Mercury body burdens in Gambusia holbrooki and Erimyzon sucetta in a wetland mesocosm amended with sulfate

This study used an experimental model of a constructed wetland to evaluate the risk of mercury methylation when the soil is amended with sulfate. The model was planted with Schoenoplectus californicus and designed to reduce copper, mercury, and metal-related toxicity in a wastestream. The sediments of the model were varied during construction to provide a control and two levels of sulfate treatment, thus allowing characterization of sulfate's effect on mercury methylation and bioaccumulation in periphyton and two species of fish--eastern mosquitofish (Gambusia holbrooki) and lake chubsucker (Erimyzon sucetta). After one year in the experimental model, mean dry-weight normalized total mercury concentrations in mosquitofish from the non-sulfate treated controls (374+/-77 ng/g) and the reference location (233+/-17 ng/g) were significantly lower than those from the low and high sulfate treatments (520+/-73 and 613+/-80 ng/g, respectively). For lake chubsucker, mean total mercury concentration in fish from the high sulfate treatment (276+/-63 ng/g) was significantly elevated over that observed in the control (109+/-47 ng/g), the low sulfate treatment (122+/-42 ng/g), and the reference population (41+/-2 ng/g). Mercury in periphyton was mostly inorganic as methylmercury ranged from 6.6 ng/g (dry weight) in the control to 9.8 ng/g in the high sulfate treatment, while total mercury concentrations ranged from 1147 ng/g in the control to a high of 1297 ng/g in the low sulfate treatment. Fish methylmercury bioaccumulation factors from sediment ranged from 52 to 390 and from 495 to 3059 for water. These results suggest that sulfate treatments add a factor of risk due to elevated production of methylmercury in sediment and porewater which biomagnified into small fish, and may potentially increase through the food web.     

Dietary mercury exposure and bioaccumulation in amphibian larvae inhabiting Carolina bay wetlands

Inorganic mercury and methylmercury concentrations were measured both in guts and remaining carcasses of southern leopard frog (Rana sphenocephala) larvae from 10 Carolina bay wetlands in South Carolina, USA. Significant variation among bays in methylmercury and inorganic mercury concentrations existed both in guts and carcasses. There was a moderate negative correlation between dissolved organic carbon concentration in bays and mean inorganic mercury concentrations in guts. There was also a weak positive correlation between pH in bays and mean methylmercury concentrations in carcasses. The ratio of methylmercury to inorganic mercury decreased with increasing total mercury concentration in guts and in larvae, but the rate of decrease was highly variable among bays. Ratios of concentrations in carcasses to concentrations in guts were inversely related to gut concentration. Mercury concentrations in carcasses in some bays were within the range of concentrations at which adverse effects have been observed in laboratory studies of R. sphenocephala.     

Mercury cycling in surface water, pore water and sediments of Mugu Lagoon, CA, USA

Mugu Lagoon is an estuary in southern California, listed as impaired for mercury. In 2005, we examined mercury cycling at ten sites within at most four habitats. In surface water (unfiltered and filtered) and pore water, the concentration of total mercury was correlated with methylmercury levels (R2=0.29, 0.26, 0.27, respectively, p<0.05), in contrast to sediments, where organic matter and reduced iron levels were most correlated with methylmercury content (R2=0.37, 0.26, respectively, p<0.05). Interestingly, levels for percent methylmercury of total mercury in sediments were higher than typical values for estuarine sediments (average 5.4%, range 0.024-38%, n=59), while pore water methylmercury Kd values were also high (average 3.1, range 2.0-4.2l kg(-1), n=39), and the estimated methylmercury flux from sediments was low (average 1.7, range 0.14-5.3ng m(-2) day(-1), n=19). Mercury levels in predatory fish tissue at Mugu are >0.3ppm, suggesting biogeochemical controls on methylmercury mobility do not completely mitigate methylmercury uptake through the food web.     

Effect of point source removal on mercury bioaccumulation in an industrial pond

A one hectare pond on the headwaters of a mercury-contaminated creek in Oak Ridge, Tennessee acted as a biochemical reactor for the production of methylmercury, increasing waterborne methylmercury concentrations in the stream below the pond discharge. The flow of the creek was diverted around the pond in order to eliminate this input. Waterborne total mercury, methylmercury, and mercury in fish, were monitored in the pond and stream before and after bypass. Waterborne methylmercury concentration in the creek downstream from the pond decreased over 800% following diversion of streamflow around the pond, but mercury in redbreast sunfish in the pond tailwater did not decline similarly. Within the pond, now isolated from fresh waterborne mercury inputs from the stream, methylmercury concentrations in the water column remained similar to levels present before bypass. However, mercury concentrations in sunfish in the pond decreased approximately 75% following bypass, despite the continued presence of highly contaminated sediments (approximately 50 mg Hg/kg dry weight). We concluded that a decrease in the fraction of 'dissolved methylmercury' in the isolated pond relative to pre-bypass conditions explained the decrease in mercury in fish within the pond. That observation also indicates that mercury associated with pond sediments was relatively unavailable for eventual bioaccumulation when compared to 'fresh' mercury contributed by upstream sources. The lack of a post-bypass decrease in mercury concentrations in tailwater fish was also likely to be associated with the particle-associated nature of waterborne methylmercury exported from the pond.     

Relationship between the loading rate of inorganic mercury to aquatic ecosystems and dissolved gaseous mercury production and evasion

The purpose of our study was to test the hypothesis that dissolved gaseous mercury (DGM) production and evasion is directly proportional to the loading rate of inorganic mercury [Hg(II)] to aquatic ecosystems. We simulated different rates of atmospheric mercury deposition in 10-m diameter mesocosms in a boreal lake by adding multiple additions of Hg(II) enriched with a stable mercury isotope (²⁰²Hg). We measured DGM concentrations in surface waters and estimated evasion rates using the thin-film gas exchange model and mass transfer coefficients derived from sulfur hexafluoride (SF₆) additions. The additions of Hg(II) stimulated DGM production, indicating that newly added Hg(II) was highly reactive. Concentrations of DGM derived from the experimental Hg(II) additions (“spike DGM”) were directly proportional to the rate of Hg(II) loading to the mesocosms. Spike DGM concentrations averaged 0.15, 0.48 and 0.94 ng l⁻¹ in mesocosms loaded at 7.1, 14.2, and 35.5 μg Hg m⁻² yr⁻¹, respectively. The evasion rates of spike DGM from these mesocosms averaged 4.2, 17.2, and 22.3 ng m⁻² h⁻¹, respectively. The percentage of Hg(II) added to the mesocosms that was lost to the atmosphere was substantial (33–59% over 8 weeks) and was unrelated to the rate of Hg(II) loading. We conclude that changes in atmospheric mercury deposition to aquatic ecosystems will not change the relative proportion of mercury recycled to the atmosphere.     

Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem

Our objective was to examine how the behavior of atmospheric mercury (Hg) deposited to boreal lake mesocosms changed over time. We added inorganic Hg enriched in a different stable isotope in each of two years, which allowed us to differentiate between Hg added in the first and second year. Although inorganic Hg and methylmercury (MeHg) continued to accumulate in sediments throughout the experiment, the availability of MeHg to the food web declined within one year. This decrease was detected in periphyton, zooplankton, and water mites, but not in gomphid larvae, amphipods, or fish. We suggest that reductions in atmospheric Hg deposition should lead to decreases in MeHg concentrations in biota, but that changes will be more easily detected in short-lived pelagic species than long-lived species associated with benthic food webs.     

Phytotoxicity of atrazine, isoproturon, and diuron to submersed macrophytes in outdoor mesocosms

The submersed macrophytes Elodea canadensis, Myriophyllum spicatum and Potamogeton lucens were constantly exposed over a five-week period to environmentally relevant concentrations of atrazine, isoproturon, diuron, and their mixture in outdoor mesocosms. Effects were evaluated investigating photosynthetic efficiency (PE) of the three macrophytes and growth of M. spicatum and E. canadensis. Adverse effects on PE were observed on days 2 and 5 after application. M. spicatum was found to be the more sensitive macrophyte. E. canadensis and P. lucens were less sensitive to atrazine, diuron and the mixture and insensitive to isoproturon. PE of M. spicatum was similarly affected by the single herbicides and the mixture demonstrating concentration addition. Growth of E. canadensis and M. spicatum was not reduced indicating that herbicide exposure did not impair plant development. Although PE measurements turned out to be a sensitive method to monitor PSII herbicides, plant growth remains the more relevant ecological endpoint in risk assessment.     

Total mercury and methylmercury in freshwater and salt marsh soils of the Mississippi river deltaic plain

Mercury entering wetland environments can be microbially methylated to methylmercury. The purpose of this study was to investigate the historical rate of mercury accumulation and distribution of total and methylmercury in soil profile of Louisiana coastal marshes. Two sediment cores each were taken from Louisiana freshwater marsh and salt marsh. Vertical accretion was determined using the 137Cs dating technique. Total and methylmercury were determined with depth in the soil profiles. The fresh marsh soil on a dry weight basis contained more total and methylmercury than the salt marsh. Average vertical accretion rates in freshwater marsh and salt marsh were 0.90 and 0.75 cm year(-1), respectively. Average total and methylmercury content (to a depth of 30 cm) was 140 and 4.19 microg kg(-1) and 80 and 1.34 microg kg(-1) for the fresh and salt marsh, respectively. Due to greater sediment input resulting in a higher bulk density the salt marsh contained more total mercury per m2 (to 30 cm depth) than the fresh water marsh (5340 microg m(-2) as compared to 2929 microg m(-2)). The amount of methylmercury per m2 to depth of 30 cm was approximately the same for each marsh.     

Methylmercury speciation in the dissolved phase of a stratified lake using the diffusive gradient in thin film technique

The diffusive gradient in thin film (DGT) technique was successfully used to monitor methylmercury (MeHg) speciation in the dissolved phase of a stratified boreal lake, Lake 658 of the Experimental Lakes Area (ELA) in Ontario, Canada. Water samples were conventionally analysed for MeHg, sulfides, and dissolved organic matter (DOM). MeHg accumulated by DGT devices was compared to MeHg concentration measured conventionally in water samples to establish MeHg speciation. In the epilimnion, MeHg was almost entirely bound to DOM. In the top of the hypolimnion an additional labile fraction was identified, and at the bottom of the lake a significant fraction of MeHg was potentially associated to colloidal material. As part of the METAALICUS project, isotope enriched inorganic mercury was applied to Lake 658 and its watershed for several years to establish the relationship between atmospheric Hg deposition and Hg in fish. Little or no difference in MeHg speciation in the dissolved phase was detected between ambient and spike MeHg.     

Importance of sulfate reducing bacteria in mercury methylation and demethylation in periphyton from Bolivian Amazon region

Sulfate reducing bacteria (SRB) are important mercury methylators in sediments, but information on mercury methylators in other compartments is ambiguous. To investigate SRB involvement in methylation in Amazonian periphyton, the relationship between Hg methylation potential and SRB (Desulfobacteraceae, Desulfobulbaceae and Desulfovibrionaceae) abundance in Eichhornia crassipes and Polygonum densiflorum root associated periphyton was examined. Periphyton subsamples of each macrophyte were amended with electron donors (lactate, acetate and propionate) or inhibitors (molybdate) of sulfate reduction to create differences in SRB subgroup abundance, which was measured by quantitative real-time PCR with primers specific for the 16S rRNA gene. Mercury methylation and demethylation potentials were determined by a stable isotope tracer technique using ²⁰⁰HgCl and CH₃²⁰²HgCl, respectively. Relative abundance of Desulfobacteraceae (<0.01-12.5%) and Desulfovibrionaceae (0.01-6.8%) were both highly variable among samples and subsamples, but a significant linear relationship (p < 0.05) was found between Desulfobacteraceae abundance and net methylmercury formation among treatments of the same macrophyte periphyton and among all P. densiflorum samples, suggesting that Desulfobacteraceae bacteria are the most important mercury methylators among SRB families. Yet, molybdate only partially inhibited mercury methylation potentials, suggesting the involvement of other microorganisms as well. The response of net methylmercury production to the different electron donors and molybdate was highly variable (3-1104 pg g⁻¹ in 12 h) among samples, as was the net formation in control samples (17-164 pg g⁻¹ in 12 h). This demonstrates the importance of community variability and complexity of microbial interactions for the overall methylmercury production in periphyton and their response to external stimulus.     

Assessing biological and chemical signatures related to nutrient removal by floating islands in stormwater mesocosms

Aquatic floating plants on BioHaven mats were tested for their potential use as a Best Management Practice to be incorporated within existing stormwater detention ponds. Plants were analyzed for their capability to remove nutrient-pollution in parallel with the study of ecological dynamics. Experiments were carried out in cylindrical mesocosms of 5 m diameter and 1.2 m height, above-ground pools with a water volume of 14 m³. The design parameters tested were for 5% and 10% vegetated floating island coverage of the mesocosm, both with and without shoreline plants called littoral zone. This littoral shelf was 0.5 m thick, graded at a downward slope of 1:5 toward the center using loamy soil with low organic matter content, excavated from below turf grass. Endemic plant species were chosen for the experimental location in central Florida based on a wetland identification manual by the Florida Department of Environmental Protection to ensure the study was not compromised by unique climate requirements of the plants. Nutrient and aquatic chemical conditions such as pH, dissolved oxygen, temperature, turbidity, and chlorophyll a were monitored to understand their relationships to the general wetland ecosystem. Real-time polymerase chain reaction analysis identified the microbial activity near the rhizospheric zone. Logistical placement considerations were made using spatial sampling across the horizontal plane of the mesocosms, beneath and around the root zone, to determine if nutrients tend to aggregate around the floating island. This study concluded that the application of floating islands as a stormwater technology can remove nutrients through plant uptake and biological activity. The most cost-effective size in the outdoor mesocosms was 5% surface area coverage of the mat.     

Mercury and selenium in wild and experimental seals

This paper describes the tissue distribution of inorganic mercury, organic mercury and selenium in Dutch and British seals as well as in seals which were dosed with methylmercury under experimental conditions.In the experimental animals, a time-related increase of both mercury and selenium was found in liver and kidney after the administration of methylmercury, while in the other tissues examined, e.g. brain, thyroid, blood, only the concentrations of mercury increased.In the wild seals, it was also demonstrated that the selenium concentrations showed a positive correlation with the concentrations of mercury.Atomic ratios of mercury and selenium were close to one in the wild seals as was also found in previous studies. However, atomic ratios above one were found in seals fed additional methylmercury.In vitro studies with liver homogenates of seals did not provide evidence for the presence of a biochemical demethylation mechanism nor for any effect of selenium on the demethylation process.     

Total mercury and methylmercury concentrations in native and invasive fish species in Shadegan International Wetland,Iran, and health risk assessment

Human exposure to mercury (Hg) mainly occurs through consumption of aquatics, especially fish. In aquatic systems, the bioaccumulation of Hg across trophic levels could be altered by invasive species through changing community composition. The present study is aimed at measuring total mercury (T-Hg) and methylmercury (MeHg) concentrations in non-native (redbelly tilapia (Tilapia zillii)) and native (Benni (Mesopotamichthys sharpeyi) and common carp (Cyprinus carpio)) fish species throughout Shadegan International Wetland and comparing health risk of their mercury contents to the local population. The concentrations were measured using a direct mercury analyzer (DMA 80). The average values of T-Hg and MeHg for native fishes were 19.8 and 10.49 μg/kg. These concentrations for the invasive fish were 28 and 14.62 μg/kg respectively. Despite having less length and weight than the native fish species, tilapia showed significantly higher T-Hg content, yet the lowest concentration of MeHg was observed in common carp with larger body length and weight. Concerning mercury health risk to consumers, tilapia demonstrated the highest estimated weekly intake (EWI) and percentages of tolerable weekly intake (%TWI) for both T-Hg and MeHg, while the highest hazard quotient (HQ) values were obtained for tilapia and Benni. Taken together, the mercury concentrations in the two native and non-native fishes were acceptable according to the international safety guidelines although the local people shall be warned for consumption of tilapia. Furthermore, the low calculated value of tissue residue criterion (TRC) for the wetland fishes sounds a warning.     

Mercury exposure in the freshwater tilapia Oreochromis niloticus

Mercury (Hg) can be strongly accumulated and biomagnified along aquatic food chain, but the exposure pathway remains little studied. In this study, we quantified the uptake and elimination of both inorganic mercury [as Hg(II)] and methylmercury (as MeHg) in an important farmed freshwater fish, the tilapia Oreochromis niloticus, using ²⁰³Hg radiotracer technique. The dissolved uptake rates of both mercury species increased linearly with Hg concentration (tested at ng/L levels), and the uptake rate constant of MeHg was 4 times higher than that of Hg(II). Dissolved uptake of mercury was highly dependent on the water pH and dissolved organic carbon concentration. The dietborne assimilation efficiency of MeHg was 3.7-7.2 times higher than that of Hg(II), while the efflux rate constant of MeHg was 7.1 times lower. The biokinetic modeling results showed that MeHg was the greater contributor to the overall mercury bioaccumulation and dietary exposure was the predominant pathway.     

Effects of pH and feeding regime on methylmercury accumulation within aquatic microcosms

The effect of pH (pH 5, 6 or 7) on accumulation of radiolabelled methylmercury was examined using a laboratory microcosm system. Accumulation of labelled mercury at three trophic levels, primary consumers (Daphnia magna), secondary consumers (rainbow trout, Salmo gairdneri) and tertiary consumers (walleye, Stizostedion vitreum) was not significantly affected by pH. Our results are in direct contrast with field observations of elevated methylmercury concentrations in fish from low pH water and indicate that the elevated mercury residues observed in the field result from factors other than the direct effects of pH on accumulation of methylmercury by aquatic organisms. Both water and diet were important as sources of the labelled mercury which was accumulated by walleye. Walleye which were fed rainbow trout, that had accumulated labelled mercury from within the experimental microcosms, accumulated almost twice as much labelled mercury as walleye fed non-labelled prey, or walleye which were not fed. Walleye fed non-labelled rainbow trout accumulated slightly more labelled mercury than walleye which were not fed, presumably as a result of the higher metabolic rate of the fish which were fed.     

Interactions between mercury and dissolved organic matter--a review

Dissolved organic matter (DOM) interacts very strongly with mercury, affecting its speciation, solubility, mobility, and toxicity in the aquatic environment. Strong binding of mercury by DOM is attributed to coordination of mercury at reduced sulfur sites within the organic matter, which are present at concentrations much higher than mercury concentrations found in most natural waters. The ability of organic matter to enhance the dissolution and inhibit the precipitation of mercuric sulfide, a highly insoluble solid, suggests that DOM competes with sulfide for mercury binding. This is confirmed by very high conditional stability constants for mercury-organic sulfur (RSHg+) complexes (10(25)-10(32)) recently reported in literature. DOM appears to play a key role in the photochemical reduction of ionic mercury to elemental mercury and subsequent reoxidation of elemental mercury to ionic mercury, thus affecting volatilization loss and bioavailability of mercury to organisms. DOM affects the production and bioaccumulation of methylmercury, the most bioaccumulative mercury species in fish.     

Floodplain methylmercury biomagnification factor higher than that of the contiguous river (South River, Virginia USA)

Mercury biomagnification on the South River floodplain (Virginia, USA) was modeled at two locations along a river reach previously modeled for methylmercury movement through the aquatic trophic web. This provided an opportunity to compare biomagnification in adjoining trophic webs. Like the aquatic modeling results, methylmercury-based models provided better prediction than those for total mercury. Total mercury Food Web Magnification Factors (FWMF, fold per trophic level) for the two locations were 4.9 and 9.5. Methylmercury FWMF for the floodplain locations were higher (9.3 and 25.1) than that of the adjacent river (4.6). Previous speculation was not resolved regarding whether the high mercury concentrations observed in floodplain birds was materially influenced by river prey consumption by riparian spiders and subsequent spider movement into the trophic web of the adjacent floodplains. Results were consistent with a gradual methylmercury concentration increase from contaminated floodplain soil, to arthropod prey, and finally, to avian predators.     

Mercury concentration in black flies Simulium spp. (Diptera, Simuliidae) from soft-water streams in Ontario, Canada

Total Hg in Simulium spp. (Diptera, Simuliidae) was measured in 17 soft-water streams in the District of Muskoka and Haliburton County (Ontario, Canada) during 2003 and 2004. Black flies contained 0.07-0.64 microg/g total Hg (dry weight). The methylmercury concentration was measured in 6 samples of the 17, and ranged from 58% to 93% of total Hg. The concentration of total Hg is much higher than has been found in other filter feeding insects, and represents a significant potential source of Hg to fish. Mercury concentrations in Simulium spp. at different sites were strongly positively correlated with dissolved organic carbon, and the proportion of land within each catchment that was wetland. There was also a strong negative correlation with pH. By examining Hg concentration in filter feeding insects we have found a significant entry point for Hg and MeHg into the food web.     

Mercury burdens in Chinese mitten crabs (Eriocheir sinensis) in three tributaries of southern San Francisco Bay, California, USA

Chinese mitten crabs (Eriocheir sinensis), endemic to Asia, were first reported in the San Francisco Bay in 1992. They are now established in nearly all San Francisco Bay tributaries. These crabs accumulate more metals, such as mercury, than crustaceans living in the water column. Because their predators include fish, birds, mammals and humans, their mercury burdens have an exceptional potential to impact the ecosystem and public health. We sought to elucidate the potential threat of mitten crab mercury burdens in three adjacent streams in southern San Francisco Bay, one of which is known to be contaminated with mercury. Mitten crabs had hepatopancreas concentrations of total mercury and methylmercury that did not differ among streams. The maximum burden we measured was below the action level of 1 ppm recommended by the USEPA. Hepatopancreas concentrations of methylmercury declined with increasing crab size, suggesting a mechanism for mercury excretion and that predators might reduce mercury exposure if they select larger crabs. Because mercury may be heterogeneously distributed among tissues, estimation of the impacts of crab mercury burdens on the environment requires more data on the feeding preferences of predators.     

Transformation of effluent organic matter during subsurface wetland treatment in the Sonoran Desert

The fate of dissolved organic matter (DOM) during subsurface wetland treatment of wastewater effluent in a hot, semi-arid environment was examined. The study objectives were to (1) discern changes in the character of dissolved organics as consequence of wetland treatment (2) establish the nature of wetland-derived organic matter, and (3) investigate the impact of wetland treatment on the formation potential of trihalomethanes (THMs). Subsurface wetland treatment produced little change in DOM polarity (hydrophobic-hydrophilic) distribution. Biodegradation of labile effluent organic matter (EfOM) and internal loading of wetland-derived natural organic matter (NOM) together produced only minor changes in the distribution of carbon moieties in hydrophobic acid (HPO-A) and transphilic acid (TPI-A) isolates of wetland effluent. Aliphatic carbon decreased as a percentage of total carbon during wetland treatment. The ratio of atomic C:N in wetland-derived NOM suggests that its character is determined by microbial activity. Formation of THMs upon chlorination of HPO-A and TPI-A isolates increased as a consequence of wetland treatment. Wetland-derived NOM was more reactive in forming THMs and less biodegradable than EfOM. For both HPO-A and TPI-A fractions, relationships between biodegradability and THM formation potential were similar among EfOM and NOM isolates; the less biodegradable isolates exhibited greater THM formation potential.