Metallothionein in intestine of red mullet, Mullus barbatus as a biomarker of copper exposure in the coastal marine areas

Dietary metal exposure in fish is studied in native red mullet, Mullus barbatus, involving metallothionein (MT) response in the intestine, a primary site for metal uptake. Intestinal MTs (microg mg(-1) proteins), total proteins (mgml(-1) S50), Cu, Zn, Fe, Mn and Cd (microg ml(-1) S50) are considered as indicators of metal exposure in specimens from near-shore and off-shore locations of the Eastern Adriatic Sea. Metallothionein and Cu are statistically significantly higher in 68 specimens from the Kastela Bay, a near-shore area (30.0+/-6.71microg MT mg(-1) proteins; 0.30+/-0.08microg Cu ml(-1) S50), in comparison to 51 specimens from off-shore area, Solta Island (25.9+/-4.21microg MT mg(-1) proteins; 0.26+/-0.09microg Cu ml(-1) S50). Cytosolic Cu, a MT inducer, is significantly correlated (p<0.05, r=0.44) with MT in specimens from the Kastela Bay, independent on fish biometry. Our study indicates that cytosolic intestinal Cu and MT represent a measurable biochemical response in red mullet specimens, dwelling above sediments contaminated with Cu.     

Application of biomarkers for assessing the biological impact of dredged materials in the Mediterranean: the relationship between antioxidant responses and susceptibility to oxidative stress in the red mullet (Mullus barbatus)

In the period 1997-2000, approximately 1,800,000 m3 of material dredged from the Port of Leghorn was discharged into a sea dumping site located 14 miles from the coast. The red mullet (Mullus barbatus) was used as a bioindicator species for monitoring the biological impact of these discharges on a geographical and temporal scale. Organisms were sampled over three years (1998-2000) at different stations and several biomarkers, both of exposure and effect, were analyzed. Bioavailability of specific classes of pollutants was evaluated by analyzing levels of metallothioneins, the activity of cytochrome P450 1A (CYPIA) and of glutathione S-transferases. Among biomarkers of effect, special attention was paid to the balance between prooxidant challenge and antioxidant defenses, and to the appearance of damage caused by oxidative stress. The analyses of the main components of the antioxidant system included superoxide dismutase, catalase, glutathione peroxidases, glutathione reductase, glyoxalase I and II, and total glutathione. These data were integrated with the measurement of total oxyradical scavenging capacity (TOSC) as an indication of the overall biological resistance to toxicity of different forms of oxyradicals (peroxyl radicals, hydroxyl radicals and peroxynitrite). Results indicated a biological impact in organisms sampled near the disposal site; the impact was particularly evident during 1999 and mainly related to organic chemicals such as PAH. Exposure to these pollutants also caused variations in the levels and activity of several antioxidants. The analysis of TOSC, however, revealed that the overall capacity of specific tissues of organisms to absorb various oxidants was not seriously compromised when challenged with increased prooxidant pressures. Variations of single antioxidants were useful in revealing early warning "biological responses", while integration with TOSC analyses indicated if such changes also reflect a more integrated and functional "biological effect" with possible consequences at the organisms level. The red mullet appears to be a useful sentinel species for a biomarker approach to monitoring impact caused by dredged materials.     

Bioaccumulation of polychlorinated biphenyls in mullet fish in a former ship dismantling harbour, a contaminated estuary, and nearby coastal fish farms

This study investigated the bioaccumulation of polychlorinated biphenyls (PCBs) toward mullet fish (Liza macrolepis) living in former PCB contaminated areas, the Ann-Ping harbour and the Er-Jen estuary, and fish farms located near the above two areas in 2003. The PCB body burdens of collected fish samples are proportional to the contamination level of their locations with the following rank order (greatest to least) from the Er-Jen estuary, the Ann-Ping harbour to the fish farms. Concentration of PCBs of the estuarine mullet has been approximately decreased to one-half of the peak concentration of the 1990s. Although the concentration of PCBs in farmed fish inhabiting near the two contaminated areas was greater than the average of those of fish from local fish markets in Taiwan, no particularly great contamination level was observed in their bodies. Using the less chlorinated PCB fraction (triCB + tetraCB)/total PCBs as the indicator of the origins of PCBs, fish near former contaminated areas had greater body burdens of the more chlorinated PCB congeners, while the farmed fish exhibited a PCB pattern more like that known to originate from air–water exchange with less chlorinated PCBs predominating. Although the PCB contamination has been stopped for a decade, the residual contaminants, supposedly existing in soil and sediments, still contribute to the body burden of fish residing in the estuary and the harbour.     

Investigating the presence of organochlorine pesticides and polychlorinated biphenyls in wild and farmed gilthead sea bream (Sparus aurata) from the Western Mediterranean sea

The presence of organochlorine pesticides and polychlorinated biphenyls in wild and farmed gilthead sea bream (Sparus aurata) from the Western Mediterranean, Spain, is investigated. These pollutants were determined in white and red muscle and liver by gas chromatography coupled to tandem mass spectrometry. Contaminant profiles present in both wild and farmed fish tissues include DDTs, PCBs and HCB. The highest concentrations of contaminants were found in liver, and an increase in pollutant levels was observed in autumn, before spawning. This fact is explained in light of increased food intake when sea water temperatures increase. Gilthead sea bream from Western Mediterranean populations showed significantly higher concentrations of DDTs and PCBs than farmed fish from the same area. This fact is attributed to the low level of organochlorine contaminants present in fish feed supplied to the cultured fish. The diet is highlighted as an important factor in understanding differences observed in organochlorine pollutants levels of fish tissues.     

Concentrations and hazard assessment of polychlorinated biphenyls and organochlorine pesticides in shark liver from the Mediterranean Sea

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (DDTs), were determined in the liver of two different shark species Prionace glauca (blue shark) and Dalatias licha (kitefin shark) from the Mediterranean Sea. In blue shark liver, the concentrations of PCBs (2482 ngg(-1)) and DDTs (2392 ngg(-1)) were comparable, while in kitefin shark the hepatic concentrations of DDTs (4554 ngg(-1)) were significantly higher than those of PCBs (1827 ngg(-1)). Contamination levels differed between species, with kitefin shark showing consistently higher concentrations of DDTs, and blue shark higher levels of PCBs. Congener-specific PCB profiles, similar between the two species were dominated by the higher chlorinated congeners (hexachlorobiphenyls: 62.8-63.9%, penta-: 15.2-21.3%, hepta-: 13.4-14.5%) with most of the lower chlorinated congeners being absent or present at very low levels. In both species, the total 2,3,7,8-tetrachlorodibenz-p-dioxin toxic equivalent (TEQs) concentrations (blue shark: 2.51 pg/g; kitefin shark: 1.46 pg/g) seem to be relatively modest. Regards to DDT component pattern, p,p'-DDE was dominant in the liver of both species (blue shark: 81.5%; kitefin shark: 38.0%), while the percentage composition of the other metabolites was differently characterized. The composition pattern of DDTs and the low value of p,p'-DDE/DDTs ratio in the specimens from Ionian Sea suggest that organochlorine pesticide contamination is still continuing in this marine environment.     

Persistent organochlorine residues and toxic evaluation of polychlorinated biphenyls in sharks from the Mediterranean Sea (Italy)

Persistent organochlorines such as polychlorinated biphenyls including coplanar congeners, DDT compounds and HCB were measured in different tissues (muscle, liver and eggs) of two Mediterranean shark species: namely Centrophorus granulosus and Squalus blainvillei. The concentrations of organochlorines in the tissues and organs of both species were in the order DDTs>PCBs>HCB. The highest values of DDTs, PCBs and HCB were found in liver followed by eggs and muscle. Among DDTs the compound found in greatest concentration was p,p^′-DDE. The PCB profiles were dominated by congeners 138, 153, and 180. The isomers with higher TEQs values were non- and mono-ortho congeners than di-ortho ones in muscle, liver and eggs of both species. Among the non-ortho, PCB 126 was the major contributing individual to the total TEQs in both species.     

Evidence for polychlorinated biphenyls dechlorination in the sediments of Sado Estuary, Portugal

Sediment gravity cores and grab samples were collected in the Sado Estuary and in its coastal area. The cores were sliced on board and the percentage of weight loss on ignition was determined in the laboratory, and analysed for polychlorinated biphenyl (PCB) congeners. PCB contents were higher in samples from the North Channel of the estuary, nearby the industrial zone (max. 114 ng g-1 dry weight), while levels in the coastal area were lower than 4.9 ng g-1. The concentrations of the quantified congeners varied irregularly with sediment depth in the estuary, but showed two opposite distribution patterns in cores from the coastal area: the proportions of lower chlorinated congeners increased with depth, while congeners with higher number of chlorines decreased. This suggests a dechlorination of the most chlorinated congeners into less toxic compounds, under reductive conditions of the sediment. Though measurements were done in natural environment it appears that dechlorination was not entirely dependent on chlorine position in the phenyl rings.     

Phthalate ester plasticizers,DDT, DDE and polychlorinated biphenyls in biota from the Gulf of Mexico

The levels of phthalate ester plasticizers, DDT, DDE and polychlorinated biphenyls (PCBs) were determined in the tissues of 18 species of marine organisms from the northwestern Gulf of Mexico. Low levels of the most widely used phthalate, di-(2-ethylhexyl) phthalate, were found in the majority of the samples; no other phthalates were detected. DDT, DDE and PCBs were found in all samples, but at somewhat lower levels than those found in our 1971 survey. A decrease in p,p′-DDT/p,p′-DDE ratios relative to 1971 was also noted.     

Distribution of polychlorinated biphenyls in the water, sediment and fish from the Pearl River estuary, China

The concentrations and distribution of polychlorinated biphenyls were determined in water, surface sediments and fishes from the estuaries of Pearl River, PR China. The results showed that the concentrations ranged from 2.47 ng l-1 to 6.75 ng l-1 in water, from 11.13 ng g-1 to 23.23 ng g-1 in sediments (dry weight) and from 68.64 ng g-1 to 316.85 ng-1 in fish (lipid weight). It was found that the feeding habits of fish were very significant in the accumulation of polychlorinated biphenyls and pattern of congeners. Carnivorous and benthic fishes such as eel (Anguilla japonica) and Chinese sea catfish (Arius sinensis) were found to have high concentrations of polychlorinated biphenyls and of high-chlorinated congeners, while herbivores such as shad (Clupanodon punctatus) and mullet (Mugil cephalus) exhibited an opposite trend. Congeners IUPAC Nos. 153, 138, 118, 87/81, 170 and 52 were found frequently in most samples (both sediment and fish). In comparison with other places in the world, the concentration of polychlorinated biphenyls in sediment and fish from the estuary of Pearl River were low.     

Distributions of polychlorinated biphenyls in the Daliao River estuary of Liaodong Bay,Bohai Sea (China)

The distributions of 41 polychlorinated biphenyls (PCBs) were determined in the aqueous phase, suspended particulate matter (SPM), and sediment of the Daliao River estuary in Liaodong Bay, Bohai Sea (China). The total PCB concentrations ranged from 5.51 to 40.28 ng L⁻¹ in the surface water, from 6.78 to 66.55 ng L⁻¹ dry weight in the SPM, and from 0.83 to 7.29 ng g⁻¹ dry weight in the sediment. The PCB concentrations in water, SPM, and sediment were moderate relative to those reported for other estuary and marine systems around the world. Sedimentary PCB concentrations decreased offshore due to the active deposition of laterally transported river-borne particles. The predominance of the highly chlorinated congeners for the water, SPM, and sediment samples are an indication of either a lack of degradation or the presence of nearby or recent releases into the environment.     

DDTs and other chlorinated organic pesticides and polychlorinated biphenyls pollution in the surface sediments of Keratsini harbour, Saronikos gulf, Greece

Sediment samples were collected from Keratsini harbour, Saronikos gulf, Greece and were analysed for chlorinated organic pesticides (DDTs, HCB, Lindane) and polychlorinated biphenyls (PCBs). High total DDTs values were detected in all the sediments samples ranging from 9.1 to 75.6 mug/g, dry weight. PCBs concentrations range from 47.8 to 351.8 ng/g. The results and especially the high concentrations of DDTs reflect the influence of the industrial and urban wastes in the pollution for the Keratsini harbour environment.     

A study of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in the livestock waste compost of Hong Kong, PR China

Composting is one of the waste disposal methods adopted for disposal of livestock waste in Hong Kong. The composting livestock waste normally undergoes 6-8 weeks fermentation, followed by 16-20 weeks maturation. The matured compost is sold as soil conditioner in the local market. In 2006, feedstock material and a time-series of compost samples were collected throughout the fermentation and maturation process from the Sha Ling Composting Plant in the New Territories. The feedstock material and compost samples were analyzed for contents of three unintentional persistent organic pollutants (POPs), i.e. dioxins/furans, dioxin-like PCBs and total PCBs. These POPs are unintentionally produced by-products of chemical industrial processes and combustion processes. Selected heavy metals were also analyzed, which served as conservative tracers to determine potential mass loss during the composting process. Levels of contamination by these POPs were found to be low in the matured compost for sale. The mean concentrations (lower-upper bound) of total dioxins/furans, total dioxin-like PCBs and total PCBs were 2.01-2.05 ng I-TEQ/kg dw, 0.04-0.05 ng WHO-TEQ/kg dw and 1.55-1.55 microg/kg dw, respectively. Progressively elevated levels of these POPs were observed in the compost samples during the fermentation process. Analysis of the congener profiles revealed that the heptaCDD and octaCDD were the main contributors to the observed increase in dioxin/furan content. The possible sources of dioxins/furans in the compost were discussed. The study results established a local dioxins/furans emission factor specific to the trade and provided a better estimate of the annual dioxins/furans emission for the livestock waste composting activity in Hong Kong.     

A study of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in the livestock waste compost of Hong Kong,PR China

Composting is one of the waste disposal methods adopted for disposal of livestock waste in Hong Kong. The composting livestock waste normally undergoes 6–8 weeks fermentation, followed by 16–20 weeks maturation. The matured compost is sold as soil conditioner in the local market. In 2006, feedstock material and a time-series of compost samples were collected throughout the fermentation and maturation process from the Sha Ling Composting Plant in the New Territories. The feedstock material and compost samples were analyzed for contents of three unintentional persistent organic pollutants (POPs), i.e. dioxins/furans, dioxin-like PCBs and total PCBs. These POPs are unintentionally produced by-products of chemical industrial processes and combustion processes. Selected heavy metals were also analyzed, which served as conservative tracers to determine potential mass loss during the composting process. Levels of contamination by these POPs were found to be low in the matured compost for sale. The mean concentrations (lower–upper bound) of total dioxins/furans, total dioxin-like PCBs and total PCBs were 2.01–2.05 ng I-TEQ/kg dw, 0.04–0.05 ng WHO-TEQ/kg dw and 1.55–1.55 μg/kg dw, respectively. Progressively elevated levels of these POPs were observed in the compost samples during the fermentation process. Analysis of the congener profiles revealed that the heptaCDD and octaCDD were the main contributors to the observed increase in dioxin/furan content. The possible sources of dioxins/furans in the compost were discussed. The study results established a local dioxins/furans emission factor specific to the trade and provided a better estimate of the annual dioxins/furans emission for the livestock waste composting activity in Hong Kong.     

Distribution and source apportionments of polychlorinated biphenyls (PCBs) in mariculture sediments from the Pearl River Delta, South China

Surface and core sediments collected from six mariculture farms in the Pearl River Delta (PRD) were analyzed to evaluate contamination levels of polychlorinated biphenyls (PCBs). The ∑PCBs (37 congeners) concentrations ranged from 5.10 to 11.0 ng g(-1) (mean 7.96 ng g(-1)) in surface and 3.19 to 22.1 ng g(-1) (mean 7.75 ng g(-1)) in core sediments, respectively. The concentrations were significantly higher than that measured in the sediments of their corresponding reference sites, whereby the average enrichment percentages were 62.0% and 42.7% in surface and core sediments, respectively. Significant correlations (R2=0.77, p<0.05) of PCB homologue group proportions between fish feeds and surface mariculture sediments suggested that fish feed input was probably the main source for the enrichment of PCBs. Due to the fact that PCBs could be transferred along food chains, PCB contamination in fish feeds and mariculture sediments should not be overlooked.     

Distribution and source apportionments of polychlorinated biphenyls (PCBs) in mariculture sediments from the Pearl River Delta,South China

Surface and core sediments collected from six mariculture farms in the Pearl River Delta (PRD) were analyzed to evaluate contamination levels of polychlorinated biphenyls (PCBs). The ∑PCBs (37 congeners) concentrations ranged from 5.10 to 11.0 ng g⁻¹ (mean 7.96 ng g⁻¹) in surface and 3.19 to 22.1 ng g⁻¹ (mean 7.75 ng g⁻¹) in core sediments, respectively. The concentrations were significantly higher than that measured in the sediments of their corresponding reference sites, whereby the average enrichment percentages were 62.0% and 42.7% in surface and core sediments, respectively. Significant correlations (R² = 0.77, p < 0.05) of PCB homologue group proportions between fish feeds and surface mariculture sediments suggested that fish feed input was probably the main source for the enrichment of PCBs. Due to the fact that PCBs could be transferred along food chains, PCB contamination in fish feeds and mariculture sediments should not be overlooked.