Tracing sources and bioaccumulation of mercury in fish of Lake Baikal--Angara River using Hg isotopic composition

This study presents the determination and comparison of isotopic compositions of Hg in sediments, plankton, roach, and perch of two freshwater systems in the Lake Baikal-Angara River aquatic ecosystem: the man-made Bratsk Water Reservoir contaminated by Hg from a chlor-alkali factory and the noncontaminated Lake Baikal. Isotopic ratios of biota exhibit both significant mass-independent fractionation (MIF) (Δ(199)Hg from 0.20 to 1.87‰) and mass-dependent fractionation (MDF) (δ(202)Hg from -0.97 to -0.16‰), whereas sediments exhibit high MDF (δ(202)Hg from -1.99 to -0.83‰) but no MIF. δ(15)N and δ(13)C are correlated with methylmercury in organisms from both sites, indicating bioaccumulation and biomagnification through food webs of both regions. Combining this with isotopic composition of samples shows that δ(202)Hg increases with the trophic level of organisms and also with methylmercury in fish from Lake Baikal. This study demonstrates that MIF in fish samples from Bratsk Water Reservoir allow to trace anthropogenic Hg, since fish with the highest levels of Hg in muscle have the same isotopic composition as the sediment in which anthropogenic Hg was deposited. Less contaminated fish do not exhibit this anthropogenic signature accumulating relatively lower Hg amount from the contaminated sediments. This work reveals that Hg isotopic composition can be used to track the contribution of anthropogenic sources in fish from a contaminated lake.     

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on unamended food pellets (0.1 μg/g MeHg) or was switched to food pellets with 1.0 μg/g or 4.0 μg/g of added MeHg, for a period of 2 months. The difference in δ(202)Hg (MDF) and Δ(199)Hg (MIF) between fish tissues and food pellets with added MeHg was within the analytical uncertainty (δ(202)Hg, 0.07 ‰; Δ(199)Hg, 0.06 ‰), indicating no isotope fractionation. In experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ(202)Hg and Δ(199)Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting reequilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.     

Mercury stable isotopes in seabird eggs reflect a gradient from terrestrial geogenic to oceanic mercury reservoirs

Elevated mercury concentrations ([Hg]) were found in Alaskan murre (Uria spp.) eggs from the coastal embayment of Norton Sound relative to insular colonies in the northern Bering Sea-Bering Strait region. Stable isotopes of Hg, carbon, and nitrogen were measured in the eggs to investigate the source of this enrichment. Lower δ(13)C values in Norton Sound eggs (-23.3‰ to -20.0‰) relative to eggs from more oceanic colonies (-20.9‰ to -18.7‰) indicated that a significant terrestrial carbon source was associated with the elevated [Hg] in Norton Sound, implicating the Yukon River and smaller Seward Peninsula watersheds as the likely Hg source. The increasing [Hg] gradient extending inshore was accompanied by strong decreasing gradients of δ(202)Hg and Δ(199)Hg in eggs, indicating lower degrees of mass-dependent (MDF) and mass-independent Hg fractionation (MIF) (respectively) in the Norton Sound food web. Negative or zero MDF and MIF signatures are typical of geological Hg sources, which suggests murres in Norton Sound integrated Hg from a more recent geological origin that has experienced a relatively limited extent of aquatic fractionation relative to more oceanic colonies. The association of low δ(202)Hg and Δ(199)Hg with elevated [Hg] and terrestrial δ(13)C values suggested that Hg stable isotopes in murre eggs effectively differentiated terrestrial/geogenic Hg sources from oceanic reservoirs.     

Influences of bioavailability, trophic position, and growth on methylmercury in hakes (Merluccius merluccius) from Northwestern Mediterranean and Northeastern Atlantic

Methylmercury (MeHg) determinations in hake, its food-chain, and the surrounding waters and sediments allowed us to show that the higher length or age normalized mercury concentrations of Northwestern Mediterranean (Gulf of Lions: GoL) muscle hakes compared to its Northeastern Atlantic (Bay of Biscay: BoB) counterpart are due to both biotic and abiotic differences between their ecosystems. Bioenergetic modeling reveals that the slower growth rate of Mediterranean hake favors the MeHg bioaccumulation in the fish muscle and explains most of the difference between GOL and BoB hake populations. In addition, the waters of the Mediterranean hake habitat favor a higher MeHg exposition, due to the upper position of the thermohalocline, where MeHg is formed. Furthermore, we show that, within the Mediterranean hake population, a major increase in the biomagnification power (the slope of the relationships between logMeHg and δ(15)N), from 0.36 up to 1.12, occurs when individuals enter adulthood, resulting from the combined effects of lowering growth rate and change in feeding habits. Finally, δ(15)N normalized Hg concentrations indicate that the highest Hg concentrations are for hake from the shelf edge and the lowest are for hake from the Rh?ne prodelta area, suggesting a lower Hg bioavailability in inshore environments, consistent with MeHg distributions in water, sediment, and preys.     

Connecting breeding and wintering habitats of migratory piscivorous birds: implications for tracking contaminants (Hg) using multiple stable isotopes

Contaminant concentrations in migratory species are complicated by differential accumulation and elimination among geographically separated biomes. Double-crested cormorants ( Phalacrocorax auritus ) are used as monitors of Hg in North America; however, migration from northern breeding colonies to southern marine, freshwater, and aquaculture systems exposes individuals to spatiotemporal variations in contaminant uptake. We used stable isotopes (δ(34)S, δ(13)C, δ(15)N, δ(2)H) in primary feathers and a combined Bayesian assignment and isotopic threshold model to identify feather origins and the potential winter use of aquaculture (δ(34)S < 10‰, δ(13)C > -14‰), freshwater (δ(34)S < 10‰, δ(13)C < -20‰), and marine habitats (δ(34)S > 10‰). This approach allowed us to contrast body burden Hg derived from the breeding and wintering grounds, as well as from marine and freshwater habitats. We found feathers grown on Lake Winnipeg had greater Hg concentrations (mean = 4.26 ± 1.47 μg/g fresh weight; n = 20) than winter-grown feathers (3.19 ± 1.64 μg/g; n = 19), but Hg in winter-grown feathers was not related to any specific habitat. Isotopic assays of tissues of migratory birds allowed the source and degree of contaminant exposure to be identified throughout the annual cycle.     

Differences in mercury bioaccumulation between polar bears (Ursus maritimus) from the Canadian high- and sub-Arctic

Polar bears (Ursus maritimus) are being impacted by climate change and increased exposure to pollutants throughout their northern circumpolar range. In this study, we quantified concentrations of total mercury (THg) in the hair of polar bears from Canadian high- (southern Beaufort Sea, SBS) and sub- (western Hudson Bay, WHB) Arctic populations. Concentrations of THg in polar bears from the SBS population (14.8 ± 6.6 μg g(-1)) were significantly higher than in polar bears from WHB (4.1 ± 1.0 μg g(-1)). On the basis of δ(15)N signatures in hair, in conjunction with published δ(15)N signatures in particulate organic matter and sediments, we estimated that the pelagic and benthic food webs in the SBS are ～ 4.7 and ～ 4.0 trophic levels long, whereas in WHB they are only ～ 3.6 and ～ 3.3 trophic levels long. Furthermore, the more depleted δ(13)C ratios in hair from SBS polar bears relative to those from WHB suggests that SBS polar bears feed on food webs that are relatively more pelagic (and longer), whereas polar bears from WHB feed on those that are relatively more benthic (and shorter). Food web length and structure accounted for ～ 67% of the variation we found in THg concentrations among all polar bears across both populations. The regional difference in polar bear hair THg concentrations was also likely due to regional differences in water-column concentrations of methyl Hg (the toxic form of Hg that biomagnifies through food webs) available for bioaccumulation at the base of the food webs. For example, concentrations of methylated Hg at mid-depths in the marine water column of the northern Canadian Arctic Archipelago were 79.8 ± 37.3 pg L(-1), whereas, in HB, they averaged only 38.3 ± 16.6 pg L(-1). We conclude that a longer food web and higher pelagic concentrations of methylated Hg available to initiate bioaccumulation in the BS resulted in higher concentrations of THg in polar bears from the SBS region compared to those inhabiting the western coast of HB.     

Mercury mass budget estimates and cycling seasonality in the Florida Everglades

We estimated the mass budget for mercury (Hg) seasonally deposited into the Florida Everglades and investigated seasonality of Hg cycling by analyzing data obtained for water, soil, flocculent detrital material (floc), periphyton, and mosquitofish collected throughout the Everglades freshwater marshes in the 2005 dry and wet seasons. Higher wet season total Hg (THg) in soil, floc, and periphyton agreed with greater Hg amounts entering these compartments during the wet season, probably owing to substantially greater Hg deposition in the wet season than in the dry season. Seasonal differences were absent for THg in surface water. Methylmercury (MeHg) showed mixed seasonal patterns, with higher water and soil MeHg and lower periphyton MeHg in the dry season but no seasonality for floc MeHg. Seasonal variations in Hg deposition, MeHg production and transport, and mass of ecosystem compartments could be responsible for the seasonality of MeHg cycling. Higher mosquitofish THg, higher bioaccumulation factors, and higher biomagnification factors from periphyton to mosquitofish were observed in the wet season than in the dry season, indicating that the wet season is more favorable for Hg bioaccumulation. The mass budget estimation agreed with this result.     

Experimental evidence of a linear relationship between inorganic mercury loading and methylmercury accumulation by aquatic biota

Developing effective regulations on mercury (Hg) emissions requires a better understanding of how atmospheric Hg deposition affects methylmercury (MeHg) levels in aquatic biota. This study tested the hypothesis that MeHg accumulation in aquatic food webs is related to atmospheric Hg deposition. We simulated a range of inorganic Hg deposition rates by adding isotopically enriched Hg(II) (90.9% 202Hg) to 10-m diameter mesocosms in a boreal lake. Concentrations of experimentally added ("spike") Hg were monitored in zooplankton, benthic invertebrates, and fish. Some Hg(II) added to the mesocosms was methylated and incorporated into the food web within weeks, demonstrating that Hg(II) deposited directly to aquatic ecosystems can become quickly available to biota. Relationships between Hg(II) loading rates and spike MeHg concentrations in zooplankton, benthic invertebrates, and fish were linear and significant. Furthermore, spike MeHg concentrations in the food web were directly proportional to Hg(II) loading rates (i.e., a percent change in Hg(II) loading rate resulted in, statistically, the same percent change in MeHg concentration). This is the first experimental determination of the relationship between Hg(II) loading and MeHg bioaccumulation in aquatic biota. We conclude that changes in atmospheric Hg deposition caused by increases or decreases in Hg emissions will ultimately affect MeHg levels in aquatic food webs.     

Antagonistic interaction of mercury and selenium in a marine fish is dependent on their chemical species

It is well-known that selenium (Se) shows protective effects against mercury (Hg) bioaccumulation and toxicity, but the underlying effects of Se chemical species, concentration, and administration method are poorly known. In this study, we conducted laboratory studies on a marine fish Terapon jurbua to explain why Hg accumulation is reduced in the presence of Se observed in field studies. When Se and Hg were administrated concurrently in the fish diets, different Se species including selenite, selenate, seleno-dl-cystine (SeCys), and seleno-dl-methionine (SeMet) affected Hg bioaccumulation differently. At high concentration in fish diet (20 μg g(-1) normally), selenate and SeCys significantly reduced the dietary Hg(II) assimilation efficiency (AE) from 38% to 26%. After the fish were pre-exposed to dietary selenite or SeMet (7 μg g(-1) normally) for 22 days with significantly elevated Se body concentrations, the Hg(II) AEs were pronouncedly reduced (from 41% to 15-26%), whereas the dissolved uptake rate constant and elimination rate constant were less affected. In contrast to Hg(II), all the MeHg biokinetic parameters remained relatively constant whether Se was administrated simultaneously with the fish diet or when the fish were pre-exposed to Se with elevated body concentrations. Basic biokinetic measurements thus revealed that Se had direct interaction with Hg(II) during dietary assimilation rather than with MeHg and that different Se species had variable effects on Hg assimilation.     

Hg speciation and stable isotope signatures in human hair as a tracer for dietary and occupational exposure to mercury

Exposure of humans and wildlife to various inorganic and organometallic forms of mercury (Hg) may induce adverse health effects. While human populations in developed countries are mainly exposed to marine fish monomethylmercury (MMHg), this is not necessarily the case for developing countries and diverse indigenous people. Identification of Hg exposure sources from biomonitor media such as urine or hair would be useful in combating exposure. Here we report on the Hg stable isotope signatures and Hg speciation in human hair across different gold miner, indigenous and urban populations in Bolivia and France. We found evidence for both mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in all hair samples. Three limiting cases of dominant exposure to inorganic Hg (IHg), freshwater fish MMHg, and marine fish MMHg sources are used to define approximate Hg isotope source signatures. Knowing the source signatures, we then estimated Hg exposure sources for the Bolivian gold miner populations. Modeled IHg levels in hair correspond well to measured IHg concentrations (R = 0.9), demonstrating that IHg exposure sources to gold miners can be monitored in hair samples following either its chemical speciation or isotopic composition. Different MMHg and inorganic exposure levels among gold miners appear to correspond to living and working conditions, including proximity to small towns, and artisanal vs large scale mining activity.     

Investigation of local mercury deposition from a coal-fired power plant using mercury isotopes

Coal combustion accounts for approximately two-thirds of global anthropogenic mercury (Hg) emissions. Enhanced deposition of Hg can occur close to coal-fired utility boilers (CFUBs), but it is difficult to link specific point sources with local deposition. Measurement of Hg stable isotope ratios in precipitation holds promise as a tool to assist in the identification of local Hg deposition related to anthropogenic emissions. We collected daily event precipitation samples in close proximity to a large CFUB in Crystal River, Florida. Precipitation samples collected in Crystal River were isotopically distinct and displayed large negative δ(202)Hg values (mean = -2.56‰, 1 SD = 1.10‰, n = 28). In contrast, precipitation samples collected at other sites in FL that were not greatly impacted by local coal combustion were characterized by δ(202)Hg values close to 0‰ (mean = 0.07‰, 1 SD = 0.17‰, n = 13). These results indicate that, depending on factors such as powdered coal isotopic composition and efficiency of Hg removal from flue gas, Hg deposited near CFUBs can be isotopically distinct. As this tool is further refined through future studies, Hg stable isotopes may eventually be used to quantify local deposition of Hg emitted by large CFUBs.     

Estimation of the major source and sink of methylmercury in the Florida Everglades

Mercury methylation and/or demethylation have been observed in several compartments [soil (saturated soils covered by standing water), floc, periphyton, and water] of the Everglades, a wetland with mercury as one of the major water quality concerns. However, it is still unclear which compartment is the major source or sink due to the lack of estimation and comparison of the net methylmercury (MeHg) production or degradation in these compartments. The lack of this information has limited our understanding of Hg cycling in this ecosystem. This study adopted a double stable isotope ((199)Hg(2+) and Me(201)Hg) addition technique to determine the methylation/demethylation rate constants and the net MeHg production rates in each compartment. This study improved the previous models for estimating these parameters by (1) taking into account the difference between newly input and ambient mercury in methylation/demethylation efficiency and (2) correcting the contribution of photodemethylation to Me(199)Hg concentration when calculating methylation rates in water. The net MeHg production rate in each compartment was then estimated to identify the major sources and sinks of MeHg. The results indicate that these improvements in modeling are necessary, as a significant error would occur otherwise. Soil was identified to be the largest source of MeHg in the Everglades, while the floc and water column were identified as the major sinks. The role of periphyton varies, appearing to be a source in the northern Everglades and a sink in the southern Everglades. Soil could be the largest source for MeHg in the water column, while methylation in periphyton could also contribute significantly in the northern Everglades.     

Elimination of mercury by yellow perch in the wild

The rate of methylmercury (MeHg) elimination by fish is important in determining the extent of bioaccumulation and for predicting recovery times of MeHg-contaminated fisheries. Rates of MeHg elimination remain uncertain in existing bioaccumulation models due to a lack of field studies. We addressed this problem by monitoring fish that had naturally accumulated isotopically enriched MeHg (spike MeHg) during a whole-ecosystem experiment. We transported yellow perch (Perca flavescens) from the experimental lake to an untreated lake and monitored spike total mercury (THg, most of which was MeHg) losses over 440 d. Spike THg was distributed among fish tissues in a similar way as ambient THg (background non-spike THg). We observed rapid loss of spike THg from liver and other visceral tissues (approximately 90 d) followed by a plateau. Subsequently, there was prolonged redistribution of spike THg into muscle (180 d). Loss of spike THg from the whole fish occurred > 5 times slower (half-life of 489 d) than in past laboratory studies using this species. We determined that MeHg bioaccumulation models with laboratory-based elimination rates produced faster losses than those observed in wild fish. The present findings provide support for refining elimination rates in MeHg models and show the importance of examining biological processes under natural conditions.     

Trophic magnification of PCBs and Its relationship to the octanol-water partition coefficient

We investigated polychlorinated biphenyl (PCB) bioaccumulation relative to octanol-water partition coefficient (K(OW)) and organism trophic position (TP) at the Lake Hartwell Superfund site (South Carolina). We measured PCBs (127 congeners) and stable isotopes (δ1?N) in sediment, organic matter, phytoplankton, zooplankton, macroinvertebrates, and fish. TP, as calculated from δ1?N, was significantly, positively related to PCB concentrations, and food web trophic magnification factors (TMFs) ranged from 1.5-6.6 among congeners. TMFs of individual congeners increased strongly with log K(OW), as did the predictive power (r2) of individual TP-PCB regression models used to calculate TMFs. We developed log K(OW)-TMF models for eight food webs with vastly different environments (freshwater, marine, arctic, temperate) and species composition (cold- vs warmblooded consumers). The effect of K(OW) on congener TMFs varied strongly across food webs (model slopes 0.0-15.0) because the range of TMFs among studies was also highly variable. We standardized TMFs within studies to mean = 0, standard deviation (SD) = 1 to normalize for scale differences and found a remarkably consistent K(OW) effect on TMFs (no difference in model slopes among food webs). Our findings underscore the importance of hydrophobicity (as characterized by K(OW)) in regulating bioaccumulation of recalcitrant compounds in aquatic systems, and demonstrate that relationships between chemical K(OW) and bioaccumulation from field studies are more generalized than previously recognized.     

Uptake and elimination routes of inorganic mercury and methylmercury in Daphnia magna

Mercury (Hg) is an important environmental pollutant due to its highly toxic nature and widespread occurrence in aquatic systems. The biokinetics of Hg in zooplankton have been largely ignored in previous studies. This study examines the assimilation, dissolved uptake, and efflux of inorganic mercury [Hg(II)] and methylmercury (MeHg) in a freshwater cladoceran, Daphnia magna, and models the exposure pathways of Hg(II) and MeHg in the daphnids. The assimilation efficiencies (AEs) of both Hg species decreased significantly with increasing algal carbon concentrations. The dissolved uptake of Hg(II) and MeHg was proportional to the ambient concentration (ranging from environmentally realistic to high concentration over a 3-4 orders of magnitude variation), whereas MeHg had a slightly higher uptake rate constant (0.46 L g(-1) h(-1)) than Hg(II) (0.35 L g(-1) h(-1)). Surprisingly, the efflux rate constants of Hg(ll) and MeHg were rather comparable (0.041 -0.063 day(-1)). The release of both Hg(II) and MeHg via different routes (excretion, egestion, molting, and neonate production) was further examined at different food concentrations. It was found that regeneration into the dissolved phase was important for D. magna to eliminate both Hg species, but maternal transfer of Hg(II) (11-15%) and MeHg (32-41%) to neonates represented another important pathway for the elimination of Hg(II) and MeHg from the mothers. Modeling results suggest that food is an important source for MeHg exposure (47-98%), but water exposure represents 31-96% of Hg(II) accumulation in D. magna, depending on the variation of Hg bioconcentration factor in ingested food. Furthermore, MeHg predominates the bioaccumulation of Hg in D. magna even though MeHg constitutes only a small percentage of the total Hg in the water. The results strongly indicate that maternal transfer of Hg(II) and MeHg in freshwater zooplankton should be considered in manytoxicity testings and risk assessment in aquatic food chains.     

Methylmercury in freshwater fish linked to atmospheric mercury deposition

A connection between accumulation of methylmercury (MeHg) in wild fish populations and atmospheric mercury deposition has not been made. Large databases for both MeHg in fish and atmospheric mercury deposition have been assimilated from monitoring efforts spanning the contiguous United States. Here, we compare results of these data sets and show that state-wide average concentrations of MeHg in a cosmopolitan freshwater fish, the largemouth bass Micropterus salmoides, are related positively to wet atmospheric Hg fluxes among most of the 25 states that are analyzed, which span a 5-fold range in Hg deposition. Differences in largemouth bass MeHg concentrations among states are unrelated to average precipitation depth, wet atmospheric acid deposition, or interstate variations in the type of water body (river, lake, reservoir) from which the fish were sampled. There are modest correlations between MeHg in bass and surface water pH, temperature, and wet atmospheric deposition of sulfate. However, when fish and atmospheric mercury results are combined at the state level, wet atmospheric Hg deposition accounts for about two-thirds of the variation in bass MeHg among most states, and stepwise multiple regression analysis reveals thatthese variables do not improve the linear model significantly. This suggests the accumulation of MeHg in wild fish populations is linked to atmospheric Hg loadings, two-thirds of which are estimated to be from anthropogenic sources.     

Stable carbon isotope ratio analysis of anhydrosugars in biomass burning aerosol particles from source samples

A new method for stable carbon isotope ratio analysis of anhydrosugars from biomass burning aerosol particle source filter samples was developed by employing Thermal Desorption--2 Dimensional Gas Chromatography--Isotope Ratio Mass Spectrometry (TD-2DGC-IRMS). Compound specific isotopic measurements of levoglucosan, mannosan, and galactosan performed by TD-2DGC-IRMS in a standard mixture show good agreement with isotopic measurements of the bulk anhydrosugars, carried out by Elemental Analyzer--Isotope Ratio Mass Spectrometry (EA-IRMS). The established method was applied to determine the isotope ratios of levoglucosan, mannosan, and galactosan from source samples collected during combustion of hard wood, softwood, and crop residues. δ(13)C values of levoglucosan were found to vary between -25.6 and -22.2‰, being higher in the case of softwood. Mannosan and galactosan were detected only in the softwood samples showing isotope ratios of -23.5‰ (mannosan) and -25.7‰ (galactosan). The isotopic composition of holocellulose in the plant material used for combustion experiments was determined with δ(13)C values between -28.5 and -23.7‰. The difference in δ(13)C of levoglucosan in biomass burning aerosol particles compared to the parent fuel holocellulose was found to be -1.89 (±0.37)‰ for the investigated biomass fuels. Compound specific δ(13)C measurements of anhydrosugars should contribute to an improved source apportionment.     

Biomagnification of DDT through the benthic and pelagic food webs of Lake Malawi, East Africa: importance of trophic level and carbon source

Lake Malawi, an East African Rift Valley lake, is internationally renowned for having the highest diversity of fish species in the world, and these cichlids are highly specialized in their dietary habits. In this lake, tissue stable carbon (delta13C) and nitrogen (delta15N) isotopes can be used over several trophic levels to distinguish those consumers relying upon carbon fixed by either benthic or pelagic primary producers. As such, it was possible to contrast the biomagnification of persistent organochlorines through the benthic and pelagic food webs. In 1996 and 1997, food-web organisms were collected from Lake Malawi and analyzed for organochlorines, delta13C and delta15N to determine the factors that affectthe biomagnification of contaminants in a tropical lake. The pesticide DDT was the most predominant pollutant in the biota from Lake Malawi and was found at the highest concentrations in the largest and fattiest fish species. As observed in temperate systems, log-transformed sigmaDDT concentrations in food-web organisms were significantly predicted by delta15N or log lipid (r2 = 0.32 and 0.40, respectively). In addition, the slope of the regression of log sigmaDDT versus delta15N was significantly higher in the pelagic than the benthic food web. These results indicate that pelagic organisms are at greater risk of accumulating these pollutants than biota relying upon benthic primary production.     

Biogeochemical cycling of methylmercury in lakes and tundra watersheds of Arctic Alaska

The fate of atmospherically deposited and environmentally active Hg is uncertain in the Arctic, and of greatest toxicological concern is the transformation to monometh-ylmercury (MMHg). Lake/watershed mass balances were developed to examine MMHg cycling in four northern Alaska lakes near the ecological research station at Toolik Lake (68 degrees 38' N, 149 degrees 36' W). Primary features of the cycle are watershed runoff, sedimentary production and mobilization, burial, and photodecomposition in the water column. The principal source of MMHg is in situ benthic production with 80-91% of total inputs provided by diffusion from sediments. The production and contribution of MMHg from tundra watersheds is modest. Photodecomposition, though confined to a short ice-free season, provides the primary control for MMHg (66-88% of total inputs) and greatly attenuates bioaccumulation. Solid-phase MMHg and gross potential rates of Hg methylation, assayed with an isotopic tracer, vary positively with the level of inorganic Hg in filtered pore water, indicating that MMHg production is Hg-limited in these lakes. Moreover, sediment-waterfluxes of MMHg (i.e., net production at steady state) are related to sediment Hg loadings from the atmosphere. These results suggest that loadings of Hg derived from atmospheric deposition are a major factor affecting MMHg cycling in arctic ecosystems. However, environmental changes associated with warming of the Arctic (e.g., increased weathering, temperature, productivity, and organic loadings) may enhance MMHg bioaccumulation by stimulating Hg methylation and inhibiting photodecomposition.