Mercury levels and liver pathology in feral fish living in the vicinity of a mercury cell chlor-alkali factory

Twenty-three barbels (Barbus graellsii), 30 bleaks (Alburnus alburnus) and 4 sediment samples were collected from four areas of the Cinca River (NE Spain), upstream and downstream of a mercury cell chlor-alkali plant. Mercury concentration in sediments downstream of the plant was about 25 times higher than the concentration upstream. Mercury levels in the muscle and liver of barbels downstream of the chlor-alkali plant were 10 and 30 times higher than those upstream. The average mercury concentration in the muscle and liver of barbels downstream of the factory was 1.48 and 1.78mg/kgw.w., with maximal concentrations of 2.43 and 3.64mg/kgw.w, respectively. Liver/muscle ratio of mercury was significantly higher in barbels sampled downstream of the factory. Bleak showed a similar pattern, with a significantly higher whole-body mercury concentration downstream of the chlor-alkali plant. Nevertheless, a progressive decrease in mercury concentration downstream of the impact area was found in bleak, but not in barbel. Histopathological analysis showed that fish downstream of the factory had significantly higher prevalence of liver pathologies (p<0.05). Although there are no specific histopathological markers of mercury exposure, barbels with the highest Hg levels in the liver also showed the most severe pathologies, and the processes found in these barbels were consistent with the pro-oxidant effect of heavy metals.     

Environmental monitoring by gene expression biomarkers in Barbus graellsii: laboratory and field studies

Barbel (Barbus graellsii) is a freshwater fish used as a sentinel species in environmental monitoring programmes and ecotoxicological studies in northern Spain, particularly in the Ebro River basin, the largest freshwater resource in Spain. We developed specific primers for the quantification of CYP1A and metallothionein (MT)-1 and -2 gene expression by QRT-PCR in barbel in order to assess their suitability in biological effect monitoring of dioxin-like compounds and metals. All three genes responded as expected in laboratory tests, using model inducers. Hepatic CYP1A mRNA levels showed a twofold induction in fish injected intraperitoneally with beta-naphthoflavone, whereas MT-1 and MT-2 gene expression was strongly induced by cadmium (15- and 13-fold, respectively) and mercury (five- and eightfold). Barbel populations from different sites on the Ebro River basin showed a good correlation between the historical records of organochlorine pollution, CYP1A expression levels and EROD activity. Nevertheless, although metallothionein protein levels in the liver of wild fish correlated with hepatic levels of mercury, MT-1 and MT-2 gene expression did not correlate with the mercury content or with the concentration of metals in sediments from the sites inhabited by the fish. These results demonstrate the utility of barbel CYP1A-mRNA expression, but not that of MT-1 or MT-2, as a biomarker in field studies. The tools and protocols developed here are likely to apply to other species of the genus Barbus, with some 700 species distributed throughout most of the Old World.     

Evaluation of the treatment efficiencies of paper mill whitewaters in terms of organic composition and toxicity

The efficiency of several lab scale treatments (aerobic, anaerobic and ozone or combination of these) was evaluated using two packaging board mill whitewaters. The effect of the different treatments on the elimination of the organic load, the chemical oxygen demand (COD) and the toxicity was tested as well as the relationship between these parameters. Biocides, phenolic compounds, surfactants, plasticiziers and wood extractives were identified in untreated and treated whitewaters by liquid chromatography coupled with mass spectrometry (LC-MS) or gas chromatography coupled with mass spectrometry (GC-MS). A strong dependency on the water type and treatment efficiency was observed, being the combination of anaerobic and aerobic treatments the best option to reduce the organic contaminants in these waters, although in some cases, the toxicity did not decrease. However, ozone as post-treatment permitted a further reduction of organic compounds, toxicity and COD.     

Decabrominated diphenyl ether in river fish and sediment samples collected downstream an industrial park

Fish, sediment and water samples from different places along the Spanish River Vero, a tributary of the Cinca River in the Ebro River basin, were collected in two different sampling campaigns, the first one during November 2004 and the second one in November 2005. The samples were collected up- and downstream from an industrial park. A total of 29 fishes, 6 sediments and 3 water samples were analyzed for polybrominated diphenyl ethers (PBDEs). Analytical work included 23 congeners, from tri- to deca-BDEs. The highest values for both sediment and fish samples were found downstream of the industrial park. High BDE-209 contamination was found in these sediment samples, with values up to 12 microg g(-1) dry weight. Moreover, BDE-209 was detected in 14 out of 15 biota samples collected downstream the industrial park, at concentration levels ranging from 20 to 707 ng g(-1) lipid weight, whereas it was not detected in samples collected upstream. These fish concentrations proved the bioavailability of BDE-209 and represented the highest deca-BDE values found in aquatic biota. The analysis of industrial effluents revealed that some industries contribute in some way to the BDE-209 contamination found in this area, but the industry focused on the polyamide polymerization is the main responsible.