Sergi Díez

Organotin contamination in sediments from the Western Mediterranean enclosures following 10 years of TBT regulation.

Organotin (OT) compounds, namely butyl and phenyl, were measured in 38 recent sediments collected in harbours of the Western Mediterranean Sea (Northern: 4 and Southern: 9) and domestic and industrial sewage disposal sites (Northern: 9 and Southern: 1). Butyltins were the predominant tin species identified as being tributyltin (TBT) widespread in the whole area which suggests recent inputs of OTs. The highest levels of TBT were detected in commercial harbours associated with inputs from large vessels (average value: 5.0 microg TBT g(-1). Moreover, relatively high TBT values were also detected in fishing and recreational boating areas (average level ca. 1.0 microg TBTg(-1)). Phenyltin derivatives occurred at lower levels than butyltins being the monophenyltin the predominant compound (average values 45-945 ng g(-1)). The large predominance of the phenyltin degradation products (i.e. mono and diphenyltin) over the parent compound (i.e. triphenyltin) suggests that there are almost no recent inputs of these compounds. Furthermore, a comparative study of the OT occurrence in the sewage sludge disposal sites offshore Barcelona and Almeria (domestic) and into the Tarragona harbour (industrial) shows that domestic primary sewage sludge effluents can contribute to coastal OT pollution (244ng TBT g(-1)). Nevertheless, sewage sludge is a secondary source of OT contamination in the coastal environment in comparison to commercial harbours. In a comparative study with previous data collected in the late 1980s, the present study reveals that OT regulations established in the Mediterranean region in 1991 on the use of TBT-based antifouling paints have been effective in marinas, but reveals a significant TBT contamination in commercial and fishing harbours.

Hair mercury levels, fish consumption, and cognitive development in preschool children from Granada, Spain .

The main source of human exposure to mercury is the consumption of fish contaminated with methylmercury, which may adversely affect early neurodevelopment. This study assessed mercury levels in hair of preschoolers in Spain, where fish consumption is elevated, with the aim of investigating the influence of their fish intake and other factors on mercury exposure, and evaluating their association with cognitive development. A population-based birth cohort from Granada (Spain) was studied at the age of 4yr. Total mercury (T-Hg) levels were determined in childrens hair, and daily fish intake was assessed by a food frequency questionnaire. The McCarthy Scales of Childrens Abilities (MSCA) were used to assess childrens motor and cognitive abilities. Complete data were gathered on 72 children, and multivariate analyses were performed to evaluate the influence of mercury exposure and fish intake on MSCA outcomes. Mean concentration of T-Hg in hair was 0.96 microg/g (95% confidence interval=0.76; 1.20 microg/g). T-Hg levels were associated with higher frequency of oily fish consumption, place of residence, maternal age, and passive smoking. After adjustment for fish intake, T-Hg levels > or =1microg/g were associated with decrements in the general cognitive (-6.6 points), memory (-8.4 points), and verbal (-7.5 points) MSCA scores. Higher mercury exposure in children from this Mediterranean area was associated with cognitive development delay. Studies on the putative benefits of fish intake during early development should consider mercury exposure from different fish species.

Human Health Effects of Methylmercury Exposure

Mercury (Hg), and the organometallic compounds formed from it, are among the most toxic of substances to the global environment. Mercury is environmentally ubiquitous, and both wildlife and humans are exposed to the toxic effects of its environmental residues, primarily elemental mercury (Hg0), divalent mercury (Hg2+) and methylmercury (MeHg). Humans are exposed to different forms of Hg, and potential health risks have been reported from such exposures; examples of Hg exposure include mercury vapor from dental amalgams, occupational exposures and exposures during artisan and small-scale gold mining operations. Despite the significance of those foregoing Hg exposures, of particular concern is human and wildlife exposure to MeHg, a potent neurotoxicant. Once incorporated into the body, MeHg easily penetrates the blood-brain barrier and causes damage to the central nervous system, particularly in fetuses. It bioaacumulates and biomagnifies in the aquatic food chain; consequently, fish and seafood consumption is the major pathway by which humans are exposed to MeHg. MeHg is the focus of this review. It adversely affects humans and is currently the subject of intense public health interest and worldwide concern. In this review, I summarize the sources and cycling of global mercury in the environment, pathways of exposure, toxicity and exposure evaluation, toxicokinetics, the common biomarkers to evaluate exposure and effects in populations, and finally review the nutritional risks and benefits from fish consumption.

Multi-biomarker responses in the freshwater mussel Dreissena polymorpha exposed to polychlorobiphenyls and metals.

Contaminant related changes in behavioral, phase I and II metabolizing enzymes and pro-oxidant/antioxidant processes in the freshwater mussels Dreissena polymorpha exposed to metals and PCBs were assessed. Behavioral and biochemical responses including filtering rates, key phase I, II and antioxidant enzymes and levels of metallothioneins, glutathione, lipid peroxidation and DNA strand breaks were determined in digestive glands of mussels after being exposed to sublethal levels of mercury chloride, methyl mercury, cadmium and Aroclor 1260 during 5 days. In 7 out of 12 responses analyzed, mussels showed significant differences across treatments. Unusual properties of measured ethoxyresorufin-O-deethylase (EROD) activities indicated that mussels lack an inducible CYP1A enzymatic activity. Despite of using similar exposure levels, inorganic and organic mercury showed different biomarker patterns of response with methyl mercury being more bio-available and unable to induce metallothionein proteins. Mussels exposed to Cd presented higher levels of metallothioneins and an enhanced metabolism of glutathione, whereas those exposed to Aroclor showed their antioxidant glutathione peroxidase related enzyme activities inhibited. Although there was evidence for increased lipid peroxidation under exposure to inorganic and organic mercury, only mussels exposed to Aroclor had significant greater levels than those in controls.

Resolution and Quantification of Complex Mixtures of Polycyclic Aromatic Hydrocarbons in Heavy Fuel Oil Sample by Means of GC × GC-TOFMS Combined to Multivariate Curve Resolution

Comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) combined to multivariate curve resolution-alternating least-squares (MCR-ALS) is proposed for the resolution and quantification of very complex mixtures of compounds such as polycyclic aromatic hydrocarbons (PAHs) in heavy fuel oil (HFO). Different GC × GC-TOFMS data slices acquired during the analysis of HFO samples and PAH standards were simultaneously analyzed using the MCR-ALS method to resolve the pure component elution profiles in the two chromatographic dimensions as well as their pure mass spectra. Outstandingly, retention time shifts within and between GC × GC runs were not affecting the results obtained using the proposed strategy and proper resolution of strongly coeluted compounds, baseline and background contributions was achieved. Calibration curves built up with standard samples of PAHs allowed the quantification of ten of them in HFO aromatic fractions. Relative errors in their estimated concentrations were in all cases below 6%. The obtained results were compared to those obtained by commercial software provided with GC × GC-TOFMS instruments and to Parallel Factor Analysis (PARAFAC). Inspection of these results showed improvement in terms of data fitting, elution process description, concentration relative errors and relative standard deviations.

The prestige oil spill. I. Biodegradation of a heavy fuel oil under simulated conditions

In vitro biodegradation of the Prestige heavy fuel oil has been carried out using two microbial consortia obtained by enrichment in different substrates to simulate its environmental fate and potential utility for bioremediation. Different conditions, such as incubation time (i.e., 20 or 40 d), oil weathering, and addition of an oleophilic fertilizer (S200), were evaluated. Weathering slowed down the degradation of the fuel oil, probably because of the loss of lower and more labile components, but the addition of S200 enhanced significantly the extension of the biodegradation. n-Alkanes, alkylcyclohexanes, alkylbenzenes, and the two- to three-ring polycyclic aromatic hydrocarbons (PAHs) were degraded in 20 or 40 d of incubation of the original oil, whereas the biodegradation efficiency decreased for higher PAHs and with the increase of alkylation. Molecular markers were degraded according to the following sequence: Acyclic isoprenoids > diasteranes > C27-steranes > betabeta-steranes > homohopanes > monoaromatic steranes > triaromatic steranes. Isomeric selectivity was observed within the C1- and C2-phenanthrenes, dibenzothiophenes, pyrenes, and chrysenes, providing source and weathering indices for the characterization of the heavy oil spill. Acyclic isoprenoids, C27-steranes, C1- and C2-naphthalenes, phenanthrenes, and dibenzothiophenes were degraded completely when S200 was used. The ratios of the C2- and C3-alkyl homologues of fluoranthene/pyrene and chrysene/benzo[a]anthracene are proposed as source ratios in moderately degraded oils. The 4-methylpyrene and 3-methylchrysene were refractory enough to serve as conserved internal markers in assessing the degradation of the aromatic fraction in a manner similar to that of hopane, as used for the aliphatic fraction.

Assessment of mercury and methylmercury pollution with zebra mussel (Dreissena polymorpha) in the Ebro River (NE Spain) impacted by industrial hazardous dumps

Large amounts of industrial waste containing high concentrations of mercury (up to 436 microg/g) are dumped in a reservoir adjacent to a chlor-alkali plant in Flix (Catalonia, Spain), on the lower Ebro River. In order to assess the spatial redistribution of mercury from the point source and its bioavailability to the aquatic food web, zebra mussels (Dreissena polymorpha) were collected at several sites. The highest total Hg (THg) and methylmercury (MeHg) concentrations ever reported for zebra mussels were found (THg: 0.02 to 0.81 microg/g ww; MeHg: 0.22 to 0.60 microg/g ww). At the most polluted site, close to the waste dump, the mean values were 20 times greater than the local background level. Concentrations decreased with increasing mussel size at all sites. The MeHg/THg ratio was ca. 60% (range: 50-80%). A comparison of similar size classes clearly indicated the hot spots of Hg bioavailability to the aquatic food web and downstream transport.

Physiological responses to mercury in feral carp populations inhabiting the low Ebro River (NE Spain), a historically contaminated site

The low Ebro River course (Northeast Spain) is historically affected by mercury pollution due to a chlor-alkali plant operating at the town of Flix for more than a century. River sediments analysed during the last 10 years showed high mercury levels in the river section starting just downstream the factory and spanning some 90km, down to the river delta. The possible environmental impact was studied by a combination of field and laboratory studies. Mercury concentrations in liver, kidney and muscle of feral carp (Cyprinus carpio) sampled downstream Flix were one to two orders of magnitude higher than those from carps sampled upstream Flix. Elevated levels of mercury in these samples associated with significant increases on the concentration of reduced glutathione (GSH) in liver and on mRNA expression of two metallothionein genes, MT1 and MT2, in kidney and, partially, in scales, but not in liver. Conversely, no biochemical evidence for oxidative stress or DNA damage was found in these tissues. Non-contaminated carps subjected to intraperitoneal mercury injection resulted in a 20-fold increase of MT1 and MT2 mRNA levels in carp kidney, with minimal changes in liver levels. Our data suggests the coordinate increase of metallothionein mRNA in kidney and of GSH in liver constitutes an excellent marker of exposure to sub-toxic mercury levels in carps. This study also demonstrates that apparently healthy fish populations may exceed the mercury contamination acceptable for human consumption.

Determination of methylmercury in human hair by ethylation followed by headspace solid-phase microextraction–gas chromatography–cold-vapour atomic fluorescence spectrometry

An analytical procedure for the determination of methylmercury in human hair after acid digestion using aqueous ethylation, headspace solid-phase microextraction sampling and final gas chromatography-cold-vapour atomic fluorescence spectrometry detection is described. Acid digestion, extraction procedure and chromatographic conditions were optimised. An optimal linear range using standard mercury solutions was found and concentration detection limits for the mercury species, MeHg and Hg2+, were about 50 and 80 ng/g, respectively, for 100 mg of human hair. The reproducibility of the developed analytical procedure assessed for hair samples with incurred MeHg was better than 18% (n=5). A certified reference material from the National Institute of Environmental Studies (Japan) was used for validation. Analysis of human hair collected from urban inhabitants was performed and the mean value of methylmercury content in hair samples was 0.764 +/- 0.732 microg/g for the population tested. The developed analytical method is simple, fast and a suitable procedure for the monitoring and screening of human exposure to methylmercury.

Methylmercury levels and bioaccumulation in the aquatic food web of a highly mercury-contaminated reservoir

The low Ebro River basin (NE Spain) represents a particular case of chronic and long-term mercury pollution due to the presence of an industrial waste (up to 436 μg/g of Hg) coming from a chlor-alkali plant Albeit high total mercury (THg) levels have been previously described in several aquatic species from the surveyed area, methylmercury (MeHg) values in fish individuals have never been reported. Accordingly, in order to investigate bioaccumulation patterns at different levels of the aquatic food web of such polluted area, crayfish and various fish species, were analysed for THg and MeHg content. At the hot spot, THg mean values of crayfish muscle tissue and hepatopancreas were 10 and 15 times, respectively, greater than the local background level. Higher mean THg concentrations were detected in piscivorous (THg=0.848 ± 0.476 μg/g wet weight (ww); MeHg=0.672 ± 0.364 μg/g ww) than in non-piscivorous fish (THg=0.305 ± 0.163 μg/g ww; MeHg=0.278 ± 0.239 μg/g ww). Although these results indicated that THg in fish increased significantly with increasing trophic position, the percentage of the methylated form of Hg was not strongly influenced by differences in relative trophic position. This is an important finding, since the fraction of THg as MeHg in the top fish predator was unexpectedly lower than for other species of the aquatic food chain. Moreover, mean THg concentrations in piscivorous fish exceed the maximum level recommended for human consumption. From our findings, it is clear that for this specific polluted system, speciation becomes almost mandatory when risk assessment is based on MeHg, since single measurements of THg are inadequate and could lead to an over- or under-estimation of contamination levels.