Organochlorine concentrations in aquatic organisms from different trophic levels of the Sundarbans mangrove ecosystem and their implications for human consumption.

The Sundarbans, a highly biodiverse tropical ecosystem stretching across India and Bangladesh, is also the largest mangrove forest in the world. Organochlorine compounds (OCs) have been extensively used for agriculture and sanitary purposes in the region. OCs can accumulate in biological tissues and biomagnify in organisms through food webs, for which reason they reach high concentrations in top predators. Because marine food webs are long and marine predators are extensively used in the region as human food, assessment of potential health-related risks caused by OC pollution is in order. This study is the first to determine the concentration of PCBs in fish and crustaceans from the Sundarbans mangroves, their accumulation trends through the food web, and the potential toxicological risk that their consumption poses to humans. DDT concentrations, which had already been assessed in the region, were also determined. The median concentrations ranged from below detection limits to 176.3 ng g-1 lipid weight for tDDT and 275.9  ng g-1 for PCBs. Overall, these concentrations were lower than those usually observed in other regions of the world, apparently as a result of the interplay of several factors: low environmental organochlorine inputs, the physical and climatic characteristics of an ecosystem dominated by high temperatures in a highly flushed ecosystem that dilutes and rapidly disperses pollutants, and the comparatively short food chain lengths that, similarly to other mangrove ecosystems, characterize the Sundarbans. Organochlorine concentrations were 2-3 orders of magnitude lower than commonly accepted tolerance levels, so their consumption do not pose a sensible risk to the population. However, concentrations of DDT in dry fish from retail markets were higher because this compound is used for pest control during fish processing. Potential risks involved in this practice likely outweigh potential benefits, so it is recommended that this compound is substituted by less hazardous alternatives.

Chemical contaminants entering the marine environment from sea-based sources: A review with a focus on European seas.

Anthropogenic contaminants reach the marine environment mostly directly from land-based sources, but there are cases in which they are emitted or re-mobilized in the marine environment itself. This paper reviews the literature, with a predominant focus on the European environment, to compile a list of contaminants potentially released into the sea from sea-based sources and provide an overview of their consideration under existing EU regulatory frameworks. The resulting list contains 276 substances and for some of them (22 antifouling biocides, 32 aquaculture medicinal products and 34 warfare agents) concentrations and toxicity data are additionally provided. The EU Marine Strategy Framework Directive Descriptor 8, together with the Water Framework Directive and the Regional Sea Conventions, provides the provisions against pollution of marine waters by chemical substances. This literature review should inform about the current state of knowledge regarding marine contaminant sources and provide support for setting-up of monitoring approaches, including hotspots screening.

Trace element accumulation and trophic relationships in aquatic organisms of the Sundarbans mangrove ecosystem (Bangladesh).

The Sundarbans forest is the largest and one of the most diverse and productive mangrove ecosystems in the world. Located at the northern shoreline of the Bay of Bengal in the Indian Ocean and straddling India and Bangladesh, the mangrove forest is the result of three primary river systems that originate further north and northwest. During recent decades, the Sundarbans have been subject to increasing pollution by trace elements caused by the progressive industrialization and urbanization of the basins of these three rivers. As a consequence, animals and plants dwelling downstream in the mangroves are exposed to these pollutants in varying degrees, and may potentially affect human health when consumed. The aim of the present study was to analyse the concentrations of seven trace elements (Zn, Cu, Cr, Hg, Pb, Cd and As) in 14 different animal and plant species collected in the Sundarbans in Bangladesh to study their transfer through the food web and to determine whether their levels in edible species are acceptable for human consumption. δ(15)N values were used as a proxy of the trophic level. A decrease in Zn, Cu, Pb and Cd levels was observed with increasing trophic position. Trace element concentrations measured in all organisms were, in general, lower than the concentrations obtained in other field studies conducted in the same region. When examined with respect to accepted international standards, the concentrations observed in fish and crustaceans were generally found to be safe for human consumption. However, the levels of Zn in Scylla serrata and Cr and Cd in Harpadon nehereus exceeded the proposed health advisory levels and may be of concern for human health.

Trace element contamination in the Guadalquivir River Estuary ten years after the Aznalcóllar mine spill.

Sediments, clams Scrobicularia plana and worms Hediste diversicolor from the Guadalquivir estuary were collected ten years after the Aznalcóllar mine spill and analyzed for metals. Significant seasonal and spatial effects were detected for most elements, so data from different sampling periods and locations were treated separately. Overall, the most polluted sites were found upstream, although Zn and Cu tended to accumulate at the estuary mouth. A significant decline of Zn in sediments and clams was observed compared to levels reported following the spill, so the estuarine ecosystem has recovered. However, the concentrations of some elements in S. plana were still higher than those of heavily contaminated regions. In this mollusk, Pb and As levels were higher in 2008 than in previous years, suggesting a new source entering into the estuary. Metals in sediments presented low bioavailability for biota, so other sources must account for the concentrations observed in these species.

Are the shells of Scrobicularia plana useful for monitoring trace metal pollution events?

The rupture of a mine dam in Aznalcóllar (SW Spain) in April 1998 entailed the contamination of Guadalquivir River and its estuary. To study the ability of bivalve shells to monitor the temporal changes on metal composition in the area, two year old Scrobicularia plana were obtained from two different locations of the estuary (Pantalan highly influenced and Pantoca less influenced) during the year 2000 and 2007. Co, Hg, Mo, Ni and Zn content was measured in shell and soft tissue of S. plana. Metal composition in shells sampled by micromilling and corresponding to the years 1999, 2000, 2006 and 2007 was higher in Pantalan (Co: 5.88 +/- 2.7 microg g(-1); Hg: 0.04 +/- 0.03 microg g(-1); Mo: 0.41 +/- 7.90 microg g(-1); Ni: 37.66 +/- 25.56 microg g(-1) and Zn: 9.19 +/- 8.88 microg g(-1)) than in Pantoca (Co: 3.64 +/- 0.50 microg g(-1); Hg: 0.02 +/- 0.02 microg g(-1); Mo: 4.70 +/- 1.20 microg g(-1); Ni: 7.21 +/- 13.60 microg g(-1) and Zn: 3.90 +/- 1.89 microg g(-1)). A marked temporal decrease was observed for all metals in Pantalan station with concentrations of Co, Hg, Mo, Ni and Zn varying respectively from 7.35 +/- 3.02, 0.05 +/- 0.03, 19.90 +/- 2.40, 70.58 +/- 21.94 and 18.04 +/- 0.98 microg g(-1), in 1999 to 3.07 +/- 1.08, 0.009 +/- 0.001, 2.40 +/- 1.43, 10.11 +/- 3.80 and 1.11 +/- 0.33 microg g(-1) in 2007, indicating that the effect of the mine accident had diminished significantly. Metal content in soft tissues did not follow the same decreasing trend indicating that soft tissues present a different capacity to accumulate metals from the environment. Our results confirm that micromilling shells are a suitable tool to assess bioaccumulation ofcontaminants during the entire life-span of bivalves.

Contamination by hazardous substances in the Gulf of Naples and nearby coastal areas: a review of sources, environmental levels and potential impacts in the MSFD perspective.

During the 7th FW EU Programme, a large group of research institutions with a strong tradition in marine science designed PERSEUS, a policy-oriented, marine research project aimed at identifying human-derived pressures and their impacts in the Southern European Seas. PERSEUS is about gathering and analyzing the data on our marine ecosystems and developing recommendations to assist policy makers in the implementation of the Marine Strategy Framework Directive (MSFD). In its initial phase, the project focuses on the analysis and evaluation of human pressures in selected coastal areas across the Mediterranean and Black Seas. This paper reports on the results about the chemical pollution pressure in the Gulf of Naples, one of the sites selected for the analysis, and surrounding waters of the Southern Tyrrhenian Sea. Based on a systematic up-to-date literature review, the paper brings together for the first time the available information on the presence, severity and distribution of contaminants on the site. In spite of methodological and sampling heterogeneity among studies, this review compiles the data in a harmonized and effective way, so that the current status, knowledge gaps and research priorities can be established. Thus, the review wishes not only to provide a contribution to the scientific community, but also to help to extract recommendations for mitigating pollution sources and risks in the area of concern. A similar process of analysis may be carried out for other areas and pressures in order to facilitate policy making at the European level.

Following the Aznalcóllar toxic spill.

Ten years after the Aznalcóllar mine spill, the decline in metal contamination in the area is evident. However, some elements are still found in elevated concentrations. In Scrobicularia plana, zinc, lead, and arsenic exceeded health advisory levels at several locations although there is no indication of risks associated with consumption of this mollusc. The estuary seems to have enhanced the bioavailability of arsenic and lead. Research should continue to understand the significance of this contamination.

Ranking sediment samples from three Spanish estuaries in relation to its toxicity for two benthic species: the microalga Cylindrotheca closterium and the copepod Tisbe battagliai.

The present study assesses the sediment toxicity levels of three Spanish estuaries, as well as the suitability of two microorganisms, the benthic microalga Cylindrotheca closterium and the harpacticoid copepod Tisbe battagliai, as test organisms in whole-sediment toxicity assays. The sensitivity of both species to potentially polluted sediments was compared. Three sites at the southwest of the Iberian Peninsula were chosen: the Ría of Huelva, the Guadalquivir Estuary, and the Bay of Algeciras. Inhibition data were based on growth for C. closterium and fecundity for T. battagliai. No toxicity was recorded for the microalga in the Guadalquivir Estuary and the Bay of Algeciras. However, for T. battagliai, inhibition of fecundity was approximately 50% in those zones, indicating higher sensitivity. Samples from stations in the Ría of Huelva were the most toxic of all those assayed; inhibition values higher than 90% were obtained for both organisms. The highest values for total metal concentrations such as arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), lead (Pb), tin (Sn), and zinc (Zn) were found in the Ría of Huelva, which can be classified as severely impacted. The Guadalquivir Estuary and the Bay of Algeciras can be considered moderately impacted. In general, both methodologies are suitable for application in ecotoxicological studies.

Ring test for whole-sediment toxicity assay with -a- benthic marine diatom.

This work presents the results of an interlaboratory proficiency exercise for whole-sediment toxicity assays with the benthic marine diatom Cylindrotheca closterium. An assay protocol was established and followed by all participating laboratories. Cell growth after 72 h exposure was the endpoint used. Four sediment samples of unknown toxicity were assayed. The main problem encountered during this exercise was the differences in the cell growth of algae exposed to reference sediment. Those differences may be associated with changes in the physiological status of the initial culture due to temperature changes during transport to the other laboratories. In general, the method proposed presented good replicability (precision between replicates) and reproducibility (interlaboratory precision). Around 80% (17 out of 21) of results obtained were classified as satisfactory (Z-scores <2). The whole-sediment assay with C. closterium presented here can be considered sufficiently successful for possible use as a standard toxicity test. The assay is simple to perform, the proposed species is ecologically relevant as an integral component of microphytobenthos, and is widely distributed around the world. These positive factors suggest that the whole-sediment assay with the benthic marine diatom C. closterium can be used as a reliable tool in marine sediment quality assessment.

Correlates of cytochrome P450 1A1 expression in bottlenose dolphin (Tursiops truncatus) integument biopsies.

Integument biopsy is a nondestructive method for sampling free-ranging cetaceans, which allows for the determination of both contaminant concentrations and biomarker responses. Cytochrome P450 1A1 (CYP1A1) expression is induced by polycyclic aromatic hydrocarbons and planar halogenated aromatic hydrocarbons such as the non-ortho and mono-ortho polychlorinated biphenyls (PCBs). CYP1A induction has been used extensively as a biomarker of exposure to such compounds in vertebrates. We measured PCB concentrations and CYP1A1 expression in integument biopsies from bottlenose dolphins (Tursiops truncatus) resident in Sarasota Bay, FL. This population of dolphins has been the subject of long-term population and health assessment, affording the opportunity to evaluate the influence of age, sex, and reproductive status on CYP1A1 expression. CYP1A1 expression was seen in endothelial cells, vascular smooth muscle, and nerve cells in the dermis, similar to what has been observed in other cetacean species. Endothelial CYP1A1 expression varied along the length of the biopsy, which could be related to differences in the structure and functionality of the blubber in different parts of the integument. Neither age nor sex was related to CYP1A1 expression in these biopsies, and reproductive status did not relate to levels of CYP1A1 in females. Total PCB and toxic equivalent quotient concentrations in blubber were positively correlated with dermal endothelial CYP1A1 expression, although Sigmamono-ortho PCBs concentrations did not show this relationship. Contaminant concentrations appear to be stronger determinants of CYP1A1 expression in integument of these dolphins, than are age, sex, or reproductive status.

Organochlorine contaminant and retinoid levels in blubber of common dolphins (Delphinus delphis) off northwestern Spain.

The effect of age, sex, nutritive condition and organochlorine concentration on blubber retinoid concentrations was examined in 74 common dolphins incidentally caught off northwestern Spain. Age and blubber lipid content were strong determinants of the retinoid concentrations in males, while these variables did not account for the variation found in females. Retinoids were positively correlated with organochlorines in males and negatively in females. However, pollution levels were moderate and likely to be below threshold levels above that a toxicological response is to be expected. Thus, a cause-effect relationship between organochlorine and retinoid concentrations could not be properly established, and the observed correlation may be the result of an independent association of the two variables with age. Further research on the influence of the best predictor variables on retinoid dynamics is required to implement the use of retinoids as biomarkers of pollutant exposure in cetaceans.

Integrating life-history and reproductive success data to examine potential relationships with organochlorine compounds for bottlenose dolphins (Tursiops truncatus) in Sarasota Bay, Florida.

Research initiated in 1970 has identified a long-term, year-round resident community of about 140 bottlenose dolphins (Tursiops truncatus) in Sarasota Bay, Florida, providing unparalleled opportunities to investigate relationships between organochlorine contaminant residues and life-history and reproductive parameters. Many individual dolphins are identifiable and of known age, sex, and maternal lineage (< or =4 generations). Observational monitoring provides data on dolphin spatial and temporal occurrence, births and fates of calves, and birth-order. Capture-release operations conducted for veterinary examinations provide biological data and samples for life-history and contaminant residue measurement. Organochlorine concentrations in blubber and blood (plasma) can be examined relative to age, sex, lipid content, and birth-order. Reproductive success is evaluated through tracking of individual female lifetime calving success. For the current study, 47 blubber samples collected during June 2000 and 2001 were analyzed for PCB concentrations of 22 congeners relative to life-history factors and reproductive success. Prior to sexual maturity, males and females exhibited similar concentrations of about 15-50 ppm. Classical patterns of accumulation with age were identified in males, but not in females. Subsequently, males accumulated higher concentrations of PCBs through their lives (>100 ppm), whereas females begin to depurate with their first calf, reaching a balance between contaminant intake and lactational loss (<15 ppm). In primiparous females, PCB concentrations in blubber and plasma and the rates of first-born calf mortality were both high. First-born calves had higher concentrations than subsequent calves of similar age (>25 vs.<25 ppm). Maternal burdens were lower early in lactation and increased as calves approached nutritional independence. Empirical data were generally consistent with a published theoretical risk assessment and supported the need for incorporation of threats from indirect anthropogenic impacts such as environmental pollutants into species management plans. Long-term observational monitoring and periodic biological sampling provide a powerful, non-lethal approach to understanding relationships between organochlorine residue concentrations in tissues and reproductive parameters for coastal dolphins.

Effect of organochlorine contaminants and individual biological traits on blubber retinoid concentrations in bottlenose dolphins (Tursiops truncatus).

Here we assessed retinoids as biomarkers of contaminant exposure by studying whether the sex, age, lipid content and organochlorine concentrations of bottlenose dolphins induced variation in retinoid status and its deposition in blubber. Blubber samples were collected from 47 individuals of known age and gender from Sarasota Bay in June 2000 and 2001. The sample included a representative cross-section of the resident dolphin community, with ages ranging from 2 to 50 years. Organochlorine levels showed the age- and sex-related variation commonly observed in other species, with concentrations increasing in youngsters of both sexes and in adult males, and decreasing in adult females after the onset of maturity. Blubber lipid content was low in the overall population and significantly decreased with age in adult males. Retinoid blubber concentrations were comparable to other odontocete species previously studied, and were strongly determined by lipid content. As a consequence of the latter, retinoid concentration was observed to decrease with age in adult males. This effect could not be statistically dissociated from the negative correlation observed between levels of organochlorines and retinoid blubber concentration. Consequently, we could not clarify whether high organochlorine loads in this population lowered retinoid concentrations or, conversely, whether depleted lipid reserves were indeed responsible for the high organochlorine concentrations and the low retinoid levels detected in blubber. With the current knowledge, both options should be considered and investigated, with initial focus on male dolphins.

Retinoid and lipid patterns in the blubber of common dolphins (Delphinus delphis): implications for monitoring vitamin A status.

We determined retinoid concentrations in various body positions of the blubber of 25 common dolphins (Delphinus delphis) to study topographical variation in concentrations. Specimens were obtained from incidental catches and were apparently healthy. We found concentrations to be high and therefore conclude that blubber represents a significant contribution to total retinoid body load. Consequently, blubber is proposed as a tissue of choice for monitoring retinoid status in this species. Anterior-ventral blubber had the highest vitamin A concentration and posterior-dorsal the lowest. Therefore, when assessing retinoid status, topographical variation should be taken into account to ensure consistent sampling. This pattern appeared to be explained by a parallel variation in lipid content. Thus, the dynamics and body distribution of retinoids appear to be basically governed by the lipophilicity of the molecules. The highest lipid richness found in the anterior-ventral region might indicate that this region is comparatively more important for insulation and lipid storage than the dorsal posterior region. Retinoid levels did not appear to vary according to sex, but they did vary with lipid content. This should be taken into account when designing sampling protocols; for monitoring purposes, biopsies from healthy, free-ranging individuals should be preferred to samples from stranded animals.