Continuous analysis of dissolved gaseous mercury and mercury volatilization in the upper St. Lawrence River: exploring temporal relationships and UV attenuation

The formation and volatilization of dissolved gaseous mercury (DGM) is an important mechanism by which freshwaters may naturally reduce their mercury burden. Continuous analysis of surface water for diurnal trends in DGM concentration (ranging from 0 to 60.4 pg L(-1); n=613), mercury volatilization (ranging from 0.2 to 1.1 ng m(-2) h(-1); n=584), and a suite of physical and chemical measurements were performed during a 68 h period in the St. Lawrence River near Cornwall (Ontario, Canada) to examine the temporal relationships governing mercury volatilization. No lag-time was observed between net radiation and OGM concentrations (highest cross-correlation of 0.817), thus supporting previous research indicating faster photoreduction kinetics in rivers as compared to lakes. A significant lag-time (55-145 min; maximum correlation = 0.625) was observed between DGM formation and mercury volatilization, which is similar to surface water Eddy diffusion times of 42-132 min previously measured in the St. Lawrence River. A depth-integrated DGM model was developed using the diffuse integrated vertical attenuation coefficients for UVA and UVB (K(dI UVA) = 1.45 m(-1) K(dI UVB)= 3.20 m(-1)) Low attenuation of solar radiation was attributed to low concentrations of dissolved organic carbon (mean = 2.58 mg L(-1) and particulate organic carbon (mean = 0.58 mg L(-1) in the St. Lawrence River. The depth-integrated DGM model developed found that the top 0.3 m of the water column accounted for only 26% of the total depth-integrated DGM. A comparison with volatilization data indicated that a large portion (76% or 10.5 ng m(-2) of the maximum depth-integrated DGM (13.8 ng m(-2))is volatilized over a 24 h period. Therefore, at least 50% of all DGM volatilized was produced at depths below 0.3 m. These results highlight the importance of solar attenuation in regulating DGM formation with depth. The results also demonstrate both the fast formation of DGM in rivers and the importance of understanding DGM dynamics with depth as opposed to surface waters.     

Change of dissolved gaseous mercury concentrations in a southern reservoir lake (Tennessee) following seasonal variation of solar radiation

A 12-month field study was conducted consecutively from June 2003 to May 2004 to quantify temporal variations of dissolved gaseous mercury (DGM) concentrations in Cane Creek Lake, a southern reservoir lake (Cookeville, TN). Diurnal changes of DGM concentrations in two periods (morning increase vs afternoon decrease with an around-noon peak) were observed, and the changes closely followed daily solar radiation variation trends. The diurnal patterns prevailed in the late spring and summer, but became vague in the late fall and winter. The monthly mean DGM concentrations peaked at 40.8 pg L(-1) in July and reached the lowest at 14.2 pg L(-1) in December and 21.9 pg L(-1) in January; this DGM concentration change closely followed the monthly mean solar radiation variation trend. The increase of the lake DGM concentration from January to July and its decrease from July to December mirror the typical daily rhythm of DGM concentration variations in the two periods. This finding supports the following hypothesis: The natural phenomenon of daily oscillation of freshwater DGM concentrations that follows diurnal solar radiation variation would manifest on a seasonal scale. High DGM concentrations were found in the spring and summer and low in the fall and winter (seasonal mean: 34.2, 37.5, 20.0, 24.4 pg L(-1), respectively). This seems to suggest an annual occurrence of two periods of the seasonal DGM level fluctuation (spring and summer high vs fall and winter low DGM levels). Linear relationships of the monthly mean DGM concentrations were found with the monthly mean global solar radiation (R2 = 0.82, P < 0.05) and UVA radiation (R2 = 0.84, P < 0.05). Linear relationships of the seasonal mean DGM concentrations were also found with the seasonal mean global solar radiation (R2 = 0.85, P = 0.08) and UVA radiation (R2 = 0.93, P < 0.05).     

Gross photoreduction kinetics of mercury in temperate freshwater lakes and rivers: application to a general model of DGM dynamics

Previous published measurements of mercury photoreduction are for net-photoreduction, since photooxidation processes occur simultaneously. In this research we combine continuous dissolved-gaseous mercury (DGM) analysis with a photoreactor and a quartz sparger in order to derive mercury gross photoreduction rate constants for UVB and UVA irradiations. The DGM concentration in each filter-sterilized freshwater was measured at 5 min intervals over a period of 23 h. Photoreduction proceeded for the initial 200 min, after which, reducible mercury was depleted in the sample. Substantial losses in DOC fluorescence were observed during the incubations for UVA radiation but not for UVB; therefore, UVB photoreduction dynamics are not linked to a loss in DOC fluorescence. Pseudo first-order reaction kinetics fit the data well (r2 > 0.87). The rate constants appear divided between lakes and rivers with the mean lake UVB rate constant (kUVB = 8.91 x 10(-5) s(-1)), significantly less than the mean rate constant (kUVB = 1.81 x 10(-4) s(-1)) for the river samples. However, while there were differences for the UVB rates between lakes and rivers, the mean and median rate constants for UVA in lakes (kUVA = 7.76 x 10(-5) s(-1)) did not differ significantly from the mean rate constant forthe river sites (kUVA = 1.78 x 10(-4) s(-1)). Here, we propose a model for mercury photoredox dynamics for both temperate lake and river systems. The lake model was validated using principal axis analysis to compare observed and predicted DGM data (n=279) from a variety of lake sites in Nova Scotia and Central Quebec. Principal axis analysis found a linear fit (correlation = 0.81; slope = 2.13) between predicted and observed environmental DGM values when log-normalized. The constant bias on the predicted values was attributed to estimates of available reducible mercury and the effect of DGM volatilization on observed data.     

Effect of dissolved organic carbon on the photoproduction of dissolved gaseous mercury in lakes: potential impacts of forestry

The production of dissolved gaseous mercury (DGM) in freshwater lakes is induced by solar radiation and is also thought to be linked to processes mediated by dissolved organic carbon (DOC). Studies investigating these processes using comparisons between lakes are often confounded by differences in DOC content and structure. In this study, we investigated the link between DOC concentrations and DGM production by using tangential ultrafiltration to manipulate DOC concentrations in water samples taken from a given lake. In this way, a range of samples with different DOC concentrations was produced without substantial changes to DOC structure or dissolved ions. This was repeated for four lakes in central Quebec: two with highly logged drainage basins and two with minimally logged drainage basins. On two separate days for each lake, water samples (filtered to remove >99% of microorganisms) with varying DOC concentrations were incubated in clear and dark Teflon bottles on the lake surface. DGM concentrations were measured at 3.5-h intervals over the course of 10.5 h. Levels of DGM concentrations increased with increasing cumulative irradiation for all lakes until approximately 4000 kJ m(-2) (400-750 nm, photosynthetically active radiation (PAR)), when DGM concentrations reached a plateau (between 20 and 200 pg L(-1)). When we assumed that DGM production was limited by the amount of photoreducible mercury, reversible first-order reaction kinetics fitted the observed data well (r2 ranging between 0.59 and 0.98, p < 0.05 with the exception of N70 100% DOC, 0% DOC, and K2 0% DOC with p = 0.06, 0.10, and 0.11, respectively). The DGM plateaus were independent of DOC concentrations but differed between lakes. In contrast, photoproduction efficiency (DGMprod) (i.e., the amount of DGM produced per unit radiation (fg L(-1) (kJ/m2)(-1)) below 4000 kJ m(-2) PAR) was linearly proportional to DOC concentration for both logged lakes (r2 = 0.97, p < 0.01) and nonlogged lakes (r2 = 0.52, p = 0.018) studied. Furthermore, logged lakes had a lower DGMprod per unit DOC (p < 0.01) than the nonlogged lakes. In these four lakes, the rate of DGM production per unit PAR was dependent on the concentration of DOC. The DGM plateau was independent of DOC concentration; however, there was a significant difference in DGM plateaus between lakes presumably due to different DOC structures and dissolved ions. This research demonstrates an important mechanism by which logging may exacerbate mercury levels in biota.     

Mercury emission to the atmosphere from experimental manipulation of DOC and UVR in mesoscale field chambers in a freshwater lake

Mesocosm experiments in an optically transparent lake allow the manipulation of both dissolved organic carbon (DOC) and incident ultraviolet radiation (UVR) in order to study mercury reduction and emission processes. In the absence of UVR and the presence of visible light, mercury emission is very low (approximately0.3 ng/m2/h). When UVR is permitted in the mesocosm chambers, mercury emission increases, with emission rates ranging from 0.3 to 2.5 ng/m2/h. At concentrations between 1.5 and 2.5 mg/L DOC, mercury emission does not appear to depend on either the concentration or the optical properties of the DOC. In particular, the addition of 1.0 mg/L DOC from a nearby wetland to a photobleached mesocosm did not increase the emission of mercury. The similarities between mercury emission from highly photobleached 1.5 mg/L DOC and from terrestrially enriched 2.5 mg/L DOC suggest that the moieties responsible for mercury reduction are far in excess of that needed for mercury reduction. Using the measured flux rate of mercury from the water surface, we calculated a dissolved gaseous mercury (DGM) concentration thatwould need to be present to drive the emissive flux. The buildup of DGM was used to approximate a kinetic rate constant for the net mercury reduction in this system of approximately 0.17 h(-1), which is consistent with existing published values.     

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.     

Continuous analysis of dissolved gaseous mercury (DGM) and mercury flux in two freshwater lakes in Kejimkujik Park,Nova Scotia: evaluating mercury flux models with quantitative data

Diurnal patterns for dissolved gaseous mercury (DGM) concentration, mercury flux, several water variables (pH, oxidation reduction potential (ORP), water temperature), and meteorological variables (wind speed, air temperature, % relative humidity, solar radiation) were measured in two lakes with contrasting dissolved organic carbon (DOC) concentrations in Kejimkujik Park, Nova Scotia. A continuous analysis system made it possible to measure quick changes in DGM over time. Consistently higher DGM concentrations were found in the high DOC lake as compared to the low DOC lake. An examination of current mercury flux models using this quantitative data indicated some good correlations between the date and predicted flux (r ranging from 0.27 to 0.83) but generally poor fit (standard deviation of residuals ranging from 0.97 to 3.39). Cross-correlation analysis indicated that DGM dynamics changed in response to solar radiation with lag-times of 65 and 90 min. This relationship with solar radiation was used to develop new predictive models of DGM and mercury flux dynamics for each lake. We suggest that a generalized approach using time-shifted solar radiation date to predict DGM can be incorporated into existing mercury flux models. It is clear from the work presented that DOC and wind speed may also play important roles in DGM and mercury flux dynamics, and these roles have not been adequately accounted for in current predictive models.     

Field,laboratory, and X-ray absorption spectroscopic studies of mercury accumulation by water hyacinths

We have studied water hyacinth (Eichhornia crassipes), a non-native nuisance plant found in the in San Francisco Bay Delta region, for its potential to phytoremediate mercury. Mercury is a common contaminant in San Francisco Bay Area waters because of gold mining activities. In this study, speciation of mercury in hyacinth roots and shoots, rates of mercury uptake by hyacinths in the laboratory, and mercury levels near the Big Break Region in the Delta were studied. In the speciation studies, Hg L3 edge X-ray absorption spectroscopic analysis of Hg model compounds and water hyacinth roots and shoots revealed that Hg was initially bound ionically to oxygen ligands in roots, most likely to carboxylate groups, and was bound covalently to sulfur groups in shoots. In laboratory uptake studies, we found that water hyacinths grown in 1 ppm Hg and one-quarter strength Hoagland's solution accumulated a maximum of 0.20 ppm in shoots and 16.0 ppm in roots, both reaching maximum concentrations after approximately 16 days. Mercury concentrations were found to be 0.26 +/- 0.20 ppm in the water and 0.86 +/- 1.70 ppm in sediment at Big Break. It was proposed that water hyacinths have the potential to phytoremediate mercury in the water at Big Break if the current herbicide treatments are replaced by physical removal.     

Mercury levels in hair from people eating large quantities of Swedish freshwater fish

Mercury concentrations in hair were related to fish-eating habits in a group of 50 people reported to have a high consumption of freshwater fish. Mercury levels in hair ranged from 0.3 to 10.8 mg/kg with a mean +/- SD of 3.2 +/- 2.3 mg/kg. The average mercury level in hair from men was significantly higher than that in hair from women (3.8 +/- 2.6 mg/kg versus 2.4 +/- 1.8 mg/kg. Seven individuals (14%) had levels above 6 mg/kg. In people with equal fish consumption, significantly higher mercury levels were found in the hair of those eating fish from lakes M?laren and V?ttern than in those eating fish from Lake Hj?lmaren. It has been reported that fish from the latter lake contains approximately 0.2 mg/kg mercury, whereas fish from the other two lakes contains approximately 0.4 mg/kg. The mean mercury level in hair was higher in the group eating freshwater fish more than three times a week (greater than or equal to 500 g fish flesh/week) than in the group eating less, although the difference was of borderline significance. Within couples (n = 16) eating equal numbers of fish meals per week, the men had significantly higher levels (mean 3.7 mg/kg) than the women (mean 2.5 mg/kg). The results from the present study show that people with a high consumption of Swedish freshwater fish have elevated levels of mercury in their hair, when compared with previously reported levels in the hair of Swedish pregnant women.     

Microbial reduction and oxidation of mercury in freshwater lakes

The evasion of elemental mercury represents a significant pathway for reducing the level of this potentially toxic material in aquatic ecosystems. The evasion rate is controlled by the concentration of dissolved gaseous mercury (DGM) across the air-water interface, water, and air temperature as well as wind speed. Here we investigate the role of microbial mercury oxidation and reduction in regulating DGM diel patterns in two freshwater lakes, Jack's Lake and Lake Ontario. Three replicate diurnal cycles of DGM in Brookes Bay, Jack's Lake peaked at 313 fM between 9:00 to 10:30 and decreased to 79.6 fM by 16:00. Microbial mercury reductase activity (converts Hg2+ to Hg0) increased with DGM concentrations and mercury oxidase activity (converts Hg0 to Hg2+) increased as DGM concentrations decreased in the mid-afternoon. This illustrates that mercury oxidase activity was linked to hydrogen peroxide (H2O2) diurnal patterns. Thirty minutes after spiking Lake Ontario water with H2O2, mercury oxidase activity increased by 250% and by 60 min, DGM decreased to 28% of its initial value. Two hours after the H2O2 spike, mercury oxidase activity had declined, but mercury reductase activity and DGM both increased. Four hours after the spike, mercury reductase and DGM levels had returned to original levels. Our results are consistent with the following sequence of events. In the morning, microbial activity produces DGM (in addition to any DGM formed through photoreduction of Hg2+). As photochemically produced H2O2 increases in concentration it induces the biologically mediated decrease in DGM concentrations throughout the afternoon. To predict concentration of DGM in surface waters and flux rates to the atmosphere, the contribution of photoreduction and photooxidation must be placed in context with reduction and oxidation rates due to microbial activity.     

Concentration and dry deposition of mercury species in arid south central New Mexico (2001-2002)

This research was initiated to characterize atmospheric deposition of reactive gaseous mercury (RGM), particulate mercury (HgP; <2.5 microm), and gaseous elemental mercury (Hg0) in the arid lands of south central New Mexico. Two methods were field-tested to estimate dry deposition of three mercury species. A manual speciation sampling train consisting of a KCl-coated denuder, 2.5 microm quartz fiber filters, and gold-coated quartz traps and an ion-exchange membrane (as a passive surrogate surface) were deployed concurrently over 24-h intervals for an entire year. The mean 24-h atmospheric concentration for RGM was 6.8 pg m(-3) with an estimated deposition of 0.10 ng m(-2) h(-1). The estimated deposition of mercury to the passive surrogate surface was much greater (4.0 ng m(-2) h(-1)) but demonstrated a diurnal pattern with elevated deposition from late afternoon to late evening (1400-2200; 8.0 ng m(-2) h(-1)) and lowest deposition during the night just prior to sunrise (2200-0600; 1.7 ng m(-2) h(-1)). The mean 24-h atmospheric concentrations for HgP and Hg0 were 1.52 pg m(-3) and 1.59 ng m(-3), respectively. Diurnal patterns were observed for RGM with atmospheric levels lowest during the night prior to sunrise (3.8 pg m(-3)) and greater during the afternoon and early evening (8.9 pg m(-3)). Discernible diurnal patterns were not observed for either HgP or Hg0. The total dry deposition of Hg was 5.9 microg m-2 year-' with the contribution from the three species as follows: RGM (0.88 microg m(-2) year(-1)), HgP (0.025 microg m(-2) year(-1)), and Hg0 (5.0 microg m(-2) year(-1)). The annual wet deposition for total mercury throughout the same collection duration was 4.2 microg m(-2) year (-1), resulting in an estimated total deposition of 10.1 microg m(-2) year(-1) for Hg. On one sampling date, enhanced HgP (12 pg m(-3)) was observed due to emissions from a wildfire approximately 250 km to the east.     

Air-water exchange and dry deposition of polybrominated diphenyl ethers at a coastal site in Izmir Bay, Turkey

The air-water exchange of polybrominated diphenyl ethers (PBDEs), an emerging class of persistent organic pollutants (POPs), was investigated using paired air-water samples (n = 15) collected in July and December, 2005 from Guzelyali Port in Izmir Bay, Turkey. Total dissolved-phase water concentrations of PBDEs (sigma7PBDEs) were 212 +/- 65 and 87 +/- 57 pg L(-1) (average +/- SD) in summer and winter, respectively. BDE-209 was the most abundant congener in all samples, followed by BDE-99 and -47. Average ambient gas-phase sigma7PBDE concentrations were between 189 +/- 61 (summer) and 76 +/- 65 pg m(-3) (winter). Net air-water exchange fluxes ranged from -0.9 +/- 1.0 (BDE-28) (volatilization) to 11.1 +/- 5.4 (BDE-209) ng m(-2) day(-1) (deposition). The BDE-28 fluxes were mainly volatilization while the other congeners were deposited. Gas- and dissolved-phase concentrations were significantly correlated (P = 0.33-0.55, p < 0.05, except for BDE-209, r = 0.05, p > 0.05) indicating thatthe atmosphere controls the surface water PBDE levels in this coastal environment. Estimated particulate dry deposition fluxes ranged between 2.7 +/- 1.9 (BDE-154) and 116 +/- 84 ng m(-2) day(-1) (BDE-209) indicating that dry deposition is also a significant input to surface waters in the study area.     

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).     

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.     

Sulfate addition increases methylmercury production in an experimental wetland

Atmospheric mercury is the dominant Hg source to fish in northern Minnesota and elsewhere. However, atmospherically derived Hg must be methylated prior to accumulating in fish. Sulfate-reducing bacteria are thought to be the primary methylators of Hg in the environment. Previous laboratory and field mesocosm studies have demonstrated an increase in methylmercury (MeHg) levels in sediment and peatland porewaters following additions of sulfate. In the current ecosystem-scale study, sulfate was added to half of an experimental wetland at the Marcell Experimental Forest located in northeastern Minnesota, increasing annual sulfate load by approximately four times relative to the control half of the wetland. Sulfate was added on four separate occasions during 2002 and delivered via a sprinkler system constructed on the southeast half (1.0 ha) of the S6 experimental wetland. MeHg levels were monitored in porewater and in outflow from the wetland. Prior to the first sulfate addition, MeHg concentrations (filtered, 0.7 microm) were not statistically different between the control (0.47 +/- 0.10 ng L(-1), n = 12; mean +/- one standard error) and experimental 0.52 +/- 0.05 ng L(-1), n = 18) halves. Following the first addition in May 2002, MeHg porewater concentrations increased to 1.63 +/- 0.27 ng L(-1) two weeks after the addition, a 3-fold increase. Subsequent additions in July and September 2002 did not raise porewater MeHg, but the applied sulfate was not observed in porewaters 24 h after addition. MeHg concentrations in outflow from the wetland also increased leading to an estimated 2.4x increase of MeHg flux from the wetland. Our results demonstrate enhanced methylation and increased MeHg concentrations within the wetland and in outflow from the wetland suggesting that decreasing sulfate deposition rates would lower MeHg export from wetlands.     

Relationship between total mercury concentration and fish size in two pelagic fish species: implications for consumer health

Total mercury concentrations were determined in different size classes of two pelagic fish species of great commercial importance, horse mackerel (Trachurus trachurus) and Mediterranean horse mackerel (Trachurus mediterraneus), to evaluate the relationship between total mercury concentration and fish size and to determine whether any differences might affect the quantitative assessment of mercury exposure for consumers. Mercury concentrations in horse mackerel and in Mediterranean horse mackerel were between 0.16 and 2.41 microg g(-1) of weight wet (mean, 0.68 microg g(-1)) and between 0.09 and 1.62 microg g(-1) (mean, 0.51 microg g(-1)), respectively. The regression curves revealed a significant relationship between mercury concentration and fish size (length and weight) for both species. Concentrations exceeding the proposed limit for human consumption were observed in 33.3% of the samples of both species and were associated with larger specimens. The consumption of the larger specimens could lead to an increase in mercury exposure for consumers. Estimated weekly intakes, calculated on the basis of concentrations relative to each size class, revealed a high exposure associated with the consumption of fish larger than 30 cm (horse mackerel, 11.63 to 20.16 microg/kg of body weight; Mediterranean horse mackerel, 5.86 to 13.55 microg/kg of body weight). An understanding of the factors leading to an increase in mercury exposure can help consumers make informed decisions about eating fish.     

Determination of trace mercury in environmental and foods samples by online coupling of flow injection displacement sorption preconcentration to electrothermal atomic absorption spectrometry

The toxic effects of mercury are well-known. To establish sources of mercury contamination and to evaluate levels of mercury pollution, sensitive, selective, and accurate analytical methods with excellent reproducibility are required. We have developed a novel methodology for the determination of trace mercury in environmental and foods samples by online coupling of flow injection (FI) displacement sorption preconcentration in a knotted reactor (KR) to electrothermal atomic absorption spectrometry (ETAAS). The developed methodology involved the online formation of copper pyrrolidine dithiocarbamate (Cu-PDC), presorption of the resulting Cu-PDC onto the inner walls of the KR, and selective retention of the analyte Hg(ll) onto the inner walls of the KR through online displacement reaction between Hg(ll) and the presorbed Cu-PDC. The retained analyte was subsequently eluted by 50 microL of ethanol and online detected by ETAAS. Interferences from coexisting heavy metal ions with lower stability of their APDC complexes relative to Cu- PDC were minimized without the need of any masking reagents. The tolerable concentrations of Cu(II), Cd(II), Fe(III), Ni(III), and Zn(II) were up to 12, 20, 16, 20, and 60 mg L(-1), respectively. No additional chemical modifiers for the stabilization of mercury were required in the present system owing to the stability of Hg-PDC at the drying stage, and no pyrolysis stage was necessary due to the effective removal of the matrices. With consumption of 2.5 mL of sample solution, an enhancement factor of 91 was obtained in comparison with direct injection of 50 microL of aqueous solution. The relative detection limit (3s) was 6.2 ng L(-1), corresponding to an absolute detection limit of 15.5 pg. The precision (RSD, n = 13) was 1.1% at the 2 microg L(-1) level. The method was successfully applied to the determination of mercury in several certified environmental and foods reference materials and locally collected water samples.     

Volatilization and recovery of mercury from mercury wastewater produced in the course of laboratory work using Acidithiobacillus ferrooxidans SUG 2-2 cells

The iron-oxidizing bacterium Acidithiobacillus ferrooxidans SUG 2-2 is markedly resistant to mercuric chloride and can volatilize mercury (Hg0) from mercuric ion (Hg2+) under acidic conditions. To develop a microbial technique to volatilize and recover mercury from acidic and organic compound-containing mercury wastewater, which is usually produced in the course of everyday laboratory work in Okayama University, the effects of organic and inorganic chemicals on the mercury volatilization activity of A. ferrooxidans cells were studied. Among 55 chemicals tested, the mercury volatilization from a reaction mixture (pH 2.5) containing resting cells of SUG 2-2 (1 mg of protein) and mercury chloride (14 nmol) was strongly inhibited by AgNO3 (0.05 mM), K2CrO7 (1.0 mM), cysteine (1.0 mM), trichloroethylene (1 microM), and commercially produced detergents (0.05%). However, the strong inhibition by trichloroethylene and detergents was not observed when these organic compounds were chemically decomposed using Fenton's method before the treatment of the wastewater with SUG 2-2 cells. When 20 ml of water acidified with sulfuric acid (pH 2.5) containing ferrous sulfate (3%), diluted mercury wastewater (17.5 nmol of Hg2+) and SUG 2-2 cells (0.05 mg of protein) were incubated for 10 d at 30 degrees C, 47% of the total mercury in the wastewater was volatilized and recovered into a trapping reagent for metal mercury. However, when the organic compounds in the mercury wastewater were decomposed using Fenton's method and then treated with A. ferrooxidans cells, approximately 100% of the total mercury in the wastewater was volatilized and recovered.     

Determination of total mercury in foods of plant origin in Poland by cold vapour atomic absorption spectrometry.

Total mercury concentrations were determined in 573 samples of agricultural crops and foods of plant origin which included cereals, fruit and vegetables and their products commercially available on the Polish market. The method of cold vapour atomic absorption spectrometry (CVAAS) after a wet-acid digestion in a closed-vessels and microwave oven was used and the reliability of the procedure demonstrated. Mercury concentrations in the agricultural crops and plant foods were generally below the maximum permissible limits in Poland and rarely exceeded 5 microg x kg(-1). Values ranged from <0.1 to 14 microg x kg(-1), mean 2.4 +/- 2.3 microg x kg(-1) in wheat and rye grains; from <0.1 to 2.4 microg x kg(-1), mean 0.5 +/- 0.4 microg x kg(-1) in nine varieties of vegetables; from <0.1 to 5.1 microg x kg(-1), mean 1.1 +/- 0.9 microg x kg(-1) in seven varieties of fruit; from <0.1 to 5.6 microg x kg(-1) in cereal products and jams; and from <0.1 to 3.0 microg x l(-1) in fruit and vegetable juices, nectars and beverages. The contribution of the mercury in the analysed agricultural crops and foods of plant origin to the weekly dietary intake of total mercury was 8 microg/person, which represents only 3% of the provisional tolerable weekly intake (PTWI) for this metal.     

Application of controlled mesocosms for understanding mercury air-soil-plant exchange

Whole system elemental mercury (Hg0) flux was measured for approximately 1.5 years using two large gas exchange mesocosms containing approximately 100 two-year old aspen trees (Populus tremuloides) planted in soil with elevated mercury concentrations (12.3 microg/g). We hypothesized that during leafout, whole mesocosm Hg0 flux would increase due to movement of Hg0 in the transpiration stream from the soil to the air. This hypothesis was not supported; plants were found to assimilate Hg0 from the contaminated air, and whole system Hg0 emissions were reduced as plants leafed-out due to shading of the soil. Surface disturbance, watering, and increases in soil moisture, light, and temperature were all found to increase whole system Hg0 flux, with light being a more significant factor. Although surface soils were maintained at 15-20% moisture, daily watering caused pulses of Hg0 to be released from the soil throughout the experiment. Data developed in this experiment suggested that those processes acting on the soil surface are the primary influence on Hg emissions and that the presence of vegetation, which shields soil surfaces from incident light, reduces Hg emissions from enriched soils.