Behavior of mercury in the Patuxent River estuary

An overview of a comprehensive study of the behavior and fate of mercury in the estuarine Patuxent River is presented. Total Hg (Hg_T) and methylmercury (MeHg) exhibited weakly non-conservative behavior in the estuary. Total Hg concentrations ranged from 6 ng L^-1 in the upper reaches of the sub-urbanized tidal freshwater river to <0.5 ng L^-1 in the mesohaline lower estuary. Filterable (0.2 µm) Hg_T ranged from 0.2 to 1.5 ng L^-1. On average, MeHg accounted for <5% of unfiltered Hg_T and <2% of filterable Hg_T. Dissolved gaseous section Hg (DGHg) concentrations were highest (up to 150 pg L^-1) in the summer in the mesohaline, but were not well correlated with primary production or chlorophyll a, demonstrating the complex nature of Hg⁰ formation and cycling in an estuarine environment. Organic matter content appeared to control the Hg_T content of sediments, while MeHg in sediments was positively correlated with Hg_T and organic matter, and negatively correlated with sulfide. MeHg in sediments was low (0.1 to 0.5% of Hg_T). Preliminary findings suggest that net MeHg production within sediments exceeds net accumulation. Although Hg_T in pore waters increased with increasing sulfide, bulk MeHg concentrations decreased. The concentration of MeHg in sediments was not related to the concentration of Hg_T in pore waters. These observations support the hypothesis that sulfide affects the speciation and therefore bioavailability of dissolved and/or solid-phase Hg for methylation. Comparison with other ecosystems, and the negative correlation between pore water sulfide and sediment MeHg, suggest that sulfide limits production and accumulation of MeHg in this system.     

Mercury dynamics in Tivoli South Bay, a freshwater tidal mudflat wetland in the Hudson River

The accumulation of total mercury (Hg_T) andmethylmercury (MeHg) was evaluated in sediments ofTivoli South Bay, a freshwater tidal mudflat wetlandin the Hudson River National Estuarine ResearchReserve system. Hg_T concentrations in sedimentcores were measured to evaluate the spatialvariability of Hg_T deposition, and to establisha chronology of Hg_T accumulation. Cores takenfrom the northern, middle, and southern sections ofthe bay had similar distribution patterns andconcentrations of Hg_T, suggesting a common sourceof Hg_T throughout the bay. Sedimentconcentrations ranged from 190 to 1040 ng Hg g^–1,2 to 10 times greater than concentrations expected insediments from non-anthropogenic sources. Hg_Tdeposition rates were similar in different regions ofthe bay, and increased from 200 ng Hg cm^–2yr^–1in the 1930s to a maximum of 300 ngHg cm^–2 yr^–1 in the 1960s. Deposition rateshave steadily declined since the 1970s and arecurrently at 80 ng Hg cm^–2 yr^–1. Transportof Hg_T by tidal waters from the Hudson River islikely the main source of Hg_T in the bay.Distribution patterns and absolute concentrations ofMeHg in sediment cores were similar throughout thebay, with concentrations ranging from 0.43 to 2.95ng g^–1. Maxima in MeHg concentration profilesoccurred just below the sediment-water interface andat a depth of 30 cm. The maximum at 30 cm wascoincident with maximum Hg_T concentrations. MeHgconcentrations in suspended particulate matter (SPM)from the Hudson River suggest that MeHg in the baycould be derived from riverine SPM rather than formedin situ.     

Methylmercury concentrations and production rates across a trophic gradient in the northern Everglades

Methylmercury (MeHg) concentrations and production rates were examined along with sulfur biogeochemistry in Everglades sediments in March, July and December, 1995, as part of a large, multi-investigator study, the Aquatic Cycling of Mercury in the Everglades (ACME) project. The sites examined constitute a trophic gradient, generated from agricultural runoff, across the Everglades Nutrient Removal (ENR) Area, which is a re-constructed wetland, and Water Conservation Areas (WCA) 2A, 2B and 3 in the northern Everglades. MeHg concentrations and %MeHg (MeHg as a percent of total Hg) were lowest in the more eutrophic areas and highest in the more pristine areas in the south. MeHg concentrations ranged from <0.1 ng gdw^-1 sediment in the ENR to 5 ng gdw^-1 in WCA3 sediments; and MeHg constituted <0.2% of total Hg (Hg_T) in ENR, but up to about 2% in two sites in WCA2B and WCA3. Methylation rates in surficial sediments, estimated using tracer-level injections of²⁰³ Hg(II) into intact sediment cores, ranged from 0 to 0.12 d^-1, or about 1 to 10 ng g^-1 d^-1when the per day values are multiplied by the ambient total Hg concentration. Methylation was generally maximal at or within centimeters of the sediment surface, and was never observed in water overlying cores. The spatial pattern of MeHg production generally matched that of MeHg concentration. The coincident distributions of MeHg and its production suggest that in situ production controls concentration, and that MeHg concentration can be used as an analog for MeHg production. In addition, the spatial pattern of MeHg in Everglades sediments matches that in biota, suggesting that MeHg bioaccumulation may be predominantly a function of the de novo methylation rate in surficial sediments.Sulfate concentrations in surficial pore waters (up to 400 µm), microbial sulfate-reduction rates (up to 800 nm cc^-1 d^-1) and resultant pore water sulfide concentrations (up to 300 µm) at the eutrophic northern sites were all high relative to most freshwater systems. All declined to the south, and sulfate concentrations in WCA2B and in central WCA3 resembled those in oligotrophic lakes (50–100 µm). MeHg concentration and production were inversely related to sulfate reduction rate and pore water sulfide. Control of MeHg production in the northern Everglades appears to mimic that in an estuary, where sulfate concentrations are high and where sulfide produced by microbial sulfate reduction inhibits MeHg production.     

Benthic transfer and speciation of mercury in wetland sediments downstream from a sewage outfall

In order to evaluate the role of hypoxic conditions of overlying water in the benthic flux and speciation of Hg, we analyzed sediment cores from hypoxic or oxic sites downstream from a sewage outfall in the Damyang Riverine Wetland, Korea. Each core was analyzed for total Hg (THg), monomethylmercury (MMHg), and elemental Hg (Hg⁰) from sediment, and for THg and MMHg from pore water. Hypoxic conditions of the overlying water near the sewage outfall were associated with a peak production of Hg⁰, but the lowest production of MMHg, in the upper 2 cm sediments. The benthic fluxes of THg and MMHg were estimated at 130-2109 ng m⁻² day⁻¹ and −12 to 260 ng m⁻² day⁻¹, respectively. The order of MMHg flux from sediment to overlying water at each site did not follow the order of MMHg concentration in sediment, but was highest in hypoxic water conditions. The results suggest that maintaining oxic conditions in wetland water is important for decreasing the transfer of MMHg from sediment into overlying water.     

MMHg production and export from intertidal sediments to the water column of a tidal lagoon (Arcachon Bay,France)

Hg cycling in biologically productive coastal areas is of special importance given the potential for bioaccumulation of monomethylmercury (MMHg) into aquatic organisms. Field experiments were performed during three different seasons in Arcachon Bay, a mesotidal lagoon (SW France), to assess the variability of the water column concentrations, sediment–water exchanges and potential formation and degradation of MMHg. The objectives were to evaluate the contribution of intertidal mudflats to MMHg production and the various pathways of Hg species export. Dissolved and bulk concentrations of Hg species in the water column downstream of tidal flats were measured throughout several tidal cycles. The Hg benthic fluxes at the sediment–water interface were determined by means of benthic chambers for three different stations. Hg methylation and demethylation potentials were determined in surficial sediments and the water column using isotopic tracers. The tidal surveys demonstrated that benthic remobilization of Hg occurs primarily in association with sediment erosion and advection during ebb tide. However, elevated dissolved Hg concentrations observed at low tide were found to be caused by a combination of pore-waters seeping, benthic fluxes and methylation in the water column. Benthic fluxes were more intense during late winter conditions (median MMHg and inorganic Hg (IHg) fluxes: 64 and 179 pmol m^?2 h^?1, respectively) and subsequently decreased in spring (median 0.7 and ?5 pmol m^?2 h^?1, respectively) and fall (median ?0.4 and ?1.3 pmol m^?2 h^?1, respectively). The trends in methylation and demethylation potentials were at the opposite of the fluxes, two times lower during winter than for spring or fall conditions. In this tidal environment, MMHg production in surface sediments and its subsequent release is estimated to be the major source of MMHg to the water column during winter and spring time. However, during the more productive summer period, the Hg methylation extent in the water column may be very significant and equivalent to the sediment contribution.     

A Michaelis–Menten type equation for describing methylmercury dependence on inorganic mercury in aquatic sediments

Methylation of mercury (Hg) is the crucial process that controls Hg biomagnification along the aquatic food chains. Aquatic sediments are of particular interest because they constitute an essential reservoir where inorganic divalent Hg (Hg^II) is methylated. Methylmercury (MeHg) concentrations in sediments mainly result from the balance between methylation and demethylation reactions, two opposite natural processes primarily mediated by aquatic microorganisms. Thus, Hg availability and the activity of methylating microbial communities control the MeHg abundance in sediments. Consistently, some studies have reported a significant positive correlation between MeHg and Hg^II or total Hg (Hg_T), taken as a proxy for Hg^II, in aquatic sediments using enzyme-catalyzed methylation/demethylation mechanisms. By compiling 1,442 published and unpublished Hg_T–MeHg couples from lacustrine, riverine, estuarine and marine sediments covering various environmental conditions, from deep pristine abyssal to heavily contaminated riverine sediments, we show that a Michaelis–Menten type relationship is an appropriate model to relate the two parameters: MeHg = aHg_T/(K _m  + Hg_T), with a = 0.277 ± 0.011 and K _m  = 188 ± 15 (R ² = 0.70, p < 0.001). From K _m variations, which depend on the various encountered environmental conditions, it appears that MeHg formation and accumulation are favoured in marine sediments compared to freshwater ones, and under oxic/suboxic conditions compared to anoxic ones, with redox potential and organic matter lability being the governing factors.     

Distribution of surface soil mercury of Wuda old mining area,Inner Mongolia,China

In this study, mercury (Hg) concentrations in dustfall and topsoil were investigated. Three hundred forty-four samples were collected, including dustfall and topsoil samples, across an area of ～180 km² in Wuda, China. Dustfall Hg concentration in Wuda ranged from 10 to 6453 ng·g^?1_, with an average of 305 ng·g^?1, and topsoil Hg concentration ranged from 3 to 1537 ng·g^?1, with an average value of 135 ng·g^?1. The average dustfall Hg concentrations in the coalfield, industrial park, and urban areas were 289 ng·g^?1, 809 ng·g^?1, and 160 ng·g^?1, respectively, and the corresponding average topsoil Hg concentrations were 216 ng·g^?1, 242 ng·g^?1, and 91 ng·g^?1. Hg concentrations were significantly higher in the coalfield, industrial park, and urban areas compared with background values for Wuda and China tide soil. The coal Hg concentrations ranged from 273 to 346 ng·g^?1, with an average value of 317 ng·g^?1. Comparison of the Hg concentrations of Wuda coal with other regions and countries, indicated that Hg concentrations were significantly enriched in coal, highlighting that coal is the primary Hg source for Wuda District. While coal fires provided the primary source of Hg, some higher Hg values were caused by factors such as gangue hills and coalfield topography, the use of activated carbon with HgCl₂ as a catalyst in the industrial park, and several coal washeries in wasteland areas. In addition to atmospheric Hg, underground coal seam emissions served as another potential Hg source in the coalfield. The surface soil Hg in the coalfield and industrial park areas should be given closer attention in the future.     

Dissolved and suspended mercury. species in the Wabigoon River (Ontario,Canada): seasonal and regional variations

Seasonal and regional variations in the speciation, sediment-water partitioning, and dynamics of mercury (Hg) were studied at selected sites along the Hg-polluted Wabigoon River, and at unpolluted headwater and tributary sites, during April–September, 1979. ‘Dissolved’ and ‘particulate’ forms of Hg in the water were separated by continuous-flow centrifugation in the field. The Hg and other pollutants such as wood chips and salt had been discharged from a chlor-alkali plant and paper mill at Dryden, Ontario. Concentrations and loadings of particulate methyl mercury (CH₃Hg⁺) and total particulate Hg (and loadings of total ‘dissolved’ Hg) were greatest during the spring flood (April-May) owing to accelerated resuspension and transport of sediments. Concentrations of ‘dissolved’ CH₃Hg⁺, however, were highest in the summer (July–September), probably reflecting stimulation of microbial methylating activity by elevated temperatures, together with factors such as reduced levels of metal-scavenging particulates and minimal dilution by runoff. Total dissolved Hg concentrations were relatively high in September at polluted sites only, possibly because of desorption from sediments due to elevated concentrations of Cl⁻ ions. Loadings of dissolved CH₃Hg⁺ tended to be high in the summer but were generally depressed (suggesting sorption by suspended particles) during the major spring-flood episode in May. During July–August dissolved CH₃Hg⁺ was a function of total dissolved Hg, suggesting rapid biomethylation of desorbed inorganic Hg; but in general dissolved and suspended CH₃Hg⁺ levels depended on environmental variables and were unrelated to total Hg concentrations. In the summer only, total dissolved Hg was a function of dissolved Cl⁻. Hg species in particulates were associated with sulfides, hydrated Fe and Mn oxides, organic matter (notably high molecular weight humic and humic-Fe components), and selenium (Se); but CH₃Hg⁺ and total Hg differed in their specific preferences for binding agents, implying that binding sites discriminate between CH₃Hg⁺ and Hg²⁺ ions. CH₃Hg⁺ was associated with sulfide and (in the spring only) with Fe oxides, whereas total Hg was associated with organic matter and Se and with DTPA- and NaOH-extractable Fe in the spring but with Mn oxide and NaOH-extractable organics in the summer. Sulfides were most abundant in May, indicating that they were eroded from bottom sediments, but Fe and Mn oxides were most abundant in the summer, probably owing to activities of filamentous iron bacteria and other micro-organisms. Particulate Hg was 98–100% nonextractable by mild solvents such as Ca acetate, CaCl₂, dilute acetic acid, and (at polluted sites only) DTPA solutions, suggesting that the particulate Hg mobilized in the spring may not be readily available to organisms; association with Se and high molecular weight humic matter also supports this hypothesis. Hg probably becomes more bio-available in the summer, as suggested by the upsurge in dissolved CH₃Hg⁺ and total dissolved Hg levels, and by increases in the solubility of particulate Hg in acetic acid, DTPA, H₂O₂, and NaOH solutions, as well as an increase in the relative importance of lower molecular weight fractions of NaOH-extractable Hg (in September). Regional variations in Hg speciation and partitioning reflected a gradient in sediment composition from wood chips near Dryden to silt-clay mud further downstream. Hg in silt-clay mud relatively far (> 35 km) downstream from the source of pollution or in unpolluted areas appeared to be more readily solubilized by Cl⁻ ions or chelators such as DTPA, more readily methylated (as indicated by downstream increases in dissolved CH₃Hg⁺ levels and CH₃Hg⁺/total Hg ratios), and was to a greater degree organically bound (H₂O₂-extractable), and thus was probably more bio-available, than Hg in wood-chip deposits. Possible explanations include weaker binding of Hg by the mud, the more finely divided state of the mud, and improved microbial growth at lower concentrations of toxic pollutants. Owing to enrichment in sulfides and Fe oxides, resuspended wood-chip sediments were especially efficient scavengers of CH₃Hg⁺. The results indicate that in any pollution abatement plan aimed at lowering the Hg levels in the biota of lakes fed by the Wabigoon River, immobilization, removal, or detoxification of dissolved as well as particulate forms of Hg in the river would probably have to be considered. Possibly, Hg species could be ‘scrubbed’ from the river water by increasing the suspended load and by sedimentation and treatment with Hg-binding agents in special receiving basins.     

Geochemistry of mercury in an intertidal flat of the Scheldt estuary

Sediments were sampled on the ‘Groot Buitenschoor’, an intertidal flat located at about 60 km from the Scheldt's river mouth. Hg concentrations ranged from 30 to 1756 ng g⁻¹. The concentrations were strongly correlated with fine grain fraction, organic matter content and sulphide concentrations. Incubation experiments were performed in order to determine the potential methylation rate of Hg as well as biotic and abiotic factors influencing this transformation. About 1 to 2% of the added inorganic Hg is converted into methylmercury. This conversion rate points to the same equilibrium ratio as was observed in natural sediments, indicating an equilibrium between methylation and demethylation reactions in the sediments. Incubation of a sterilised sediment sample significantly decreased the methylation rate, but the methylmercury concentrations observed are still ten times higher than the natural (unspiked) sediment. This result could be due to a chemical (non-enzymatic) methylation of mercury. Sulphate reducing bacteria are the main species responsible for the methylation of Hg at this site. Addition of Na₂MoO₄, a specific inhibitor of sulphate reducing bacteria, decreased the methylation rate to the abiotic level (sterilised sediment). High sulphate reduction rates, however, lead to lower methylation rates. Increased formation of sulphides due to microbial sulphate reduction leads to enhanced HgS formation and this reaction competes with the methylation process. HgS is in fact the major product formed by the reaction of sulphate reducing bacteria with Hg species. About 50% of the Hg spiked to the sediments is transformed into HgS during the incubation experiments, and that compound is practically unavailable for methylation in contrast to other bound forms of Hg.     

Biogeochemical cycling of methylmercury at Barn Island Salt Marsh,Stonington, CT,USA

Monomethylmercury (MMHg) is toxic, and is the primary form of Hg thatbioaccumulates in the food web. An understanding of its distribution,production, and transport is needed. Prior investigations indicate thatmethylation is mediated by sulfate-reducing bacteria, yet limited in highsulfate environments. High rates of microbial respiration and strong oxygengradients are found in salt marshes. It is hypothesized that significant in situ methylation takes place in the redox transition zone of sulfate rich( 28 mM) salt marsh sediment. Results from a water column surveyof Barn Island Salt Marsh in October 1996 showed that ca. 61pmol m^-2 d^-1 of dissolved MMHg were discharged toadjacent coastal waters, while 16 pmol m^-2 d^-1 ofparticulate MMHg were entrained in the marsh, implying an in situsource. In-sediment MMHg production rates were determined by²⁰³Hg radiotracer studies. At the surface, methylation rates variedover both long (i.e., 100's m; 11–1120 pmol m^-2 d^-1) andshort (i.e., 10 cm; 11–108 pmol m^-2 d^-1) spatial scales. Methylation rate profiles from both low and high MMHg production sitesexhibited an exponential decrease below the redox transition zone. Porewater was collected with multi-chambered in situ dialysis (30 kDa)samplers [Peepers] and analyzed for MMHg. Temporal differences in porewater MMHg accumulation (i.e., May > September > November)were found. Results from May showed a significant gradient at thesediment water interface. The transport out of the sediments estimated byFick's Law (ca. 390 pmol MMHg m-2 d^-1) suggeststhat MMHg entered the marsh water by diffusion. This workdemonstrates the potential for elevated in situ Hg methylation in highsulfate environments.     

Mercury Concentration in Sediment Cores from Sundarban Mangrove Wetland,India

The work presents an extended database (n = 123) of total mercury (T_Hg) in fine-grained sediment fraction (<63 μm) of core samples in 10 sampling stations of the Sundarban mangrove wetland, India, formed at the estuarine realm of the Hugli (Ganga) River. Results revealed a wide range of spatial, seasonal, and intertidal flat variations of T_Hg (7.3 to 93.3 ng/g) with a definite enhancement level at the lower stretch of the estuary, which has extreme mangrove vegetation. An overall enrichment of T_Hg in surface/subsurface layers of the core is tentatively explained by remobilization and resuspension of the metal from deeper sediments (36–40 cm). A strong positive correlation was observed between the Hg and clay fraction content of the sediments, while correlations of Hg with organic carbon was poor. Based on the index of geoaccumulation (I_geo), enrichment factor (EF), and anthropogenic factor (AF) values, it is suggested that the sediments of Sundarban were found to be less polluted with respect to total mercury. The data reported are a useful baseline for T_Hg in Sundarban and would be of importance in future sediment quality studies.     

Mercury accumulation in sediment cores and along food chains in two regions of the Brazilian Pantanal

The Pantanal is a 140,000 km² floodplain wetland stretching acrosswestern Brazil and parts of Bolivia and Paraguay. Gold mining withmercury (Hg) amalgamation has thrived since 1980 along its northern rim. We quantified Hg accumulation in sediment cores (N = 5) and food chainsin this general region of the northern Pantanal and in a reference region,200 km deeper into the wetland (Acurizal). Cores were dated with²¹⁰Pb and ¹³⁷Cs using direct gamma-assay. Total Hg wasanalyzed by cold-vapor atomic fluorescence using a gold-meshpre-concentration trap. Average pre-1940 Hg accumulation in cores wasnot significantly different (N = 5, p= 0.14) between both regions andcomparable with rates calculated for global reference sites. Post gold-rushHg (post-1980) deposition averaged 55 ± 11.3 g m^-2yr^-1 in the northern impacted region and was more than 1.5 timeshigher than the post-1980 rate in Acurizal, implying a regional Hg effectof gold mining. Post-1980 Hg accumulation in Acurizal, in turn, was 2.1times the rate reported for a global reference during that time period,suggesting an additional basin-wide effect over such reference sites. Bycombining our core data with assessments of the size of the impacted areaand the amount of Hg released to the region since 1980, we estimated thatonly 2–8% of this Hg was recovered as a sedimentary signal. Theremainder of the Hg was lost to the atmosphere, downstream areas, orstored in biota. Hg concentrations in surface sediments in the northernPantanal (45.5 ± 5.5 ng g_dry ^-1) were significantlyhigher than those in our reference region (29.1 ± 0.7ng g_dry ^-1). Hg levels in primary producers were alsoelevated in the northern Pantanal. Eichhornia crassipes rootscontained 2.7–3.0 times more mercury than shoots in both regions and Salvinia auriculata, suggested as a biological monitor for Hg pollution,contained almost four times more mercury in the northern Pantanal (90.7± 9.1 ng g_dry ^-1) than in Acurizal (24.5 ± 3.3ng g_dry ^-1). Plant grazers and scavengers, such as apple snails(Pomacea sp.) and adult water beetles (Fam. Hydrophilidae), werelow in Hg, confirming previous data showing that the channeling of mercuryfrom lower to higher trophic levels along herbivorous links was inefficientcompared to transfer along carnivorous links. Collections of 12–16individuals of four species of Characidae (Aphyocharax sp., Tetragonopterus sp., Serrasalmus spiropleura and Pygocentrisnattereri) in both regions showed elevated Hg body burdens in bothpiranhas S. spiropleura and P. nattereri from the northernPantanal (149.9 ± 84.2 and 302.2 ± 159.1ng g_dry ^-1, respectively). Fish length for each species was notstatistically different between regions. P. nattereri length correlatedsignificantly (p<0.001) with Hg content in both regions, but the slopeof the regression in the northern Pantanal was 2.6 times the slope for theAcurizal collection, indicating an elevated rate of biomagnification in theHg-impacted region. Signals of Hg use in mining can be quantified insediment core chronologies and biological tissues, although species atdifferent trophic levels show dissimilar impacts. Mechanisms involved in Hgmagnification along food chains deserve more attention, particularly intropical regions where the threat of chronic exposure to this neurotoxinmay have the greatest implications for biodiversity.     

Ecotoxicological Risk Assessment of Polychlorinated Biphenyls (PCBs) in Bank Sediments from along the Yamuna River in Delhi,India

The River Yamuna originates from the Yamunotri glacier of the Himalayas and travels 22 km in the Delhi region. The river is used for various purposes in Delhi including drinking water supply. Twenty-eight polychlorinated biphenyls (PCBs) congeners were measured in bank sediments along the river, and their ecotoxicological risk was evaluated. Concentrations of ∑28PCBs varied from 0.20–21.16 ng g^?1 (dry wt.) with mean and median values of 6.63 ng g^?1 and 5.84 ng g^?1 (±0.69 ng g^?1), respectively. The concentration of 12 dl-PCBs concentrations varied from 0.04–2.86 ng g^?1 with a mean of 1.04 ± 0.11 ng g^?1, and their toxic equivalency ranged between <0.01–28.67 pg WHO-TEQ g^?1 with a mean of 10.77 ± 1.06 pg WHO-TEQ g^?1. CB-37, CB-44, CB-114, and CB-118 congeners were dominant among all PCBs congeners. The tri-PCBs (49%) were the main contributors to the PCB homolog followed by tetra-PCBs (35%), and penta-PCB (14%). Because there are no environmental guidelines in India for PCBs in river and marine sediments, concentrations of PCBs and their toxic equivalents were compared in a screening-level assessment with established freshwater sediment quality guidelines and found lower than those guideline values, which suggests no adverse ecotoxicological effect.     

Distribution and bioaccumulation of butyltins in the edible gastropod Odontocymbiola magellanica

Butyltins (BTs) were found in sediments and body tissues of the edible gastropod Odontocymbiola magellanica, in which imposex has been recorded since 2000. BTs in sediments ranged from < MDL to 174.8?ng (Sn) g^?1 for TBT, < MDL to 19.2?ng (Sn) g^?1 for DBT, and < MDL to 71.8?ng (Sn) g^?1 for MBT. In body tissues BTs varied from??1 for TBT, DBT and MBT, respectively. BT concentrations were higher in gonads and digestive glands than in the albumen gland and foot (edible). The highest concentrations of BTs in both sediments and gastropods were found in the harbour area, decreasing with distance to the harbour and areas with less maritime traffic. The Biota-Sediment Accumulation Factor (BSAF) in the different organs was between 0.02–0.42, 0.09–0.35 and 0.08–5.25 for TBT, DBT and MBT, respectively. There were positive correlations between concentrations of BTs in sediments and gastropod body tissues, suggesting that xenobiotic accumulation in O. magellanica occurs mainly through contaminated sediments, rather than water or the food chain. Considering current sediment quality guidelines, our results indicate that acute toxic effects would be expected from TBT exposure, which represents a serious environmental threat for the benthic community. Although the levels of BTs found in the foot of this edible gastropod did not exceed the recommended Tolerable Daily Intake in polluted areas, they should be monitored to ensure the safety of seafood consumers. The alternative antifouling biocides Irgarol and Diuron were not detected in sediments.     

Concomitant Antibiotic and Mercury Resistance Among Gastrointestinal Microflora of Feral Brook Trout, Salvelinus fontinalis

Twenty-nine bacterial isolates representing eight genera from the gastrointestinal tracts of feral brook trout Salvelinus fontinalis (Mitchell) demonstrated multiple maximal antibiotic resistances and concomitant broad-spectrum mercury (Hg) resistance. Equivalent viable plate counts on tryptic soy agar supplemented with either 0 or 25?μM HgCl₂ verified the ubiquity of mercury resistance in this microbial environment. Mercury levels in lake water samples measured 1.5?ng?L^?1; mercury concentrations in fish filets ranged from 81.8 to 1,080?ng?g^?1 and correlated with fish length. The presence of similar antibiotic and Hg resistance patterns in multiple genera of gastrointestinal microflora supports a growing body of research that multiple selective genes can be transferred horizontally in the presence of an unrelated individual selective pressure. We present data that bioaccumulation of non-point source Hg pollution could be a selective pressure to accumulate both antibiotic and Hg resistant bacteria.     

Seasonal Variation of Acid Volatile Sulfide and Simultaneously Extracted Metals in Sediment Cores from the Pearl River Estuary

The simultaneously extracted metals/acid volatile sulfide (SEM/AVS) method is widely used to estimate the toxicity of metals in sediment. In this study, SEM and AVS concentrations were obtained by the cold-acid purge-and-trap technique during spring (April) and winter (December) at six sites in the Pearl River estuary. Total organic carbon, grain size distribution, and total metals were also measured in winter samples. AVS concentrations in spring sediments were slightly higher than those in winter sediments, except at site 2. AVS concentrations showed more distinct locational and temporal variation compared with SEM concentrations. Generally, AVS contents increased downcore, whereas SEM concentrations decreased slightly with depth. Higher SEM concentrations were observed in the west shoal (sites 2, 6, and 7) and site 4 (1.24 ～ 4.28 μmol?g^?1) compared with those at sites 1 and 3 (0.73 ～ 2.14 μmol?g^?1) in the middle shoal. Most SEM metals have a significant linear positive correlation with the total metals, especially for Cd, Zn, and Pb, which were easily extracted by 1 M HCl compared with Cr and Ni. According to the toxicity threshold value of 1.7 μmol?g^?1 for the difference of SEM-AVS, a toxic effect is expected at sites 1, 2, and 4 in spring and at sites 4, 6, and 7 in winter, which also indicates a relatively obvious seasonal variation in heavy metal bioavailability. However, comparisons between the total heavy metal concentrations in winter sediments with the sediment quality guidelines of ERLs/ERMs and TELs/PELs showed that adverse biological effects may occasionally occur at sites 2, 4, 6, and 7. Therefore, SEM/AVS prediction in conjunction with sediment quality guidelines can give a more reliable evaluation of the bioavailability of heavy metal in sediments.     

Mercury concentrations in Irish headwater lake catchments

An estimated 215,000 tonnes of mercury (Hg) have been emitted to the atmosphere from anthropogenic sources since the nineteenth century, igniting widespread environmental monitoring owing to its toxicity. The environmental fate of Hg is strongly determined by catchment characteristics, especially soil organic matter. In this study, concentrations and pools of Hg were determined for lakes and soils in upland peat-dominated catchments in Ireland to assess controls of aquatic Hg and soil response to changes in emissions. Headwater lakes in upland coastal regions were surveyed for water chemistry and total Hg (THg) during spring 2008. In addition, a sub-set of lakes (n = 5) were repeatedly sampled during 2009–2011, and their surface soils collected for Hg analysis, including a short (30 cm) peat core to assess temporal Hg fluxes using radiometric ²¹⁰Pb dating. Peat cores indicated a significant decrease in Hg deposition since the 1980s, in broad agreement with other ‘background’ regions. Total Hg was correlated with total organic carbon (TOC) in the survey and intensive study lakes (r = 0.70 and 0.45), indicative of the strong affinity of Hg to organic matter. At the intensive lakes, monomethylmercury (MMHg) made up 3.3 % of mean THg and exhibited a positive correlation with total SO₄ ^2? (r = 0.55). Further, both THg and MMHg were significantly correlated with conductivity (r = 0.48 and 0.54, respectively) potentially owing to marine inputs, and negatively correlated with pH (r = ?0.59 and ?0.56 respectively). Significant differences in THg (and MMHg) were observed between the five lakes, the highest concentrations (4.45 and 0.16 ng L^?1, respectively) tended to be associated with TOC in lakes and occurred at sites in the northwest, characterized by higher levels of soil organic matter (peat) and soil moisture relative to the other sites. In contrast, surface soil pools of THg ranged between 13.6 and 20.8 μg m^?2 across study sites and did not vary significantly, but were typical of global background regions. Nonetheless, the organic rich soils that dominate Ireland are a natural sink for THg, and peat harvesting for energy production may release long-term stores of Hg from deeper soil layers.     

Role of Organic Carbon Sources and Sulfate in Controlling Net Methylmercury Production in Riverbank Sediments of the South River,VA (USA)

Mercury (Hg) transport and methylmercury (MeHg) production in riverbank sediments are complex processes influenced by site-specific physical and biogeochemical conditions. The South River watershed in VA, USA, contains elevated concentrations of Hg in riverbank and floodplain sediments, which has the potential to methylate. The role of specific organic carbon sources in promoting methylation reactions in natural sediments under dynamic flow conditions is not well understood. Four saturated column experiments were conducted, including a control column, which received South River water as an influent solution, and three columns that received South River water amended with: acetate (5.8 mM); lactate (5.7 mM); and lactate (5.7 mM) with SO₄^2? (10.1 mM). The amendments were selected to promote growth of different microorganisms to gain an understanding of the microbial processes, controlling rates of methylation. The column receiving lactate and SO₄^2? had the highest MeHg concentrations in the effluent and in the pore water near the effluent at 1.8 and 4.9 μg L^?1, respectively. At the cessation of the column experiments, the lactate–sulfate column sediments contained the highest populations of enumerable sulfur-reducing bacteria and the highest solid-phase MeHg at 530 ± 100 ng g^?1 dry wt. from the interval closest to the influent. The results suggest that the form and availability of electron donors and acceptors are primary factors controlling rates of methylation in the South River sediment.     

Aspects of Bioavailability of Mercury for Methylation in Pure Cultures of Desulfobulbus propionicus (1pr3)

We have previously hypothesized that sulfide inhibits Hg methylation by decreasing its bioavailability to sulfate-reducing bacteria (SRB), the important methylators of Hg in natural sediments. With a view to designing a bioassay to test this hypothesis, we investigated a number of aspects of Hg methylation by the SRB Desulfobulbus propionicus, including (i) the relationship between cell density and methylmercury (MeHg) production, (ii) the time course of Hg methylation relative to growth stage, (iii) changes in the bioavailability of an added inorganic Hg (Hg_I) spike over time, and (iv) the dependence of methylation on the concentration of dissolved Hg_I present in the culture. We then tested the effect of sulfide on MeHg production by this microorganism. These experiments demonstrated that under conditions of equal bioavailability, per-cell MeHg production was constant through log-phase culture growth. However, the methylation rate of a new Hg spike dramatically decreased after the first 5 h. This result was seen whether methylation rate was expressed as a fraction of the total added Hg or the filtered Hg_I concentration, which suggests that Hg bioavailability decreased through both changes in Hg complexation and formation of solid phases. At low sulfide concentration, MeHg production was linearly related to the concentration of filtered Hg_I. The methylation of filtered Hg_I decreased about fourfold as sulfide concentration was increased from 10⁻⁶ to 10⁻³ M. This decline is consistent with a decrease in the bioavailability of Hg_I, possibly due to a decline in the dissolved neutral complex, HgS⁰.     

Effect of Elodea nuttallii Roots on Bacterial Communities and MMHg Proportion in a Hg Polluted Sediment

The objective of this study was to assess the effect of a rooted macrophyte Elodea nuttallii on rhizosphere bacterial communities in Hg contaminated sediments. Specimens of E. nuttallii were exposed to sediments from the Hg contaminated Babeni reservoir (Olt River, Romania) in our microcosm. Plants were allowed to grow for two months until they occupied the entirety of the sediments. Total Hg and MMHg were analysed in sediments where an increased MMHg percentage of the total Hg in pore water of rhizosphere sediments was found. E. nuttallii roots also significantly changed the bacterial community structure in rhizosphere sediments compared to bulk sediments. Deltaproteobacteria dominated the rhizosphere bacterial community where members of Geobacteraceae within the Desulfuromonadales and Desulfobacteraceae were identified. Two bacterial operational taxonomic units (OTUs) which were phylogenetically related to sulfate-reducing bacteria (SRB) became abundant in the rhizosphere. We suggest that these phylotypes could be potentially methylating bacteria and might be responsible for the higher MMHg percentage of the total Hg in rhizosphere sediments. However, SRB were not significantly favoured in rhizosphere sediments as shown by qPCR. Our findings support the hypothesis that rooted macrophytes created a microenvironment favorable for Hg methylation. The presence of E. nuttallii in Hg contaminated sediments should therefore not be overlooked.