Metal and metallothionein concentrations in Paracentrotus lividus from Amvrakikos gulf (Ionian Sea-Greece)

Concentrations of Cd, Cu, Cr, Ni, Zn, Fe and metallothioneins (MTs) were measured in the gonads of Paracentrotus lividus from Amvrakikos gulf (Ionian Sea, Greece). Three natural populations were selected; two of them, growing inside the gulf (Agios Thomas and Koronisia), presented higher density and smaller body size than the population living in a coastal area just outside the gulf (Mytikas). Metal and MT levels were not elevated, with the exception of Zn, showing high values related to the reproduction stage of the sea urchins. Significant geographical variations were recorded in the concentrations of Cu, Zn, Cd, Cr and MTs. The highest mean and maximum values of Cu, Zn and MTs were recorded in Agios Thomas while Cd and Cr were higher in Mytikas population. Copper, Zn, Fe and MT concentrations were negatively correlated to the sea urchin body size, while a positive concentration-size relationship was observed for Cd. Although all studied populations grow in a low metal level marine environment, urchins with smaller body size living in a food limited marine environment showed higher gonadosomatic index, metal concentrations and MT levels in their gonads (Agios Thomas and Koronisia) than larger specimens growing in a food unlimited area (Mytikas).     

Ecological risk assessment of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in marine environment using Isochrysis galbana, Paracentrotus lividus, Siriella armata and Psetta maxima

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are anthropogenic substances classified as persistent bioaccumulative compounds and are found in various environmental compartments throughout the world, from industrialized regions to remote zones far from areas of production. In this study, we assessed the effects of PFOA and PFOS on early life stages of marine test species belonging to three different trophic levels: one microalga (Isochrysis galbana), a primary consumer (Paracentrotus lividus) and two secondary consumers (Siriella armata and Psetta maxima). Acute EC(50) values for PFOS were 0.11 mg L(-1) in P. maxima, 6.9 mg L(-1) in S. armata, 20 mg L(-1) in P. lividus and 37.5 mg L(-1) in I. galbana. In the case of PFOA, the toxicity was lower but the ranking was the same; 11.9 mg L(-1) in P. maxima, 15.5 mg L(-1) in S. armata, 110 mg L(-1) in P. lividus and 163.6 mg L(-1) in I. galbana. The Predicted No Effect Concentration (PNEC) for PFOS and PFOA in marine water derived from these acute toxicity values are 1.1 μg L(-1) for PFOS and 119 μg L(-1) for PFOA. This study established a baseline dataset of toxicity of PFOS and PFOA on saltwater organisms. The data obtained suggest that PFOA pose a minor risk to these organisms through direct exposure. In the perspective of risk assessment, early life stage (ELS) endpoints provide rapid, cost-effective and ecologically relevant information, and links should be sought between these short-term tests and effects of long-term exposures in more realistic scenarios.     

Organophosphate pesticide environmental exposure: analysis of salivary cholinesterase and carboxilesterase activities in preschool children and their mothers

A pilot study was conducted to evaluate the usefulness of salivary cholinesterase and carboxylesterase as biomarkers of exposure to environmental organophosphate pesticides. Ninety samples were obtained from women and 62 samples from their preschool-aged children who live near an agricultural area of the Upper Valley of the Negro River (Patagonia, Argentina) where pesticides are applied 6 months a year. Each participant donated two samples under similar conditions: one in the pre-exposure period and another during the pulverization period. Demographic information, potential confounders, and risk behaviors were registered. Active or passive smoking had no effect on these enzyme activities in either group. During the pulverization period, cholinesterase activity was not detectable in 76% of the children's samples and 23% of the mothers' samples. Comparing samples collected during the pulverization period with respect to the pre-pulverization period, the average mother and child cholinesterase activity decreased by 65.7% (p < 0.001) and 85.8% (p < 0.001), respectively. Also, mother and child carboxylesterase activity decreased by 27.5% (p < 0.001) and 41.9% (p < 0.01), respectively. Child carboxylesterase activity in the pulverization period was associated to the habit of eating dust outdoors (p < 0.01). The most frequent inhibition levels observed for cholinesterase and carboxylesterase activity were between 70–100% and 0–29%, respectively, in both groups studied. This shows that at the same level of exposure, cholinesterase was more sensitive to inhibition than carboxylesterase. Therefore, carboxylesterase might more properly reflect the degree of environmental organophosphate exposure and may have potential as a novel tool for biomonitoring.     

Comparison of ALAD activities of Citrobacter and Pseudomonas strains and their usage as biomarker for Pb contamination

Delta-aminolevulinate dehydratase (ALAD) activity has been used in prokaryotes and eukaryotes as a biomarker for environmental lead (Pb) exposure and toxicity. Microorganisms are sensitive indicators of toxicity at the fundamental level of ecological organization, but bacterial biomarker studies are focused on the Pseudomonas strains in Group I and E coli. The objectives of the present work were to determine if Burkholderia gladioli belonging to group II, due to its 16SrRNA similarity, can be used as biomarker in metal contamination and compare its possible usage with Pseudomonas aeruginosa and Citrobacter freundii (previously known as Esherichia freundii) and Bacterium freundii which are classified in Group I. In this study, ALAD activity in an environmental strains of Burkholderia gladioli, Pseudomonas aeruginosa, Citrobacter freundii were investigated to evaluate potential inhibition by Pb and other toxic metals. When the ALAD activity of Burkholderia gladioli was tested, Co and Pb decreased activity by 27 and 71%, respectively. In addition to these findings, Zn increased the activity up to 26%. These effects were found to be statistically meaningful (p < 0.05). It was determined that the increase of lead concentration inhibites the ALAD activity at each of the three strains. There was a statistically significant dose–response relationship between ALAD activity in cells of Burkholderia gladioli and Pb (Pearson correlation coefficent = −0.665; r ² = 0.665, and p < 0.001). The strongest ALAD inhibition which was measured was 90% at Burkholderia gladioli when protein extracts were incubated with 750 μM of Pb. The relationship between Pb and ALAD activity was statistically described by [ALAD Activity] = 0.476−0.000597 × [Pb]. According to the obtained results, we suggest that the ALAD of Burkholderia gladioli can be used as a biomarker for lead contamination in the environment.     

Influence of feeding procedure on biomarkers in caged rainbow trout (Oncorhynchus mykiss) used in environmental monitoring

Biomarkers in feral fish can be a useful tool for environmental monitoring of aquatic ecosystems. Drawbacks, however, are that suitable fish species are not always available and that natural variations can bias the results. An alternative strategy is to use farmed fish placed in cages. There is, however, still a risk that factors other than pollution level could have an impact on the biomarkers and the observed responses in the fish. The present study evaluates the effects of feeding procedure on biomarkers in caged fish. Two feeding rations (2% and 8% weekly feeding) have been examined for a large number of biomarkers in caged rainbow trout (Oncorhynchus mykiss). Significant effects of feeding rations were found on hepatic ethoxyresorufin-O-deethylase (EROD) and catalase activity, PAH metabolites in bile, plasma ion concentrations and the presence of immature red blood cells. The influence on EROD activity and PAH metabolites seems to be caused by elevated uptake of pollutants when feeding ratios are higher. The effects on other biochemical and physiological variables are more likely caused by stress due to insufficient feeding. According to these results, valid comparison of fish groups in environmental monitoring requires standardized feeding levels.     

Cattle egret (Bubulcus ibis) and Little egret (Egretta garzetta) as monitors of mercury contamination in Shadegan Wetlands of south-western Iran

Mercury concentrations in feather, liver, kidney, and muscle tissue of Little egret (n?=?8) and Cattle egret (n?=?3) from Shadegan Wetlands in south-western Iran were examined. Liver of Little egret had significantly higher mercury compared to Cattle egret (p?<?0.05). In addition, mercury values were consistently larger in Little egret when compared to Cattle egret, but mercury levels found in feather, kidney, and muscle did not differ statistically between the two bird species (p?>?0.05). The small Cattle egret sample size, however, makes it difficult to conclude that the same trend would persist had we been able to include more Cattle egrets in this study. An interesting regional comparison between mercury concentrations in the feather of Little egret chicks, from China, Hong Kong, and Pakistan, and adult Little egrets, from Shadegan wetlands, revealed higher mercury in the adult of the species, as one would expect. Conversely, feathers of adult Cattle egrets form Shadegan had less mercury than values reported for young birds of the same species from Aswan in Egypt; but our Cattle egrets had higher or similar mercury concentrations to Cattle egrets from Pakistan, New York, Delaware, Puerto Rico, Hong Kong, and Cairo in Egypt.     

Protein adducts as biomarkers of exposure to aromatic diisocyanates in workers manufacturing polyurethane (PUR) foam

This work was undertaken to investigate the usefulness of diisocyanate-related protein adducts in blood samples as biomarkers of occupational exposure to toluene diisocyanate (TDI; 2,4- and 2,6-isomers) and 4,4'-methylenediphenyl diisocyanate (MDI). Quantification of adducts as toluene diamines (TDAs) and methylenedianiline (MDA) was performed on perfluoroacylated derivatives by gas chromatography-mass spectrometry (GC-MS/MS) in negative chemical ionisation mode. TDI-derived adducts were found in 77% of plasma and in 59% of globin samples from exposed workers manufacturing flexible polyurethane foam. The plasma levels ranged from 0.003 to 0.58 nmol mL(-1) and those in globin from 0.012 to 0.33 nmol g(-1). The 2,6-isomer amounted to about two-thirds of the sum concentration of TDA isomers. MDI-derived adducts were detected in 3.5% of plasma and in 7% of globin samples from exposed workers manufacturing rigid polyurethane foam. A good correlation was found between the sum of TDA isomers in urine and that in plasma. The relationship between globin adducts and urinary metabolites was ambiguous. Monitoring TDI-derived TDA in plasma thus appears to be an appropriate method for assessing occupational exposure. Contrary to TDI exposure, adducts in plasma or globin were not useful in assessing workers' exposure to MDI. An important outcome of the study was that no amine-related adducts were detected in globin samples from TDI- or MDI-exposed workers, alleviating concerns that TDI or MDI might pose a carcinogenic hazard. Further studies are nevertheless required to judge whether diisocyanates per se could be such a hazard.     

Honeybees (<Emphasis Type="Italic">Apis mellifera</Emphasis>) as a biological barrier for contamination of honey by environmental toxic metals

The aim of the study was to investigate the transfer of toxic metals from honeybee workers (Apis mellifera L.) to bee honey in relation to the ecological state of the environment. The materials of the study consisted of samples of honeybee bodies and varietal honeys taken from the same apiary located in three areas: R1—urbanized (16), R2—ecologically clean (16) and R3—industrialized (15) of south-eastern Poland. The contents of 14 elements in all tested samples, including toxic metals (Cd, Pb, Hg, Al, Ni, Tl) as well as bioelements (K, Mg, Ca, Mn, Fe, Zn, Cu, Se), were analysed by the ICP-OES method with prior microwave mineralization. The concentrations of the majority of the studied elements, excluding aluminum and lead, were significantly higher in bee bodies than in honey samples (P?<?0.05). The pollution of bee bodies by toxic metals was dependent on the environmental cleanliness, and the most pollution was observed in the industrialized area. The bee body was the most effective barrier for Cd and Tl transfer to the honey, while the level of Ni was similar in both tested materials. The Al concentration was significantly higher in honey than bee bodies (14.81?±?24.69 and 6.51?±?5.83 mg kg^?1, respectively), which suggests the possibility of secondary contamination of honey. The greatest sensitivity to heavy metal pollution was observed in honeydew honey compared to nectar honeys (P?<?0.05). It was proved for the first time that bees work as biofilters for toxic metals and prevent honey contamination.     

Spatial and temporal properties of environmental exposure assessments related to ground water contamination

This paper describes a new methodology for modeling contaminant transport in ground water for (1) better quantifying the magnitude of exposure in a contaminated aquifer, (2) characterizing the spatial and temporal variation of exposure in a heterogeneous aquifer, and (3) providing more tools for characterizing population exposure. This methodology is also applied to a semi-hypothetical case study.     

Enteromorpha flexuosa (Wulfen) J. Agardh (Chlorophyta: Ulvales)--evaluation as an indicator of heavy metal contamination in a tropical estuary

The use of bioindicators for contaminant monitoring ispopular in all sectors of the environment but quite oftenbioindicators are utilised without rigorous evaluation oftheir viability as an indicator. We report field andlaboratory investigations into the value of a commonlyfound macroalga, Enteromorpha flexuosa (Wulfen) J.Agardh (Chlorophyta: Ulvales) as an indicator of copper,zinc and lead contamination in a tropical estuary inFiji. In the laboratory, metal content of E.flexuosa after 60 days of growth in seawater containingincreasing concentrations of the metals showed almostperfect correlation with metal concentrations in waterfor all three metals, and concentration factors obtainedwere generally higher than values reported for otherspecies of Enteromorpha. Performance in the fieldwas evaluated by a one-year monitoring of metals in E. flexuosa, water and sediments from a contaminatedestuary. Metal concentrations in water were always belowdetection limits and field concentration factors couldnot be determined but the concentration of lead in E. flexuosa showed a high correlation with the leadcontent of sediments. Lack of such correlation forcopper and zinc in the field suggests that otherenvironmental factors besides metal load in the physicalenvironment could be controlling the bioaccumulation ofthese two metals. Whilst demonstrating E. flexuosato be a viable bioindicator for lead, these results alsohighlight the need for proper assessment before anorganism is considered for environmental monitoring.     

Natural and anthropogenic contamination of the Fratta-Gorzone river (Veneto, Italy)

Stream-bed sediment samples were collected in 2001 and 2004 along the Fratta-Gorzone River (Italy) to assess the level of heavy metal contamination. The river stretch most affected by discharges of tannery effluent showed total and pseudo-total Cr levels (up to 2,860 mg/kg) that greatly exceed national and international chemical sediment quality standards. The most contaminated section of the river bed is located downstream of the main industrial discharge. However, a large fraction of the Cr present in the sediment appears to be of lithogenic origin. At most sites, more than 50% of Cr is not soluble in aqua-regia and thus unlikely to be very mobile or easily bio-available. A negligible risk to the benthic community can be inferred for Pb, Zn, Cd, Cu and Ni. This work highlights the limitation of using existing chemical sediment quality standards alone for risk assessment. The collection and analysis of suspended solids, the determination of river discharge and of dissolved Cr at 10 field stations allowed to estimate the particulate and dissolved Cr load and to locate the river stretch that was the likely source of contaminated sediment. The pumping of dilution water from the Adige River into the Fratta-Gorzone River did not produce the expected contaminant dilution effect due to re-suspension of contaminated solid particles and the release of Cr in solution.     

Sewage contamination of a densely populated coral 'atoll' (Bermuda)

Bermuda is a densely populated coral 'atoll' located on a seamount in the mid-Atlantic (Sargasso Sea). There is no national sewerage system and the ～20 × 10(6)?L of sewage generated daily is disposed of via marine outfalls, cess pits/septic tanks underneath houses and through waste disposal (injection) wells. Gastrointestinal (GI) enterococci concentrations were measured in surface seawater samples collected monthly at multiple locations across the island over a 5-year period. According to the EU Bathing Water Directive microbial classification categories, 18 of the sites were in the 'excellent' category, four sites in the 'good', five sites were in the 'sufficient' and three sites in the 'poor' categories. One of the sites in the 'poor' category is beside a popular swimming beach. Between 20-30% of 58 sub tidal sediment samples collected from creeks, coves, bays, harbours and marinas in the Great Sound complex on the western side of Bermuda tested positive for the presence of the human specific bacterial biomarker Bacteroides (using culture-independent PCR-based methods) and for the faecal biomarker coprostanol (5β-cholestan-3-β-ol, which ranged in concentration from <0.05-0.77?mg?kg(?-?1). There was a significant statistical correlation between these two independent techniques for faecal contamination identification. Overall the microbial water quality and sedimentary biomarker surveys suggest sewage contamination in Bermuda was quite low compared with other published studies; nevertheless, several sewage contamination hotpots exist, and these could be attributed to discharge of raw sewage from house boats, from nearby sewage outfalls and leakage from septic tanks/cess pits.     

Use of feathers of feral pigeons (Columba livia) as a technique for metal quantification and environmental monitoring

This study quantifies metal concentrations in washed and unwashed feathers of feral pigeons (Columba livia). The material was collected in two different sites: Goiania (capital of Goiás State), with high anthropic activities, and Jataí (a city in Goiás), with low anthropic activities. Results revealed that metals such as Pb, Cr, and Cd were deposited in the feathers originating from air and soil (exogenous process). Other metals such as Cu, Fe, Mn, and Zn, which are part of the tissue constitution of a living being, were absorbed through the pigeons' diet (endogenous process). There was a statistically significant difference between mean values of Cd, Pb, and Cr in the three collection sites. The order of metal concentrations were Civic Square > Zoo > Jataí, which shows highest levels of metal contamination in anthropic environments. Significant differences between Cd, Pb, and Cr in washed and unwashed feathers suggest that metal concentrations are directly related to exposure time due to exogenous sources. We concluded that it is possible to quantify and monitor metal levels in the environment by analyzing the feathers of urban feral pigeons. Furthermore, unwashed feathers were especially efficient to investigate endogenous and exogenous absorption of the metals in our study.     

Urban activity and mercury contamination in estuarine and marine sediments (Southern Brazil)

The distribution of mercury in sediments of the Patos Lagoon estuary and nearby coastal marine deposits has been investigated for the period 1998-2008. Polluted urban soils and coastal reclamation fills are the principal sources of high mercury concentrations for shallow estuarine sediments. The shallow sediments that form near the urban area enter the navigation canal and are transported into the ocean. The mercury concentration in sediments of the navigation canal has considerably increased since 2004, due to intense reconstruction activity in the urban area. Periodic dredging of the canal strengthens the preconditions for coastal marine sediment contamination by mercury. However, this does not occur because the resuspended dredged sediments are significantly diluted by natural suspended particulate matter.     

Influence of multi-industrial activities on trace metal contamination: an approach towards surface water body in the vicinity of Dhaka Export Processing Zone (DEPZ)

Industrial wastewater discharged into aquatic ecosystems either directly or because of inadequate treatment of process water can increase the concentrations of pollutants such as toxic metals and others, and subsequently deteriorate water quality, environmental ecology and human health in the Dhaka Export Processing Zone (DEPZ), the largest industrial belt of 6-EPZ in Bangladesh. Therefore, in order to monitor the contamination levels, this study collected water samples from composite effluent points inside DEPZ and the surrounding surface water body connected to effluent disposal sites and determined the environmental hazards by chemical analysis and statistical approach. The water samples were analysed by inductively coupled plasma mass spectrometry to determine 12 trace metals such as As, Ag, Cr, Co, Cu, Li, Ni, Pb, Se, Sr, V and Zn in order to assess the influence of multi-industrial activities on metal concentrations. The composite effluents and surface waters from lagoons were characterized by a strong colour and high concentrations of biochemical oxygen demand, chemical oxygen demand, electrical conductivity, pH, total alkalinity, total hardness, total organic carbon, Turb., Cl(-), total suspended solids and total dissolved solids, which were above the limit of Bangladesh industrial effluent standards, but dissolved oxygen concentration was lower than the standard value. The measurement of skewness and kurtosis values showed asymmetric and abnormal distribution of the elements in the respective phases. The mean trend of variation was found in a decreasing order: Zn > Cu > Sr > Pb > Ni > Cr > Li > Co > V > Se > As > Ag in composite industrial effluents and Zn > Cu > Sr > Pb > Ni > Cr > Li > V > As > Ag > Co > Se in surface waters near the DEPZ. The strong correlations between effluent and surface water metal contents indicate that industrial wastewaters discharged from DEPZ have a strong influence on the contamination of the surrounding water bodies by toxic metals. The average contamination factors were reported to be 0.70-96.57 and 2.85-1,462 for industrial effluents and surface waters, respectively. The results reveal that the surface water in the area is highly contaminated with very high concentrations of some heavy/toxic metals like Zn, Pb, Cu, Ni and Cr; their average contamination factors are 1,460, 860, 136, 74.71 and 4.9, respectively. The concentrations of the metals in effluent and surface water were much higher than the permissible limits for drinking water and the world average concentrations in surface water. Therefore, the discharged effluent and surface water may create health hazards especially for people working and living inside and in the surrounding area of DEPZ.     

Chironomid mouthpart deformities as indicator of environmental quality: a case study in Lake Trasimeno (Italy)

The aim of the present study was to monitor mouthpart deformities of Chironomus plumosus (Insecta-Diptera) in Lake Trasimeno (2000-2010) in relation with sediment contamination by heavy metals, which is one of the main causes of deformity induction. In Lake Trasimeno, concentrations of heavy metals in the investigated littoral zone were low, in comparison with those of the central area. By contrast, the incidence of deformities was much higher in the littoral station (2006-2009) than in the central area. In the littoral zone, the deformities progressively decreased and by 2010 reached values similar to those observed in the central area (2000-2002, 2010). This decrease was mainly due to the reduction of severe deformities, thus indicating an environmental quality recovery of this littoral sector. Chemical analysis revealed that the higher incidence of deformities in the littoral zone was not caused by heavy metal contamination, unless they may have contributed to a joint action with other toxicants. The present study on Lake Trasimeno provided additional evidence that chironomid mouthpart deformities can be used in biomonitoring programs to evaluate sediment contamination by toxicants. Since mouthpart deformities may also be induced by compounds not included in routine chemical analyses, they may better reflect sediment quality than chemical analysis alone.     

Monitoring metal contamination levels and fecal pollution in clam (Tapes decussatus) collected from Izmir Bay (Turkey)

The aim of this study was to monitor the heavy metal contents and fecal pollution in Tapes decussatus (carpet shell clam) from Izmir Bay (Eastern Aegean). Bivalve mollusks were sampled on January, March, July, and October 2007 in the Izmir Bay. Izmir Bay is one of the great natural bays of the Mediterranean. Concentrations of heavy metals were determined in the clams from the different seasons. Fecal coliform densities were determined to evaluate the degree of water pollution and clams’ microbiological accumulation of the classical microbial pollution indicators. The concentration of heavy metals in T. decussatus from Izmir Bay were Hg 0.044–0.13; Cd 0.026–0.24; Pb 0.38–1.2; Cr 2.3–3.7; Cu 6.4–8.4; Zn 56.0–81.8, and Ni 8.1–9.6 μg/g (dry weight). The maximum values were generally obtained in July and March except Ni. This study found that the levels of heavy metals except Cr in T. decussatus were below Spanish and European Communities legislations for shellfish as food. Microbial pollution indicators (heterotrophic bacteria and fecal coliform) were measured in T. decussatus. Maximum heterotrophic bacteria and fecal coliforms were recorded in the winter while the lowest were detected in summer.