Cláudia Carvalhinho Windmöller

Mercury speciation in fluorescent lamps by thermal release analysis

In this work, mercury speciation in phosphorus powder matrices and soda lime glass waste from new and spent fluorescent lamp wastes has been studied by thermo-desorption/atomic absorption spectrometry (TDAAS), X-ray diffraction (XRD), cold vapor-atomic absorption (CV-AAS) and atomic emission spectrometry/inductively coupled plasma (ICP/AES). TDAAS results show the presence of oxidized forms of mercury, i.e., Hg(1+) and Hg(2+), especially in wastes with high mercury concentration. Such forms are mobile, and therefore represent a potential hazard waste material. Glass TD profiles of spent fluorescent lamps suggested the presence of mercury strongly linked to the matrix, which desorbs only at high temperatures.

Mercury speciation in contaminated soils by thermal release analysis

Thermal release analysis of mercury species in contaminated soils was performed by temperature controlled continuous heating of the samples in a furnace coupled to an Atomic Absorption Spectrophotometer (AAS). It was shown that this method allows the identification of different redox states of Hg-species through their characteristic releasing temperature ranges. The method was applied to Hg-contaminated samples from an inactive chlor-alkali production plant in former East Germany (GER), and from a gold mining area in Poconé, Mato Grosso, Brazil (BRA), as well as synthetic soil samples obtained by spiking pre-heated soil matrices (GER and BRA) with the following mercury species: Hg0, Hg2Cl2, HgCl2, HgO and HgS.The samples GER, in general, frequently showed the presence of Hg2+ probably bound to humic substances, in the case of samples with higher total carbon content. Only in highly contaminated samples (>3000 ppm of mercury) was Hg0 the predominant species. The samples BRA more frequently showed the presence of mercury species in the lower oxidation states, i.e. Hg1+ in combination with Hg0. The method allows observing changes in Hg-speciation in the samples with time, mainly changes among the oxidation states Hg0, Hg1+ and Hg2+.The treated GER matrix showed a stronger tendency to oxidise Hf-species than the BRA treated matrix, in which only added Hg0 is partially oxidised to Hg2+ and Hg1+. In contrast, the BRA matrix showed a pronounced tendency to reduce spiked Hg2+ to Hg1+. This may be the reason for the presence of Hg1+ in the majority of original BRA samples.The method appears to be very useful to study speciation of mercury and its dynamics. It can be used as a tool for monitoring mercury oxidation states and/or reactions of mercury in soils.

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.

Arsenic and Mercury mobility in brazilian sediments from the São Francisco River Basin

Os sedimentos possuem propriedades de acumulacao de poluentes e a determinacao de elementos toxicos nessas amostras permite avaliar o seu ciclo geoquimico. Arsenio e mercurio foram determinados em 28 amostras de sedimento da Bacia do Rio Sao Francisco, Minas Gerais, Brasil, por geracao de hidretos acoplada a espectrometria de absorcao atomica (HG AAS). Foram empregados procedimentos de digestao pseudo-total empregando HCl:HNO3 (3:1 v/v) e extracao parcial com HCl 1 mol L-1. Realizou-se ainda a determinacao de Hg nas amostras solidas, utilizando-se um analisador direto de mercurio. Observou-se que 46% das amostras apresentaram concentracoes de As acima do limite de nivel 1 estabelecido pela Resolucao 344/2004 do CONAMA e que 14% excederam o limite de nivel 1 para Hg. As amostras com altas concentracoes de Hg foram tambem analisadas por termodessorcao acoplada a espectrometria de absorcao atomica (TDAAS) para especiacao e os termogramas apontaram somente a presenca da especie Hg(II)

Fast determination of trace elements in organic fertilizers using a cup-horn reactor for ultrasound-assisted extraction and fast sequential flame atomic absorption spectrometry

A fast and accurate method based on ultrasound-assisted extraction in a cup-horn sonoreactor was developed to determine the total content of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn in organic fertilizers by fast sequential flame atomic absorption spectrometry (FS FAAS). Multivariate optimization was used to establish the optimal conditions for the extraction procedure. An aliquot containing approximately 120 mg of the sample was added to a 500 µL volume of an acid mixture (HNO3/HCl/HF, 5:3:3, v/v/v). After a few minutes, 500 µL of deionized water was added and eight samples were simultaneously sonicated for 10 min at 50% amplitude, allowing a sample throughput of 32 extractions per hour. The performance of the method was evaluated with a certified reference material of sewage sludge (CRM 029). The precision, expressed as the relative standard deviation, ranged from 0.58% to 5.6%. The recoveries of analytes were found to 100%, 109%, 96%, 92%, 101%, 104% and 102% for Cd, Cr, Cu, Mn, Ni, Pb and Zn, respectively. The linearity, limit of detection and limit of quantification were calculated and the values obtained were adequate for the quality control of organic fertilizers. The method was applied to the analysis of several commercial organic fertilizers and organic wastes used as fertilizers, and the results were compared with those obtained using the microwave digestion procedure. A good agreement was found between the results obtained by microwave and ultrasound procedures with recoveries ranging from 80.4% to 117%. Two organic waste samples were not in accordance with the Brazilian legislation regarding the acceptable levels of contaminants.

Distribuição e especiação de mercúrio em sedimentos de áreas de garimpo de ouro do quadrilátero ferrífero (MG)

The concentration and thermodesorption speciation of mercury in sediments from four different Iron Quadrangle sites impacted by gold mining activity were determined. The mercury content of some samples was considerably high (ranging from 0.04 to 1.1 µg g-1). Only Hg2+ was found and it was preferably distributed in the silt/clay fraction in all samples. Cluster analysis showed that mercury and manganese can be associated. The occurrence of cinnabar in this region as another mercury source was also discussed, corroborating earlier works showing the importance of natural mercury in the geochemical cycle of the metal in this region.

Accumulation and oxidation of elemental mercury in tropical soils

The role of chemical and mineralogical soil properties in the retention and oxidation of atmospheric mercury in tropical soils is discussed based on thermal desorption analysis. The retention of gaseous mercury by tropical soils varied greatly both quantitatively and qualitatively with soil type. The average natural mercury content of soils was 0.08 ± 0.06 μg g(-1) with a maximum of 0.215 ± 0.009 μg g(-1). After gaseous Hg(0) incubation experiments, mercury content of investigated soils ranged from 0.6 ± 0.2 to 735 ± 23 μg g(-1), with a mean value of 44 ± 146 μg g(-1). Comparatively, A horizon of almost all soil types adsorbed more mercury than B horizon from the same soil, which demonstrates the key role of organic matter in mercury adsorption. In addition to organic matter, pH and CEC also appear to be important soil characteristics for the adsorption of mercury. All thermograms showed Hg(2+) peaks, which were predominant in most of them, indicating that elemental mercury oxidized in tropical soils. After four months of incubation, the thermograms showed oxidation levels from 70% to 100%. As none of the samples presented only the Hg(0) peak, and the soils retained varying amounts of mercury despite exposure under the same incubation conditions, it became clear that oxidation occurred on soil surface. Organic matter seemed to play a key role in mercury oxidation through complexation/stabilization of the oxidized forms. The lower percentages of available mercury (extracted with KNO3) in A horizons when compared to B horizons support this idea.

Evaluation of Arsenic Availability in Sulfidic Materials from Gold Mining Areas in Brazil

This study is aimed at evaluating the availability and mobility of arsenic in sulfidic materials from gold mining areas in Minas Gerais State, Brazil. Eight extraction media were employed in a sequential extraction scheme, as follows: exchangeable As; strongly adsorbed As; As coprecipitated with acid-volatile sulfide, carbonates, MnO2, and Al2O3; As coprecipitated with amorphous iron; As linked to crystalline iron oxide; As coprecipitated with silicates; As coprecipitated with amorphous FeS2 and As2S3, and residual As, which was determined by GFAAS. Results demonstrated that in spite of differences in arsenic concentrations, the availability of the metalloid was found to be low for all samples. In general, arsenic was found in less available forms. Nevertheless, most of the arsenic in the environment is retained in the fractions 3, 4, and 5 which are susceptible to dissolution in acid medium, which in turn might be due to oxidation of the sulfide present in the samples.

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).

Determination of cadmium and lead in cassava employing slurry sampling and graphite furnace atomic absorption spectrometry after multivariate optimization

A low cost and efficient method to determine Cd and Pb levels in cassava by graphite furnace atomization atomic absorption spectrometry (GF AAS) employing slurry sampling was developed. Slurries were prepared by cryogenic grinding of samples (40 mg), sieving for grain size at 50 mesh and addition of 2% v/v nitric acid and 1% v/v hydrogenous peroxide up to 2 mL of volume. The slurry was maintained homogeneous using air bubbling by an aquarium pump. Tungsten (500 μg) and titanium (500 μg) were the best permanent modifiers for Cd and Pb, respectively. The parameters of merit obtained under optimized conditions, AT (atomization temperature) = 1400 °C, PT (pyrolysis temperature) = 600 °C, pt (pyrolysis time) = 20 s and permanent W (500 μg) for Cd; AT = 1400 °C, PT = 450 °C, pt = 20 s, and Ti (500 μg) for Pb were: linear working range up to 6 and 50 μg L−1 for Cd and Pb, respectively; limit of detection (0.001 and 0.02) μg g−1 for Cd and Pb, respectively; and aqueous calibration, with r2 > 0.99. The accuracy was evaluated by recovery tests and by analysis of certified reference material (NIST – SRM 1568a, rice flour) and was in agreement with the certified values for the two analytes: 0.021 ± 0.002 (n = 5 replicates) for Cd (certified value 0.022 ± 0.002) and <LOQ (n = 5) for Pb (certified value <0.010). The average sample concentrations (n = 3) were between <LOQ to 5.8 ng g−1 and 0.08 to 3.18 μg g−1 for Cd and Pb, respectively.