Challenges in mercury speciation and fractionation in soil and sediment

This investigation focused on the development, test and validation of methodologies for mercury fractionation and speciation in soil and sediment. After an exhaustive review of the literature, several methods were chosen and tested in well characterised soil and sediment samples. Sequential extraction procedures that divide mercury fractions according to their mobility and potential availability in the environment were investigated. The efficiency of different solvents for fractionation of mercury was evaluated, as well as the adequacy of different analytical instruments for quantification of mercury in the extracts. Kinetic experiments to establish the equilibrium time for mercury release from soil or sediment were also performed. It was found that in the studied areas, only a very small percentage of mercury is present as mobile species and that mobility is associated to higher aluminium and manganese contents, and that high contents of organic matter and sulfur result in mercury tightly bound to the matrix. Sandy soils tend to release mercury faster that clayey soils, and therefore, texture of soil or sediment has a strong influence on the mobility of mercury. It was also understood that analytical techniques for quantification of mercury need to be further developed, with lower quantification limits, particularly for mercury quantification of less concentrated fractions: water-soluble e exchangeable. Although the results provided a better understanding of the distribution of mercury in the sample, the complexity of the procedure limits its applicability and robustness. A proficiency-testing scheme targeting total mercury determination in soil, sediment, fish and human hair was organised in order to evaluate the consistency of results obtained by different laboratories, applying their routine methods to the same test samples. Additionally, single extractions by 1 mol L-1 ammonium acetate solution, 0.1 mol L-1 HCl and 0.1 mol L-1 CaCl2, as well as extraction of the organometallic fraction were proposed for soil; the last was also suggested for sediment and fish. This study was important to update the knowledge on analytical techniques that are being used for mercury quantification, the associated problems and sources of error, and to improve and standardize mercury extraction techniques, as well as to implement effective strategies for quality control in mercury determination. A different, “non chemical-like” method for mercury species identification was developed, optimised and validated, based on the thermo-desorption of the different mercury species. Compared to conventional extraction procedures, this method has advantages: it requires little to no sample treatment; a complete identification of species present is obtained in less than two hours; mercury losses are almost neglectable; can be considered “clean”, as no residues are produced; the worldwide comparison of results obtained is easier and reliable, an important step towards the validation of the method. Therefore, the main deliverables of this PhD thesis are an improved knowledge on analytical procedures for identification and quantification of mercury species in soils and sediments, as well as a better understanding of the factors controlling the behaviour of mercury in these matrices.

Effects of coastal managed retreat on mercury biogeochemistry

We investigated the impact of managed retreat on mercury (Hg) biogeochemistry at a site subject to diffuse contamination with Hg. We collected sediment cores from an area of land behind a dyke one year before and one year after it was intentionally breached. These sediments were compared to those of an adjacent mudflat and a salt marsh. The concentration of total mercury (THg) in the sediment doubled after the dyke was breached due to the deposition of fresh sediment that had a smaller particle size, and higher pH. The concentration of methylmercury (MeHg) was 27% lower in the sediments after the dyke was breached. We conclude that coastal flooding during managed retreat of coastal flood defences at this site has not increased the risk of Hg methylation or bioavailability during the first year. As the sediment becomes vegetated, increased activity of Hg-methylating bacteria may accelerate Hg-methylation rate.

Mercury and DDT exposure risk to fish-eating human populations in Amazon

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Mercury in soils and sediments from gold mining liabilities in Southern Amazonia

The 1980-1990 Amazonian gold rush left an enormous liability that increasingly has been substituted by developing fish aquaculture. This work aimed at the identification of the mercury levels in the environment, associated with fish farms located in the North of Mato Grosso State, Southern Amazon. Sediment and soil samples were analyzed for total organic carbon and total mercury. Results indicate that the chemical characteristics of the sediment largely depend on the management procedures of the fish pond (liming, fish food used and fish population). The soils presented relatively low concentrations when compared with other data from the literature.

Chronopotentiometric stripping analysis using gold electrodes, an efficient technique for mercury quantification in natural waters

This paper proposes a simple methodology for mercury quantification in natural water by stripping chronopotentiometry at constant current, using gold (film) electrodes constructed from recordable CDs in stationary cell. The proposed method allows the direct measurement of labile mercury in natural waters. To quantify total mercury, a robust and low cost UV irradiation system was developed for the degradation of organic constituents of water. The proposed system presents such advantages as excellent sensitivity, low cost, versatility, and smaller dimensions (portability for on-field applications) when compared with other techniques (ICP, GFAAS, fluorimetry) traditionally utilized for mercury quantification. A large linear region of responses was observed, situated over the range 0.02 - 200 μ g L-1. Various experimental parameters were optimized and the system allowed quantifications in natural samples, with detection limit of 8 ng L-1 and excellent reproducibility (RSD of 1.4% for 48 repetitive measurements using a 10 μ g L-1 mercury solution). Different metal ions were evaluated, including copper, as possible interferences on stripping mercury signals. Applications of the new method were demonstrated for the analysis of certified and groundwater samples spiked with a known amount of mercury and for the quantification of methylmercury in synthetic oceanic water, originally utilized for fishes contamination experiment.

Seasonal behavior of mercury species in waters and sediments from the Negro River Basin, Amazon, Brazil

Total (HgT), reactive (HgR) and organic (Hg ORG) mercury species have been quantified in non-filtered waters collected from the Negro River Basin, Amazon (from January/2002 through January/2004), in both black and white water bodies. Black waters presented the highest HgT, HgORG and HgR concentration (29.1 ng L-1, 1.63 ng L-1 and 3.9 ng L-1, respectively), while, white waters presented the lowest HgT, Hg ORG and HgR concentration (8.8 ng L-1, 0.49 ng L-1 and 1.2 ng L-1, respectively). An inverse correlation between HgT and the water level over the basin was obtained, although the HgORG concentration has increased in the first rainy months and then decreased as the water level rose. Total mercury in surface sediments (0-10 cm) ranged from 70 to 271 mg kg-1 being the methylmercury 0.47-1.79 % of this stock. The results indicate that HgR and the labile dissolved organic matter were introduced into the aquatic environment during the flooding season, especially in the earlier stages, thus contributing to mercury methylation. ©2007 Sociedade Brasileira de Química.

A first evaluation on the use of Ardea albus feathers as bioindicators of mercury burden in Amazonian ecosystems

O objetivo deste estudo foi avaliar as concentrações de mercúrio total em penas de Ardea albus coletadas em uma assembléia de aves localizada nas imediações da cidade de Belém, Pará, com vistas a investigar a possibilidade do uso desta espécie nos estudos de biomonitoramento deste metal. Para determinação de mercúrio total foi utilizada a espectrofotometria de absorção atômica com amalgamação. A concentração média de mercúrio total nas penas do corpo foi 2,2 ± 1,5 µg.g-1 e nas penas das asas foi 1.3 ± 0.9 µg/g-1. Não foi observada correlação entre a concentração de mercúrio total e o comprimento das penas do corpo e da asa. Foi observado teor de mercúrio total superior a 5 µg.g-1 em apenas uma amostra de pena do corpo.

Avaliação da contaminação mercurial mediante análise do teor de Hg total em amostras de cabelo em comunidades ribeirinhas do Tapajós, Pará, Brasil

Este estudo avalia a contaminação mercurial em comunidades de pescadores em quatro localidades nas margens do rio Tapajós: Rainha, Barreiras, São Luís do Tapajós e Paraná-Mirim. Análises toxocológicas das amostras de cabelo foram realizadas por espectofotometria de absorção atômica. Os níveis de mercúrio total em amostras de cabelo variaram entre 2,9µg/g e 71,5µg/g. Os valores mais baixos foram encontrados na comunidade de Paraná-Mirim. Os mais elevados, em São Luís do Tapajós e Barreiras, cerca de seis a sete vezes superiores ao valor estabelecido. As diferenças entre as concentrações médias de mercúrio total nas amostras, coletadas em populações ribeirinhas, a montante e a jusante do rio Tapajós em Itaituba, não apresentaram significância estatística (p > 0,05). Conclui-se que a exposição humana ao mercúrio por ingestão de peixes contaminados constitui risco potencial para o aparecimento de sintomas e sinais da doença de Minamata, o que recomenda a manutenção de um programa de vigilância epidemiológica.

Determinação de mercúrio total em amostras de água, sedimento e sólidos em suspensão de corpos aquáticos por espectrofotometria de absorção atômica com gerador de vapor a frio

O emprego de mercúrio metálico nos processos de extração do ouro libera toneladas de mercúrio ao meio ambiente, provocando um aumento considerável nas concentrações presentes. Com a finalidade de prevenir a exposição humana a concentrações excessivas, o que poderá resultar em graves episódios de intoxicação mercurial, bem como avaliar a possibilidade de sedimentos tornarem-se fontes potenciais de contaminação para os seres vivos, é de fundamental importância a monitorização do mercúrio em diversos compartimentos ambientais. Efetuou-se a padronização de uma metodologia analítica para determinação de mercúrio total em amostras de água, sólidos em suspensão e sedimentos de corpos aquáticos para monitorização ambiental do xenobiótico. Posteriormente, foram analisadas amostras oriundas de regiões garimpeiras, com vistas a avaliar o desempenho do método em amostras reais e efetuar levantamento preliminar sobre a contaminação mercurial na área de estudo.

Distribuição de mercúrio total em sedimentos da plataforma continental Amazônica: Brasil

Este estudo foi desenvolvido na Plataforma Continental do Amazonas (PCA) com o objetivo de determinar os níveis de Hg total no sedimento de fundo, e assim contribuir como matriz ambiental indicadora para o plano geral de gerenciamento costeiro na região norte do Brasil. Foram amostrados 20 pontos entre maio e junho dos anos de 1999 a 2002, 2005 e 2007. Os resultados indicam não haver evidências de atividades antrópicas relacionadas à contaminação de mercúrio na região. Os teores encontrados variaram entre 0,047 e 0,166 mg kg^-1 com média 0,085±0,026 mg kg^-1, estando dentro do intervalo de "background" referido para os rios amazônicos não contaminados, que é de 0,05 a 0,28 mg kg^-1. As concentrações de Hg no sedimento, especialmente no sedimento lamoso, mostraram uma estreita dependência com os teores de argila (material fino) e matéria orgânica, corroborando mecanismos geoquímicos importantes na dinâmica do metal. A maior adsorção do mercúrio pode estar associada ao aumento dos teores de compostos (óxidos e hidróxidos) de ferro, alumínio, manganês e os minerais primários e secundários formadores das rochas da bacia de drenagem amazônica.

Mercury and Nitrogen Isotope in a Marine Species from a Tropical Coastal Food Web

The present study raised the hypothesis that the trophic status in a tropical coastal food web from southeastern Brazil can be measured by the relation between total mercury (THg) and nitrogen isotope (delta(15)N) in their components. The analysed species were grouped into six trophic positions: primary producer (phytoplankton), primary consumer (zooplankton), consumer 1 (omnivore shrimp), consumer 2 (pelagic carnivores represented by squid and fish species), consumer 3 (demersal carnivores represented by fish species) and consumer 4 (pelagic-demersal top carnivore represented by the fish Trichiurus lepturus). The values of THg, delta(15)N, and trophic level (TLv) increased significantly from primary producer toward top carnivore. Our data regarding trophic magnification (6.84) and biomagnification powers (0.25 for delta(15)N and 0.83 for TLv) indicated that Hg biomagnification throughout trophic positions is high in this tropical food web, which could be primarily related to the quality of the local water.

Morphological alterations in the liver of yellow perch (Perca flavescens) from a biological mercury hotspot

Mercury (Hg) contamination is a global issue due to its anthropogenic release, long-range transport, and deposition in remote areas. In Kejimkujik National Park and National Historic Site, Nova Scotia, Canada, high concentrations of total mercury (THg) were found in tissues of yellow perch (Perca flavescens). The aim of this study was to evaluate a possible relationship between THg concentrations and the morphology of perch liver as a main site of metal storage and toxicity. Yellow perch were sampled from five lakes known to contain fish representing a wide range in Hg concentrations in fall 2013. The ultrastructure of hepatocytes and the distribution of Hg within the liver parenchyma were analyzed by transmission electron microscopy (TEM) and electron energy loss spectrometry (EELS). The relative area of macrophage aggregates (MAs) in the liver was determined using image analysis software and fluorescence microscopy. No relation between general health indicators (Fulton's condition index) and THg was observed. In line with this, TEM examination of the liver ultrastructure revealed no prominent pathologies related to THg accumulation. However, a morphological parameter that appeared to increase with muscle THg was the relative area of MAs in the liver. The hepatic lysosomes appeared to be enlarged in samples with the highest THg concentrations. Interestingly, EELS analysis revealed that the MAs and hepatic lysosomes contained Hg.

(Table 2) Mercury and selenium concentration in the brain stem of wild polar bears (Ursus maritimus), east Greenland

Polar bears (Ursus maritimus) are exposed to high concentrations of mercury because they are apex predators in the Arctic ecosystem. Although mercury is a potent neurotoxic heavy metal, it is not known whether current exposures are of neurotoxicological concern to polar bears. We tested the hypotheses that polar bears accumulate levels of mercury in their brains that exceed the estimated lowest observable adverse effect level (20 µg/g dry wt) for mammalian wildlife and that such exposures are associated with subtle neurological damage, as determined by measuring neurochemical biomarkers previously shown to be disrupted by mercury in other high-trophic wildlife. Brain stem (medulla oblongata) tissues from 82 polar bears subsistence hunted in East Greenland were studied. Despite surprisingly low levels of mercury in the brain stem region (total mercury = 0.36 ± 0.12 µg/g dry wt), a significant negative correlation was measured between N-methyl-D-aspartate (NMDA) receptor levels and both total mercury (r = -0.34, p < 0.01) and methylmercury (r = -0.89, p < 0.05). No relationships were observed among mercury, selenium, and several other neurochemical biomarkers (dopamine-2, gamma-aminobutyric acid type A, muscarinic cholinergic, and nicotinic cholinergic receptors; cholinesterase and monoamine oxidase enzymes). These data show that East Greenland polar bears do not accumulate high levels of mercury in their brain stems. However, decreased levels of NMDA receptors could be one of the most sensitive indicators of mercury's subclinical and early effects.

(Table 1) Mercury concentrations and carbon and nitrogen isotopic ratios in 14 marine species from West Greenland sampled between 2003-2004

Total mercury (THg), methylmercury (MeHg) and stable isotopes of nitrogen (d15N) and carbon (d13C) were measured in three invertebrate, five fish, three seabird and three marine mammal species of central West Greenland to investigate trophic transfer of mercury in this Arctic marine food web. The food web magnification factor (FWMF) estimated as the slope of the regression between the natural logarithm of THg or MeHg concentrations (mg/kg dw) and tissue d15N (per mil) was estimated to 0.183 (SE = 0.052) for THg and 0.339 (SE = 0.075) for MeHg. The FWMFs were not only comparable with those reported for other Arctic marine food webs but also with quite different food webs such as freshwater lakes in the sub-Arctic, East Africa and Papua New Guinea. This suggests similar mechanisms of mercury assimilation and isotopic (d15N) discrimination among a broad range of aquatic taxa and underlines the possibility of broad ecosystem comparisons using the combined contaminant and stable isotope approach.

Mercury concentrations in waters of the Atlantic Ocean and Mediterranean Sea

Total mercury concentration in waters of the Atlantic Ocean and Mediterranean Sea measured in January-April 1982 varied from 0.007 to 0.192 µg/l. Particulate form was 1.6-16% of dissolved form. Inorganic mercury accounted for 16-67% of dissolved mercury. Total mercury concentration in the surface film was 0.74-1.85 µg/l, 10-40 times higher than in seawater. Concentration of particulate form in the film was from 100 to 400 times higher than in seawater.