Water and sediment toxicity and hazard assessment of DCOIT towards neotropical marine organisms.

DCOIT is an effective antifouling biocide, which presence in the environment and toxicity towards non-target species has been generating great concern. This study evaluated the waterborne toxicity of DCOIT on marine invertebrates (i.e., survival of brine shrimp Artemia sp., larval development of the sea urchin Echinometra lucunter and the mussel Perna perna), as well as DCOIT-spiked-sediment toxicity on the fecundity rate of the copepod Nitrocra sp. And the mortality of the amphipod Tiburonella viscana. The data outcomes were used to calculate environmental hazards and risks, which were compared to their corresponding values obtained from temperate regions. Waterborne toxicity can be summarized as follows: Artemia sp. (LC50-48h = 163 (135-169) µg/L), E. lucunter (EC50-36h = 33.9 (17-65) µg/L), and P. perna (EC50-48h = 8.3 (7-9) µg/L). For whole-sediment toxicity, metrics were calculated for T. viscana (LC50-10d = 0.5 (0.1-2.6) µg/g) and Nitrocra sp, (EC50-10d = 200 (10-480) µg/kg). The DCOIT hazard was assessed for both tropical and non-tropical pelagic organisms. The predicted no-effect concentration (PNEC) for tropical species (0.19 µg/L) was 1.7-fold lower than that for non-tropical organisms (0.34 µg/L). In whole-sediment exposures, DCOIT presented a PNEC of 0.97 µg/kg, and the risk quotients (RQs) were >1 for areas with constant input of DCOIT such as ports ship/boatyards, marinas, and maritime traffic zones of Korea, Japan, Spain, Malaysia, Indonesia, Vietnam, and Brazil. The presented data are important for supporting the establishment of policies and regulations for booster biocides worldwide.

Sex steroid imbalances in the muricid Stramonita haemastoma from TBT contaminated sites.

Imposex incidence, organotin tissue levels, and sex steroid (free and esterified testosterone and estradiol) levels were assessed in Stramonita haemastoma from Babitonga Bay (Santa Catarina State, Southern Brazil). The imposex levels showed a reduction when compared to a previous evaluation performed in the same area. In spite of that, the detected imposex incidence indicated the occurrence of tributyltin (TBT) inputs that were still able to produce endocrine disruption in local gastropods. In addition, a high level of organotins was observed in tissues of imposexed females. These females also showed a hormonal imbalance, especially in the total testosterone/total estradiol ratio. These findings obtained under realistic field conditions suggest that the steroid pathway could be responsible by the imposex induction after exposure to TBT. In this case, measurements of sex steroid levels can be an additional evidence for monitoring sites and impose affected gastropod populations.

Different carbon sources affect PCB accumulation by marine bivalves.

Pampean creeks were evaluated in the present study as potential land-based sources of PCB marine contamination. Different carbon and nitrogen sources from such creeks were analysed as boosters of PCB bioaccumulation by the filter feeder bivalve Brachidontes rodriguezii and grazer limpet Siphonaria lessoni. Carbon of different source than marine and anthropogenic nitrogen assimilated by organisms were estimated through their C and N isotopic composition. PCB concentration in surface sediments and mollusc samples ranged from 2.68 to 6.46 ng g(-1) (wet weight) and from 1074 to 4583 ng g(-1) lipid, respectively, reflecting a punctual source of PCB contamination related to a landfill area. Thus, despite the low flow of creeks, they should not be underestimated as contamination vectors to the marine environment. On the other hand, mussels PCB bioaccumulation was related with the carbon source uptake which highlights the importance to consider this factor when studying PCB distribution in organisms of coastal systems.

Butyltin and PAH Contamination of Mar del Plata Port (Argentina) Sediments and Their Influence on Adjacent Coastal Regions.

The distribution of butyltins (BTs) and polycyclic aromatic hydrocarbons (PAHs) were studied in surface sediments to assess how relevant is Mar del Plata port (Argentina) as a source of contamination to the surrounding environments. Within the port, TBT concentrations ranged from 24.2 to 150 ng Sn g(-1) and PAHs (Σ16) from 180 to 17,094 ng g(-1). At the surrounding beaches, PAHs were detected at low concentrations and TBT concentrations reached 10.9 ng Sn g(-1). Although those low levels indicate that the Port might not be an important source of contamination to the surrounding beaches, the very low TOC content and the coarse grain size of the beaches sediments could explain the sedimentary levels. The results show a reduction in TBT levels in Mar del Plata port after national and international use restrictions of TBT-based antifouling paints.

PBDE levels in franciscana dolphin (Pontoporia blainvillei): temporal trend and geographical comparison.

Total PBDE concentrations determined in archived blubber samples from franciscana dolphins (Pontoporia blainvillei) unintentionally captured in the Brazilian coastal region off Rio Grande do Sul State (FMA III) between 1994 and 2004 (n = 73) ranged from 7.9 to 65 ng g(-1) lipid weight in mature males, with an increase over the ten-year period. Total PBDE concentrations in blubber samples collected from the FAM II (n = 41) between 2002 and 2005 were higher (67.8 to 763.7 ng g(-1)lw) than those from FMA III. This is possibly due to the proximity to important industrial development sites in the state of São Paulo. Despite the differences in total concentrations, PBDE profiles were comparable and the PBDE concentrations decreased in the following order BDE 47>BDE99>BDE 100 for both FMA and for males and females as well as adults, juveniles and pups.

Multimatrix measurement of persistent organic pollutants in Mar Chiquita, a continental saline shallow lake.

RAMSAR sites are determined by specific characteristics of the environment in terms of ecological productivity as well services for human development, but they are also one of the most threatened ecosystems. Thus, the objective of this work was to evaluate the dynamic of Persistent Organic Pollutants (POPs) in different biotic and abiotic matrixes of the RAMSAR site (wetlands with international importance), Mar Chiquita Lake. Sampling was performed according to land use (agricultural, urban, and industrial) at two stations: Laguna del Plata and Campo Mare. POPs were analyzed in superficial water (Sw), suspended particulate material (SPM), bottom sediment (Bs) and fish tissues (Odontesthes bonariensis). Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were analyzed by GC-ECD. HCHs, Endosulfans, DDTs, PCBs and PBDEs were found in all matrixes at both stations. The high persistence and transport processes are responsible for the occurrence of HCHs, DDTs and PCBs in Bs, SPM and fish tissues, even many years after their prohibition. PBDEs showed lower levels according to the scarcity of punctual sources in the area. Endosulfan showed variable amounts in agreement with application periods since this pesticide was used until a few years ago in this area. Finally, PCB levels overpassed the acceptable daily intake for human consumption being a risk for human health Thus, the present report confirms the occurrence of POPs in Mar Chiquita lake, alerting on the contribution of agricultural and urban pollutants in a RAMSAR site. Current results also raise concerns on biomagnification processes through the food web.

PBDEs, PCBs and organochlorine pesticides distribution in edible fish from Negro River basin, Argentinean Patagonia.

DDTs, endosulfans, HCHs, chlordanes, PCBs and PBDEs levels were determined in different tissues of patagonian silverside (Odontesthes hatcheri) from the Upper (UV), Middle (MV) and Lower (LV) valleys of the Negro River, Argentina. Results showed a direct relation between pollutant levels in fish and land uses along the basin. All tissues showed decreasing levels from headwaters (UV) to downstream (LV). A significant predominance of organochlorine pesticides (306-3,449 ng g(-1) lipid) followed by ΣPCBs (65-3,102 ng g(-1) lipid) and ΣPBDEs (22-870 ng g(-1) lipid) was observed in all tissues and valleys, suggesting agriculture as the main source of pollutants in this basin. Pesticides were dominated by DDTs (90% pp'-DDE) followed by endosulfan (α->ß->sulfate), γ-HCH and γ-chlordane showing the prevalence of legacy compounds. Endosulfan levels point out the current use of technical endosulfan in the surrounding areas. The highest PCBs and PBDEs concentrations observed in fish from UV were associated to hydroelectric power plants and industries established upstream. PCB fingerprint presented a prevailing contribution of hexa-CBs (66 ± 7%) and penta-CBs (27 ± 9%), with a similar composition to Aroclor 1254-1260. The predominance of BDE-47 (69 ± 17%) among PBDEs, followed by BDE-100 and BDE-99, suggests possible debromination processes. These results were similar to worldwide trends found in fishes and environmental compartments. PCBs levels in silverside muscles along the Negro River exceeded the maximum limits for safe consumption, suggesting a possible human health risk related to silverside ingest. Therefore, a continued long-term monitoring of organic contaminants in fishes is needed in order to assess the potential risk for human health.

Lysosomal responses as a diagnostic tool for the detection of chronic petroleum pollution at Todos os Santos Bay, Brazil.

Coastal marine environments, especially semienclosed systems such as bays, are under unrelenting stress caused by urban and industrial development. Biomonitoring plays a vital role in strategies to identify, assess, and control stressors. However, due to the magnitude of the challenge there is a demand for new and innovative approaches to provide timely and accessible information to environmental managers and policy makers. The present work aimed to assess hydrocarbon levels in sediments from petroleum-related industrial areas at Todos os Santos Bay (Brazil) and associate them to toxicity-induced responses (neutral red retention (NRR) assay) by the burrowing clam Anomalocardia brasiliana. Surface sediments collected during the dry and rainy seasons were analyzed for aliphatic and aromatic hydrocarbons. At the control site, hydrocarbon levels were low and mainly biogenic. The aliphatic hydrocarbon ("total unresolved complex mixture," alkanes, and isoprenoids) concentrations indicated a chronic situation with very little "fresh" oil contamination at the oil-related sites. The polycyclic aromatic hydrocarbons indicated sites moderately contaminated by chronic oil and some pyrolytic input. The effects of those contaminants were assessed by the lysosomal NRR assay applied to A. brasiliana hemocytes. Sediment toxicity at the oil-related sites was evidenced by the lowered capacity of the lysosomes to retain the neutral red dye compared to results from the control site. This research indicates that the NRR assay is a useful and efficient screening technique able to discriminate polluted from clean sites.

The use of steroid markers to assess sewage contamination of the Black Sea.

Analyses of faecal steroids in coastal sediments taken from throughout the Black Sea indicate chronic sewage contamination at some locations. These include Sochi, where concentrations of coprostanol up to 5400 ng g(-1) (dry wt) were recorded, and in the coastal areas adjacent to the Danube delta (2600 ng g(-1) dry wt). Comparatively high values of 5beta/(5beta+5alpha) isomeric ratios of cholestan-3-ol and cholestan-3-one are reported at these locations and are characteristic of sediments contaminated with sewage. Lower concentrations of coprostanol are reported for Bosphorus sediments (12-440 ng g(-1) dry wt) and in the region of Odessa (130-290 ng g(-1) dry wt). Isomeric ratios at these locations also confirm sewage as a significant contributor to steroids in the Bosphorus, but lower values of the ratios indicate only minor sewage inputs in Odessa. In contrast, steroid concentrations and compositions from most Ukrainian sites are characteristic of uncontaminated environments. To place these results into perspective, the range in levels of coprostanol in the Black Sea sediments compares to the lower to mid-range of concentrations reported for coastal sediments on a world-wide basis, with Black Sea sedimentary levels substantially below those previously reported for heavily impacted sites.

Contamination by persistent organochlorines in cetaceans incidentally caught along Brazilian coastal waters.

Wide ranges of organochlorine residues were determined in the blubber of franciscana (Pontoporia blainvillei), estuarine dolphin (Sotalia guianensis), Atlantic spotted dolphin (Stenella frontalis), and long-beaked common dolphin (Delphinus capensis) incidentally caught along Brazilian coastal waters. Concentrations of DDTs and PCBs were the highest, followed by CHLs, TCPMOH, dieldrin, TCPMe, heptachlor epoxide, HCB, and HCHs. Unexpectedly, significant pollution of PCBs, DDTs, TCPMe, and TCPMOH were observed in cetaceans from Brazil, implying the occurrence of local sources in the Southern Hemisphere comparable to those in the Northern Hemisphere, probably by high industrialization in Brazil. On the other hand, CHLs, HCB, HCHs, heptachlor epoxide, and dieldrin residue levels in Brazilian dolphins were much lower than those in other species from the Northern Hemisphere. Significant correlations of TCPMe and TCPMOH were found along with PCBs and DDTs, indicating the highly bioaccumulative nature of all these compounds and/or possible similar pollution sources.

Global pollution monitoring of butyltin compounds using skipjack tuna as a bioindicator.

Butyltin compounds (BTs) including mono- (MBT), di- (DBT), tri-butyltin (TBT) and total tin (sigmaSn), were determined in the liver of skipjack tuna (Katsuwonus pelamis) collected from Asian offshore waters (off-Japan, the Japan Sea, off-Taiwan, the East China Sea, the South China Sea, off-Philippines, off-Indonesia, the Bay of Bengal), off-Seychelles, off-Brazil and open seas (the North Pacific). BTs were detected in all the skipjack tuna collected, suggesting widespread contamination of BTs even in offshore waters and open seas on a global scale. Considering specific accumulation, Sex-, body length- differences and migration of skipjack tuna did not seem to affect BT concentrations, indicating rapid reflection of the pollution levels in seawater where and when they were collected. Skipjack tuna is a suitable bioindicator for monitoring the global distribution of BTs in offshore waters and open seas. High concentrations of BTs were observed in skipjack tuna from offshore waters around Japan, a highly developed and industrialized region (up to 400 ng/g wet weight). Moreover skipjack tuna collected from offshore waters around Asian developing countries also revealed the levels comparable to those in Japan (up to 270 ng/g wet weight) which may be due to the recent improvement in economic status in Asian developing countries. High percentages (almost 90%) of BTs in total tin (sigmaSn: sum of inorganic tin+organic tin) were found in the liver of skipjack tuna from offshore waters around Asian developing countries. This finding suggests that the anthropogenic BTs represent the major source of Sn accumulation in skipjack tuna from these regions.

Global pollution monitoring of PCBs and organochlorine pesticides using skipjack tuna as a bioindicator.

Concentrations of organochlorines (OCs) representing persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), hexachlorocyclohexane isomers (HCHs), and hexachlorobenzene (HCB), were determined in the liver of skipjack tuna (Katsuwonus pelamis) collected from the offshore waters of various regions in the world (offshore waters around Japan, Taiwan, Philippines, Indonesia, Seychelles, and Brazil, and the Japan Sea, the East China Sea, the South China Sea, the Bay of Bengal, and the North Pacific Ocean). OCs were detected in livers of all of the skipjack tuna collected from the locations surveyed, supporting the thesis that there is widespread contamination of persistent OCs in the marine environment. Within a location, no significant relationship between growth-stage (body length and weight) and OC concentrations (lipid weight basis) was observed, and the OC residue levels were rather uniform among the individuals. Interestingly, the distribution of OC concentrations in skipjack tuna was similar to those in surface seawaters from which they were taken. These results suggest that OC concentrations in skipjack tuna could reflect the pollution levels in seawater from which they are collected and that this species is a suitable bioindicator for monitoring the global distribution of OCs in offshore waters and the open ocean. Concentrations of PCBs and CHLs in skipjack tuna were higher in offshore waters around Japan (up to 1100 and 250 ng/g lipid wt, respectively), suggesting the presence of sources of PCBs and CHLs in Japan. High concentrations of DDTs and HCHs were observed in samples from the Japan Sea, the East China Sea, the South China Sea, and the Bay of Bengal (up to 1300 and 22 ng/g lipid wt, respectively). This result suggests recent use of technical DDT and HCH for agricultural and/or public health purposes in Russia, China, India, and some other developing Asian countries. Relatively high concentrations of PCBs, CHLs, HCHs, and HCB were also observed in samples collected from some locations in the middle of the Pacific Ocean, indicating the expansion of OC contamination on a global scale. Considering these facts, continuous studies monitoring these compounds in offshore waters and the open seas, using skipjack tuna as a bioindicator, are needed to further understand the future trend of contamination.

Evaluation of a commercially available ELISA kit as a tool to determine BTEX in groundwater.

The reliability of enzyme-linked immunosorbent assay (ELISA) tests as a screening technique to address groundwater contamination was tested in an area following leakage of gasoline from a petrol station. Immunoassay data of benzene, toluene, ethylbenzene, and o-, m- and p-xylene (BTEX) were compared with results obtained using capillary gas chromatographic analysis. Detection limits were of 20 microg l(-1) for ELISA and 0.3 microg l(-1) for gas chromatography with flame ionization and photoionization detectors (GC-FID/PID) determination. Despite an observed overestimation of BTEX concentrations as given by ELISA, the tests responded reliably to different levels of contamination.

A non-destructive assessment of the exposure of crabs to PAH using ELISA analyses of their urine and haemolymph.

Urine and haemolymph can be repeatedly sampled from crabs with no (or limited) damage to the organism. Their analysis offers a measure of the animals' exposure to biologically available contaminants. Shore crabs (Carcinus maenas) were exposed to the PAHs phenanthrene and pyrene at concentrations ranging from 20 to 200 microg l(-1). After 48 h, urine and haemolymph samples were taken and analysed using ELISA and UV-fluorescence spectrophotometry. High correlations were recorded between the two sets of results from the urine analyses (r2 = 0.83 for phenanthrene and r2 = 0.88 for pyrene). Contaminant concentrations were much lower in haemolymph than in the urine. Analyses of urine taken from crabs collected from clean and contaminated sites confirm the suitability of these analyses for environmentally exposed organisms. Again, a good correlation was recorded between the ELISA and spectrofluorimetric analysis (r2 = 0.83). In this instance, difficulties were experienced with haemolymph analyses owing to a lack of sensitivity.

Persistent organochlorine residues in sediments from the Black Sea.

The extent of contamination of the Black Sea by selected organochlorine compounds has been assessed through the analysis of surficial sediments taken from throughout the region. Concentrations of HCHs at sites influenced by the Danube delta are among the highest recorded on a global basis (up to 40 ng g(-1) dry wt). The ratio between the alpha- and gamma-isomers was relatively low indicating contamination through the use of lindane. Concentrations of DDTs (0.06-72 ng g(-1) dry wt) and PCBs (0.06-72 ng g(-1) dry wt) were not especially high in comparison to levels reported from throughout the world. The DDE/DDT ratio was, however, low indicating fresh inputs and hence current usage of DDT within the Black Sea region.

Petroleum and PAH contamination of the Black Sea.

Concern has been expressed regarding the extent of contamination of the Black Sea. Analyses of coastal sediments taken from throughout the region indicate, however, that levels of petroleum hydrocarbons (2-300 microg g(-1) dry wt total hydrocarbons) are generally comparable to those encountered in the Mediterranean and are lower than concentrations reported for highly contaminated areas such as the Gulf, Hong Kong, Taiwan and New York Bight. Highest concentrations of total hydrocarbons (>100 microg g(-1) dry wt) were associated with discharges from Odessa, Sochi and the River Danube. Chronic/degraded petroleum was the major contributor at these sites. Samples from the Ukrainian coastline were comparatively clean (<10 microg g(-1) dry wt total hydrocarbons). Major contributions of fresh oil (as indicated by sigma n-C14-34) occur through the River Danube. Concerning total PAH, concentrations (7-638 ng g(-1) dry wt) compare to relatively unpolluted locations in the Mediterranean and are much lower than levels reported for polluted UK estuaries (e.g. Mersey, Tyne, Thames). Both pyrolytic and petrogenic PAH are present in most samples, although petroleum derived PAH are dominant at Sochi and pyrolytic sources are prevalent in the Bosphorus region. The absence of a correlation between total hydrocarbons and PAH (R2 = 0.04) indicates different primary sources for the two.