Proof of concept for a passive sampler for monitoring of gaseous elemental mercury in artisanal gold mining.

Mercury emissions from artisanal gold mining operations occurring in roughly 80 developing countries are a major workplace health hazard for millions of people as well as the largest contributor to global mercury pollution. There are no portable, cheap, and rapid methods able to inform workers or health practitioners of mercury exposure on site in remote locations. In this work, a proof of concept for a miniaturized mercury sampler, prepared by the direct reduction of gold into the porous nanostructures of Vycor glass (PVG), is introduced. Mercury retention on the PVG/Au sampler induces significant color changes, due to the formation of Au-Hg amalgam that affects the surface plasmon resonance characteristics of the material. The color change can potentially be quantified by the analysis of pictures obtained with a cell phone camera rapidly and onsite. Laboratory experiments showed the viability of using PVG/Au as passive sampler for monitoring of Hg°. PVG/Au samplers were then deployed in an artisanal and small-scale gold mining (ASGM) operations in Burkina Faso and it was able to indicate personal mercury exposures. The amount of mercury quantified in the samplers for all miners was higher than the current personal exposure limit set by the US Occupational Safety & Health Administration (OSHA).

Toward an Assessment of the Global Inventory of Present-Day Mercury Releases to Freshwater Environments.

Aquatic ecosystems are an essential component of the biogeochemical cycle of mercury (Hg), as inorganic Hg can be converted to toxic methylmercury (MeHg) in these environments and reemissions of elemental Hg rival anthropogenic Hg releases on a global scale. Quantification of effluent Hg releases to aquatic systems globally has focused on discharges to the global oceans, rather than contributions to freshwater systems that affect local exposures and risks associated with MeHg. Here we produce a first-estimate of sector-specific, spatially resolved global aquatic Hg discharges to freshwater systems. We compare our release estimates to atmospheric sources that have been quantified elsewhere. By analyzing available quantitative and qualitative information, we estimate that present-day global Hg releases to freshwater environments (rivers and lakes) associated with anthropogenic activities have a lower bound of ~1000 Mg· a-1. Artisanal and small-scale gold mining (ASGM) represents the single largest source, followed by disposal of mercury-containing products and domestic waste water, metal production, and releases from industrial installations such as chlor-alkali plants and oil refineries. In addition to these direct anthropogenic inputs, diffuse inputs from land management activities and remobilization of Hg previously accumulated in terrestrial ecosystems are likely comparable in magnitude. Aquatic discharges of Hg are greatly understudied and further constraining associated data gaps is crucial for reducing the uncertainties in the global biogeochemical Hg budget.

Assessing occupational mercury exposures and behaviours of artisanal and small-scale gold miners in Burkina Faso using passive mercury vapour badges.

Artisanal and small-scale gold mining (ASGM) is a crucial economic activity in Burkina Faso, however it is associated with significant mercury exposure and health concerns. The aim of the present study was to assess the level of mercury (Hg) vapour exposures and occupational behaviours at a representative site using Hg vapour monitor badges and questionnaires. To our knowledge this is the first time that personal exposure to Hg vapour during ASGM activities has been reported. The study population were ASGM workers who completed a questionnaire (n=100) or participated with an occupational exposure assessment using commercially available passive Hg vapour samplers (n=44). Occupational exposure to Hg was high during open-air burn events with a time weighted average (TWA) exposure of 7026±6857µg/m3 for burners, and 1412±2870µg/m3 for bystanders. Most (82%) of the people present at the burn exceeded the Permissible Exposure Limit (PEL) of 100µg/m3, and 11% exceeded the level considered to be Immediately Dangerous to Life and Health (IDLH) of 10,000µg/m3. Even control workers who were not present at the burn exceeded the PEL (24%), likely due to legacy Hg contamination producing latent Hg releases to the atmosphere. Similarly, 86% of the miners at the burn and 59% of control workers had an 8-h TWA that exceeded the Recommended Exposures Limit (REL). Several occupational behaviours that may contribute to Hg exposures were documented. This study corroborates previous studies suggesting that Hg exposure during amalgam burning is very high, and demonstrates the plausibility of using passive vapour monitoring badges rather than costly and logistically difficult biomonitoring methods. Mercury reduction and elimination interventions are strongly needed to reduce Hg exposure in ASGM communities, particularly as countries come into compliance with the Minamata Convention.

Mercury Accumulation in Harbour Seals from the Northeastern Pacific Ocean: The Role of Transplacental Transfer, Lactation, Age and Location.

Mercury (Hg) bioaccumulates in the aquatic food chain in the form of methylmercury, a compound well known for its neurotoxicity. We analyzed total mercury (THg) in hair collected from 209 harbour seals captured at 10 sites in British Columbia (Canada) and Washington State (USA) between 2003 and 2010. In addition, laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) allowed for a highly refined analysis of THg accumulation over time by examining nine whiskers taken from 4- to 6-week-old pups. We estimate that THg concentrations in pups increased sharply at a point corresponding to mid- to late gestation of their time in utero (4.7 ± 0.8 and 6.6 ± 1.3 µg/g dry weight (dw), respectively), and then again at the onset of nursing (8.1 ± 1.3 µg/g dw). These abrupt changes highlight the importance of both pre- and post-natal THg transfer from the mother to the growing fetus and the newborn pup. While THg levels varied among sites, hair analyses from seals collected at the same site demonstrated the influence of age in THg accumulation with pups (5.3 ± 0.3 µg/g) and juveniles (4.5 ± 0.5 µg/g) having lower levels than those in adults (8.3 ± 0.8 µg/g). Our results revealed that 33 % of the pups sampled (n = 167) had THg levels that surpassed a mammalian hair threshold for neurochemical alterations. This study suggests that Hg could represent a health concern to marine wildlife, especially as atmospheric emissions of this toxic element from human activities in the Pacific Rim and worldwide continue.

The source and fate of sediment and mercury in the Tapajós River, Pará, Brazilian Amazon: Ground- and space-based evidence.

We present results of mercury (Hg) in surface waters and soils and an analysis of satellite imagery from the Tapajós River basin, Brazilian Amazon, and the Reserva Garimpeira do Tapajós, the legal gold mining district of the basin. Hg bound to suspended sediment was roughly 600 and 200 times the concentration of dissolved Hg per litre of water, in impacted and pristine areas, respectively. Suspended sediments thus represent the major pathway of river-borne Hg. Median concentrations of Hg in suspended load from both impacted and pristine waters were 134 ppb, and 80% of samples were below 300ppb-in the range of naturally occurring surficial materials in the tropics. Regionally, riverine Hg fluxes were proportional to the concentration of total suspended solids. This shows that the dominant source of Hg is the sediment itself rather than anthropogenic mercury discharge from the small-scale mines. To independently test this conclusion, a mass balance was performed. A conservative calculation of the annual export of mercury (Hg) from the Creporí River (a minimum) was 1.6 tonnes for the year 1998-it could be significantly larger. This amount of Hg is difficult to account for by anthropogenic discharge alone, confirming that enhanced physical erosion caused by sluicing and dredging operations is the dominant source of Hg. We therefore conclude that gold mining operations are primarily responsible for elevated Hg concentrations. The dominant source of contamination is not, however, the loss of Hg in the gold amalgamation process. Rather, the disturbance and mobilization of large quantities of Hg-rich sediment and floodplain soil into the water column during mining operations is the source of contamination. These findings shift the focus of remediation and prevention efforts away from Hg control toward soil and sediment erosion control. The minimization or elimination of Hg losses in the mining process remains important for the health of local peoples and environments, but keeping basin soils and sediments in place would be a much more effective means of minimizing Hg fluxes to the region's rivers. To gain a spatial and historical perspective on the source and extent of emissions, satellite imagery was used. We were able to reconstruct historical mining activity, locate impacted areas, and estimate historical Hg fluxes with the imagery. To do so, the spectral characteristics of satellite images were calibrated to the concentration of suspended sediment in the rivers, which, in turn, is proportional to the Hg concentration. This analysis shows that mining-induced sediment plumes have been a dominant source of sediment to the Tapajós River system for decades. As well, the intensity and location of these emissions has varied through time. For example, sediment discharge from the Creporí River was greater in 1985 than in 1998; and the tributaries on the west bank of the Tapajós were actively being mined in 1985 but had been abandoned in 1998. This type of information should greatly assist in understanding original and ongoing sources of emissions, and in managing prevention and remediation efforts.

Preparation and characterization of a soil reference material from a mercury contaminated site for comparability studies.

The preparation and characterization of a soil reference material (SOIL-1) from a site polluted with mercury due to the past mercury mining in Idrija, Slovenia is reported. Homogeneity tests and intercomparison exercises for total (T-Hg) and methylmercury (MeHg) were performed. In addition, selective sequential extraction was applied for Hg fractionation, and multielemental analyses were performed by k(0) standardization neutron activation analysis (k(0)-INAA) and inductively coupled mass spectrometry (ICP-MS) for other trace elements. Comparison of different analytical methods, as well as the distribution of data were critically evaluated using descriptive statistics and analysis of variance (ANOVA). Due to the nugget effect (cinnabar particles representing more than 90% of the mercury), homogeneity for T-Hg determination was difficult to achieve. The intercomparison exercise indicated that in order to obtain comparable results for total mercury (T-Hg) sample decomposition by HF must be performed. These data are then in good agreement with non-destructive methods such as k(0)-INAA. Accepted reference values calculated taking into account the results obtained by six and three laboratories, respectively, were 67.1+/-11.3 mg kg(-1) for T-Hg and 4.0+/-1.3 ng g(-1) for MeHg (95% confidence intervals). However, the results obtained for Hg fractionation displayed significant differences in the organically bound fraction and elemental Hg. Results obtained by two laboratories using totally different analytical protocols for other elements showed excellent agreement for most elements. In summary, the results obtained for the SOIL-1 sample were of sufficient quality to suggest its use for quality control in laboratories dealing with mercury contaminated soils.

Bioaccumulation patterns of methyl mercury and essential fatty acids in lacustrine planktonic food webs and fish.

Organisms of the planktonic food web convey essential nutrients as well as contaminants to animals at higher trophic levels. We measured concentrations of methyl mercury (MeHg) and essential fatty acids (EFAs, key nutrients for aquatic food webs) in four size categories of planktonic organisms - seston (10-64 microm), micro-(100-200 microm), meso-(200-500 microm), and macrozooplankton (>500 microm) - as well as total mercury (THg) and EFAs in rainbow trout (Oncorhynchus mykiss) in coastal lakes. We demonstrate that, in all lakes during this summer sampling, MeHg concentrations of planktonic organisms increase significantly with plankton size, independent of their taxonomic composition, and that their MeHg accumulation patterns predict significantly THg concentrations in rainbow trout (R2=0.71, p<0.05). However, concentrations of total EFAs do not follow this pattern. Total EFAs increased from seston to mesozooplankton but decreased in the largest zooplankton size fraction. Moreover, concentrations of individual EFA compounds in rainbow trout are consistently lower, with the exception of docosahexaenoic acid, than those in macrozooplankton. The continuous increase of MeHg concentrations in aquatic organisms, therefore, differs from patterns of EFA accumulation in zooplankton and fish. We interpret these contrasting accumulation patterns of MeHg and EFA compounds as the inability of aquatic organisms to regulate the assimilation of dietary MeHg, whereas the rate of EFA retention may be controlled to optimize their physiological performance. Therefore, we conclude that bioaccumulation patterns of Hg in these aquatic food webs are not controlled by lipid solubility and/or the retention of EFA compounds.