Chemical availability of mercury in stream sediments from the Almadén area, Spain

The chemical speciation, fractionation and availability of mercury in sediments from a cinnabar mining area (Almadén, Spain) was studied with different extraction and analytical procedures, in order to determine the degree to which the ecosystem is harmed by this pollutant. Three total extraction procedures, a sequential extraction and the speciation of organo-mercury compounds were performed in nine sediment samples. In the study area, although concentrations of mercury can be extremely high (up to 1,000 mg kg(-1)), no organomercury compounds were detected (< 2 microg kg(-1) and the availability of this element seems restricted. One of the methods for total extraction presented considerably lower recovery in Almadén's sediments, yet the results were controlled with certified reference materials. This disagreement was attributed to the fact that the mercury is in a refractory form. Sequential extraction was able to show that most of the mercury is associated with sulfides (probably as metacinnabar) or in the residual refractory phase (probably as red cinnabar).     

Determination of metal and organometal trophic bioaccumulation in the benthic macrofauna of the Adour estuary coastal zone (SW France, Bay of Biscay)

A multidisciplinary approach has been adopted in order to investigate the bioaccumulation of metals and organometals in macrobenthic populations. A complete method coupling a sampling strategy and classification of benthic organisms with a performant analytical procedure for the analysis of both metals and organometals has been developed. A single sample preparation method using a TMAH extraction and species specific isotope dilution makes it possible to analyse metals and organometals in the same extract, which is especially interesting for situations where only a limited amount of sample is available. Low detection limits have been obtained in the range of 12-250 pg g(-1) for mercury and butyltin compounds and 0.4-50 ng g(-1) for metals with good precision (1-10% RSD) even for a very low mass of sample (0.02 g). This method has been applied for monitoring contamination and bioaccumulation of metals and organometals as well as the biodiversity and trophic structure of the macrobenthic population of the Adour Estuary (South-West, France). The benthic macrofauna diversity indicates that inner estuarine stations are moderately polluted whereas outer estuarine stations are less impacted. However, metals concentrations in both sediment and benthic biomass do not change drastically between stations. Moreover, the bioaccumulation has been determined in relation to the feeding guild of benthic organisms. The results demonstrate that higher bioaccumulation is generally observed for deposit feeders directly impacted by sediment contamination compared to suspensive feeders and predators. Biomagnification along the trophic levels was highlighted for MMHg but no significant trend was observed for the other metallic compounds.     

Survey of butyltin contamination in Portuguese coastal environments

Butyltin compounds (MBT, DBT and TBT) in intertidal sediments collected in four different Portuguese coastal environments have been measured in order to evaluate the extent of contamination. The sites chosen were the Rias of Aveiro and Faro, and the Sado and Tejo estuaries. These zones were traditional areas for shellfish production in the recent past, but the effects of industrial development have caused a deterioration of the environment. Specific contaminations were derived from the harbour (commercial and/or fisheries) and shipyard activities, resulting in a release of TBT and causing the oyster populations of the above mentioned estuaries to almost disappear. Results presented in this study give a survey of TBT contamination levels found in the four areas. The paper discusses the importance of the pollution in comparison with other European coastal areas.     

Determination of butyltins in harbour sediment and water by aqueous phase ethylation GC-ICP-MS and hydride generation GC-AAS

Sediment and water samples have been collected between 1992 and 1995 for evaluating butyltin contamination in two marinas from the coastal area in The Netherlands, two years after the ban of TBT. Sediments extracts were analysed by capillary gas chromatography-inductively coupled plasma-mass spectrometry. Sediment concentrations for TBT showed no trend of decrease between 1992 and 1995 and were extremely high in the marina secluded from tidal action; 17.5 +/- 8.0 microg g(-1) and much lower for the marina with tidal action; 0.117 +/- 0.073 microg g(-1). High ratios between TBT and DBT in the sediments indicate that degradation mechanisms in the sediments are of minor importance. Dissolved butyltin compounds were analysed in water by means of gas chromatography-atomic absorption spectrometry. Water concentrations of TBT showed no clear trend of decrease between 1992 and 1995 and were high in the marina secluded from tidal action; 139 +/- 166 ng litre(-1) but much lower for the marina with tidal action; 48 +/- 98 ng litre(-1). An active degradation mechanism during summer periods was indicated by low (<1) TBT/DBT ratios in the water phase of the marina secluded from tidal action.     

Ensuring quality in long term environmental monitoring for chemical speciation

The awareness regarding quality assurance (QA) and quality control (QC) for environmental monitoring has considerably increased in the past few years, especially with respect to the determination of chemical species, since errors occurring at various levels may considerably affect the interpretation of results (e.g. studies of toxic impact, geochemical pathways, etc.). QA for environmental analysis covers a broad range of activities from sample collection to laboratory work and the approach for ensuring quality data should be considered in a global context. However, whereas great emphasis has been placed on QA within the laboratory, there have been few systematic attempts to evaluate risks of discrepancies related, for example, to field manipulations. The situation is even worse when monitoring is applied to relatively new fields such as chemical speciation. This paper outlines some of the main aspects of quality control of environmental analysis, including the validation of methods, sampling and sample handling, storage, etc., with special emphasis on the monitoring of chemical forms of elements (e.g. species of tin, mercury, lead and selenium).     

Heavy metals and organochlorinated compounds in the European eel (Anguilla anguilla) from the Adour estuary and associated wetlands (France)

Heavy metals and organic pollutants were investigated in the Adour estuary (South West France) and associated wetlands using the European eel (Anguilla anguilla) as a bioindicator. Heavy metals (Cu, Cd, Zn, Pb, and Ag) were measured in soft tissue of yellow eels. Mercury (total Hg and MeHg) and organochlorinated compounds (7 PCBs, 11 OCPs) were analysed in muscle. Concentrations in muscle were in agreement with moderately contaminated environments in Europe and were below the norms fixed for eel consumption for heavy metals and OCPs. Analyses of liver showed a higher pressure of Ag and Zn in the downstream estuary than in the freshwater sites whereas Cd was lower in the estuary probably because of the salinity influence. According to quality classes 100% of eels from freshwater sites indicated clean or slightly polluted environments. However, total mercury concentrations were close to the thresholds fixed by the European Community in the downstream estuary, whereas the sum of PCBs was found to be greatly above the fixed value. 100% of the individuals from the estuary were classified in quality classes corresponding to polluted or highly polluted sites. These first results highlight the need of further investigations focused on mercury and PCBs in this area taking the seasonal temperature influence into account for a better understanding of the pollution distribution and the possible threat on the eel population from the Adour basin.