RESUMEN

Many rivers have been impacted by heavy metal pollution in the past but the long-term legacies on biodiversity are difficult to estimate. The River Ulla (NW Spain) was impacted by tailings from a copper mine during the 1970-1980s but absence of baseline values and lack of subsequent monitoring have prevented a full impact assessment. We used archived fish scales of Atlantic salmon to reconstruct levels of historical copper pollution and its effects on salmon fitness. Copper bioaccumulation significantly increased over baseline values during the operation of the mine, reaching sublethal levels for salmon survival. Juvenile growth and relative population abundance decreased during mining, but no such effects were observed in a neighbouring river unaffected by mining. Our results indicate that historical copper exposure has probably compromised the fitness of this Atlantic salmon population to the present day, and that fish scales are suitable biomarkers of past river pollution.

Asunto(s)

RESUMEN

The chemical composition of fish scales has been reported to reflect the composition of the waters in which fish have been resident, therefore having the potential for the assessment of temporal trends in watershed water quality. Here we studied the historical (1983-2007) metal contamination in the Ulla river (NW Iberian Peninsula) watershed - impacted by a Cu mine that was in operation from 1973 until 1988 - by means of the analysis of major and trace elements in salmon scales. Results indicate the presence of a significant contamination for several metals (especially Cu, Au, Ag, Sb, Zn) during the 1980's. Concentrations of Cu in salmon scales during the influence of the mine (1983-1990) were 20 ± 5 µg/g, exceeding the values for the recent years (1995-2007): 1.8 ± 0.4 µg/g. Concentrations for Au in these two periods were 31 ± 12 and 2.1 ± 1.2 ng/g; for Ag: 21 ± 4 and 4 ± 2 ng/g; for Sb: 48 ± 21 and 15 ± 4 ng/g; and for Zn: 133 ± 16 and 93 ± 10 µg/g. The estimated concentrations of dissolved copper during the operation of the mine indicate a scenario of toxic effects due to sensory impairments in the salmon, and a reduction in scales calcification. The results presented here demonstrate that the analysis of trace elements in archived fish scales is a suitable tool for the reconstruction of the past contamination in aquatic systems, and it can be also used as a non-lethal approach for biomonitoring purposes.

Asunto(s)

RESUMEN

Catalytic converters in automobiles have significantly increased the input of platinum group elements (PGE) to the environment, and their coupled geochemical behavior has been proposed. To check this hypothesis, Pt and Os concentrations and (187)Os/(188)Os ratios were determined in sediment cores and interstitial waters from the Tagus Estuary (SW Europe) affected by different traffic pressure. Platinum concentration in surface sediments nearby the high traffic zone (up to 40 ng g(-1)) indicated severe contamination. Although lower than Pt, Os enrichment was also observed in surface sediments, with lower (187)Os/(188)Os ratios than in deeper layers. Dissolved Pt and Os in interstitial waters, 0.1-0.7 pg g(-1) and 0.03-0.10 pg g(-1), respectively, were higher than in typical uncontaminated waters. Results indicate two sources of Pt and Os into the Tagus Estuary salt marshes: a regional input associated with industrial activities, fossil fuel combustions, and regional traffic and a local source linked to nearby traffic density emissions. Estimations of Os and Pt released by catalytic converters support this two-source model. Differences in geochemical reactivity and range of dispersion from their sources lead to a decoupled behavior of Os and Pt, questioning the use of Os isotopes as proxies of PGE sources to the environment.

Asunto(s)

RESUMEN

The determination of trace elements using stripping voltammetry may be seriously affected by the presence of intensive matrix background or interfering peaks, leading to poorer detection limits and/or inaccurate quantitative results. In this work, we have tested the use of signal transformation (e.g., second derivative) in the analysis of platinum in seawater and sediment digests by means of catalytic adsorptive stripping voltammetry. In natural waters, the limit of detection of Pt is affected by a broad background wave due to the formazone complex used in the sample matrix for its determination, while in sediment digests, the Pt peak may be interfered with due to the presence of elevated concentrations of Zn, affecting the accuracy of the determination. Results applying second derivative signal transformation revealed a significant improvement (2-3-fold) of the detection limit in water due to the minimization of background effects, therefore allowing shorter accumulation times and faster determinations. In the presence of interfering peaks, the inaccuracy resulting from erroneous baseline selection in the original signal is eliminated when the second derivative is used. Signal processing should be considered as a useful tool for other voltammetric methodologies where more accurate or faster determinations are needed.