Distribution and biogeochemical controls on net methylmercury production in Penobscot River marshes and sediment.

The distribution of mercury and methylmercury (MeHg) in sediment, mudflats, and marsh soils of the Hg-contaminated tidal Penobscot River was investigated, along with biogeochemical controls on production. Average total Hg in surface samples (0-3 cm) ranged from 100 to 1200 ng/g; average MeHg ranged from 5 to 50 ng/g. MeHg was usually highest at or near the surface except in highly mobile mudflats. Although total Hg concentrations in the Penobscot are elevated, it is the accumulation of MeHg that stands out in comparison to other ecosystems. Surface soils in the large Mendall Marsh, about 17 km downstream from the contamination source, contained particularly high %MeHg (averaging 8%). In Mendall marsh soil porewaters, MeHg often accounted for more than half of total Hg. Salt marshes are areas of particular concern in the Penobscot River, for they are depositional environments for a Hg-contaminated mobile pool of river sediment, hot spots for net MeHg production, and sources of risk to marsh animals. We hypothesized that exceptionally low mercury partitioning between the solid and aqueous phases (with log Kd averaging ~4.5) drives high MeHg in Penobscot marshes. The co-occurrence of iron and sulfide in filtered soil porewaters, sometimes both above 100 µM, suggests the presence of nanoparticulate and/or colloidal metal sulfides. These colloids may be stabilized by high concentrations of aromatic and potentially sulfurized dissolved organic matter (DOM) in marsh soils. Thus, Hg in Penobscot marsh soils appears to be in a highly available for microbial methylation through the formation of DOM-associated HgS complexes. Additionally, low partitioning of MeHg to marsh soils suggests high MeHg bioavailability to animals. Overall, drivers of high MeHg in Penobscot marshes include elevated Hg in soils, low partitioning of Hg to solids, high Hg bioavailability for methylation, rapidly shifting redox conditions in surface marsh soils, and high rates of microbial activity.

Activated carbon thin-layer placement as an in situ mercury remediation tool in a Penobscot River salt marsh.

The efficacy of thin layer in situ soil amendments was tested as a potential tool for methylmercury (MeHg) risk mitigation in Penobscot River, ME, salt marsh. Salt marshes are sites of high MeHg accumulation within the Penobscot, and key targets for remediation. The study was a fully-crossed small plot study, with four treatments (activated carbon (AC), biochar, FeCl2, and lime) and unamended controls at two sites. Plots were monitored for two years. Porewater MeHg concentrations were the main endpoint, with impacts on sediment biogeochemistry as a secondary study goal. AC-based SediMite™ was effective in reducing MeHg, and to a less extent total Hg, in surficial pore waters. AC reduced MeHg concentrations by >90% at the one month time point, and continued to significantly reduce pore water MeHg through about a year. AC was less effective in reducing total Hg in pore water, yielding about 70% reduction at one month, and 50-65% reduction at 8months. Biochar provided lower, and more variable reduction in porewater MeHg, but was not effective in reducing total Hg. Biochar amendment also increased soil MeHg. Neither FeCl2 nor lime amendments reduced pore water Hg or MeHg levels. About 50% of AC treatment applied as SediMite™ pellets was retained in marsh soils after one year. This study is one of the first field trials of in situ amendment for MeHg remediation. Our results show that thin-layer AC placement is a potential remediation tool for Hg risk to biota, especially in marshes where net MeHg accumulation is often strong.

Activated carbon mitigates mercury and methylmercury bioavailability in contaminated sediments.

There are few available in situ remediation options for Hg contaminated sediments, short of capping. Here we present the first tests of activated carbon and other sorbents as potential in situ amendments for remediation of mercury and methylmercury (MeHg), using a study design that combined 2 L sediment/water microcosms with 14 day bioaccumulation assays. Our key end points were pore water concentrations, and bioaccumulation of total Hg and MeHg by a deposit-feeding oligochaete Lumbriculus variegatus. Four amendments were tested: an activated carbon (AC); CETCO Organoclay MRM (MRM); Thiol-SAMMS (TS), a thiol-functionalized mesoporous silica; and AMBERSEP GT74, an ion-exchange resin. Amendments were tested in four separate microcosm assays using Hg-contaminated sediments from two freshwater and two estuarine sites. AC and TS amendments, added at 2-7% of the dry weight of sediments significantly reduced both MeHg concentrations in pore waters, relative to unamended controls (by 45-95%) and bioaccumulation of MeHg by Lumbriculus (by between 30 and 90%). Both amendments had only small impacts on microcosm surface water, sediment and pore water chemistry, with the exception of significant reductions in pore water dissolved organic matter. The effectiveness of amendments in reducing bioaccumulation was well-correlated with their effectiveness in increasing sediment:water partitioning, especially of MeHg. Sediments with low native sediment:water MeHg partition coefficients were most effectively treated. Thus, in situ sediment sorbent amendments may be able to reduce the risk of biotic Hg and MeHg uptake in contaminated sediments, and subsequent contamination of food webs.

Historical contamination of the Anacostia River, Washington, D.C.

The tidal Anacostia River in Washington DC has long been impacted by various sources of chemical pollution over the past 200 years. To explore more recent inputs of various chemicals, six sediment cores were collected for dating and chemical analysis in the downstream section of the tidal Anacostia River. Profiles of contaminants in sediment cores can be useful in determining management direction and effectiveness of pollution controls over time. There were two main objectives for this investigation: (1) determine current sediment contaminant levels; (2) determine a historical perspective of the sediment changes in contamination using (137)Cs and (210)Pb dating. The determination of an age-depth relationship using (210)Pb and (137)Cs dating gave somewhat different results, suggesting that the assumptions of (210)Pb dating were not met. Using the (137)Cs horizon allowed an assignment of approximate sediment accumulation rates and hence an age-depth relationship to contaminant events in the upper portions of the cores. Total PAHs showed higher concentrations at depth and lower surface concentrations. In the upper sections, PAHs were a mixture of combustion and petrogenic sources, while at depth the signature appeared to be of natural origins. Total PCBs, DDTs and chlordane concentrations showed a maximum in recent sediments, decreasing towards the surface. PCBs had lower molecular weight congeners near the surface and higher molecular weights at depth. A phthalate ester, DEHP, appeared in the mid 1940-1950s, and decreased towards the surface. Trace elements fell roughly into three groups. Fe, Mn, and As were in approximately constant proportion to Al, except in some deeper, sandy sediments, where they showed enrichments linked to redox conditions. Ag, Cd, Cu, Hg, Pb, and Zn had low concentrations in the deepest sediments, high concentrations at mid-depths, and declines to intermediate levels at the surface. Ni and Cr followed neither of these patterns closely. We observed that many contaminants appeared in the Anacostia sediments at various times, and reached relatively high concentrations in the past, but are now showing declines in loadings. In some cases, such as PCBs, DDT, chlordane, and Pb from leaded gasoline, these declines can be clearly linked to the discontinuation of their use for environmental reasons. For other contaminants (e.g., PAHs, DEHP, selected metals) these declines are more likely the result of changes in production, usage and waste control.

The effects of copper pollution on fouling assemblage diversity: a tropical-temperate comparison.

BACKGROUND: The invasion of habitats by non-indigenous species (NIS) occurs at a global scale and can generate significant ecological, evolutionary, economic and social consequences. Estuarine and coastal ecosystems are particularly vulnerable to pollution from numerous sources due to years of human-induced degradation and shipping. Pollution is considered as a class of disturbance with anthropogenic roots and recent studies have concluded that high frequencies of disturbance may facilitate invasions by increasing the availability of resources. METHODOLOGY/PRINCIPAL FINDINGS: To examine the effects of heavy metal pollution as disturbance in shaping patterns of exotic versus native diversity in marine fouling communities we exposed fouling communities to different concentrations of copper in one temperate (Virginia) and one tropical (Panama) region. Diversity was categorized as total, native and non-indigenous and we also incorporated taxonomic and functional richness. Our findings indicate that total fouling diversity decreased with increasing copper pollution, whether taxonomic or functional diversity is considered. Both native and non-indigenous richness decreased with increasing copper concentrations at the tropical site whereas at the temperate site, non-indigenous richness was too low to detect any effect. CONCLUSIONS/SIGNIFICANCE: Non-indigenous richness decreased with increasing metal concentrations, contradicting previous investigations that evaluate the influence of heavy metal pollution on diversity and invasibility of fouling assemblages. These results provide first insights on how the invasive species pool in a certain region may play a key role in the disturbance vs. non-indigenous diversity relationship.

Shellfish face uncertain future in high CO2 world: influence of acidification on oyster larvae calcification and growth in estuaries.

BACKGROUND: Human activities have increased atmospheric concentrations of carbon dioxide by 36% during the past 200 years. One third of all anthropogenic CO(2) has been absorbed by the oceans, reducing pH by about 0.1 of a unit and significantly altering their carbonate chemistry. There is widespread concern that these changes are altering marine habitats severely, but little or no attention has been given to the biota of estuarine and coastal settings, ecosystems that are less pH buffered because of naturally reduced alkalinity. METHODOLOGY/PRINCIPAL FINDINGS: To address CO(2)-induced changes to estuarine calcification, veliger larvae of two oyster species, the Eastern oyster (Crassostrea virginica), and the Suminoe oyster (Crassostrea ariakensis) were grown in estuarine water under four pCO(2) regimes, 280, 380, 560 and 800 microatm, to simulate atmospheric conditions in the pre-industrial era, present, and projected future concentrations in 50 and 100 years respectively. CO(2) manipulations were made using an automated negative feedback control system that allowed continuous and precise control over the pCO(2) in experimental aquaria. Larval growth was measured using image analysis, and calcification was measured by chemical analysis of calcium in their shells. C. virginica experienced a 16% decrease in shell area and a 42% reduction in calcium content when pre-industrial and end of 21(st) century pCO(2) treatments were compared. C. ariakensis showed no change to either growth or calcification. Both species demonstrated net calcification and growth, even when aragonite was undersaturated, a result that runs counter to previous expectations for invertebrate larvae that produce aragonite shells. CONCLUSIONS AND SIGNIFICANCE: Our results suggest that temperate estuarine and coastal ecosystems are vulnerable to the expected changes in water chemistry due to elevated atmospheric CO(2) and that biological responses to acidification, especially calcifying biota, will be species-specific and therefore much more variable and complex than reported previously.

Cadmium distribution in coastal sediments and mollusks of the US.

Cadmium (Cd) concentrations in the coastal United States were assessed using the National Status and Trends (NS&T) Mussel Watch dataset, which is based on the analysis of sediments and bivalves collected from 280 sites since 1986. Using the 1997 sediment data, Pearson correlation (r=0.44, p<0.0001) suggested that Cd distributions in sediment can, be to some extent, explained by the proximity of sites to population centers. The 2003 tissue data indicated that "high" Cd concentrations (greater than 5.6 microg/g dry weights [dw] for mussel and 5.4 microg/g dw for oysters) were related to salinity along the East and Gulf coasts. Along the West coast, however, these "high" sites appeared to be related to upwelling phenomenon. Additionally, sedimentary diagenesis was found to be the most likely explanation of why sediment and mollusk Cd content were not well correlated.

Modeling arsenic in the Patuxent Estuary.

A water quality model was developed to track the fate and transport of four arsenic species in the Patuxent Estuary: arsenate (As(V)), arsenite (As(III)), methylarsonate (MMA), and dimethylarsinate (DMA). Processes simulated include mass transport, solid-liquid partitioning with suspended solids, uptake and transformation of As(V) by phytoplankton, oxidation of As(III), demethylation of MMA and DMA, and settling/deposition/ resuspension of particulate arsenic in the water column. A sediment module was also developed and linked with the water column to generate fluxes of inorganic arsenic from the sediment bed. The arsenic model was calibrated using water quality data from the Patuxent Estuary over a period ranging from May 24, 1995 to October 29, 1997. Model results indicated that transformation of arsenic by phytoplankton is not a significant source of DMA to the lower Patuxent. Instead, results suggested that the primary source of methylated arsenic (DMA and MMA) to the lower estuary is beyond the downstream boundary (Chesapeake Bay). However, model results supported the hypothesis that flux of arsenic from the sediment is a significant source of inorganic arsenic to the lower estuary.

Differences in the bioaccumulation of arsenic by oysters from Southeast coastal US and Chesapeake Bay: environmental versus genetic control.

The potential sources of relatively great concentrations of arsenic (As) in oysters from the Southeastern United States coast was examined in a study conducted from August 1998 through October 1999. A transplant experiment was conducted to determine whether genetic or environmental differences accounted for the observed difference between Southeastern oysters, and oysters elsewhere on the east coast. Oysters originating in South Carolina (a region where As in oysters is usually greater) and Maryland (a region where arsenic is oysters is less) were reciprocally transplanted to determine whether site of growth or site of origin would determine the accumulation of As. To examine the potential role of various potential sources of As exposure on the concentrations of As in oysters, samples of native oysters, water, pore water and suspended particles were collected and analyzed for As monthly, while the sediments were examined four times during the year. Concentrations of As in transplanted oysters matched the concentrations of As in oysters native to the area in which they were grown, rather than that of oysters from their site of origin. Oysters from South Carolina had average concentrations of As approximately 3.2 times that of oysters from Maryland. This enrichment was similar to enrichments of water (3.4 times), sediment (2.5 times), suspended particles (1.7 times), and pore water (3.1 times) from South Carolina compared to Maryland. This supports the hypothesis that the cause of the apparent As enrichments in the Southeastern oysters is environmental, but leaves the question of the primary source for arsenic incorporation by oysters open.