Geochemistry signatures of mercury in soils of the Amazon rainforest biome.

Mercury (Hg) toxicity in soils depends on Hg species and other physical and chemical attributes, as selenium (Se) hotspots in soils, particularly relevant in Amazonian soils. The study of Hg species and their relations in representative locations of the Amazon rainforest biome is critical for assessing the potential risks of Hg in this environment. This work aimed to determine the concentration of total Hg and its species (Hg0, Hg22+ and Hg2+), and to correlate Hgtotal concentration with total elemental composition, magnetic susceptibility, and physicochemical attributes of Amazon soils. Nine sites in the Amazon rainforest biome, Brazil, were selected and analyzed for their chemical, physical, and mineralogical attributes. The clay fraction of the studied Amazon soils is dominated by kaolinite, goethite, hematite, gibbsite, and quartz. Mica was also found in soils from the States of Acre and Amazonas. Hgtotal ranged from 21.5 to 208 µg kg-1 (median = 104 µg kg-1), and the concentrations did not exceed the threshold value established for Brazilian soils (500 µg kg-1). The Hg2+ was notably the predominant species. Its occurrence and concentration were correlated with the landscape position and soil attributes. Hgtotal was moderately and positively correlated with TiO2, clay, and Se. The findings showed that geographic location, geological formation, and pedological differences influence the heterogeneity and distribution of Hgtotal in the studied soil classes. Thus, a detailed characterization and knowledgment of the soil classes is very important to clarify the complex behavior of this metal in the Amazon rainforest biome.

Adsorption of gaseous elemental mercury on soils: Influence of chemical and/or mineralogical characteristics.

Gaseous elemental Hg is stable enough to be transported over long distances. Some of the most important sources of Hg in the atmosphere are artisanal gold mining activities and forest fires. Both of these sources are particularly prevalent in the Amazonia region. Information regarding the capacity of soils for retaining Hg transported by the atmosphere is very important for understanding the metal cycle in the environment. The aim of this work was to study gaseous elemental Hg adsorption in soils with different physical and chemical characteristics. For this purpose, soils from different regions in Brazil and Colombia influenced or possibly influenced by gold mining activities and forest fires were studied. Hg adsorption tests were conducted by exposing soil samples to a gaseous elemental Hg atmosphere for 144 h. The total Hg concentration (THg) and Hg oxidation states were monitored using a direct Hg analyzer. Sample characterization analyses were performed. THg values obtained before the adsorption tests were 43-413 and 144-590 µg kg-1 for grain size fractions below 2 and 0.063 mm, respectively. The predominant species found was Hg2+, with abundance levels from 68% to 99%. The results show a wide range of enhanced Hg retention capacities among the samples, ranging from 13 to 2236 times the initial concentration, and the speciation results demonstrate a decrease in the oxidized species range, from 21% to 78%. The statistical analysis indicated the importance of Mn-bearing minerals for the processes of adsorption/oxidation of gaseous elemental Hg in soils. These results contribute to the elucidation of the processes that occur with Hg at the soil/atmosphere interface and may help to explain the high concentrations of Hg found in Amazonian soils where no gold mining activities are practiced.

The redox processes in Hg-contaminated soils from Descoberto (Minas Gerais, Brazil): implications for the mercury cycle.

Investigations of the redox process and chemical speciation of Hg(II) lead to a better understanding of biogeochemical processes controlling the transformation of Hg(II) into toxic and bioaccumulative monomethyl mercury, mainly in areas contaminated with Hg(0). This study investigates the speciation and redox processes of Hg in soil samples from a small area contaminated with Hg(0) as a result of gold mining activities in the rural municipality of Descoberto (Minas Gerais, Brazil). Soil samples were prepared by adding Hg(0) and HgCl2 separately to dry soil, and the Hg redox process was monitored using thermodesorption coupled to atomic absorption spectrometry. A portion of the Hg(0) added was volatilized (up to 37.4±2.0%) or oxidized (from 36±7% to 88±16%). A correlation with Mn suggests that this oxidation is favored, but many other factors must be evaluated, such as the presence of microorganisms and the types of organic matter present. The interaction of Hg with the matrix is suggested to involve Hg(II)-complexes formed with inorganic and organic sulfur ligands and/or nonspecific adsorption onto oxides of Fe, Al and/or Mn. The kinetics of the oxidation reaction was approximated for two first-order reactions; the faster reaction was attributed to the oxidation of Hg(0)/Hg(I), and the slower reaction corresponded to Hg(I)/Hg(II). The second stage was 43-139 times slower than the first. The samples spiked with Hg(II) showed low volatilization and a shifting of the signal of Hg(II) to lower temperatures. These results show that the extent, rate and type of redox process can be adverse in soils. Descoberto can serve as an example for areas contaminated with Hg(0).

Methylmercury chronic exposure affects the expression of DNA single-strand break repair genes, induces oxidative stress, and chromosomal abnormalities in young dyslipidemic APOE knockout mice.

Mercury (Hg) is one of the most toxic environmental pollutants, especially when methylated, forming methylmercury (MeHg). MeHg affects DNA repair, increases oxidative stress, and predisposes to cancer. MeHg neurotoxicity is well-known, but recently MeHg-associated cardiovascular effects were recognized. This study evaluated circulating lipids, oxidative stress, and genotoxicity after MeHg-chronic exposure (20 mg/L in drinking water) in C57BL/6J wild-type and APOE knockout (ko) mice, the latter, being spontaneously dyslipidemic. Experimental mice were assigned to four groups: non-intoxicated and MeHg-intoxicated wild-type mice and non-intoxicated and MeHg-intoxicated APOE ko mice. Plasma levels of triglycerides, total cholesterol (TC), HDL, and LDL were analyzed. Liver lipid peroxidation and splenic gene expression of xeroderma pigmentosum complementation groups A, C, D, and G (XPA, XPC, XPD, and XPG), X-ray repair cross-complementing protein 1 (XRCC1), and telomerase reverse transcriptase (TERT) were measured. Fur Hg levels confirmed chronic MeHg intoxication. MeHg exposure raises TC levels both in wild-type and APOE ko mice. HDL and LDL-cholesterol levels were increased only in the MeHg-challenged APOE ko mice. MeHg increased liver lipid peroxidation, regardless of the genetic background. Unintoxicated APOE ko mice showed higher expression of TERT than all other groups. APOE deficiency increases XPA expression, regardless of MeHg intoxication. Furthermore, MeHg-intoxicated mice had more cytogenetic abnormalities, effect which was independent of APOE deficiency. More studies are needed to dissect the interactions between circulating lipids, MeHg intoxication, and DNA-repair pathways even at young age, interactions that likely play critical roles in cell senescence and the risk for chronic disorders later in life.

Oral methylmercury intoxication aggravates cardiovascular risk factors and accelerates atherosclerosis lesion development in ApoE knockout and C57BL/6 mice.

Methylmercury (MeHg) intoxication is associated with hypertension, hypercholesterolemia, and atherosclerosis by mechanisms that are not yet fully understood. We investigated the effects of MeHg intoxication in atherosclerosis-prone (ApoE-KO) and resistant C57BL/6 mice. Mice were submitted to carotid stenosis surgery (to induce atherosclerosis faster) and received water or MeHg solution (20 mg/L) for 15 days. Tail plethysmography was performed before and after MeHg exposure. Food and MeHg solution intakes were monitored weekly. On the 15th day, mice were submitted to intravital fluorescence microscopy of mesenteric vasculature to observe in vivo leukocyte rolling and adhesion. Results showed that despite the high hair and liver Hg concentrations in the MeHg group, food and water (or MeHg solution) consumption and liver function marker levels were similar to those in controls. MeHg exposure increased total cholesterol, the atherogenic (non-HDL) fraction and systolic and diastolic blood pressure. MeHg exposure also induced inflammation, as seen by the increased rolling and adhered leukocytes in the mesenteric vasculature. Atherosclerosis lesions were more extensive in the aorta and carotid sites of MeHg-ApoE knockout mice. Surprisingly, MeHg exposure also induced atherosclerosis lesions in C57BL/6 mice, which are resistant to atherosclerosis formation. We concluded that MeHg intoxication might represent a risk for cardiovascular diseases since it accelerates atherogenesis by exacerbating several independent risk factors.

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.

Mercury conversion processes in Amazon soils evaluated by thermodesorption analysis.

This paper reports on the speciation study and the Hg redox behavior in Amazon soils not influenced by gold mining and collected near Manaus, AM, Brazil. The samples were incubated by adding Hg(0) and HgCl(2) to dry soil. Solid phase Hg speciation analysis was carried out using a Hg thermodesorption technique with the aim of distinguishing elemental Hg(0) from Hg(II) binding forms. In the first case, we observed the conversion of Hg(0) to Hg(II) binding forms in the range of 28-68% and a correlation between the percent of oxidation and OM content. Samples incubated with Hg(II) showed the formation of Hg(I) and/or Hg(0) in the range of 19-69%. The lowest values corresponded to the samples with the lowest clay contents. The kinetics of conversion of Hg(0) as well as HgCl(2) were roughly fitted to the two first order reactions, a fast one and a slow one. It was not possible to evaluate differences between sampling sites and types of soils, but the mean half-life of the first order reaction obtained by the addition of Hg(II) was slower (t(1/2)=365d) than the one obtained by the addition of Hg(0) (t(1/2)=148d). Previous studies have shown the predominance of organically bound Hg in these samples. Thus, the kinetic difference between Hg oxidation and reduction in combination with the efficient retention processes by OM may explain the high background values found in Amazon soils.

Speciation and quantification of mercury in Oxisol, Ultisol, and Spodosol from Amazon (Manaus, Brazil).

In order to investigate the content and distribution of Hg in soils from Amazon areas not impacted by gold mining activities, the concentration and granulometric distribution of Hg were determined in three different types of soils. Hg speciation data were obtained by a thermodesorption atomic spectrometry system and the role of physico-chemical and mineralogical characteristics on Hg content were also studied. Hg concentrations found in the soil fraction <2000 microm were similar to values found in other Amazon areas without anthropogenic sources. The fine fraction (<53 microm) of podzolized soils had a higher Hg content than clayey soils. Multivariate analysis shows that there are marking differences between Spodosols of two distinct areas (fine fraction Hg contents up to 10-fold as high) indicating the importance of pedogenic processes. All statistical data analysis indicated that organic matter plays an important role in Hg accumulation in the types of soils studied. Thermodesorption analysis revealed the presence of only Hg2+, and the predominance of organically bound Hg in the majority of the studied samples.

Shellfish from Todos os Santos Bay, Bahia, Brazil: treat or threat?

This study determined the concentrations of major and trace elements in shellfish (oysters, clams and mussels) and conducted an assessment of the health risks due to the consumption of contaminated seafood. Samples were collected at 34 sites along Todos os Santos Bay, Brazil. The elements were determined by ICP OES and Hg by Direct Mercury Analysis. Relatively high concentrations of trace elements (As, Zn, Se and Cu) were found in seafood tissues. Potential daily intake of As, Co, Se, Zn and Cu associated to shellfish consumption suggested relevant non-carcinogenic risk for all studied locations. Copper was the element that posed the greatest non-carcinogenic risk, while Pb posed the highest carcinogenic risk. Health risks for humans were greatest from the consumption of mussels. Contaminated shellfish offer the greatest risk for children, subsistence fishers and subsistence shellfish consumers.