This study compares the techniques cold vapour atomic fluorescence spectrometry (CV-AFS) and inductively coupled plasma mass spectrometry (ICP-MS) for the determination of Hg in biological samples (hepatic tissue from marine tetrapods). Acid digestions were performed for the samples and aliquots of them were analysed by ICP-MS and CV-AFS. To minimize the Hg memory effect in its determination by ICP-MS, gold (200 µg L-1 in 5% v v-1 HCl) was added to the sample digests. The detection limits were 0.02 mg kg-1 for ICP-MS and 0.01 mg kg-1 for CV-AFS. Accuracy was assessed by the calculation of the recovery obtained from TORT-3 (lobster hepatopancreas) certified reference material analysis. Accurate results were obtained for both CV-AFS and ICP-MS. The comparison of the results obtained for hepatic tissue with and without lyophilization showed a significant difference among them (at 95% of confidence level), evidencing losses of Hg in the lyophilization process.

This research was aimed to evaluate the concentration of 15 chemical elements as a reference base for the quality of the litter in a forest in the central region of the Amazon. The sampling of the litter was performed monthly in two topographic positions for one year. For the quantification of the elements, digestion by nitroperchloric solution and reading by ICP OES were performed. The mean of macronutrient contents in the litter in decreasing order were Ca>K>Mg>Na. For micronutrients, the order was Al>Mn>Fe>Sr>Zn>Cu>Ba>Cr>Ni>Co>Cd for the Plateau and Al>Mn>Fe Sr>Zn>Cu>Ba>Cr>Ni>Cd>Co for the Baixio. Among the fractions, calcium had its highest concentration in the woody material, potassium in the reproductive material, while magnesium, sodium, and aluminum showed higher concentrations in the leaf fraction. Also, it was observed that the return of the elements to the soil by litter was greater in the dry period of the region, due to the greater fall in plant material. Calcium differed significantly within the same area, obtaining the highest concentrations compared to the other elements, while aluminum and zinc differed significantly between the areas studied, with a higher return for both elements on the Plateau.

Espécies de mercúrio total (HgT), reativo (HgR) e orgânico (HgORG) foram quantificadas em amostras de água não filtradas da Bacia do Rio Negro, Amazonia (de Janeiro/2002 a Janeiro/2004) em ambos corpos aquáticos de águas brancas e pretas. As águas pretas apresentaram as maiores concentrações de mercúrio total, orgânico e reativo (29,1; 1,63 e 3,9 ng L-1, respectivamente), sendo que as águas brancas apresentaram as menores concentrações de HgT, HgORG e HgR (8,8; 0,49 e 1,2 ng L-1, respectivamente). Uma correlação inversa entre HgT e o nível da água sobre a bacia foi obtido, embora a concentração de HgORG tenha aumentado nos primeiros meses chuvosos decrescendo com o aumento do nível da água. A concentração de HgT em sedimentos superficiais (0-10 cm) variou de 70 a 271 mg kg-1, com o metilmercúrio sendo 0,47-1,79% deste estoque. Os resultados indicaram que HgR e a matéria orgânica dissolvida e lábil estão sendo introduzidos no ambiente aquático durante a estação chuvosa, especialmente nos estágios iniciais contribuindo para a metilação de mercúrio.

Total (HgT), reactive (HgR) and organic (HgORG) 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, HgORG 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.

In this work was developed an alternative methodology to separation of aquatic organic matter (AOM) present in natural river waters. The process is based in temperature decreasing of the aqueous sample under controlled conditions that provoke the freezing of the sample and separation of the dark extract, not frozen and rich in organic matter. The results showed that speed of temperature decreasing exerts strongly influence in relative recovery of organic carbon, enrichment and time separation of the organic matter present in water samples. Elemental composition, infrared spectra and thermal analysis results showed that the alternative methodology is less aggressive possible in the attempt of maintaining the integrity of the sample.

The aquatic humic substances (AHS) investigated in this study were conventionally isolated from Rio Negro waters - Amazonas State/Brazil by means of the collector XAD 8. A special five-stage tangential-flow ultrafiltration device was used for analytical fractionation of AHS. The fractionation patterns (6 fractions each) showed that metal traces remaining in AHS after their XAD 8 isolation have different size distributions. For instance, the major percentage of traces of Ni, Cu, Zn, Cd and Pb (determined using ICP-AES) was preferably complexed by molecules with relatively high molecular size (30-100 kDa) and the following complexation order was characterized: F2 >> F1 = F4 = F5 > F3 > F6. Moreover, the species formed between AHS and metals prepared by spiking, showed distribution patterns changing as a function of the complexation time (ageing process), indicating a slow transformation process and an inner rearrangements in the binding sites within the AHS molecules.

A sequential system for fractionation by ultrafiltration (SSFU) equipped with advanced membranes filters (molecular size cut-off: 5, 10, 30, 50 and 100 kDalton) of the polyethersulfone type was developed for analytical fractionation of humic substances (HS) extracted from aquatic systems or soils. The device consists of five membrane filters (Sartocon® Micro) operated by a multi-channel peristaltic pump, enabling an easy handling, working in a closed system and with simple collection of the six obtained fractions (F1>100; F2: 100-50; F3: 50-30; F4:30-10; F5: 10-5 and F6 <5 kDalton). Then, the HS sample (250 mL solution 1.0 mg/mL, pH 5.0 to 6.0) to be fractionated is pumped by pump through the series of membrane filters with a tangential flow of 85 mL/min, initial pressure 0.2 to 0.3 bar and permeation flux through the membranes of 0.8 to 1.4 mL/min. The overall time for fractionation and cleaning of the device is about 10 h and 25 mL of each fraction is obtained.