Seasonal variations in pore water and sediment geochemistry of littoral lake sediments (Asylum Lake, MI, USA)

BACKGROUND: Seasonal changes in pore water and sediment redox geochemistry have been observed in many near-surface sediments. Such changes have the potential to strongly influence trace metal distribution and thus create seasonal fluctuations in metal mobility and bioavailability. RESULTS: Seasonal trends in pore water and sediment geochemistry are assessed in the upper 50 cm of littoral kettle lake sediments. Pore waters are always redox stratified, with the least compressed redox stratification observed during fall and the most compressed redox stratification observed during summer. A 2-step sequential sediment extraction yields much more Fe in the first step, targeted at amorphous Fe(III) (hydr)oxides (AEF), then in the second step, which targets Fe(II) monosulfides. Fe extracted in the second step is relatively invariant with depth or season. In contrast, AEF decreases with sediment depth, and is seasonally variable, in agreement with changes in redox stratification inferred from pore water profiles. A 5-step Tessier extraction scheme was used to assess metal association with operationally-defined exchangeable, carbonate, iron and manganese oxide (FMO), organic/sulfide and microwave-digestible residual fractions in cores collected during winter and spring. Distribution of metals in these two seasons is similar. Co, As, Cd, and U concentrations approach detection limits. Fe, Cu and Pb are mostly associated with the organics/sulfides fraction. Cr and Zn are mostly associated with FMO. Mn is primarily associated with carbonates, and Co is nearly equally distributed between the FMO and organics/sulfide fractions. CONCLUSION: This study clearly demonstrates that near-surface lake sediment pore water redox stratification and associated solid phase geochemistry vary significantly with season. This has important ramifications for seasonal changes in the bioavailability and mobility of trace elements. Without rate measurements, it is not possible to quantify the contribution of various processes to natural organic matter degradation. However, the pore water and solid phase data suggest that iron reduction and sulfate reduction are the dominant pathways in the upper 50 cm of these sediments

Weight-of-evidence on environmental impact assessment of metal contaminated sediments in the São Francisco river (Três Marias - Minas Gerais - Brazil): a case study

The weight-of-evidence - WOE approach was used to assess the environmental impact of sediments contaminated by metals in the São Francisco river and one of its tributaries, Consciência creek, both affected by anthropic activities, in the region of Três Marias (Minas Gerais/Brazil). The assessment provided support to a risk management decision. The WOE was based on bulk metal analysis, AVS-SEM assays, elutriate tests, ecotoxicity assays, benthic community assessment and a comparison for the reference area. Brazilian legislation and other available literature were used as criteria to evaluate the lines of evidence. All samples, except for the reference area, presented some contamination. However, geochemical testing for bioavailability studies showed that toxicity is unlikely as suggested by the chemical results. Ecotoxicity and benthic structure studies provided further information to support decision making. Metal acid volatile sulfide formation mechanisms were identified, which can eventually attenuate metal toxicity observed. The removal of active sources of contamination (for example, from tailings dumps) associated with Monitoring Natural Recovery could be sufficient to eventually lessen the risk of the biota in São Francisco river sediments