Urinary mercury in people living near point sources of mercury emissions

As part of the European Mercury Emissions from Chlor Alkali Plants (EMECAP) project, we tested the hypothesis that contamination of ambient air with mercury around chlor alkali plants using mercury cells would increase the internal dose of mercury in people living close to the plants. Mercury in urine (U-Hg) was determined in 225 individuals living near a Swedish or an Italian chlor alkali plant, and in 256 age- and sex-matched individuals from two reference areas. Other factors possibly affecting mercury exposure were examined. Emissions and concentrations of total gaseous mercury (TGM) around the plants were measured and modeled. No increase in U-Hg could be demonstrated in the populations living close to the plants. This was the case also when the comparison was restricted to subjects with no dental amalgam and low fish consumption. The emissions of mercury to air doubled the background level, but contributed only about 2 ng/m(3) to long-term averages in the residential areas. The median U-Hg levels in subjects with dental amalgam were 1.2 microg/g creatinine (micro/gC) in Italy and 0.6 microg/gC in Sweden. In individuals without dental amalgam, the medians were 0.9 microg/gC and 0.2 microg/gC, respectively. The number of amalgam fillings, as well as chewing, fish consumption, and female sex were associated with higher U-Hg. The difference between the countries is probably due to higher fish consumption in Italy, demethylated methyl mercury (MeHg) being partly excreted in urine. Post hoc power calculations showed that if the background mercury exposure is low it may be possible to demonstrate an increase in U-Hg of as little as about 10 ng/m(3) as a contribution to ambient mercury from a point source.     

Biological monitoring of mercury exposure in individuals referred to a toxicological center in Venezuela

People in developing countries are often considered at greater risk of mercury (Hg) poisoning due to a variety of factors including a lack of awareness regarding their occupational risks. Individuals requiring urine mercury (U-Hg) analysis at the Center for Toxicological Investigations of the University of Carabobo (CITUC), between 1998 and 2002 were studied to identify demographic characteristics associated to U-Hg levels. The studied population included individuals with a history of exposure (or related exposures) to Hg processes, and was comprised of 1159 individuals (65 children, 1094 adults) ages 0.58-79 years old, mean 36.63+/-12.4. Children's geometric mean U-Hg levels were 2.73 microg/g Creatinine (Ct) and in adults 2.55 microg/g Ct. The highest frequency of adults' occupations were shipyard workers (35.47%), dentists (23.5%), lab technicians (11.43%), dental employees 10.42% and miners (10.2%). Chemical laboratory technicians had the highest mean U-Hg (4.46 microg/g Ct). Mean U-Hg levels in female adults (3.45 microg/g Ct) were statistically superior to levels in male adults (2.15 microg/g Ct). Two of the 172 women in reproductive age, had U-Hg levels higher than 78 microg/g Ct. Individuals from Falcon State were found to have the highest mean U-Hg (4.53 microg/g Ct). U-Hg levels higher than permissible limits were found in only 2 states (Carabobo and Bolivar) with a total of 24 cases. Although the results of this investigation were highly variable, the findings can be used to examine circumstances which influence mercury toxicity trends, and possibly used in future studies working to identify Hg exposures.     

Fish consumption and bioindicators of inorganic mercury exposure

BACKGROUND: The direct and close relationship between fish consumption and blood and hair mercury (Hg) levels is well known, but the influence of fish consumption on inorganic mercury in blood (B-IHg) and in urine (U-Hg) is unclear. OBJECTIVE: Examine the relationship between fish consumption, total, inorganic and organic blood Hg levels and urinary Hg concentration. METHODS: A cross-sectional study was carried out on 171 persons from 7 riparian communities on the Tapajós River (Brazilian Amazon), with no history of inorganic Hg exposure from occupation or dental amalgams. During the rising water season in 2004, participants responded to a dietary survey, based on a seven-day recall of fish and fruit consumption frequency, and socio-demographic information was recorded. Blood and urine samples were collected. Total, organic and inorganic Hg in blood as well as U-Hg were determined by Atomic Absorption Spectrometry. RESULTS: On average, participants consumed 7.4 fish meals/week and 8.8 fruits/week. Blood total Hg averaged 38.6+/-21.7 microg/L, and the average percentage of B-IHg was 13.8%. Average organic Hg (MeHg) was 33.6+/-19.4 microg/L, B-IHg was 5.0+/-2.6 microg/L, while average U-Hg was 7.5+/-6.9 microg/L, with 19.9% of participants presenting U-Hg levels above 10 microg/L. B-IHg was highly significantly related to the number of meals of carnivorous fish, but no relation was observed with non-carnivorous fish; it was negatively related to fruit consumption, increased with age, was higher among those who were born in the Tapajós region, and varied with community. U-Hg was also significantly related to carnivorous but not non-carnivorous fish consumption, showed a tendency towards a negative relation with fruit consumption, was higher among men compared to women and higher among those born in the region. U-Hg was strongly related to I-Hg, blood methyl Hg (B-MeHg) and blood total Hg (B-THg). The Odds Ratio (OR) for U-Hg above 10 microg/L for those who ate >4 carnivorous fish meals/week was 4.00 [1.83-9.20]. CONCLUSION: This study adds further evidence to a positive relation between fish consumption and IHg in both blood and urine, which may result from absorption of IHg from fish or from demethylation of MeHg. The findings support the importance of assessing IHg exposure in fish-eating communities. Further studies should examine the potential toxicity of IHg in heavy fish consumers.     

Assessment of reference values for mercury in urine: the results of an Italian polycentric study

The results of a polycentric study to assess the reference values of urinary mercury (U-Hg) in four Italian cities are presented. A total of 383 subjects were selected on the basis of standardised criteria by a questionnaire on personal habits, lifestyle, occupational or non-occupational exposure to Hg, medical history, number and area of dental amalgams. U-Hg was determined by hydride generation atomic absorption method (HG-AAS), with a detection limit of 0.5 microg/l and by flow injection (FI) inductively coupled plasma mass spectrometry (ICP-MS), with a detection limit of 0.03 microg/l. The median value of U-Hg, determined by HG-AAS, was 0.78 microg/g creatinine (0.75 for males and 0.83 for females), with 5 degrees and 95 degrees percentiles, respectively, of 0.17 and 3.66 microg/g creatinine. When determined by FI ICP-MS, the median value was 0.79 microg/g creatinine (0.77 for males and 0.79 for females) with 5 degrees and 95 degrees percentiles of, respectively, 0.12 and 5.02 microg/g creatinine. Among the independent variables, city of origin, area of dental amalgams, fish intake and tobacco smoking significantly influenced the U-Hg levels. The U-Hg reference values from this survey are lower than those from other recent investigations, probably due to characteristics and selection of the examined individuals and to the strict control of pre-analytical and analytical factors of variability.     

Hair can be a good biomarker of occupational exposure to mercury vapor: simulated experiments and field data analysis

Generally, urine mercury (U-Hg) is widely used for assessment of inorganic mercury (I-Hg) exposure in humans. The reliability of scalp hair as an indicator of mercury vapor exposure is contentious. However, significant correlations were found between hair total mercury (T-Hg) and U-Hg and between hair I-Hg and total gaseous mercury (TGM) in ambient air in our previous studies. Simulated experiments were designed to assess the contribution of direct absorption/adsorption of mercury vapor in the hair. Results indicated that the increases of hair T-Hg concentrations were less than 1 μg/g, which was negligible compared with hair T-Hg concentrations in occupationally exposed workers. The β-mercaptoethanol washing can remove 30% of mercury (Hg) in the exposed hair samples. The inhaled Hg constituted the major fraction (97.4%) of I-Hg exposure for the artisanal Hg mining workers. From the simulated experiments and field data analysis, we can conclude that hair I-Hg can be a useful tool for monitoring occupational exposure to Hg vapor.     

Mercury exposure in the population from Wuchuan mercury mining area, Guizhou, China

Mercury (Hg) exposure in the population from Wuchuan mercury mining area (WMMA), Guizhou, China, was evaluated by human hair Hg investigation. Total gaseous mercury (TGM) in the ambient air and Hg in rice were measured to assess human risk of Hg exposure. High TGM concentrations in the ambient air were found near smelting workshop. Rice not only contained high total mercury (T-Hg) which ranged from 6.0-113 ng/g, but also contained highly elevated methylmercury (Me-Hg) which ranged from 3.1-13.4 ng/g. The means of hair T-Hg concentrations were 33.9 microg/g and 21.5 microg/g at YQG and JXC sites, respectively. Residents from other sites also reflected a certain level of Hg exposure. Age had no significant effect on hair Hg levels, but male had higher hair T-Hg concentrations due to occupational exposure and also higher Me-Hg levels which might be related to larger amount of rice consumption. Hair may be a useful tool for monitoring human exposure of Hg vapor in Hg-mining areas. By a preliminary estimation, the inhalation of Hg polluted air was the main route of inorganic Hg exposure to the smelting workers and vicinal residents; but the population in the study area was also at a potential risk of Me-Hg exposure via rice intake.     

Photo-induced formation of dissolved gaseous mercury in coastal and offshore seawater of the Mediterranean basin

The first measurements on the daily trend of dissolved gaseous mercury (DGM) concentration determined in coastal and offshore waters of the Mediterranean basin are reported. Marked daily behaviour tracking solar radiation has been observed at the coastal sampling station with DGM values ranging from 11.0 to 38.9 pg/l. Contrary to these observations the DGM values in offshore water samples (11.9-20.0 pg/l) were independent of the sampling time, thus identifying the absence of higher levels during the hours of maximum insolation. The availability of Hg2+ substrate necessary for the photo-reaction processes of DGM formation has been evaluated by measuring the reactive mercury concentration. In offshore waters the lower DGM concentrations are attributable to the substrate as a limiting factor. The highest concentration of DOC measured in coastal seawater with respect to the offshore one could moreover enhance the reaction rates of DGM production through the formation of inorganic mercury complexes and weaker organic associations.     

Fish as a source of exposure to mercury and selenium.

In a total of 395 subjects with varying fish consumption habits, mercury levels in whole blood (B-Hg), and selenium levels in plasma (P-Se) were studied. Also, in subcohorts, mercury levels in blood cells (Ery-Hg; n = 79), plasma (P-Hg; n = 158) and urine (U-Hg; n = 125) were analysed. There were statistically significant associations between fish intake on the one hand, and B-Hg, Ery-Hg and P-Hg, on the other, but not so with U-Hg. In subjects who never had fish, the average B-Hg was 1.8 ng/g, in subjects who had at least two fish meals each week, 6.7 ng/g. Ery-Hg, and to a less extent P-Hg, were associated with levels of marine n-3 polyunsaturated fatty acids (PUFA) in serum phosphatidylcholine. P-Hg and U-Hg were associated with numbers of teeth with amalgam fillings. P-Se also correlated with fish intake. In subjects who never had fish, P-Se averaged 80 micrograms/l, in subjects who had at least two fish meals per week, 91 micrograms/l. There was an association between PUFA and P-Se. Further, there were statistically significant associations between P-Se on the one hand, and B-Hg, Ery-Hg and P-Hg on the other. The data clearly demonstrate the importance of fish for the exposure to methylmercury and selenium in the Swedish diet, and the impact of amalgam as a source of exposure to inorganic mercury.     

Mercury speciation in the hair of pre-school children living near a chlor-alkali plant

Exposure to mercury species was assessed in the hair of 130 Spanish children (age 4) from the general population in two areas. Both areas are exposed to different sources of mercury: a point source in Ribera d'Ebre (northeastern Spain) and a diffuse source on the island of Menorca (northwestern Mediterranean). The median MeHg values in the hair of children from Ribera d'Ebre (RE) were nearly twice (0.631 microg/g vs. 0.370 microg/g) those of children from Menorca (MC) (p < 0.05). Total Hg showed a similar trend (REmedian: 0.720 microg/g vs. MCmedian: 0.476 microg/g). Nevertheless, inorganic mercury levels were similar in the two groups of children (REmedian: 0.186 microg/g vs. MCmedian: 0.210 microg/g). Two subgroups of the Ribera d'Ebre group were defined: children living in Flix (a village near a chlor-alkali plant) (RE1) and children living on the outskirts of Flix with no clear, direct influence of the plant (RE2). The mercury concentrations in RE1 were also significantly higher than those in Menorca, but no significant differences were found between Menorca and the RE2 subgroup. We evaluated the fish consumption of RE1, RE2 and MC and found that the Menorcan children consumed significantly less fish (p < 0.05) than the other two subgroups. Children who consumed fish more than three times a week had higher MeHg concentrations (beta (SE) = 0.991 (0.279) than those who ate it less than once a week. Nevertheless, the differences in MeHg levels between children from Ribera d'Ebre and Menorca remained statistically significant after adjustment for fish intake and other variables (beta (SE) = 0.779 (0.203) for children from RE1). In conclusion, local sources other than seafood contribute significantly to MeHg content in hair in the two Ribera d'Ebre subgroups.     

Monitoring mercury in two South African herbaria

Mercury [Hg] emissions from old plant collections treated with mercuric chloride (HgCl(2)) may present a high health risk for staff working in certain herbaria. The present study evaluated Hg concentrations in ambient air, plant specimens and biological samples from staff working in the Pretoria National Herbarium (PRE) and the H.G.W.J. Schweickerdt Herbarium (PRU), University of Pretoria. Biological samples from a group of 15 people exposed to HgCl(2) in herbaria and a non-exposed control group of five people were studied. Additionally, plant samples from herbarium specimens treated and non-treated with HgCl(2) were analysed. Plant materials treated with HgCl(2) had persistent high concentrations of Hg in the range of 114-432 microg g(-1), whereas untreated materials were in the range of 0.20-0.45 microg g(-1). The HgCl(2)-treated plant specimens induced elevated concentrations of Hg into the herbarium rooms near storage cabinets, where up to 1 microg m(-3) of Hg was measured in the air of both herbaria. However, no significant difference in mean Hg concentrations in hair was found between herbarium workers and members of the control group, 0.46 and 0.64 microg g(-1) respectively (p0.05, Student's t-test). For both groups, Hg concentrations were lower than that indicated by the World Health Organization [WHO] for non-exposed adults, namely 2 microg g(-1). The mean concentration of total Hg in urine from the mercury-exposed herbarium group, 2.28 microg g(-1) creatinine, was significantly higher than in the control group, 1.05 microg g(-1) of creatinine. For both populations, the concentrations of Hg in their urine were below the threshold Hg values set by the WHO, i.e., 5 microg g(-1) creatinine. We concluded that there was no strong response by individual herbarium staff from long-term exposure to Hg concentrations in the range of 0.28-1.1 microg m(-3).     

Mercury in Arctic air: The long-term trend

The long-term (1974-2000) time trend of total filterable mercury (TFM) in the air in the Canadian Arctic is reported. The concentration of TFM had declined by (3.0 ± 0.8) % and (3.1 ± 0.9) % per year in the summer and fall, respectively, over the 27 years, which coincided with the calculated reduction rate of world-wide mercury emission (~ 3.3% per year) from human activities between 1983 and 1995. The time trend for winter and early spring was not statistically significant as the variability of TFM was very large, partly due to Arctic Mercury Depletion Events and partly due to Arctic haze.     

Sediment mercury dynamics and historical trends of mercury deposition in the St. Lawrence River area of concern near Cornwall, Ontario, Canada

The St. Lawrence River near Cornwall, Ontario was designated an Area of Concern by the International Joint Commission in 1985. Sediments from this area have historically been contaminated with mercury (Hg), and although concentrations have decreased since the 1970s, they still remain high. Nine sediment cores were collected from three sites within the Area of Concern in 2004/05 to determine the variability in historical profiles of Hg deposition to the river. Sediment and pore water phases were analyzed for total mercury (THg) and methyl mercury (MeHg) and cores were analyzed for ²¹⁰Pb to determine chronologies of sedimentation at these sites. Mercury diffusion rates in pore waters within the sediment column were determined to be very low (between 0 and 2.15 ng cm^− 2 year^− 1, n = 3) compared to the recent Hg sedimentation rates at these sites (183 ± 30 ng cm^− 2 year^− 1 SE, n = 9) determined by multiplying surface Hg concentrations with ²¹⁰Pb-derived sedimentation rates. These results indicate that Hg profiles in these cores accurately depict historical releases of Hg to the river bed. The influence of federal regulations in the early 1970s to restrict Hg emissions to the river was apparent in these dated sediment cores, as were the closures of several local industries in the mid 1990s. Mercury accumulation rates prior to 1970 were 60 times higher than those occurring after 1995. Methyl mercury showed surface enrichment in most of these sediment cores providing evidence that mercury methylation occurred most rapidly near the sediment surface.     

Monocyte-macrophage system and polymorphonuclear leukocytes in workers exposed to low levels of metallic mercury

Our previous research (Soleo L, Vacca A, Vimercati L et al. Occup Environ Med 1997;54:437-442) showed a reduction in tumor necrosis factor-alpha (TNF-alpha) serum levels in workers with prolonged exposure to low doses of inorganic mercury, suggesting an in vivo functional defect of the monocyte-macrophage system. On this basis, here we wondered whether workers exposed to lower doses of metallic mercury displayed possible changes in the monocyte-macrophage system. In this particular cohort of workers, we also sought for the effects of the exposure on the polymorphonuclear leukocytes (PMNL) chemotaxis. The monocyte-macrophage system and the natural killer (NK) cells were examined in 19 exposed workers and in 25 unexposed workers, as the control group (controls). Specifically, the circulating monocyte-macrophage cells and their CD13, CD15 and CD33 subsets, serum cytokines (IL-8, GM-CSF and TNF-alpha) and the NK cells were analyzed. In seven exposed and seven controls randomly chosen workers the PMNL chemotaxis was also assessed. The selected indicator of mercury exposure were the levels of mercury in the urine (U-Hg), that was significantly higher in exposed workers than the controls (9.7 +/- 5.5 microg/l and 2.4 +/- 1.2 microg/l, respectively). None of the exposed workers had shown signs of either acute or chronic inorganic mercury toxicity or any form of hypersensitivity. Several immunological variables tested, monocyte-macrophage cells and their subsets, NK cells and serum cytokines overlapped between the exposed and the control workers. When the workers were considered as a whole (exposed plus controls), no correlation was found between current U-Hg and all immunological parameters. However, when exposed workers were studied separately, an inverse correlation was disclosed between cumulative U-Hg and cells (as percentage) expressing the CD13 (r = -0.599; P = 0.007) and CD15 (r = -0.614; P = 0.005) molecules, and NK cells (r = -0.455; P = 0.05). Moreover, a significant impairment in the PMNL chemotaxis (t = 3.70; P = 0.003) was observed in the exposed workers. The results of our study suggest that the exposure to very low levels of metallic mercury led to subtle impairment of circulating monocyte and NK cells (as percentages) according to the increase in U-Hg levels, as well as of the PMNL chemotactic function in this particular group of workers, even though they remain clinically asymptomatic. Therefore, we suggest that impairment of these parameters provide a sensitive indicator of metallic mercury and other chemical contaminants present in the environment.     

Distribution, speciation, and transport of mercury in stream-sediment, stream-water, and fish collected near abandoned mercury mines in southwestern Alaska, USA

Concentrations of total Hg, Hg (II), and methylmercury were measured in stream-sediment, stream-water, and fish collected downstream from abandoned mercury mines in southwestern Alaska to evaluate environmental effects to surrounding ecosystems. These mines are found in a broad belt covering several tens of thousands of square kilometers, primarily in the Kuskokwim River basin. Mercury ore is dominantly cinnabar (HgS), but elemental mercury (Hg degrees) is present in ore at one mine and near retorts and in streams at several mine sites. Approximately 1400 t of mercury have been produced from the region, which is approximately 99% of all mercury produced from Alaska. These mines are not presently operating because of low prices and low demand for mercury. Stream-sediment samples collected downstream from the mines contain as much as 5500 microg/g Hg. Such high Hg concentrations are related to the abundance of cinnabar, which is highly resistant to physical and chemical weathering, and is visible in streams below mine sites. Although total Hg concentrations in the stream-sediment samples collected near mines are high, Hg speciation data indicate that concentrations of Hg (II) are generally less than 5%, and methylmercury concentrations are less than 1% of the total Hg. Stream waters below the mines are neutral to slightly alkaline (pH 6.8-8.4), which is a result of the insolubility of cinnabar and the lack of acid-generating minerals such as pyrite in the deposits. Unfiltered stream-water samples collected below the mines generally contain 500-2500 ng/l Hg; whereas, corresponding stream-water samples filtered through a 0.45-microm membrane contain less than 50 ng/l Hg. These stream-water results indicate that most of the Hg transported downstream from the mines is as finely-suspended material rather than dissolved Hg. Mercury speciation data show that concentrations of Hg (II) and methylmercury in stream-water samples are typically less than 22 ng/l, and generally less than 5% of the total Hg. Muscle samples of fish collected downstream from mines contain as much as 620 ng/g Hg (wet wt.), of which 90-100% is methylmercury. Although these Hg concentrations are several times higher than that in fish collected from regional baseline sites, the concentration of Hg in fish is below the 1000 ng/g action level for edible fish established by the US Food and Drug Administration (FDA). Salmon contain less than 100 ng/g Hg, which are among the lowest Hg contents observed for fish in the study, and well below the FDA action level.     

Impacts of mercury contaminated mining waste on soil quality, crops, bivalves, and fish in the Naboc River area, Mindanao, Philippines

Rice paddy fields in the Naboc area, near Monkayo on the island of Mindanao, Philippines, have been irrigated four times a year over the last decade using Naboc River water contaminated with mercury (Hg) by artisanal gold mining in the Diwalwal area. Silt containing up to at least 90 mg Hg/kg (d.w.) has been deposited in rice paddy fields during the 1990s and this has been repeatedly mixed into the rice root zone through ploughing. Hg in the rice paddy field soils averages 24 mg Hg/kg and generally exceeds the UK and Canadian soil quality thresholds for agricultural soils as well as the proposed Dutch Intervention value and the USEPA soil ingestion Soil Screening Level (SSL) for inorganic Hg. Much lower Hg concentrations (0.05-0.99 mg/kg) within the range expected for uncontaminated soils, characterise soils on which corn and bananas are cultivated, largely because these are not irrigated with Hg-contaminated water from the Naboc River. The estimated total weekly MeHg intake for a person living in the Naboc area related to the weekly consumption of 2.1 kg of rice grown on Hg-contaminated soils (15 microg MeHg) in conjunction with 1 kg of fish (220 microg MeHg) and 100 g of mussels (50 microg MeHg) from the Naboc River, would total 285 microg MeHg (equivalent to 4.75 microg/kg bw for a 60 kg adult), which is nearly three times the JECFA PTWI of 1.6 microg/kg bw. This will significantly contribute to the population mercury exposure and might explain why 38% of the local inhabitants were classified as Hg intoxicated during a mercury toxicity assessment [Drasch GS, B?se, O'Reilly S, Beinhoff C, Roider G, Maydl S. The Mt. Diwata study on the Philippines 1999-assessing mercury intoxication of the population by small scale gold mining. Sci Total Environ 2001; 267(1-3): 151-168.].     

Mercury contamination in fish from gold mining areas in Indonesia and human health risk assessment

This study investigates the effects on fish and assesses human health hazards from mercury released in two gold mining areas in Indonesia: Tatelu (North Sulawesi Province) and Galangan (Katingan District, Central Kalimatan Province). In Tatelu, 154 fish specimens of 10 freshwater species were collected, as well as five marine species from the fish market. The mean concentration of total mercury in muscles of freshwater fish from this area was 0.58+/-0.44 microg/g, with more than 45% of fish having Hg levels above the WHO guideline for human consumption of 0.5 microg/g. In Galangan, where 263 fish specimens of 25 species were collected, the total mercury in muscles averaged 0.25+/-0.69 microg/g. Excluding data from flooded open pits in sub-area P4, mean Hg levels in fish from Galangan were 2 to 4 times lower than 0.5 microg/g, while fewer than 10% of fish from Galangan exceeded WHO guidelines. The Hazard Quotient (HQ) was applied to both areas to determine the threat of MeHg exposure for communities in both areas. The HQ is a risk assessment indicator which defines the ratio of exposure level to a single substance in relation to a reference dose. Samples from Tatelu (excluding marine species) had an HQ above one, while those from Galangan resulted in values of 2.4 for the whole area and 9.9 for sub-area P4, pointing to potentially harmful fish consumption for the local population. By using the single-compartment model to estimate mercury levels in blood and hair from daily intake dose, sub-area P4 showed the highest levels, higher than the upper limit guideline for pregnant women, but still lower than threshold levels associated with observed clinical effects.     

Changes in the non-protein thiol pool and production of dissolved gaseous mercury in the marine diatom Thalassiosira weissflogii under mercury exposure

Two detoxification mechanisms working in the marine diatom Thalassiosira weissflogii to cope with mercury toxicity were investigated. Initially, the effect of mercury on the intracellular pool of non-protein thiols was studied in exponentially growing cultures exposed to sub-toxic HgCl₂ concentrations. T. weissflogii cells responded by synthesizing metal-binding peptides, named phytochelatins (PCs), besides increasing the intracellular pool of glutathione and γ-glutamylcysteine (γ-EC). Intracellular Hg and PC concentrations increased with the Hg concentration in the culture medium, exhibiting a distinct dose-response relationship. However, considerations of the PCs-SH:Hg molar ratio suggest that glutathione could also be involved in the intracellular mercury sequestration. The time course of the non-protein thiol pool and Hg intracellular concentration shows that PCs, glutathione and γ-EC represent a rapid cellular response to mercury, although their role in Hg detoxification seems to lose importance at longer incubation times. The occurrence of a process of reduction of Hg(II) to Hg° and subsequent production of dissolved gaseous mercury (DGM) was also investigated at lower Hg concentrations, at which the PC synthesis doesn't seem to be involved. The significant (P < 0.01) correlation between the cellular density in solution and the production of DGM suggests that this diatom is capable of directly producing DGM, both in light and dark conditions. This finding has been confirmed by the absence of DGM production in the culture media containing formaldehyde-killed cells. Finally, the relationship between these two different pathways of Hg detoxification is discussed.     

Assessment of mercury and methylmercury pollution with zebra mussel (Dreissena polymorpha) in the Ebro River (NE Spain) impacted by industrial hazardous dumps

Large amounts of industrial waste containing high concentrations of mercury (up to 436 microg/g) are dumped in a reservoir adjacent to a chlor-alkali plant in Flix (Catalonia, Spain), on the lower Ebro River. In order to assess the spatial redistribution of mercury from the point source and its bioavailability to the aquatic food web, zebra mussels (Dreissena polymorpha) were collected at several sites. The highest total Hg (THg) and methylmercury (MeHg) concentrations ever reported for zebra mussels were found (THg: 0.02 to 0.81 microg/g ww; MeHg: 0.22 to 0.60 microg/g ww). At the most polluted site, close to the waste dump, the mean values were 20 times greater than the local background level. Concentrations decreased with increasing mussel size at all sites. The MeHg/THg ratio was ca. 60% (range: 50-80%). A comparison of similar size classes clearly indicated the hot spots of Hg bioavailability to the aquatic food web and downstream transport.     

Total mercury,methylmercury and selenium in mercury polluted areas in the province Guizhou,China

The province of Guizhou in Southwestern China is currently one of the world's most important mercury production areas. Emissions of mercury from the province to the global atmosphere have been estimated to be approximately 12% of the world total anthropogenic emissions. The main objective of this study was to assess the level of contamination with Hg in two geographical areas of Guizhou province. Mercury pollution in the areas concerned originates from mercury mining and ore processing in the area of Wanshan, while in the area of Quingzhen mercury pollution originates from the chemical industry discharging Hg through wastewaters and emissions to the atmosphere due to coal burning for electricity production. The results of this study confirmed high contamination with Hg in soil, sediments and rice in the Hg mining area in Wanshan. High levels of Hg in soil and rice were also found in the vicinity of the chemical plant in Quingzhen. The concentrations of Hg decreased with distance from the main sources of pollution considerably. The general conclusion is that Hg contamination in Wanshan is geographically more widespread, due to deposition and scavenging of Hg from contaminated air and deposition on land. In Quingzhen Hg contamination of soil is very high close to the chemical plant but the levels reach background concentrations at a distance of several km. Even though the major source of Hg in both areas is inorganic Hg, it was observed that active transformation of inorganic Hg to organic Hg species (MeHg) takes place in water, sediments and soils. The concentration of Hg in rice grains can reach up to 569 microg/kg of total Hg of which 145 microg/kg was in MeHg form. The percentage of Hg as MeHg varied from 5 to 83%. The concentrations of selenium can reach up to 16 mg/kg in soil and up to 1 mg/g in rice. A correlation exists between the concentration of Se in soil and rice, indicating that a portion of Se is bioavailable to plants. No correlation between Hg and Se in rice was found. Exposure of the local population to Hg may occur due to inhalation of Hg present in air (in particular in Hg mining area) and consumption of Hg contaminated food (in particular rice and fish) and water. Comparison of intake through these different routes showed that the values of Hg considerably exceed the USA EPA Reference Concentration (RfC) for chronic Hg exposure (RfC is 0.0004 mg/m(3)) close to the emission sources. Intake of Hg through food consumption, particularly rice and fish, is also an important route of Hg exposure in study area. In general, it can be concluded that the population mostly at risk is located in the vicinity of smelting facilities, mining activities and close to the waste disposal sites in the wider area of Wanshan. In order to assess the real level of contamination in the local population, it is recommended that biomonitoring should be performed, including Hg and MeHg measurements in hair, blood and urine samples.     

Quantification and speciation of mercury in soils from the Tripuí Ecological Station, Minas Gerais, Brazil

Contents of total mercury, organic carbon, total sulfur, iron, aluminum and grain size and clay mineralogy were used along with Pearson's correlation and Hg thermal desorption technique to investigate the presence, distribution and binding behavior of Hg in soils from three depths from the Tripuí Ecological Station, located near Ouro Preto, Minas Gerais State, Brazil. The soils studied had predominantly medium and fine sand texture (0.59-0.062 mm), acid character and Hg contents ranging from 0.09 to 1.23 microg/g. The granulometric distribution revealed that Hg is associated with coarse sand (2-0.59 mm) and silt and clay (<0.062 mm) and presents similar Hg concentrations in both fractions. Mercury distribution in soil profiles showed that Hg was homogeneously distributed throughout the depths at most sites. Hg thermal desorption curves show that mercury occurs not only as Hg2+ predominantly bound to organic components in most of the samples, but also in the form of cinnabar in some. Pearson's correlation confirmed that mercury is associated with organic matter and sulfur and possibly with sulfur-bearing organic matter in most samples.