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.     

Studies of mercury pollution in a lake due to a thermometer factory situated in a tourist resort: Kodaikkanal, India

Kodaikkanal, India, suffered mercury contamination due to emissions and waste from a thermometer factory. Kodai Lake is situated to the north of the factory. The present study determined mercury in waters, sediment and fish samples and compared the values with those from two other lakes, Berijam and Kukkal. Total mercury (Hg(T)) of 356-465 ng l(-1), and 50 ng l(-1) of mercury in methyl mercury form were seen in Kodai waters while Berijam and Kukkal waters showed significantly lower values. Kodai sediment showed 276-350 mg/kg Hg(T) with about 6% methyl mercury. Berijam and Kukkal sediments showed Hg(T) of 189-226 mg/kg and 85-91 mg/kg and lower methylation at 3-4% and 2%, respectively. Hg(T) in fish from Kodai lake ranged from 120 to 290 mg/kg. The results show that pollution of the lake has taken place due to mercury emissions by the factory.     

Content and bioconcentration factors of mercury by Parasol Mushroom Macrolepiota procera

The carpophores of Parasol Mushroom and underlying soil substrate collected from several unpolluted and spatially distant sites across Poland were examined to know content and bioconcentration potential of mercury by this species. The total mercury content of the caps of Parasol Mushroom for the particular sites ranged from 1.1 +/- 1.0 to 8.4 +/- 7.4 microg/g dry matter (total range from 0.05 to 22 microg/g dm), while in the stalks were from 0.53 +/- 0.27 to 6.8 +/- 7.1 microg/g dm (total range from 0.078 to 20 microg/g dm). A top soil layer (0-10 cm) showed baseline mercury concentration from 0.022 +/- 0.011 to 0.36 +/- 0.16 microg/g dm (total range from 0.010 to 0.54 microg/g dm). Parasol Mushroom is an effective mercury accumulator in the carpophores and bioconcentration factor (BCF) values of this element in the caps and depending on the sampling site ranged from 16 +/- 6 to 220 +/- 110 (total range from 0.52 to 470), while for the stalks were from 7.6 +/- 2.6 to 130 +/- 96 (total range from 0.52 to 340). It seems reasonable to state that tolerance (maximum allowable concentration) of the total mercury in a single cap of Parasol Mushroom at unpolluted areas should not exceed 25 microg/g dm. A value greater then 25 mu g/g dm will imply an elevated content due to site pollution problems. Nevertheless, knowledge on highly toxic methylmercury content and its fraction in the total mercury content of Parasol Mushroom is lacking.     

Leeches as indicators of dietary mercury exposure in non-piscivorous waterfowl in central Ontario, Canada

We collected and analysed 113 leeches (Hirudinea) from 17 small lakes in the acid-stressed Muskoka region of central Ontario, Canada to examine the relationship between lake chemistry and mercury (Hg) concentrations in leeches, and thus determine whether leeches and other benthic invertebrates posed a dietary risk of Hg exposure for non-piscivorous waterfowl. Hg concentrations in leeches were generally low and only a few-fold above the detection limit (0.78 ng g(-1) wet weight (ww)). Mean Hg concentration in the bloodsucker Macrobdella decora was 6.94 +/- 0.78 SE ng g(-1) ww (n=49) and was 5.98 +/- 0.46 ng g(-1) ww (n=64) in the scavenger Percymoorensis marmoratis. Leech Hg concentrations were correlated with calcium and dissolved organic carbon concentrations in the water, respectively. These data suggest that leeches are not suitable monitors of Hg (usually as methylmercury) biomagnification in central Ontario lakes, and do not pose a dietary risk to non-piscivorous waterfowl.     

Mercury methylation in aquatic systems affected by acid deposition

Recently, it has been noted that fish in acidified lakes may contain elevated levels of mercury. While there is correlation among lakes between depressed pH and high mercury concentrations in fish, the cause of this problem is unknown. A number of hypotheses have been advanced in explanation, including increased mercury deposition, changes in mercury mobility due to acidification, pH dependent changes in mercury uptake by biota, and alterations in population size and/or structure which result in increased bioaccumulation in fish. Because fish accumulate mercury mainly in an organic form, methylmercury, changes in the biogeochemical cycling of this compound might account for elevated bioaccumulation. Mercury methylation is predominantly a microbial process which occurs in situ in lakes. This review focuses on microbiological and biogeochemical changes that may lead to increased levels of methylmercury in fresh waters impacted by acid-deposition. In particular, we focus on the hypothesis that sulfate-reducing bacteria are important mediators of metal methylation in aquatic systems and, moreover, that sulfate-deposition may stimulate methylmercury production by enhancing the activity of sulfate-reducing bacteria in sediments.     

Guidelines for routine mercury speciation analysis in seafood by gas chromatography coupled to a home-modified AFS detector. Application to the Andalusian coast (south Spain)

A home-modified atomic fluorescence detector (mAFS) has been employed for mercury and methylmercury determination in bivalves from the Andalusian coast (south Spain). This modification consists on the inclusion of a quartz flow cell into the detector, which increases the concentration of mercury atoms in the detector and therefore enhances sensitivity about two fold. Two analytical approaches for mercury speciation based on the coupling of gas chromatography on-line pyrolysis and mAFS (GC-Pyro-mAFS) have been tested. The first approach (Method 1) is based on aqueous ethylation followed by extraction into an organic solvent, and the second one (Method 2) in the extraction of monoalkylated mercury as chloride. Method 1 is a rapid procedure but not sensitive enough for the analysis of methylmercury in non-polluted sites (detection limit: 20 ng g(-1) as mercury, wet basis). The second one is quite more sensitive (detection limit: 0.2 ng g(-1), wet weight), but sample treatment is cumbersome and time-consuming. The optimum range for mercury determination for both methods are complementary and exhibit an overlapping measurable concentration range (OMCR) in which methylmercury can be indistinctly determined (75-100 ng g(-1) as mercury, wet basis). The suitability of both methods has been assayed with spiking experiences at levels within the OMCR with good recoveries. Both approaches have been validated with two certified reference materials (BCR-463, mercury and methylmercury in tuna fish; and NIST-2977, organic contaminants and trace metals in mussel tissue). Both procedures have been used for the analysis of three species of bivalve molluscs collected along the Andalusian coast (south Spain), all of them employed for human consumption (Chamelea gallina, Donax trunculus and Scrobicularia plana), and their potential use in routine analysis has been established.     

Modeling Mercury Fluxes and Concentrations in a Georgia Watershed Receiving Atmospheric Deposition Load from Direct and Indirect Sources

Abstract

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 μg/m². Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Modeling mercury fluxes and concentrations in a Georgia watershed receiving atmospheric deposition load from direct and indirect sources

This paper presents a modeling analysis of airborne mercury (Hg) deposited on the Ochlockonee River watershed located in Georgia. Atmospheric deposition monitoring and source attribution data were used along with simulation models to calculate Hg buildup in the subwatershed soils, its subsequent runoff loading and delivery through the tributaries, and its ultimate fate in the mainstem river. The terrestrial model calculated annual watershed yields for total Hg ranging from 0.7 to 1.1 microg/m2. Results suggest that approximately two-thirds of the atmospherically deposited Hg to the watershed is returned to the atmosphere, 10% is delivered to the river, and the rest is retained in the watershed. A check of the aquatic model results against survey data showed a reasonable agreement. Comparing observed and simulated total and methylmercury concentrations gave root mean square error values of 0.26 and 0.10 ng/L, respectively, in the water column, and 5.9 and 1 ng/g, respectively, in the upper sediment layer. Sensitivity analysis results imply that mercury in the Ochlockonee River is dominated by watershed runoff inputs and not by direct atmospheric deposition, and that methylmercury concentrations in the river are determined mainly by net methylation rates in the watershed, presumably in wetted soils and in the wetlands feeding the river.     

Improved preparation of small biological samples for mercury analysis using cold vapor atomic absorption spectroscopy

Concentrations of mercury in biological samples collected for environmental studies are often less than 0.1 microgram/g. Low mercury concentrations and small organ sizes in many wildlife species (approximately 0.1 g) increase the difficulty of mercury determination at environmentally relevant concentrations. We have developed a digestion technique to extract mercury from small (0.1 g), biological samples at these relevant concentrations. Mean recoveries (+/- standard error) from validation trials of mercury fortified tissue samples using cold vapor atomic absorption spectroscopy for analysis ranged from 102 +/- 4.3% (2.5 micrograms/L, n = 15) to 108 +/- 1.4% (25 micrograms/L, n = 15). Recoveries of inorganic mercury were 99 +/- 5 (n = 19) for quality assurance samples analyzed during environmental evaluations conducted during a 24 month period. This technique can be used to determine total mercury concentrations of 60 ng Hg/g sample. Samples can be analyzed in standard laboratories in a short time, at minimal cost. The technique is versatile and can be used to determine mercury concentrations in several different matrices, limiting the time and expense of method development and validation.     

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).     

Spatial distribution of polybrominated diphenyl ethers and polybrominated biphenyls in lake trout from the Laurentian Great Lakes

Concentrations of two types of brominated flame-retardants (BFRs); polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) were determined in a single age class of lake trout (Salvelinus namaycush) collected from the Laurentian Great Lakes in 1997. Mean concentrations of total PBDE were highest in samples from Lake Ontario at 95+/-22 ng/g wet weight (ww) or 434+/-100 ng/g lipid weight (lw) while the lowest concentrations were observed in Lake Erie lake trout (27+/-8.6 ng/g ww, 117+/-37 ng/g lw). In all samples, the predominant PBDE congeners were 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4', 6-pentabromodiphenyl ether (BDE-100), which are the primary components of the commonly used penta-BDE formulation flame retardant. Lake trout collected from Lake Huron had the highest concentrations of PBBs (3.1+/-1.7 ng/g ww, 15+/-8.5 ng/g lw), while the lowest levels were detected in fish from Lake Superior (0.25+/-0.13 ng/g ww, 1.7+/-0.89 ng/g lw). In all lake trout samples, 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), a major constituent of the flame-retardant FireMaster BP-6, was the predominant PBB congener.     

Bioaccumulation of mercury in a vestimentiferan worm living in Kagoshima Bay,Japan

The present study reports on the mercury concentrations of the vestimentiferan worm, Lamellibrachia satsuma, (Annelida: Pogonophora) found near hydrothermal vents at a depth of 80-100 m in the northern parts of Kagoshima Bay. The vestimentiferan worms had total mercury concentrations of 238 ng/g in the anterior muscle of the body and 164 ng/g in the posterior trophosome. Methylmercury constituted only 7.6% of total mercury detected anteriorly and 16.3% posteriorly. The mean total mercury concentration in filtrated ambient seawater of the worm habitat was 1.1 ng/l. The worm should accumulate mercury in seawater by a one-step into the anterior and posterior parts as 2.2 x 10(%) and 1.5 x 10(5) times those of the filtered ambient seawater, respectively. The bioaccumulation factor of mercury by the worms with only their respiration would be actually larger than that by other marine animals through food webs. The high bioaccumulation factor of mercury in the worms suggest the following two possibilities: (i) the biological half-life of organomercury in the worm could be exceptionally long; or (ii) the lifetime of vestimentiferan worms examined in the present study could be extremely long. Various metals in one specimen of the worm were analyzed by using ICP-MS, and then gold as well as silver were detected in the worm. Gold was detected for the first time from marine animals.     

Changes in trace metal concentrations in lake water and biota during experimental acidification of Little Rock Lake, Wisconsin, USA

Little Rock Lake, a small (18 ha), low-alkalinity (25 microeq litre(-1), pH 6.1) seepage lake in northern Wisconsin, was divided into two basins by a flexible, inert barrier and, beginning in spring 1985, the north basin was acidified in three 2-year steps to pH 5.6, 5.1 and 4.7. The annual average pH of the reference basin remained near 6.1. As part of a comprehensive programme to determine the chemical and biological responses to acidification, minor metals (Al, Fe, Mn) and trace metals (Cd, Cu, Pb, Zn) in lake water (0.4 microm pore filtered samples), periphyton, zooplankton, and yellow perch (Perca flavescens) were measured. At pH 5.6, dissolved Mn and Fe increased in the acidified basin. At pH 5.1 and 4.7, dissolved Al, Fe, Mn, Cd and Zn were elevated in the acidified basin. At pH 4.7, dissolved Pb in the acidified basin became elevated over reference basin levels. Dissolved Cu remained similar in both basins down to pH 4.7. Cd burdens in periphyton collected on artificial substrates were lower in the treatment basin at pH 5.1 (1.8 microg g(-1) dry wt.) than in the reference basin at pH 6.1 (7.5 microg g(-1) dry wt.), but Al and Fe burdens in periphyton were similar in both basins. Likewise, Cd levels in muscle tissue of perch from the treatment basin at pH 4.7 were lower (26 ng g(-1) dry wt.) than in the reference basin at pH 6.1 (36 ng g(-1) dry wt.); Al and Fe burdens were similar in perch muscle tissue from both basins. Levels of Cd and Fe in zooplankton from the acidified basin at pH 4.7 were approximately equal to 2x higher than in animals from the reference basin. In both basins of the lake, Al and Cd levels in lake biota decreased with increasing trophic level, demonstrating that food chain biomagnification does not occur for these metals.     

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.     

Distribution of total and methylmercury in different ecosystem compartments in the Everglades: implications for mercury bioaccumulation

We analyzed Hg species distribution patterns among ecosystem compartments in the Everglades at the landscape level in order to explore the implications of Hg distribution for Hg bioaccumulation and to investigate major biogeochemical processes that are pertinent to the observed Hg distribution patterns. At an Everglade-wide scale, THg concentrations were significantly increased in the following order: periphyton相似文献   

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.     

Measured summertime concentrations of particulate components,Hg0, and speciated polycyclic aromatic hydrocarbons at rural sites in New York State

Daily PM2.5 samples, Hg0 and speciated polycyclic aromatic hydrocarbon (PAH) were simultaneously collected at Potsdam and Stockton site in NY during the summers of 2000 and 2001. Samples for determination of the mass concentration and chemical composition of the PM2.5 were obtained with a speciation network PM2.5 sampler. Chemical composition including trace elemental composition, water-soluble ions, and elemental carbon were analyzed. Elemental mercury and PAHs were sampled separately. Daily PM2.5 concentrations ranged from 0.47 to 53.7 microg m(-3) at the Potsdam site, and from 0.82 to 47.23 microg m(-3) at the Stockton site with large daily differences between the two sites. Potsdam consistently had lower mass values than Stockton. The greatest contributors to the PM2.5 mass (generally >0.1 microg/m(3)) were sulfate, nitrate, ammonium, and BC at both sites. Seventeen PAHs were identified at each site in 2000 and the average total concentrations were 3.2 ng/m(3) and 2.9 ng/m(3) at the Potsdam and Stockton sites, respectively. The mean vapor phase mercury concentration at the Potsdam site (2.4 +/-1.2 ng m(-3), n=93) was higher than that at the Stockton site (1.2 +/- 1.0 ng m(-3), n=60) in 2000, whereas in 2001, the average concentrations were 1.1 ng m(-3) and 1.6 ng m(-3) at the Potsdam and Stockton sites, respectively. In general, vapor phase mercury concentrations increased with increasing ambient temperature at the Stockton site in 2000. These differences in values between 2000 and 2001 can be largely explained by distinct differences in the meteorological regimes that dominated in the different years.     

Distribution of total mercury and methylmercury in lake sediments in Arctic Ny-Ålesund

The toxicities and bioavailabilities of total mercury (THg) and methylmercury (MeHg) in aquatic systems have made them the subjects of recent research. In this study, we collected a lake sediment core from Ny-Ålesund in Svalbard and analyzed the distributions of THg and MeHg in the sediments. The increased trend of THg was caused by anthropogenic contamination since the 14th century through long-range transportation, especially after the industrial era. However, the peak values of Hg in surface sediment samples could be explained by the increased algal scavenging process in recent decades. All the biogeochemical proxies (e.g., pigments and diatom biomass) revealed recent sharp increases in aquatic primary production due to the current climate warming. Rock-Eval analyses indicated that algal-derived organic matter took up a large portion, and quantitative calculation showed that 89.6-95.8% of the Hg in post-1950 could be explained by scavenging. The distribution of MeHg has a close relationship with total Hg and organic matter. The oxidation-reduction condition is one of the possible factors affecting the methylation rates in H2 lake sediments. Higher algal productivity and organic matter actually led to the increased trend of methylation in the uppermost sediment. This study supports some new key hypotheses on climate-driven factors affecting Hg and MeHg cycling in High Arctic lake sediments.     

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.