 1 SD, n = 7) provides a fingerprint of inorganic Hg (IHg) that could be methylated locally or after transport downstream. The isotopic composition of MMHg in the Yuba River food web was estimated using biota with a range of %MMHg (the percent of THg present as MMHg) and compared to IHg in sediment, algae, and the food web. The estimated δ 202 Hg of MMHg prior to photodegradation (−1.29 to −1.07‰) was lower than that of IHg and we suggest this is due to mass-dependent fractionation (MDF) of up to −0.9‰ between IHg and MMHg. This result is in contrast to net positive MDF (+0.4 to +0.8‰) previously observed in lakes, estuaries, coastal oceans, and forests. We hypothesize that this unique relationship could be due to differences in the extent or pathway of biotic MMHg degradation in stream environments.

California

Mercury remediation in wetland sediment using zero-valent iron and granular activated carbon

Wetlands are hotspots for production of toxic methylmercury (MeHg) that can bioaccumulate in the food web. The objective of this study was to determine whether the application of zero-valent iron (ZVI) or granular activated carbon (GAC) to wetland sediment could reduce MeHg production and bioavailability to benthic organisms. Field mesocosms were installed in a wetland fringing Hodgdon Pond (Maine, USA), and ZVI and GAC were applied. Pore-water MeHg concentrations were lower in treated compared with untreated mesocosms; however, sediment MeHg, as well as total Hg (THg), concentrations were not significantly different between treated and untreated mesocosms, suggesting that smaller pore-water MeHg concentrations in treated sediment were likely due to adsorption to ZVI and GAC, rather than inhibition of MeHg production. In laboratory experiments with intact vegetated sediment clumps, amendments did not significantly change sediment THg and MeHg concentrations; however, the mean pore-water MeHg and MeHg:THg ratios were lower in the amended sediment than the control. In the laboratory microcosms, snails ( Lymnaea stagnalis ) accumulated less MeHg in sediment treated with ZVI or GAC. The study results suggest that both GAC and ZVI have potential for reducing MeHg bioaccumulation in wetland sediment.

Environmental Pollution

Hydrologic indicators of hot spots and hot moments of mercury methylation potential along river corridors

The biogeochemical cycling of metals and other contaminants in river-floodplain corridors is controlled by microbial activity responding to dynamic redox conditions. Riverine flooding thus has the potential to affect speciation of redox-sensitive metals such as mercury (Hg). Therefore, inundation history over a period of decades potentially holds information on past production of bioavailable Hg. We investigate this within a Northern California river system with a legacy of landscape-scale 19th century hydraulic gold mining. We combine hydraulic modeling, Hg measurements in sediment and biota, and first-order calculations of mercury transformation to assess the potential role of river floodplains in producing monomethylmercury (MMHg), a neurotoxin which accumulates in local and migratory food webs. We identify frequently inundated floodplain areas, as well as floodplain areas inundated for long periods. We quantify the probability of MMHg production potential (MPP) associated with hydrology in each sector of the river system as a function of the spatial patterns of overbank inundation and drainage, which affect long-term redox history of contaminated sediments. Our findings identify river floodplains as periodic, temporary, yet potentially important, loci of biogeochemical transformation in which contaminants may undergo change during limited periods of the hydrologic record. We suggest that inundation is an important driver of MPP in river corridors and that the entire flow history must be analyzed retrospectively in terms of inundation magnitude and frequency in order to accurately assess biogeochemical risks, rather than merely highlighting the largest floods or low-flow periods. MMHg bioaccumulation within the aquatic food web in this system may pose a major risk to humans and waterfowl that eat migratory salmonids, which are being encouraged to come up these rivers to spawn. There is a long-term pattern of MPP under the current flow regime that is likely to be accentuated by increasingly common large floods with extended duration.

California

Mercury and methylmercury in aquatic sediment across western North America

Large-scale assessments are valuable in identifying primary factors controlling total mercury (THg) and monomethyl mercury (MeHg) concentrations, and distribution in aquatic ecosystems. Bed sediment THg and MeHg concentrations were compiled for > 16,000 samples collected from aquatic habitats throughout the West between 1965 and 2013. The influence of aquatic feature type (canals, estuaries, lakes, and streams), and environmental setting (agriculture, forest, open-water, range, wetland, and urban) on THg and MeHg concentrations was examined. THg concentrations were highest in lake (29.3 ± 6.5 μg kg − 1 ) and canal (28.6 ± 6.9 μg kg − 1 ) sites, and lowest in stream (20.7 ± 4.6 μg kg − 1 ) and estuarine (23.6 ± 5.6 μg kg − 1 ) sites, which was partially a result of differences in grain size related to hydrologic gradients. By environmental setting, open-water (36.8 ± 2.2 μg kg − 1 ) and forested (32.0 ± 2.7 μg kg − 1 ) sites generally had the highest THg concentrations, followed by wetland sites (28.9 ± 1.7 μg kg − 1 ), rangeland (25.5 ± 1.5 μg kg − 1 ), agriculture (23.4 ± 2.0 μg kg − 1 ), and urban (22.7 ± 2.1 μg kg − 1 ) sites. MeHg concentrations also were highest in lakes (0.55 ± 0.05 μg kg − 1 ) and canals (0.54 ± 0.11 μg kg − 1 ), but, in contrast to THg, MeHg concentrations were lowest in open-water sites (0.22 ± 0.03 μg kg − 1 ). The median percent MeHg (relative to THg) for the western region was 0.7%, indicating an overall low methylation efficiency; however, a significant subset of data (n > 100) had percentages that represent elevated methylation efficiency (> 6%). MeHg concentrations were weakly correlated with THg (r 2 = 0.25) across western North America. Overall, these results highlight the large spatial variability in sediment THg and MeHg concentrations throughout western North America and underscore the important roles that landscape and land-use characteristics have on the MeHg cycle.

Science of the Total Environment

Methylmercury degradation and exposure pathways in streams and wetlands impacted by historical mining

Monomethyl mercury (MMHg) and total mercury (THg) concentrations and Hg stable isotope ratios (δ 202 Hg and Δ 199 Hg) were measured in sediment and aquatic organisms from Cache Creek (California Coast Range) and Yolo Bypass (Sacramento Valley). Cache Creek sediment had a large range in THg (87 to 3870 ng/g) and δ 202 Hg (−1.69 to −0.20‰) reflecting the heterogeneity of Hg mining sources in sediment. The δ 202 Hg of Yolo Bypass wetland sediment suggests a mixture of high and low THg sediment sources. Relationships between %MMHg (the percent ratio of MMHg to THg) and Hg isotope values (δ 202 Hg and Δ 199 Hg) in fish and macroinvertebrates were used to identify and estimate the isotopic composition of MMHg. Deviation from linear relationships was found between %MMHg and Hg isotope values, which is indicative of the bioaccumulation of isotopically distinct pools of MMHg. The isotopic composition of pre-photodegraded MMHg (i.e., subtracting fractionation from photochemical reactions) was estimated and contrasting relationships were observed between the estimated δ 202 Hg of pre-photodegraded MMHg and sediment IHg. Cache Creek had mass dependent fractionation (MDF; δ 202 Hg) of at least −0.4‰ whereas Yolo Bypass had MDF of +0.2 to +0.5‰. This result supports the hypothesis that Hg isotope fractionation between IHg and MMHg observed in rivers (−MDF) is unique compared to +MDF observed in non-flowing water environments such as wetlands, lakes, and the coastal ocean.

California

High-resolution remote sensing of water quality in the San Francisco Bay-Delta Estuary

The San Francisco Bay–Delta Estuary watershed is a major source of freshwater for California and a profoundly human-impacted environment. The water quality monitoring that is critical to the management of this important water resource and ecosystem relies primarily on a system of fixed water-quality monitoring stations, but the limited spatial coverage often hinders understanding. Here, we show how the latest technology in visible/near-infrared imaging spectroscopy can facilitate water quality monitoring in this highly dynamic and heterogeneous system by enabling simultaneous depictions of several water quality indicators at very high spatial resolution. The airborne portable remote imaging spectrometer (PRISM) was used to derive high-spatial-resolution (2.6 × 2.6 m) distributions of turbidity, and dissolved organic carbon (DOC) and chlorophyll-a concentrations in a wetland-influenced region of this estuary. A filter-passing methylmercury vs DOC relationship was also developed using in situ samples and enabled the high-spatial-resolution depiction of surface methylmercury concentrations in this area. The results illustrate how high-resolution imaging spectroscopy can inform management and policy development in important inland and estuarine water bodies by facilitating the detection of point- and nonpoint-source pollution, and by providing data to help assess the complex impacts of wetland restoration and climate change on water quality and ecosystem productivity.

California

Influence of a chlor-alkali superfund site on mercury bioaccumulation in periphyton and low-trophic level fauna

In Berlin, New Hampshire, USA, the Androscoggin River flows adjacent to a former chlor-alkali facility that is a US Environmental Protection Agency Superfund site and source of mercury (Hg) to the river. The present study was conducted to determine the fate and bioaccumulation of methylmercury (MeHg) to lower trophic-level taxa in the river. Surface sediment directly adjacent to the source showed significantly elevated MeHg (10–40× increase, mean ± standard deviation [SD]: 20.1 ± 24.8 ng g –1 dry wt) and total mercury (THg; 10–30× increase, mean ± SD: 2045 ± 2669 ng g –1 dry wt) compared with all other reaches, with sediment THg and MeHg from downstream reaches elevated (3–7× on average) relative to the reference (THg mean ± SD: 33.5 ± 9.33 ng g –1 dry wt; MeHg mean ± SD: 0.52 ± 0.21 ng g –1 dry wt). Water column THg concentrations adjacent to the point source for both particulate (0.23 ng L –1 ) and dissolved (0.76 ng L –1 ) fractions were 5-fold higher than at the reference sites, and 2-fold to 5-fold higher than downstream. Methylmercury production potential of periphyton material was highest (2–9 ng g –1 d –1 dry wt) adjacent to the Superfund site; other reaches were close to or below reporting limits (0. 1 ng g –1 d –1 dry wt). Total Hg and MeHg bioaccumulation in fauna was variable across sites and taxa, with no clear spatial patterns downstream of the contamination source. Crayfish, mayflies, and shiners showed a weak positive relationship with porewater MeHg concentration.

New Hampshire

Total- and methyl-mercury concentrations and methylation rates across the freshwater to hypersaline continuum of the Great Salt Lake, Utah, USA

We examined mercury (Hg) speciation in water and sediment of the Great Salt Lake and surrounding wetlands, a locale spanning fresh to hypersaline and oxic to anoxic conditions, in order to test the hypothesis that spatial and temporal variations in Hg concentration and methylation rates correspond to observed spatial and temporal trends in Hg burdens previously reported in biota. Water column, sediment, and pore water concentrations of methylmercury (MeHg) and total mercury (THg), as well as related aquatic chemical parameters were examined. Inorganic Hg(II)-methylation rates were determined in selected water column and sediment subsamples spiked with inorganic divalent mercury ( 204 Hg(II)). Net production of Me 204 Hg was expressed as apparent first-order rate constants for methylation ( k meth ), which were also expanded to MeHg production potential (MPP) rates via combination with tin reducible ‘reactive’ Hg(II) (Hg(II) R ) as a proxy for bioavailable Hg(II). Notable findings include: 1) elevated Hg concentrations previously reported in birds and brine flies were spatially proximal to the measured highest MeHg concentrations, the latter occurring in the anoxic deep brine layer (DBL) of the Great Salt Lake; 2) timing of reduced Hg(II)-methylation rates in the DBL (according to both k meth and MPP) coincides with reduced Hg burdens among aquatic invertebrates (brine shrimp and brine flies) that act as potential vectors of Hg propagation to the terrestrial ecosystem; 3) values of k meth were found to fall within the range reported by other studies; and 4) MPP rates were on the lower end of the range reported in methodologically comparable studies, suggesting the possibility that elevated MeHg in the anoxic deep brine layer results from its accumulation and persistence in this quasi-isolated environment, due to the absence of light (restricting abiotic photo demethylation) and/or minimal microbiological demethylation.

Utah

Assessment of the use of sorbent amendments for reduction of mercury methylation in wetland sediments at Acadia National Park, Maine

Mercury is a contaminant of ecological concern because of its ubiquity and toxicity to fish and wildlife, and is considered a severe and ongoing threat to biota at Acadia National Park in Maine. The formation and biomagnification of methylmercury is the primary concern of resource managers at Acadia, and information is needed to develop strategies for remediation or mitigation of this contaminant. The U.S. Geological Survey in cooperation with Acadia National Park, National Park Service carried out a series of laboratory and field experiments to evaluate the potential of zero-valent iron and granular activated carbon to reduce the rate of the bacterially mediated process of mercury methylation and subsequent biological uptake by the great pond snail Lymnaea stagnalis . The addition of zero-valent iron resulted in an increase in ferrous iron that was then further oxidized to poorly crystalline amorphous ferric iron, as was anticipated. Our original hypothesis was that these reactions would reduce methylation by decreasing the concentrations of substrates for bacterial methylation (sulfide and divalent mercury) through sorption to ferric iron surfaces, formation of iron sulfide compounds, or conversion of mercury to gaseous forms and subsequent evasion. The results of our experiments did not consistently support this hypothesis. In one experiment the application of zero-valent iron increased the amount of methylmercury associated with surficial sediment. In another experiment zero-valent iron decreased the amount of methylmercury associated with surficial sediment. The addition of zero-valent iron may have stimulated mercury methylation by iron reducing bacteria and if that effect outweighed the processes that could have decreased methylation then methylation would not be decreased. The results of field mesocosm experiments indicated that there was a decreasing trend in pore-water methylmercury concentration after application of granular activated carbon but methylation was not affected because there was no corresponding decrease in sediment methylmercury concentration. The application of granular activated carbon resulted in the sorption of methylmercury. The application of granular activated carbon resulted in an increase in the distribution coefficient for methylmercury indicating that this amendment caused a higher proportion of methylmercury to be associated with the sediment than the pore water in comparison to the reference (untreated) condition. Experiments to test whether zero-valent iron or granular activated carbon would reduce the biouptake of methylmercury in snails were inconsistent; zero-valent iron had no effect on uptake in one experiment but resulted in a significant decrease in uptake in a second experiment. Granular activated carbon did not affect biouptake in either experiment.

Maine

Mercury cycling in agricultural and managed wetlands, Yolo Bypass, California: Spatial and seasonal variations in water quality

The seasonal and spatial variability of water quality, including mercury species, was evaluated in agricultural and managed, non-agricultural wetlands in the Yolo Bypass Wildlife Area, an area managed for multiple beneficial uses including bird habitat and rice farming. The study was conducted during an 11-month period (June 2007 to April 2008) that included a summer growing season and flooded conditions during winter. Methylmercury (MeHg) concentrations in surface water varied over a wide range (0.1 to 37 ng L−1 unfiltered; 0.04 to 7.3 ng L−1 filtered). Maximum MeHg values are among the highest ever recorded in wetlands. Highest MeHg concentrations in unfiltered surface water were observed in drainage from wild rice fields during harvest (September 2007), and in white rice fields with decomposing rice straw during regional flooding (February 2008). The ratio of MeHg to total mercury (MeHg/THg) increased about 20-fold in both unfiltered and filtered water during the growing season (June to August 2007) in the white and wild rice fields, and about 5-fold in fallow fields (July to August 2007), while there was little to no change in MeHg/THg in the permanent wetland. Sulfate-bearing fertilizer had no effect on Hg(II) methylation, as sulfate-reducing bacteria were not sulfate limited in these agricultural wetlands. Concentrations of MeHg in filtered and unfiltered water correlated with filtered Fe, filtered Mn, DOC, and two indicators of sulfate reduction: the SO4 2 −/Cl− ratio, and δ34S in aqueous sulfate. These relationships suggest that microbial reduction of SO4 2−, Fe(III), and possibly Mn(IV) may contribute to net Hg(II)-methylation in this setting.

California

Mercury cycling in agricultural and managed wetlands: a synthesis of methylmercury production, hydrologic export, and bioaccumulation from an integrated field study

With seasonal wetting and drying, and high biological productivity, agricultural wetlands (rice paddies) may enhance the conversion of inorganic mercury (Hg(II)) to methylmercury (MeHg), the more toxic, organic form that biomagnifies through food webs. Yet, the net balance of MeHg sources and sinks in seasonal wetland environments is poorly understood because it requires an annual, integrated assessment across biota, sediment, and water components. We examined a suite of wetlands managed for rice crops or wildlife during 2007–2008 in California's Central Valley, in an area affected by Hg contamination from historic mining practices. Hydrologic management of agricultural wetlands for rice, wild rice, or fallowed — drying for field preparation and harvest, and flooding for crop growth and post-harvest rice straw decay — led to pronounced seasonality in sediment and aqueous MeHg concentrations that were up to 95-fold higher than those measured concurrently in adjacent, non-agricultural permanently-flooded and seasonally-flooded wetlands. Flooding promoted microbial MeHg production in surface sediment of all wetlands, but extended water residence time appeared to preferentially enhance MeHg degradation and storage. When incoming MeHg loads were elevated, individual fields often served as a MeHg sink, rather than a source. Slow, horizontal flow of shallow water in the agricultural wetlands led to increased importance of vertical hydrologic fluxes, including evapoconcentration of surface water MeHg and transpiration-driven advection into the root zone, promoting temporary soil storage of MeHg. Although this hydrology limited MeHg export from wetlands, it also increased MeHg exposure to resident fish via greater in situ aqueous MeHg concentrations. Our results suggest that the combined traits of agricultural wetlands — slow-moving shallow water, manipulated flooding and drying, abundant labile plant matter, and management for wildlife — may enhance microbial methylation of Hg(II) and MeHg exposure to local biota, as well as export to downstream habitats during uncontrolled winter-flow events.

California

Kinetics of homogeneous and surface-catalyzed mercury(II) reduction by iron(II)

Production of elemental mercury, Hg(0), via Hg(II) reduction is an important pathway that should be considered when studying Hg fate in environment. We conducted a kinetic study of abiotic homogeneous and surface-catalyzed Hg(0) production by Fe(II) under dark anoxic conditions. Hg(0) production rate, from initial 50 pM Hg(II) concentration, increased with increasing pH (5.5–8.1) and aqueous Fe(II) concentration (0.1–1 mM). The homogeneous rate was best described by the expression, r hom = k hom [FeOH + ] [Hg(OH) 2 ]; k hom = 7.19 × 10 +3 L (mol min) −1 . Compared to the homogeneous case, goethite (α-FeOOH) and hematite (α-Fe 2 O 3 ) increased and γ-alumina (γ-Al 2 O 3 ) decreased the Hg(0) production rate. Heterogeneous Hg(0) production rates were well described by a model incorporating equilibrium Fe(II) adsorption, rate-limited Hg(II) reduction by dissolved and adsorbed Fe(II), and rate-limited Hg(II) adsorption. Equilibrium Fe(II) adsorption was described using a surface complexation model calibrated with previously published experimental data. The Hg(0) production rate was well described by the expression r het = k het [>SOFe (II) ] [Hg(OH) 2 ], where >SOFe (II) is the total adsorbed Fe(II) concentration; k het values were 5.36 × 10 +3 , 4.69 × 10 +3 , and 1.08 × 10 +2 L (mol min) −1 for hematite, goethite, and γ-alumina, respectively. Hg(0) production coupled to reduction by Fe(II) may be an important process to consider in ecosystem Hg studies.

Environmental Science & Technology

Mercury cycling in agricultural and managed wetlands of California: seasonal influences of vegetation on mercury methylation, storage, and transport

Plants are a dominant biologic and physical component of many wetland capable of influencing the internal pools and fluxes of methylmercury (MeHg). To investigate their role with respect to the latter, we examined the changing seasonal roles of vegetation biomass and Hg, C and N composition from May 2007-February 2008 in 3 types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields), and in adjacent managed natural wetlands dominated by cattail and bulrush (tule). We also determined the impact of vegetation on seasonal microbial Hg methylation rates, and Hg and MeHg export via seasonal storage in vegetation, and biotic consumption of rice seed. Despite a compressed growing season of ~ 3 months, annual net primary productivity (NPP) was greatest in white rice fields and carbon more labile (leaf median C:N ratio = 27). Decay of senescent litter (residue) was correlated with microbial MeHg production in winter among all wetlands. As agricultural biomass accumulated from July to August, THg concentrations declined in leaves but MeHg concentrations remained consistent, such that MeHg pools generally increased with growth. Vegetation provided a small, temporary, but significant storage term for MeHg in agricultural fields when compared with hydrologic export. White rice and wild rice seeds reached mean MeHg concentrations of 4.1 and 6.2 ng g dw - 1 , respectively. In white rice and wild rice fields, seed MeHg concentrations were correlated with root MeHg concentrations (r = 0.90, p < 0.001), suggesting transport of MeHg to seeds from belowground tissues. Given the proportionally elevated concentrations of MeHg in rice seeds, white and wild rice crops may act as a conduit of MeHg into biota, especially waterfowl which forage heavily on rice seeds within the Central Valley of California, USA. Thus, while plant tissues and rhizosphere soils provide temporary storage for MeHg during the growing season, export of MeHg is enhanced post-harvest through increased hydrologic and biotic export.

California

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms: an experimental study using oligotrophic water from Patagonian lakes

Ligands present in dissolved organic matter (DOM) form complexes with inorganic divalent mercury (Hg 2+ ) affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg 2+ (the prevailing mercury species in the water column of these lakes) by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg 2+ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended with 197 Hg 2+ . The bioavailability of Hg 2+ was affected by the concentration and character of DOM. The entrance of Hg 2+ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg 2+ by Cryptomonas, up to 27% of the Hg 2+ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg 2+ in the dissolved phase, resulting in the lowest Hg 2+ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg 2+ amended. The dietary incorporation of Hg 2+ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg 2+ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg 2+ by algae through competitive binding, while the incorporation of Hg 2+ into the zooplankton was dominated by trophic or dietary transfer.

Patagonia

Characterization of mercury contamination in the Androscoggin River, Coos County, New Hampshire

The former chloralkali facility in Berlin, New Hampshire, was designated a Superfund site in 2005. Historic paper mill activities resulted in the contamination of groundwater, surface water, and sediments with many organic compounds and mercury (Hg). Hg continues to seep into the Androscoggin River in elemental form through bedrock fractures. The objective of this study was to spatially characterize (1) the extent of Hg contamination in water, sediment, and biota; (2) Hg speciation and methylmercury (MeHg) production potential rates in sediment; (3) the availability of inorganic divalent Hg (Hg(II)) for Hg(II)-methylation (MeHg production); and (4) ancillary sediment geochemistry necessary to better understand Hg speciation and MeHg production potential rates in this system. Concentrations of total mercury (THg) and MeHg in sediment, pore water, and biota in the Androscoggin River were elevated downstream from the former chloralkali facility compared with those upstream from reference sites. Sequential extraction of surface sediment showed a distinct difference in Hg speciation upstream compared with downstream from the contamination site. An upstream site was dominated by potassium hydroxide-extractable forms (for example, organic-Hg or particle-bound Hg(II)), whereas sites downstream from the point source were dominated by more chemically recalcitrant forms (largely concentrated nitric acid-extractable), indicative of elemental mercury or mercurous chloride. At all sites, only a minor fraction (less than 0.1 percent) of THg existed in chemically labile forms (for example, water extractable or weak acid extractable). All metrics indicated that a greater percentage of mercury at an upstream site was available for Hg(II)-methylation compared with sites downstream from the point source, but the absolute concentration of bioavailable Hg(II) was greater downstream from the point source. In addition, the concentration of tin-reducible inorganic reactive mercury, a surrogate measure of bioavailable Hg(II) generally increased with distance downstream from the point source. Whereas concentrations of mercury species on a sediment-dry-weight basis generally reflected the relative location of the sample to the point source, river-reach integrated mercury-species inventories and MeHg production potential (MPP) rates reflected the amount of fine-grained sediment in a given reach. THg concentrations in biota were significantly higher downstream from the point source compared with upstream reference sites for smallmouth bass, white sucker, crayfish, oligochaetes, bat fur, nestling tree swallow blood and feathers, adult tree swallow blood, and tree swallow eggs. As with tin-reducible inorganic reactive mercury, THg in smallmouth bass also increased with distance downstream from the point source. Toxicity tests and invertebrate community assessments suggested that invertebrates were not impaired at the current (2009 and 2010) levels of mercury contamination downstream from the point source. Concentrations of THg and MeHg in most water and sediment samples from the Androscoggin River were below U.S. Environmental Protection Agency (USEPA), the Canadian Council of Ministers of the Environment, and probable effects level guidelines. Surface-water and sediment samples from the Androscoggin River had similar THg concentrations but lower MeHg concentrations compared with other rivers in the region. Concentrations of THg in fish tissue were all above regional and U.S. Environmental Protection Agency guidelines. Moreover, median THg concentrations in smallmouth bass from the Androscoggin River were significantly higher than those reported in regional surveys of river and streams nationwide and in the Northeastern United States and Canada. The higher concentrations of mercury in smallmouth bass suggest conditions may be more favorable for Hg(II)-methylation and bioaccumulation in the Androscoggin River compared with many other rivers in the United States and Canada.

New Hampshire

Shallow groundwater mercury supply in a coastal plain stream

Fluvial methylmercury (MeHg) is attributed to methylation in up-gradient wetland areas. This hypothesis depends on efficient wetland-to-stream hydraulic transport under nonflood and flood conditions. Fluxes of water and dissolved (filtered) mercury (Hg) species (FMeHg and total Hg (FTHg)) were quantified in April and July of 2009 in a reach at McTier Creek, South Carolina to determine the relative importance of tributary surface water and shallow groundwater Hg transport from wetland/floodplain areas to the stream under nonflood conditions. The reach represented less than 6% of upstream main-channel distance and 2% of upstream basin area. Surface-water discharge increased within the reach by approximately 10%. Mean FMeHg and FTHg fluxes increased within the reach by 23&ndash;27% and 9&ndash;15%, respectively. Mass balances indicated that, under nonflood conditions, the primary supply of water, FMeHg, and FTHg within the reach (excluding upstream surface water influx) was groundwater discharge, rather than tributary transport from wetlands, in-stream MeHg production, or atmospheric Hg deposition. These results illustrate the importance of riparian wetland/floodplain areas as sources of fluvial MeHg and of groundwater Hg transport as a fundamental control on Hg supply to Coastal Plain streams.

South Carolina

Geophysical bed sediment characterization of the Androscoggin River from the former Chlor-Alkali Facility Superfund Site, Berlin, New Hampshire, to the state border with Maine, August 2009

The former Chlor-Alkali Facility in Berlin, New Hampshire, was listed on the U.S. Environmental Protection Agency National Priorities List in 2005 as a Superfund site. The Chlor-Alkali Facility lies on the east bank of the Androscoggin River. Elemental mercury currently discharges from that bank into the Androscoggin River. The nature, extent, and the speciation of mercury and the production of methyl mercury contamination in the adjacent Androscoggin River is the subject of continuing investigations. The U.S. Geological Survey, in cooperation with Region I of the U.S. Environmental Protection Agency, used geophysical methods to determine the distribution, thickness, and physical properties of sediments in the Androscoggin River channel at a small area of an upstream reference reach and downstream from the site to the New Hampshire&ndash;Maine State border. Separate reaches of the Androscoggin River in the study area were surveyed with surface geophysical methods including ground-penetrating radar and step-frequency electromagnetics. Results were processed to assess sediment characteristics including grain size, electrical conductivity, and pore-water specific conductance. Specific conductance measured during surface- and pore-water sampling was used to help interpret the results of the geophysical surveys. The electrical resistivity of sediment samples was measured in the laboratory with intact pore water for comparison with survey results. In some instances, anthropogenic features and land uses, such as roads and power lines affected the detection of riverbed properties using geophysical methods; when this occurred, the data were removed. Through combining results, detailed riverbed sediment characterizations were made. Results from ground-penetrating radar surveys were used to image and measure the depth to the riverbed, depth to buried riverbeds, riverbed thickness and to interpret material-type variations in terms of relative grain size. Fifty two percent of the riverbed in the study area was covered with gravel and finer sediments. The electrically resistive river water and sediment in this study area were conducive to the penetration of the ground-penetrating radar and step-frequency electromagnetic signals and allowed for effective sediment characterization by geophysical methods. The reach between the former Chlor-Alkali Facility and the Riverside Dam, had small areas of fine sediment (estimated 11 percent of riverbed area), found on the upstream left bank and the downstream right bank, with an electromagnetic conductivity (31.4 millisiemens per meter (mS/m) maximum) that was higher than the upstream reference reach. The greatest electromagnetic conductivity (195 mS/m), pore-water specific conductance (324 mS/m) and lab measured sediment conductivity of (76.8 mS/m, measured with a direct-current resistivity test box) in the study were measured approximately 1 mile (mi) downstream of the site from a sandbar on the left bank. Reaches adjacent to and within 2 mi downstream from the site had elevated electromagnetic conductivity despite having lower estimated percentages of riverbed area covered in sediment (11, 25, and 61 percent, respectively) than the reference reach (97). Typically finer grained sediment with similar mineralogy will be more conductive. The Shelburne Reservoir is approximately 8 mi downstream from the site had the second greatest pore-water specific conductance measured, 45.8 mS/m. Many of the locations with the largest step-frequency electromagnetic values have not been sampled for pore water and sediment.

New Hampshire