Spatial and habitat-based variations in total and methyl mercury concentrations in surficial sediments in the San Francisco Bay-Delta

Recent studies indicate significant amounts of mercury (Hg) are annually transported into the San Francisco Bay-Delta (Bay-Delta) as a result of historic gold and Hg mining activities. We examined temporal and spatial variation in concentrations of total Hg (Hg(T)) and monomethylmercury (MMHg) in surficial sediments of various ecosystem types in the Bay-Delta. We sampled surficial sediments across the Bay-Delta system and found Hg(T) sediment concentrations in the central Delta were generally 100-200 ng g(-1) and increased westward through Suisun Bay to 250-350 ng g(-1). MMHg concentrations in the central Delta were between 1 and 3 ng g(-1), while those in sediments in the perimeter waterways and adjacent bays were less than 1 ng g(-1). Six sites were monitored monthly for over a year to identify seasonal changes in Hg sediment concentrations. Hgtau sediment concentrations ranged from 48 to 382 ng g(-1) and varied as a function of location not season. However, MMHg concentrations varied seasonally, increasing from 1 ng g(-1) during winter months to 6 ng g(-1) during spring and summer. Transects conducted at three marshes in the central Delta revealed MMHg sediment concentrations of 4-8 ng g(-1) at the interior and 2 ng g(-1) at the exterior of the marshes. Habitat type was a major factor controlling MMHg concentration and the MMHg to Hg(T) ratio in sediments of the Bay-Delta. MMHg was significantly correlated to Hgt (r2 = 0.49) in marsh sediments.     

Polybrominated diphenyl ether trends in eggs of marine and freshwater birds from British Columbia, Canada, 1979-2002

Temporal, spatial, and interspecific trends in polybrominated diphenyl ether (PBDE) flame retardants were determined in eggs of marine and freshwater bird species from the province of British Columbia, Canada. Temporal trends in the Fraser River estuary, 1983-2002, were examined by analysis of eggs of great blue herons (Ardea herodias) and from the Strait of Georgia marine ecosystem, 1979-2002, in eggs of double-crested cormorants (Phalacrocorax auritus). Results were compared to those from eggs of the osprey (Pandion haliaetus) taken along the lower Fraser River and along the Columbia River near Castlegar, British Columbia, and of a pelagic seabird, the Leach's storm-petrel (Oceanodroma leucorhoa), collected at a colony on the Queen Charlotte Islands. Mean concentration of sigmaPBDE, 455 microg/kg w.w., were highest in heron eggs collected in 2002 from the Fraser estuary. Concentrations in eggs of cormorants and ospreys taken from sites of varying urban influence tended to be about half that value. Leach's storm petrel eggs had only trace amounts of sigmaPBDE (3.38 microg/kg), despite having similar concentrations of PCBs and organochlorine pesticides to the other species. PBDEs increased exponentially with a doubling time of 5.7 years in eggs of both herons and cormorants. Over this period of increasing PBDEs, major chlorinated hydrocarbons, such as PCBs and DDE, were stable or decreased. The PBDE pattern was relatively consistent in most years and sites, with BDEs 47 > 100 > 99 > 153 > 154 > 28 > 183. This was interpreted as evidence of technical pentaBDE formulations as primary sources of the contamination, with the octaBDE formulations as secondary. Higher resolution analysis of a subsample of the eggs revealed the presence of up to nine other congeners, including BDE209 (range: 0.9-1.8 microg/kg), indicating exposure and uptake of decaBDE sourced congeners in North American foodchains. At some locations, concentrations of pentabrominated congeners and mixtures in fish are approaching levels potentially toxic to fish-eating birds, based on rodent studies and calculations of dietary intake from fish data.     

Decrease in net mercury methylation rates following iron amendment to anoxic wetland sediment slurries

The rate of mercury methylation in anoxic wetland sediments is affected by the concentration of bioavailable complexes between Hg and sulfide. Previous research with pure bacterial cultures has shown that addition of ferrous iron reduces the net rate of mercury methylation by decreasing the concentration of dissolved sulfide. To assess the possibility of using this approach to decrease net mercury methylation in restored and constructed wetlands, laboratory experiments were conducted by adding Hg(II) and Fe(II) to sediments collected from six sites in five estuarine wetlands. Addition of 30 mM (0.07 mmol g(-1) or 3.9 mg g(-1)) Fe(II) decreased net mercury methylation relative to that of unamended controls by a factor of 2.1-6.6. In all cases, the observed decrease in net mercury methylation was accompanied by a decrease in the concentrations of sulfide and filterable mercury in the water overlying the sediments. When iron was added to one of the sediment samples at doses that were small relative to the concentration of sulfide present, net mercury methylation either increased slightly or was unaffected. Comparison of the results to speciation model predictions suggests that dissolved reduced sulfur-containing species play a role in the formation of uncharged, bioavailable Hg complexes. Although further research is needed to determine the long-term effect of iron amendment, these results suggest that iron addition decreases mercury methylation in authentic wetland sediments.     

Mercury mobilization in estuarine sediment porewaters: a diffusive gel time-series study

To assess the lability of porewater and sediment solid-phase mercury (Hg), mercapto-substituted siloxane gels were deployed within the sediments of the Penobscot estuary in Maine. Gel deployments occurred in time series and at discrete sediment depths. A sediment distribution coefficient (K(D)) was estimated by modeling the resultant gel Hg uptake. For deployments > 1 day, depth-averaged gel Hg uptake was significantly greater at depth (Zone B 6-20 cm) than in the vicinity of the sediment-water interface (Zone A 0-5 cm), with uptake ultimately reaching 16.7 +/- 4.9 ng Hg g(-1) gel versus 35.5 +/- 3.8 ng Hg g(-1) gel for Zone A versus Zone B, respectively. For Zone A, a simple diffusive model adequately describes gel mass flux, suggesting that Hg repartitioning from the solid phase does not generate a net Hg source term within the time frame of gel deployment. For Zone B, model-determined values of K(D) (K(D) = 25-75) were considerably smaller than literature values typically based on total sediment Hg concentration. The magnitude of the modeled K(D) suggests that it is a small fraction of total sediment-sequestered Hg that is likely sensitive, via interaction with porewater ligands, to the presence of an external sink. These observations of low general Hg reactivity suggest that the net porewater Hg pool may be properly defined as a function of porewater ligand production. Such a definition highlights the importance of microbially mediated diagenesis in controlling Hg cycling within estuarine sediments.     

Sediment-bound inorganic Hg extraction mechanisms in the gut fluids of marine deposit feeders

The contributions of different free amino acids and proteins to the overall extraction of sediment-bound inorganic mercury (Hg) by gut fluids collected from deposit-feeding sipunculans and sea cucumbers were evaluated. The organic content and the Hg concentration in the sediment were modified to investigate their effects on Hg extraction. Cysteine was the key free amino acid in complexing Hg while proteins in the gut fluids also contributed significantly to the extraction. Different size fractions of gut fluids had different bindings with Hg at different Hg concentrations. Hg first bound with the <10 kD and 50-100 kD fractions and then with the > 100 kD fraction when the Hg concentration was increased. Removing the organic matter (OM) from the sediments enhanced Hg extraction, indicating that competition for Hg binding between the strong binding sites in sediments (the organic matter) and gut fluids (cysteine) may control the extraction. However, Hg complexation with weak binding sites (e.g., Fe/Mn oxides) in sediments should not be ignored. We identified two sediment Hg pools with different mobilities based on Hg binding, which was influenced by the Hg concentration in the sediment and the ratio of binding sites between gutfluids and sediments. Our results help to explain the variations in gut fluid extraction and Hg bioaccumulation in different marine deposit feeders.     

Assessing the stability of mercury and methylmercury in a varved lake sediment deposit

Using lake sediments to infer past total mercury and methylmercury loading to the environment requires that diagenetic processes within the sediment do not significantly affect the concentrations or net accumulation rates of the mercury species. Because carbon is lost during early sediment diagenesis, the close link between carbon and mercury raises the question of how reliable lake sediments are as archives of total mercury and methylmercury loading. In this study we used a series of freeze cores taken in a lake with varved (annually laminated) sediment to assess the stability of total mercury and methylmercury over time. By tracking material deposited in specific years in cores collected in different years, we found that despite a 20--25% loss of carbon in the first 10--15 years, there was no apparent loss of total mercury over time; hence, lake sediments can be considered as reliable archives. However, over the first 5--8 years after sedimentation, about 30--40% of the methylmercury was lost (a decrease of 0.025--0.030 microg MeHg m(-2) yr(-1)), suggesting that sediment profiles showing increasing methylmercury concentrations toward the sediment surface are in large part an artifact of diagenetic processes (net demethylation), rather than a record of changes in methylmercury loading.     

An integrated approach to the assessment of pollutant delivery chronologies to impacted areas: Hg in the Augusta Bay (Italy)

Assessing pollution levels and trends in heavily impacted environments is important but hardly achievable due to the difficulty of recovering suitable undisturbed sediment records. An integrated approach is here presented to solve this kind of problem. It was adopted in the Augusta Bay (Italy) for the study of Hg historical inputs and present trends. Archive information on dredging and mud disposal, together with bathymetry and high-resolution seismic profiles, were used to identify suitable sampling sites. Undisturbed sediment cores were collected in the port and bay. Sediments were analyzed for depth distributions of radiotracers ((210)Pb and (137)Cs), Hg, and main sediment parameters (magnetic susceptibility, grain size, dry bulk density, mineralogy, and organic carbon and nitrogen contents). Hexachlorobenzene (HCB) was also analyzed as an additional time tracer, since its production history in the area was well-known. Results show that peak Hg contamination (up to 575 mg·kg(-1)) was reached in the 1970s. Technological improvements and waste treatment in the following years determined a consistent decrease, but high concentrations still affect surficial sediments (0.25-92 mg·kg(-1)). Hg-HCB correlation suggests that this situation is likely the effect of resuspension and redistribution of deep sediments by dredging and naval traffic.     

Spatial and Temporal Assessment of Mercury and Organic Matter in Thermokarst Affected Lakes of the Mackenzie Delta Uplands, NT, Canada

We examined dated sediment cores from 14 thermokarst affected lakes in the Mackenzie Delta uplands, NT, Arctic Canada, using a case-control analysis to determine how retrogressive thaw slump development from degrading permafrost affected the delivery of mercury (Hg) and organic carbon (OC) to lakes. We show that sediments from the lakes with retrogressive thaw slump development on their shorelines (slump-affected lakes) had higher sedimentation rates and lower total Hg (THg), methyl mercury (MeHg), and lower organic carbon concentrations compared to lakes where thaw slumps were absent (reference lakes). There was no difference in focus-corrected Hg flux to sediments between reference lakes and slump-affected lakes, indicating that the lower sediment Hg concentration in slump-affected lakes was due to dilution by rapid inorganic sedimentation in the slump-affected lakes. Sedimentation rates were inversely correlated with THg concentrations in sediments among the 14 lakes considered, and explained 68% of the variance in THg concentration in surface sediment, further supporting the dilution hypothesis. We observed higher S2 (algal-derived carbon) and particulate organic carbon (POC) concentrations in sediment profiles from reference lakes than in slump lakes, likely because of dilution by inorganic siliciclastic matter in cores from slump-affected lakes. We conclude that retrogressive thaw slump development increases inorganic sedimentation in lakes, and decreases concentrations of organic carbon and associated Hg and MeHg in sediments.     

Mercury emissions from cement-stabilized dredged material

Upland placement of dredged materials from navigation channels in the New York/New Jersey Harbor is currently being used to manage sediments deemed inappropriate for open water disposal. Although upland placement sites are equipped with engineering controls (leachate collection and/or barrier walls), little is known of the potential impacts of this approach to air quality. The aim of this study was to estimate the flux of mercury to the atmosphere from New York/New Jersey Harbor stabilized dredged material (SDM) that was used for land reclamation at a site in northeastern New Jersey. Total gaseous mercury (TGM) was measured at a site receiving SDM in August and October 2001 and May and November 2002. TGM was also monitored at an urban reference site 3.5 km west of the SDM site in September 2001 and from February 2002 to July 2002 and from October 2002 to February 2003. The concentration of TGM at the urban reference site averaged 2.2 +/- 1.1 ng m(-3), indicating some local contribution to the Northern Hemisphere background. TGM concentrations exhibited seasonality with the highest values in summer (3.3 +/- 2.1 ng m(-3) in June 2002) and the lowest in winter (1.7 +/- 0.6 ng m(-3) in January 2003). TGM concentrations at the SDM placement site ranged from 2 to 7 ng m(-3) and were significantly higher (p < 0.001) than those at the urban reference site. Sediment-air fluxes of Hg at the SDM placement site estimated by the micrometeorological technique ranged from -13 to 1040 ng m(-2) h(-1) (sediment to air fluxes being positive) and were significantly correlated to solar radiation (r2 = 0.81). The estimated contribution of Hg emissions from land-applied SDM to local TGM concentrations was found to be negligible (<4%). However, the estimated annual volatilization rate of TGM atthe SDM site (130 kg y(-1))was comparable to those of other industrial sources in New Jersey (140-450 kg y(-1)).     

Organic material: the primary control on mercury methylation and ambient methyl mercury concentrations in estuarine sediments

Estuarine environments that have no direct sources of mercury (Hg) pollution may have sediment concentrations of methylmercury (MeHg) as high as those of polluted marine environments. In this study we examined the biogeochemical factors affecting net methylation and sediment MeHg concentrations in an unpolluted estuarine environment, the Ore River estuary, which discharges into the Bothnian Bay (20-120 ng total Hg g(-1) dry sediment, salinity 3-5% per hundred). We analyzed the spatial and temporal differences in surface sediment profiles of MeHg concentration, Hg methylation, MeHg demethylation, and concentrations of sulfide and oxygen between accumulation and erosion type bottoms. The main difference between the bottoms studied was in the proportion of organic material (OM) in the sediment, ranging between 0.8% and 10.8%. The pore water sulfide concentration profiles also differed considerably between sites and seasons, from 0 to 20 microM, with 100 microM as the extreme maximum. The sediment MeHg concentration profiles (0-10 cm) mostly varied between 0.1 and 7 ng g(-1) dry weight (dw, as Hg). The MeHg demethylation rates were relatively low and the depth profiles of the rates were relatively constant over season, site, and depth. In contrast, both rates and depths of maximum Hg methylation differed between the bottoms. The results indicate that the amount of OM accumulated at the bottoms was the main factor affecting net MeHg production, while the total amount of Hg had little or no influence on the amount of MeHg in the sediment.     

Rapid release of mercury from intertidal sediments exposed to solar radiation: a field experiment

There is increasing evidence of the primary importance of photochemical reactions and transfer of gaseous mercury to the atmosphere. Although mercury in aquatic sediments is efficiently retained, resuspension and bioturbation in intertidal sediments may expose temporarily anoxic sediments to solar radiation. Field experiments were performed to investigate these processes. Anoxic sediments from two areas in the Tagus estuary with different degrees of Hg contamination (experiments I and II) were homogenized and distributed into two sets of 36 uncovered Petri dishes. The samples were placed on the intertidal sediments and exposed to direct solar radiation and kept under dark (control) for 6-8 h. The decrease rates of acid volatile sulfides (abrupt in the first 3 h) and of pyrite (linear) were the same in sediments under solar radiation and dark. The total Hg concentrations were relatively constant in sediments kept in dark, but decreased from 17.6 to 7.65 and 3.45 to 1.35 nmol g(-1) in experiments I and II, respectively. In those exposed to solar radiation during the period of higher UV intensity. Similar evolutions were found in nonreactive Hg in pore waters (3.00-2.59 and 0.725-0.105 nM). On the contrary, reactive Hg was higher in pore waters of the sediments exposed to solar radiation and increased with time, from 424 to 845 pM and 53 to 193 pM. These results indicate that most mercury released in pore waters was photochemically reduced in a short period of time and escaped rapidly to the atmosphere. Episodes of bottom resuspension and bioturbation in the intertidal sediments enhance the transfer of gaseous mercury to the atmosphere.     

Deposition and emission of gaseous mercury to and from Lake Michigan during the Lake Michigan Mass Balance Study (July, 1994-October, 1995)

This paper presents measurements of dissolved gaseous mercury (DGM) concentrations in Lake Michigan and the application of a mechanistic approach to estimate deposition and emission fluxes of gaseous mercury (Hg2+ and Hg0) to and from Lake Michigan. Measurements of DGM concentrations made during May and July, 1994 and January, 1995 indicate that Lake Michigan was supersaturated with DGM suggesting that transfer of Hg0 occurs from the water to the atmosphere. Over-water concentrations of gaseous Hg2+ were estimated from total gaseous Hg (TGM) concentrations measured at five sites in the basin and used to model dry deposition fluxes of Hg2+. The modeling approach combines estimates of dry deposited Hg2+ with known photochemical and biotic reduction rates to form Hg0, which is available for re-emission. The model accounts for temporal and spatial variations in the deposition velocity of gaseous Hg2+ and the transfer velocity of Hg0 using high temporal and spatial resolution meteorological data. The modeled DGM concentrations agree well with the observed DGM concentrations in Lake Michigan. The modeled dry deposition fluxes of Hg2+ (286-797 kg yr(-1)) are very similar to the emission fluxes of Hg0 (320-959 kg yr(-1)), depending on the gaseous Hg2+ concentration used in the model.     

Importance of dissolved neutral mercury sulfides for methyl mercury production in contaminated sediments

Biotic transformation of inorganic mercury, Hg(II), to mono methyl mercury (MeHg) is proposed to be largely controlled by passive uptake of neutral Hg complexes by sulfate reducing bacteria (SRB). In this study, the chemical speciation of Hg(II) in seven locally contaminated sediments covering environments such as (i) brackish water, (ii) low-productivity freshwater, and, (iii) high-productivity freshwater was related to potential Hg methylation rates, determined by incubation at 23 degrees C for 48 h under N2(g), and to total MeHg concentrations in sediments. Pore water speciation was modeled considering Hg complexes with halides, organic thiols [Hg(SR)2(aq), associated to dissolved organic matter], monosulfides, and bisulfides. The sum of neutral mercury sulfides [Hg(SH)20(aq)] and [HgS0(aq)] was significantly, positively (p < 0.001, n = 20) correlated to the specific methylation rate constant (Km, day(-1)) at depths of 5-100 cm in two brackish water sediments. Total Hg, total mercury sulfides or Hg(SR)2(aq) in pore water gave no significant relationships with Km. In two subsets of freshwater sediments, neutral mercury sulfides were positively correlated to total Hg in pore water, and therefore, total Hg also gave significant relationships with Km. The sum of [Hg(SH)20(aq)] and [HgS0(aq)] was significantly, positively correlated to total sediment MeHg (microg kg-1) in brackish waters (p < 0.001, n = 23), in southern, high-productivity freshwaters (p < 0.001, n = 20), as well as in northern, low-productivity freshwater (p = 0.048, n = 6). The slopes (b, b') of the relationships Km (day-1) = a + b([Hg(SH)20(aq)] + [HgS0(aq)]) and MeHg (microg kg-1) = a' + b'([Hg(SH)20(aq)] + [HgS0(aq)]) showed an inverse relationship with the C/N ratio, supposedly reflecting differences in primary production and energy-rich organic matter availability among sites. We conclude that concentrations of neutral inorganic mercury sulfide species, together with the availability of energy-rich organic matter, largely control Hg methylation rates in contaminated sediments. Furthermore, Hg(SH)20(aq) is suggested to be the dominant species taken up by MeHg producing bacteria in organic-rich sediments without formation of HgS(s).     

Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the mercury district of Almadén in Spain

Metallurgic calcines with very high mercury and methylmercury content from the Almadén mining district were analyzed by synchrotron-based microprobe techniques. Information about mercury speciation was obtained by micro-EXAFS (microscopic extended X-ray absorption fine structure) spectroscopy, whereas elemental associations were evaluated by micro-XRF (microscopic X-ray fluorescence analysis) mapping. Complementary characterization methodologies, including X-ray diffraction (XRD), inductively coupled plasma-optical spectroscopy (ICP-OES), as well as a sequential extraction scheme (SES), were used to predict the potential availability of mercury. Analysis of total metal content revealed extremely high concentrations of mercury and iron (between 7 and 35 and 65-70 g kg(-1), respectively) and high zinc concentrations (2.2-2.5 g kg(-1)), whereas other metals such as copper, nickel, and lead were found at low concentration levels (30-300 mg kg(-1)). Micro-EXAFS results indicate that cinnabar (HgS(red)) is one of the main species within the studied mercury-rich particles (5-89% of total mercury content), together with more soluble mercury compounds such as Hg3(SO4)02 (schuetteite) and HgO (5-55% of total mercury content). Additionally, element-specific micro-XRF maps of selected mercury-rich particles in the studied samples revealed an evident correlation among Hg-Pb-Ni (and S), indicating a possible geochemical linkage of these elements. Correlations were also found among Fe-Mn and Hg, which have been attributed to sorption of mercury onto oxyhydroxides of Fe and Mn. This finding was supported by results from a sequential extraction scheme, where a significant     

Modeling the past atmospheric deposition of mercury using natural archives

Historical records of mercury (Hg) accumulation in lake sediments and peat bogs are often used to estimate human impacts on the biogeochemical cycling of mercury. On the basis of studies of lake sediments, modern atmospheric mercury deposition rates are estimated to have increased by a factor of 3-5 compared to background values: i.e., from about 3-3.5 microg Hg m(-2) yr(-1) to 10-20 microg Hg m(-2) yr(-1). However, recent studies of the historical mercury record in peat bogs suggest significantly higher increases (9-400 fold, median 40x), i.e., from about 0.6-1.7 microg Hg m(-2) yr(-1) to 8-184 microg Hg m(-2) yr(-1). We compared published data of background and modern mercury accumulation rates derived from globally distributed lake sediments and peat bogs and discuss reasons for the differences observed in absolute values and in the relative increase in the industrial age. Direct measurements of modern wet mercury deposition rates in remote areas are presently about 1-4 microg m(-2) yr(-1), but were possibly as high as 20 microg Hg m(-2) yr(-1) during the 1980s. These values are closer to the estimates of past deposition determined from lake sediments, which suggests that modern mercury accumulation rates derived from peat bogs tend to overestimate deposition. We suggest that smearing of 210Pb in the uppermost peat sections contributes to an underestimation of peat ages, which is the most important reason for the overestimation of mercury accumulation rates in many bogs. The lower background mercury accumulation rates in peat as compared to lake sediments we believe is the result of nonquantitative retention and loss of mercury during peat diagenesis. As many processes controlling time-resolved mercury accumulation in mires are still poorly understood, lake sediments appear to be the more reliable archive for estimating historical mercury accumulation rates.     

Synergic effect of gold mining and damming on mercury contamination in fish

Since the late 1980s, several studies have shown that human populations in the Amazon basin are exposed to high mercury levels in their fish diet. Gold mining, which releases the metal during the amalgamation process and erodes soils naturally rich in mercury, is regarded as the main contamination source. Here, we present the results of a comparative study of mercury distribution in the water and fish of two adjacent rivers in French Guiana, with and without gold mining activities. As a consequence of a marked difference in suspended particulate matter between the two systems, total mercury concentrations in unfiltered water samples were higher in the mined river (25.4-34.9 ng L(-1)) as compared to the reference one (2.1-5.4 ng L(-1)). Surprisingly, no significant differences were observed in mercury concentrations between 13 common fish species at upstream sites. In sharp contrast, mercury concentration of fish caught downstream a hydroelectric reservoir, where the two rivers flow, was up to 8-fold higher than that upstream. Mercury speciation measurements allowed one to relate these differences in fish to the water distribution of monomethylmercury, the mercury chemical species that biomagnifies along aquatic foodwebs. Indeed, mean dissolved monomethylmercury concentrations were low and similar in both rivers (0.03-0.06 ng L(-1)), while they were 10 times higher (up to 0.56 ng L(-1)) in the water outflowing the hydroelectric dam. Dissolved monomethylmercury determinations along a water column profile suggest that methylation of inorganic mercury occurs in the deep anoxic part in reservoir. We conclude that mercury mobilization related to gold mining is not solely sufficient to account for high concentrations in fish and that environmental conditions that favor mercury methylation, such as anoxia, are needed.     

Microbial mercury transformation in anoxic freshwater sediments under iron-reducing and other electron-accepting conditions

Potential rates of microbial methylation of inorganic mercury (added as HgCl2) and degradation of methyl mercury (MeHg) (added as CH3HgCl) were investigated in anoxic sediments from the Mobile Alabama River Basin (MARB) dominated by different terminal electron-accepting processes (TEAPs). Potential rates of methylation were comparable under methanogenic and sulfate-reducing conditions but suppressed under iron-reducing conditions, in slurries of freshwater wetland sediment In contrast, MeHg degradation rates were similar under all three TEAPs. Microbial Hg methylation and MeHg degradation were also investigated in surface sediment from three riverine sites, two of which had iron reduction and one sulfate reduction, as the dominant TEAP (as determined by 14C-acetate metabolism and other biogeochemical measurements). Methylation was active in sulfate-reducing sediments of a tributary creek and suppressed in iron-reducing, sandy sediments from the open river, whereas MeHg degradation was active at all three sites. Although iron-reducing conditions often suppressed methylation, some methylation activity was observed in two out of three replicates from iron-reducing sediments collected near a dam. Given that MeHg degradation was consistently observed under all TEAPs, our results suggest that the net flux of MeHg from iron-reducing surface sediments may be suppressed (due to inhibition of gross MeHg production) compared to sediments supporting other TEAPs.     

Contribution of coexisting sulfate and iron reducing bacteria to methylmercury production in freshwater river sediments

We investigated microbial methylmercury (CH(3)Hg) production in sediments from the South River (SR), VA, an ecosystem contaminated with industrial mercury (Hg). Potential Hg methylation rates in samples collected at nine sites were low in late spring and significantly higher in late summer. Demethylation of (14)CH(3)Hg was dominated by (14)CH(4) production in spring, but switched to producing mostly (14)CO(2) in the summer. Fine-grained sediments originating from the erosion of river banks had the highest CH(3)Hg concentrations and were potential hot spots for both methylation and demethylation activities. Sequencing of 16S rRNA genes of cDNA recovered from sediment RNA extracts indicated that at least three groups of sulfate-reducing bacteria (SRB) and one group of iron-reducing bacteria (IRB), potential Hg methylators, were active in SR sediments. SRB were confirmed as a methylating guild by amendment experiments showing significant sulfate stimulation and molybdate inhibition of methylation in SR sediments. The addition of low levels of amorphous iron(III) oxyhydroxide significantly stimulated methylation rates, suggesting a role for IRB in CH(3)Hg synthesis. Overall, our studies suggest that coexisting SRB and IRB populations in river sediments contribute to Hg methylation, possibly by temporally and spatially separated processes.     

Evidence for the migration of steroidal estrogens through river bed sediments

Estrogenic substances discharged from wastewater treatment plants have been detected in surface sediments of receiving waters, but little is known of their vertical migration through buried sediments and their potential to contaminate subsurface waters. The vertical profiles of estrogenic chemicals were investigated in sediment cores at an alluvial freshwater site (Ditchling) and a clay-rich estuarine site (Lewes), both of which are downstream of wastewater discharges into the River Ouse (Sussex, U.K.). Estrone (E1) was the predominant estrogen detected in surface and buried sediments at both sites and was detected in undisturbed clay sediments > 120 years old. Profiles of E1 at Ditchling were characterized by a prominent subsurface peak of E1 at the alluvium/clay interface (-15 cm) at a concentration (28.8 +/- 6.0 ng/g of dry wt) that was 9-fold higher than in the surface sediment. In contrast, a steady downcore decline in E1 concentrations was observed in the clay-rich Lewes core. This work provides the first in situ evidence of estrogen migration through river bed sediments and reveals that movement of estrogens through unconsolidated sediment can result in penetration to the underlying substrata and therefore the potential for groundwater contamination.     

Methylated mercury species in Canadian high Arctic marine surface waters and snowpacks

We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (Hg). We discovered that, although seawater sampled under the sea ice had very low concentrations of total Hg (THg, all forms of Hg in a sample; on average 0.14-0.24 ng L(-1)), 30-45% of the THg was in the monomethyl Hg (MMHg) form (on average 0.057-0.095 ng L(-1)), making seawater itself a direct source of MMHg for biomagnification through marine food webs. Seawater under the ice also contained high concentrations of gaseous elemental Hg (GEM; 129 +/- 36 pg L(-1)), suggesting that open water regions such as polynyas and ice leads were a net source of approximately 130 +/- 30 ng Hg m(-2) day(-1) to the atmosphere. We also found 11.1 +/- 4.1 pg L(-1) of dimethyl Hg (DMHg) in seawater and calculated that there could be a significant flux of DMHg to the atmosphere from open water regions. This flux could then resultin MMHg deposition into nearby snowpacks via oxidation of DMHg to MMHg in the atmosphere. In fact, we found high concentrations of MMHg in a few snowpacks near regions of open water. Interestingly, we discovered a significant log-log relationship between Cl- concentrations in snowpacks and concentrations of THg. We hypothesize that as Cl- concentrations in snowpacks increase, inorganic Hg(II) occurs principally as less reducible chloro complexes and, hence, remains in an oxidized state. As a result, snowpacks that receive both marine aerosol deposition of Cl- and deposition of Hg(II) via springtime atmospheric Hg depletion events, for example, may contain significant loads of Hg(II). Overall, though, the median wet/dry loads of Hg in the snowpacks we sampled in the high Arctic (5.2 mg THg ha(-1) and 0.03 mg MMHg ha(-1)) were far below wet-only annual THg loadings throughout southern Canada and most of the U.S. (22-200 mg ha(-1)). Therefore, most Arctic snowpacks contribute