Methylmercury in hair samples from different riverine groups,Amazon, Brazil

The present study was aimed to evaluate comparatively the levels of methylmercury (MeHg) in human hair, collected from different groups of Amazonian populations exposed to contamined fish. The study was undertaken in fishing villages and gold mining areas, mainly in the Tapajós and Madeira river basins, two of the main tributaries of Amazon river. The study population included 125 hair samples, chosen from a collection of over one thousand samples collected in different periods. Hair analyses were conducted with a new efficient extraction technique and measured with ECD-gas chromatographer. This analytical method presented good accuracy and precision when compared with standard hair samples from IAEA. A highly significant correlation was found at the interlaboratory exercise between National Institute for Minamata Disease and our laboratory at Federal University of Rio de Janeiro. The results of the present study showed, through hair analysis, a relationship between environmental contamination by mercury and methylmercury and dietary habits of the Amazon population. The highest levels of MeHg in hair samples were found in riverine population from upper Tapajós river and in riverine population from some tributaries of Madeira river, followed by population of fishing villages from Madeira river. Majority of the women of child-bearing age presented high MeHg concentration in hair samples (10 mg.kg-1). On the other hand, Yanomami Indians presented MeHg concentration below the limit tolerable of 6 mg.kg-1.     

Follow-up of mercury levels in fish,human hair and urine in the Madeira and Tapajós basins,Amazon, Brazil

Informal economy of gold mining has contaminated some important river basins in Amazon. Follow-up studies on critical compartments showed some areas with high Hg levels in fish as well as in human hair samples. Average Hg in piscivorous fish in the Madeira river itself was 846 ppb (N=284) with a maximum of 3921 ppb. Mercury in fish from non polluted areas in this basin shows high variability, even for single species. A seasonal variation in Hg content was observed, with higher values at the end of the dry season. In the upper Tapajós basin comparable values were found for fish but with a definite decreasing trend downstream. Average value for piscivorous fish in the whole Tapajós basin is 482 ppb (N=122) with a maximum value of 3770 ppb. Hair Hg was higher in fishing villages in the Tapajós (average: 17 ppm; with N=432 and maximum value of 176 ppm) than in the Madeira (average: 9 ppm; N=169; maximum 71 ppm), and data from some areas of the Tapajós suggest a decrease with time. Mercury was much higher in urine of goldshop workers in Santarém (low Tapajós) than in Alta Floresta (high Tapajbs) and show a decreasing trend in both cases, probably related to the significant decline in gold mining activities during the study period (1986–1994).     

Distribution and Accumulation of Mercury Derived from Gold Mining in Marine Environment and Its Impact on Residents of Buyat Bay, North Sulawesi, Indonesia

Buyat Bay (BB), North Sulawesi, Indonesia, was a submarine tailings disposal (STD) site for an industrial gold mine that extracted mercury (Hg)-containing ores from 1996 to 2004. To evaluate the distribution and influence of such a Hg release into the environment, particularly into BB, we quantified the total mercury (THg) and methyl mercury (MeHg) in the surface sediments (beach, river estuary, and marine) and biota of the bay, as well as the scalp hair of residents in the adjacent community. A nearby body of water, Totok Bay, polluted by Hg from artisanal gold mining, and a reference area of the Bajo Coast (Bajo) free of any anthropogenic sources of Hg were also sampled. Both THg and MeHg were detected in all samples measured showed concentrations to be highest at the artisanal mining site, intermediate at the STD site and at their lowest in the control area. THg and MeHg concentrations in marine biota and human hair increased with trophic levels and were significantly higher at the STD site than among the controls. Besides examining the source and distribution of Hg, its accumulation in biota, and its potential impact on humans, we also studied the role of the mine management so as to provide a recommendation for future actions.     

Mercury contamination in the Brazilian Amazon. Environmental and occupational aspects

Mercury (Hg) contamination of miners, riparian and Indian populations and fish in the Amazon region, due to gold extracting activities, has been studied. Samples of hair, urine, and blood of Indians and prospectors, and hair from riparian fish-eating population and fishes from Madeira river, respectively, were collected and analyzed by Cold Vapor, Atomic Absorption Spectrometry (CV-AAS) techniques. The results obtained showed that the aquatic food chains in the Amazonian ecosystems are contaminated by methylmercury (MeHg), exposing Indians, prospectors and riverines to thr risk of severe health hazard. The highest levels of contamination, based upon hair analysis, were found in riparian of the Madeira river, followed by Cuniã Lake population, Indians (Fresco river) and prospectors, in that order. Blood analysis showed 59% of the samples from Indians and 33% from prospectors with Hg contents above 10 ng mL^?1. Analysis of urine, on the other hand, showed 44% of Indians with Hg levels below the detection limit (d.l.), and 30% above 20 ng mL^?1, whereas 38% of the prospectors presented Hg concentrations over 20 ng mL^?1, and 20% below the d.l. These results prove that prospectors, who hardly ever eat fish but are badly exposed to inorganic Hg vapor, are ocupationally contaminated, while the rest of the populations under survey are exposed to environmental contamination by Hg, through polluted fish ingestion.     

Field analysis of mercury in water,sediment and soil using static headspace analysis

We developed a field screening method for the rapid analysis of mercury (Hg) in water, soil and sediment which can be applied cost-effectively at Hg-contaminated sites. The samples are chemically pretreated in ordinary containers, followed by analysis of the sample headspace Hg vapor using a portable commercially-available analyzer. Mercury in water samples is reduced directly by the addition of stannous chloride, while solids are first digested with aqua regia or piranha solution to liberate the Hg from the solids. Aided by vigorous agitation after addition of the reductant, the elemental Hg partitions between the solution and headspace according to Henry's Law. The method requires about 2 and 15 minutes to complete for water and solids, respectively. The method provides very useful detection limits for water (0.1μg/L) and solids (≤ 2μg/g). Intercomparisons with laboratory-analyzed environmental samples have shown reasonable agreement.     

Mercury Cycling in Lake Gordon and Lake Pedder,Tasmania (Australia). II: Catchment Processes

The sources and concentrations of total mercury (total Hg) and methylmercury (MeHg) in the upper catchment of the Lake Gordon/Lake Pedder system in Tasmania, Australia were investigated. The catchment area, which contains over 50% wetlands, is located in a temperate region with no obvious point sources of mercury. Surface waters in the region had concentrations of total Hg ranging from 1.2 to 14.4 ng L^-1 and MeHg from < 0.04 to 1.4 ng L^-1. MeHg concentrations were seasonally dependent, with the highest concentrations occurring in summer. Sediments/soils in the catchment had concentrations of total Hg ranging from 4.0 to 194 ng g^-1 and MeHg from <0.02 to 20.1 ng g^-1. The low concentrations of total Hg confirmed that this region is pristine as regards mercury and has no geological enrichment of total Hg. The highest total Hg and MeHg concentrations in both sediment/soils and waters were found in bogs whereas the lowest concentrations typically occurred on the wetlandplains. MeHg concentrations, in bog and swamp sediments were correlatedwith the organic matter content (r = 0.942, P < 0.001). Acid volatile sulfide (AVS) measurements indicate that in most sediments AVS was greater than total Hg. Given the high reactivity of inorganic mercury and sulfide, this suggests that most of the particulate mercury in sediments is present as mercuric sulfide. The yield of MeHg from the catchment was estimated to be 3.2 mg ha^-1 yr^-1 and is higher than published rates measured in non-contaminated temperate catchments in the northern hemisphere. The higher yield was attributed to the generally warmer climatic conditions that favour net methylation and the relatively high rainfall (2–3 m yr^-1) of the region, which supplies reactive inorganic mercury to the active zones ofmercury methylation and also flushes MeHg from the catchment.     

Online YPA4 resin microcolumn separation/preconcentration coupled with inductively coupled plasma optical emission spectrometry (ICP-OES) for the speciation analysis of mercury in seafood

A simple and effective method for the determination of trace amounts of methylmercury (MeHg(+)) and inorganic mercury (Hg(2+)) in seafood was developed by online microcolumn separation/preconcentration combined with inductively coupled plasma optical emission spectrometry (ICP-OES). It was found that Hg(2+) could be quantitatively adsorbed by YPA 4 resin from pH 7.0 to strong acidic medium (6 mol L(-1) HCl) and that MeHg(+) was retained by the YPA 4 microcolumn only at pH 1.0-7.0. Therefore, a strong acidic medium (about 5 mol L(-1) HCl), which could liberate mercury species from biological samples, was used to directly separate inorganic Hg(2+) from total Hg, and MeHg(+) in effluent was retained by YPA 4 column after the effluent was adjusted to pH 1.5. The effects of acidity, sample flow rate and volume, elution solution, and interfering ions on recovery of the two mercury species have been systematically investigated. Under optimal conditions, the limits of detection (LODs) were 72 and 44 ng L(-1) for Hg(2+) and MeHg(+) (as Hg) with online concentration factors of 12.5 and 12.1, respectively. The relative standard deviations (RSDs) for nine replicate determinations at 5 ng mL(-1) levels of mercury species were 2.7 and 2.0% for Hg(2+) and MeHg(+), respectively. The calibration graphs were linear with a correlation coefficient of 0.9902 in the range of 0.5-100 ng mL(-1) for Hg(2+) and 0.9976 in the range of 0.1-100 ng mL(-1) for MeHg(+), respectively. The developed method was successfully applied to the direct determination of MeHg(+) and Hg(2+) in seafood samples, and the recoveries for the spiked samples were in the range of 89.9-102.4% (MeHg(+)) and 87.0-104.6% (Hg(2+)), respectively. The method was validated by analyzing a certified reference material DORM-2 (dogfish muscle), and the determined values were in good agreement with certified values.     

Exposure to mercury in Canada: A multimedia analysis

A thorough assessment of Canadian exposure to mercury (Hg) has not been undertaken since 1970. A multimedia approach was used to update estimates of Hg exposure to members of the general population in Canada, based on currently available information. Adult Canadians have an estimated intake of all Hg species via all routes of 7.7μg/day (0.11μg/kg body weight/day), which equated to an absorbed dose of 5.3μg/day (0.076μg/kg bw/day). Fish consumption accounts for much of this exposure (27% of intake, 40% of absorbed dose), in the form of methylmercury. However, dental amalgam appears to account for a greater proportion of total Hg exposure than fish consumption. Exposure from amalgam was estimated for intake and absorbed doses (of Hg⁰) at 2.81 and 2.25μg/day, respectively. This represents 36% of total Hg intake and 42% of absorbed dose. Hg²⁺ arises principally from foods other than fish. Intake of Hg²⁺ by adults was determined to be 1.82μg/day and absorbed dose only 0.18μg/day. Exposures for four other age groups of the population were also evaluated.     

Mercury in the Aquatic Environment of the Village of Caimito at the Mojana Region,North of Colombia

During May–September 1999, several aquatic environmental samples were collected from the village of Caimito, in the San Jorge River basin area, state of Sucre (Colombia), and analyzed for total mercury (T-Hg). Mean T-Hg concentration in sediments from surrounded marshes was 0.155 ± 0.016 g Hg/g. Low Hg concentrations were found in the phytoplanktivorous fish species Prochilodus magdalenae (0.087 ± 0.01 g Hg/g), while four-fold greater concentrations were found in all the carnivorous species. In average, T-Hg concentrations for fish samples did not exceed the limit consumption level (0.5 g Hg/g). However, risk assessment based on the hazard index suggested that the consumption of 0.1 kg per day of carnivorous fish could increase the risk of mercury poisoning in local population.     

Mercury exposure in humans through food consumption from the Everglades of Florida

In March 1989, The Florida Department of Health and Rehabilitative Services (HRS) issued a Health Advisory recommending the limited consumption of several fish species caught from the Everglades region of South Florida due to elevated methylmercury (MeHg) levels (average 2–3 ppm in fish meat). There were no reports of clinical MeHg poisoning in humans in Florida, although deaths of Florida panthers were attributed to mercury (Hg). poisoning. This study evaluated the extent of MeHg exposure in persons eating contaminated fish in the Everglades region. Populations at risk were identified including sport fishermen, Everglades Residents and subsistence fishermen. Over 1700 individuals were approached; those who had eaten fish or wildlife from the contaminated areas at least once/month for the prior three months were asked to participate. Three hundred and fifty (350) participants completed a brief questionnaire and provided a hair sample for Hg analysis. In 119 (36%) of individuals with levels above the limits of detection, the mean total Hg in hair was 3.62±3.0μg/g [± standard deviation] with a range of 1.28 – 15.57. The most at risk populations identified with respect to Hg levels were Blacks and men. Although the majority of the participants had fished in the Everglades for many years (>15 years), they reported relatively low intake of fish and had low hair Hg levels compared with similar populations in prior studies of other populations at risk. Although 71% of participants knew of the State Health Advisories concerning ingestion of Hg contaminated fish from the Everglades, this did not change their consumption habits. In addition, Blacks, individuals of lower income and of lower education levels were less likely to know about the Health Advisories. Given recent studies of neurologic effects from relatively low in utero MeHg exposure, the continuation of the Mercury Health Advisories and wildlife monitoring in the Everglades are warranted, especially for women of childbearing age and children. However, public education must be targeted for the populations at risk identified in this study in order to reach these populations more effectively.     

Cycling of methyl mercury and mercury — Responses in the forest roof catchment to three years of decreased atmospheric deposition

Studies of the biogeochemistry of total mercury (Hg) and methyl mercury (MeHg) in the Lake Gårdsjön watershed have shown that the atmosphere is the most important source of Hg and MeHg in the ecosystem. Soils are accumulating most of the deposited Hg and MeHg, but transport of Hg and MeHg from the forested catchments into the lake ecosystems is enough to explain elevated concentrations of MeHg in fish in more than 10 000 Swedish lakes. An experimental roof was constructed to study effects of decreased atmospheric input on an entire forested catchment. The experiment started in April 1991, and decreases in the output of both MeHg and Hg occurred during 1991, 1992 and 1993. Runoff fluxes from the control catchment during the pre-treatment period were related to the experimental catchment using regression analyses. Since April 1991, after three year experiment, predicted compared to measured fluxes showed that Hg output decreased by 32% and MeHg by 28%. The decrease in Hg was most obvious during high water flows in winter/spring while MeHg decreased during all seasons of the year. The decreased input of Hg and MeHg to the Forest Roof Catchment is the most probable explanation to the rapid decrease in output of Hg and MeHg by runoff from the catchment basin.     

Mercuty in Precipitation and Its Relation to Bioaccumulation in Fish: A Literature Review

Increases in industrial mercury (Hg) emissions in recent years have led many researchers to believe that Hg from the atmosphere constitutes a main source of Hg to aquatic biota in the absence of point source discharges. Established background levels for fish (0.2–1.0 mg kg^-1) now exceed the pre industrial level of 0.15 mg kg^-1, suggesting an anthropogenic origin. This review of recent literature illustrates how levels of mercury (Hg) species in the atmosphere are effectively transported into the aquatic arena, where chemical parameters combine to determine bioaccumulation rates in fish. Limited studies on methyl mercury (MeHg) in precipitation shown that concentrations average from 5% of total-Hg (T-Hg), to 1% in industrial regions. Observations of increased Hg is snow and precipitation from the Arctic Circle, related to poleward atmospheric circulation patterns, also demonstrate a spring maximum accompanying ozone depletion. Increases in oxidants and soil derived Hg in the atmosphere during the summer best explain summer Hg maximums observed in precipitation, while increased temperatures raise fish metabolism increasing Hg uptake through respiration and ingestion rate. The major route of entry for MeHg to fish appears to be biomagnification, after input from precipitation, runoff and inlake methylation. Regions buffered against acid precipitation maintain low fish-Hg levels by reduced MeHg production and maintaining gill function. When considering the bioaccumulation of Hg in fish this study shows that there are many variables to consider, not all of which originate from inside the aquatic arena. Both catchment and atmospheric processes combine with aquatic variables to dictate the overall levels of MeHg observed in fish tissue. There now appears to be sufficient knowledge to develop an axiom for the identification of aquatic systems likely to be susceptible to bioaccumulation from atmospheric derived Hg.     

Mechanisms of deposition of methylmercury and mercury to coniferous forests

Deposition of methylmercury (MeHg) and mercury (Hg) to a coniferous forest have been investigated using field measurements. Samples of open field (OF) wet deposition, throughfall (TF) and litterfall (LF) have been collected and analyzed for MeHg and Hg during the period November 1991 to April 1994. Average concentrations in TF were 22.8 and 0.38 ng L^?1, for Hg and MeHg, respectively. Concentrations in OF precipitation were 11.9 and 0.37 ng L^?1, for Hg and MeHg, respectively, during the same period. Considerable differences were found for Hg in TF and OF which was attributed to a dry deposition of Hg. Hg in LF contributes a deposition of equal size as in TF. The relations between OF, TF and total Hg deposition were approximately 1∶1,5∶3. A decrease in OF Hg was found over the three year period studied. MeHg deposition in OF was also found to decrease during the same period whereas the TF MeHg showed a slight increase. Dry deposition of MeHg is also an important process in a coniferous forest although the flux to the forest floor is not via TF but rather as MeHg in LF.     

Mercury Cycling in Lake Gordon and Lake Pedder,Tasmania (Australia). I: In-lake Processes

The processes affecting the concentrations of total mercury (total Hg) and methylmercury (MeHg) in a freshwater system comprising two connected reservoirs in southwest Tasmania were investigated. Surface concentrations of total mercury (total Hg)were temporally and spatially uniform in both Lake Gordon (2.3±0.4 ng L^-1, n = 27) and Lake Pedder (2.3±0.3 ng L^-1, n = 11). The surface concentrations of MeHg in Lake Gordon (0.35±0.39 ng L^-1, n = 25) were more variable than total Hg and MeHg typically comprised 10–20% of total Hg. The relatively high amount of total mercury present as MeHg in Lake Gordon was attributed to the high proportion of wetlandsin the upper catchment (50% of total area) and in-lake contributions (ca. 40% of total MeHg). Despite the close proximity of the two lakes, MeHg concentrations in Lake Pedder were consistently lower than in Lake Gordon. This phenomenon canbe explained in part by the greater contribution of direct rainfall to Lake Pedder leading to the dilution of MeHg. Water column MeHg concentrations were higher in warmer months in bothlakes, reflecting increased net methylation of inorganic mercury.Unlike previous studies of seasonally anoxic lakes, depth profiles of total mercury and MeHg in Lake Gordon were uniform and were not affected by water column stratification occurringin the summer months, and oxygen depletion with depth. This suggests that redox cycling and accumulation of MeHg in the hypolimnion following seasonally-induced anoxia is not a significant part of the mercury cycle in Lake Gordon. The primary location of MeHg production within the lake's water column is not conspicuous. Mercury speciation measurements made above and below the lake system over a period of 19 months indicates that after 20 yr of impoundment, the reservoirs are not significantly affecting MeHg concentrations in the downstreamriverine environment.     

Mercury and Mining in Africa with Special Reference to Tanzania

A study of gold (Au) mining areas in Tanzania is being undertaken to assess environmental impacts arising Gum the use of mercury (Hg) in gold extraction. Initial results already indicated the presence of elevated Hg concentrations in environmental samples from the mining areas. The mean Hg concentration in river sediments in 4.19 μg l. soils within gold mining and processing centres exhibit high Hg content (mean 3.39 μg/g) that decreases rapidly to background regional values within a distance of a few kilometres. A review of published Hg data for sediments, fish and aquatic plants from African inland and coastal waters revealed. with a few exceptions. low Hg concentrations close to natural background levels.     

Bioaccumulation of Total Mercury and Monomethylmercury in the Earthworm Eisenia Fetida

Bioaccumulation factors (BAFs) for inorganic mercury in earthworms are usually < 1; however, factors up to ～10 have been reported. Little information is available concerning the bioaccumulation of organic mercury in earthworms from actual contaminated soils and thus there has been uncertainty in the risk characterization phase of ecological risk assessments of mercury-contaminated sites. This study was initiated to determine the rate of uptake and bioaccumulation of total mercury (T-Hg) and monomethylmercury (MMHg) in Eisenia fetida from soils which have been contaminated with mercury for approximately 30 years. The study consisted of a 28-day uptake phase in three mercury-contaminated soils and one soil with background concentrations of mercury followed by a 14-day depuration phase in background soil only. Total mercury concentrations in the study soils ranged from 85 to 11,542 μg kg^?1 dry weight soil; MMHg concentrations ranged from 1.12 to 7.35 μg kg^?1 dry weight soil. Time to 90% steady states for T-Hg ranged from 36 to 42 days. A steady state did not occur for any of the MMHg exposures during the 42-day study; estimated time to 90% steady state varied from 97 to 192 days. BAFs for T-Hg ranged from 0.6 to 3.3. BAFs for MMHg ranged from 175 to 249. The BAFs for T-Hg and MMHg were larger in earthworms exposed to the lower contaminated soils and smaller in the higher mercury-contaminated soils. The absolute concentrations of T-Hg and MMHg bioaccumulated in E. fetida, however, were higher in the earthworms exposed to the higher mercury soils and lower in the less mercury-contaminated soils.     

Is total mercury concentration a good predictor of methyl mercury concentration in aquatic systems?

Methyl mercury (MeHg) concentrations were compared to total mercury (THg) concentrations in a variety of types of aqueous samples collected at the Experimental Lakes Area during 1991 through 1993. In several streams, an experimentally flooded wetland, and peat pore water, there was no relationship between MeHg and THg concentrations. %MeHg (compared to THg) ranged from < 1% to over 90%. In three ELA lakes, as in groups of lakes from other regions, a linear relationship between MeHg and THg concentration was found. However, these relationships differed by a factor of three from one region to another. This study shows that THg inputs and/or concentrations are not very useful in predicting MeHg concentrations, and that factors within ecosystems are very important in controlling MeHg concentrations.     

Mercury methylation,uptake and bioaccumulation by the earthworm Lumbricus terrestris (Oligochaeta)

To date, most studies about mercury (Hg) methylation and bioaccumulation have focused on aquatic ecosystems. In contrast, information regarding the biogeochemical cycle of Hg in terrestrial ecosystems is scarce. Considering the relevance of earthworms in soils, it is very important to study their role in the bioaccumulation and transformation of Hg species (inorganic Hg, IHg, and monomethylmercury, MeHg). The aim of this experimental study was to compare the uptake and bioaccumulation of MeHg and IHg in the earthworm Lumbricus terrestris exposed to soils freshly spiked with inorganic Hg as well as historically contaminated soils. The study consisted of a 28-day uptake phase in Hg (spiked and natural) contaminated and non-contaminated soils followed by a 14-day depuration phase in non-contaminated soils. Soils were characterized by determining not only Hg concentrations (total Hg, MeHg and acid-labile Hg) but also analysed for other physicochemical parameters that can influence the fate of Hg within the earthworm–soil system. Mercury species were determined in earthworms (whole organism) exposed to Hg contaminated and non-contaminated soils. Mercury availability in soils seems to be the main factor controlling the uptake and bioaccumulation of Hg species because, according to kinetic data, the spiked IHg was more readily assimilated and methylated by earthworms. Bioaccumulation factors (BAFs) for MeHg and total Hg were also higher in spiked than in naturally Hg-contaminated soils. In addition, BAFs for MeHg (ranging from 0.8 to 17.3) were higher than those for total Hg (between 0.02 and 0.62) which suggests that MeHg was more easily bioaccumulated by this earthworm species and also that earthworms may actively contribute to MeHg production in soils.     

天津污灌区水稻土壤汞形态特征及其食品安全评估

选择天津污水灌溉区作为研究区域,该文的主要研究目的是分析土壤不同形态汞对水稻不同组织中总（THg）和甲基汞MeHg富集的影响以及评估污灌区稻米食用汞暴露风险,并对污灌区土壤溶解与可交换态汞安全阀值进行了初步分析。结果表明,北塘、大沽和北京污灌区稻田土壤THg和MeHg浓度显著高于对照区海河土壤THg浓度。大沽、北京河污灌区和海河土壤汞的形态为残渣态浓度最高,而北塘污灌区为有机结合态浓度最高。由于水稻地上组织中THg浓度受到大气汞浓度影响,各组织中汞浓度在不同污灌区分布规律不同。水稻籽粒的 MeHg 富集系数为1.63～3.70,通过人体每天摄入MeHg量的安全值计算得出土壤溶解与可交换态汞质量分数应低于9.19 ng/g。污灌区食用稻米MeHg暴露对居民健康存在较大风险,人体MeHg每天摄入量超标率达到20.83%。因此,可以对超标土壤进行治理或改变耕作方式来降低土壤污染对人体MeHg暴露造成的影响。