Worldwide occurrence and effects of antifouling paint booster biocides in the aquatic environment: a review

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Replacement products are generally based on copper metal oxides and organic biocides. This ban has led to an increase in alternative coating products containing the above biocides. The most commonly used biocides in antifouling paints are: Irgarol 1051, diuron, Sea-nine 211, dichlofluanid, chlorothalonil, zinc pyrithione, TCMS (2,3,3,6-tetrachloro-4-methylsulfonyl) pyridine, TCMTB [2-(thiocyanomethylthio) benzothiazole], and zineb. Since 1993, several studies have demonstrated the presence of these biocides in European coastal environment as a result of their increased use. More recently, the presence of these biocides was also revealed in waters from Japan, United States, Singapore, Australia and Bermuda. This paper reviews the currently available data on the occurrence of these biocides in the aquatic environment. Some data dealing with the environmental fate, partitioning, behaviour and risk assessment of antifouling paint booster biocides are also reported in order to discuss the detected levels of contamination.     

Polycyclic aromatic hydrocarbons in the bulk precipitation and surface waters of Northern Greece

Bulk (wet and dry) precipitation and surface water sampling was undertaken in the main plain of central Macedonia in Northern Greece. Fourteen polycyclic aromatic hydrocarbons (PAHs) included in the US EPA's priority pollutant list were analysed. The concentrations determined in bulk precipitation were in general within the range of values worldwide reported. Concentrations were highest in the cold months. Deposition fluxes of PAHs were of the same order of magnitude as reported data. The greatest values were found when high concentrations of PAHs in precipitation coincided with large precipitation amounts. The concentrations of PAHs in surface waters (main rivers, tributaries, ditches, etc) were in general lower than those in bulk precipitation, and among the lowest reported for European rivers, excepting Np and Ph. Bulk deposition and domestic effluents are suggested as being the main PAH sources into surface waters.     

Organochlorine contaminants in eggs of the yellow-legged gull (Larus cachinnans michahellis) in the North Eastern Mediterranean: is this gull a suitable biomonitor for the region?

Levels of eight PCB congeners and thirteen organochlorine pesticides were measured in eggs sampled at four yellow-legged gull colonies from the Aegean Sea (NorthEastern Mediterranean) in 1997. There were no significant differences among colony areas in the median concentrations in any of the pollutants whereas cluster analyses did not generally reveal reasonable pollution patterns. The maximum concentrations of four congeners were found at Kinaros colony and of nine compounds were found at Lipsos colony. Fingerprints in both groups were similar in all areas. Of PCBs, congener 28, 118, 138, 180 and of pesticides beta-BHC and 2,4'-DDD were prominently dominant suggesting a particular pollution pattern in this region. Statistically significant correlations were found between most of the higher PCBs in all areas studied. The DDT metabolites correlated mostly with other OCs. We suggest that regional pollution by both groups is not adequately reflected in the eggs of this gull probably due to its extensive scavenging habits and, though information is needed from more colonies, it seems to be a poor biomonitor for organochlorines in this region.     

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO₂-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10 mg L⁻¹) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the OH radical attack. Moreover, products resulted from the cleavage of the amide and NHdichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.     

Accumulation profiles of persistent organochlorines in liver and fat tissues of various waterbird species from Greece

Waterbirds are particularly subject to accumulation of persistent organic pollutants (POPs) that have been shown to constitute a major hazard for this group of birds. Liver and fat tissue from ten species belonging to the orders Ciconiformes (Ardeidae, Ciconiidae, Phoenicopteridae) and Pelicaniformes (Pelecanidae, Phalacrocoracidae) were used as bioindicators in order to assess environmental pollution by POPs (HCHs, DDTs, cyclodienes, PCBs) in Greek wetlands. To our knowledge, this is the first study on POPs in livers of water birds in Greece and Eastern Mediterranean area. The DDTs consisted mainly of p,p'-DDE with percentages over 60% in the great majority of the samples. The highest summation SigmaDDT concentrations were measured in the liver and subcutaneous fat of Phoenicopterus rubber and in Ardea purpurea liver (15565, 24706 and 10406 ng g(-1) wet weight, respectively). Low concentrations of cyclodienes (Cycls) and HCHs were detected occasionally and the contamination pattern of OCPs in most species of waterbirds followed the order summation SigmaDDTs> summation SigmaCycls> summation SigmaHCHs. Individual values of total PCBs reached the levels of 4468 and 3252 ng g(-1) wet weight, for Nycticorax nycticorax and Egretta garzetta samples respectively. Some of the recorded differences in organochlorine concentrations could be due to different causes of death, with a subsequent effect on body lipid levels. Organochlorine pesticides and PCBs residues were lower than those commonly associated with mortality and reduced reproductive success in most species. However, low level exposure to these contaminants may constitute one of the many stressors that in combination could adversely affect bird populations.     

Organochlorine residues in blood of cinereous vultures and Eurasian griffon vultures in a northeastern Mediterranean area of nature conservation

In the National Park of Dadia-Lefkimi-Soufli Forest (Dadia NP, Greece), seven "target" PCBs and 16 organochlorine pesticides (OCs) were analysed in blood samples of cinereous vultures (Aegypius monachus) and Eurasian griffon vultures (Gyps fulvus). PCB congeners 138, 153 and 180 predominated in both species' blood samples. In both species, no differences were detected in congener levels between successive age classes, but in cinereous vulture, there were significant differences between adult and nestling in levels of PCB 28, 52, 101, 118 and between nestling and immature in levels of PCB 101. Regarding pesticides, p,p'-DDE dominated in both vultures followed by β-HCH, lindane and endosulfan sulphate, but ∑OCs were higher in griffon vulture. Significant differences were detected only between nestling and sub-adult cinereous vultures in heptachlor levels and between nestling and adult in p,p'-DDT. The origin of pollutants differs between the two vulture species and pollution patterns may not reflect those at Dadia NP.     

Passive sampling of selected pesticides in aquatic environment using polar organic chemical integrative samplers

Purpose  

Polar chemical integrative samplers (POCIS) were examined for their sampling efficiency of 12 pesticides and one metabolite commonly detected in surface waters. Laboratory-based calibration experiments of POCISs were conducted. The determined passive sampling rates were applied for the monitoring of pesticides levels in Lake Amvrakia, Western Greece. Spot sampling was also performed for comparison purposes.     

Dissipation and runoff transport of metazachlor herbicide in rapeseed cultivated and uncultivated plots in field conditions

The environmental fate of metazachlor herbicide was investigated under field conditions in rapeseed cultivated and uncultivated plots, over a period of 225 days. The cultivation was carried out in silty clay soil plots with two surface slopes, 1 and 5 %. The herbicide was detectable in soil up to 170 days after application (DAA), while the dissipation rate was best described by first-order kinetics and its half-life ranged between 10.92 and 12.68 days. The herbicide was detected in the soil layer of 10–20 cm from 5 to 48 DAA, and its vertical movement can be described by the continuous stirred tank reactor (CSTR) in series model. Relatively low amounts of metazachlor (less than 0.31 % of the initial applied active ingredient) were transferred by runoff water. More than 80 % of the total losses were transferred at the first runoff event (12 DAA), with herbicide concentrations in runoff water ranging between 70.14 and 79.67 μg L⁻¹. Minor amounts of the herbicide (less than 0.07 % of the initial applied active ingredient) were transferred by the sediment, with a maximum concentration of 0.57 μg g⁻¹ (12 DAA), in plots with 5 % inclination. Finally, in rapeseed plants, metazachlor was detected only in the first sampling (28 DAA) at concentrations slightly higher than the limit of quantification; when in seeds, no residues of the herbicide were detected.

     

Simulation and multicriteria analysis in sustainable coastal planning: the case of aquaculture in Thermaikos Gulf, Greece

Mussel aquaculture in Thermaikos Gulf is facing a great challenge to tackle both institutional and production planning aspects. Local stakeholders are concerned about the future design of an efficient and equitable legal planning framework for the aquaculture, as well as about the improvement of production planning in order to optimize the total economic outcome of mussel activity in the area. The present paper focuses on the assessment of alternative production planning decisions, under the assumption that an efficient and socially acceptable institutional framework is already established. To this end, a case-specific decision-making tool is designed aiming to combine simulation modelling and multicriteria analysis. The main interactions between the environmental and cultivation conditions and the socio-economic parameters of the local aquaculture are specified according to a previous modelling effort concerning the long-line mussel farms of the study area. These interactions are then incorporated into a multicriteria model, which is formulated to handle the decision-making problem of selecting the best alternative planning decisions. This is actually a problem of evaluating and choosing the most promising policy options in terms of local society preferences. An integrated approach is followed, by means of an analytic hierarchy process, aiming at analysing the preferences of local community by determining the weights for a specific set of (sustainability) criteria. The relative importance of these criteria is determined through a questionnaire survey among the local stakeholders. The results from this application show that future planning policies should focus on production techniques, which are likely to enhance the quality of mussel production and, at the same time, to minimize the economic risk associated with the local occurrence of Harmful Algal Bloom events.     

Microbiological risk assessment of Agios Georgios source supplies in Northwestern Greece based on faecal coliforms determination and sanitary inspection survey

The assessment of potential risks from microbiological contamination of drinking water supplies is of greatest concern to human health. The study involves the examination of water samples from Agios Georgios source that supplies the capitals, the major towns and several villages of Arta, Preveza and Lefkada prefectures, in Northwestern Greece. The study includes the sanitary inspection survey of the source and the microbiological examination of water samples on a monthly basis during the period February 1996-June 1999 except of Augusts (n=38). The microbiological risk assessment (MRA) approach of World Health Organisation (WHO) guidelines was applied to enhance the source protection. The faecal contamination of the source water was quantified using faecal coliforms (FC) as indicator bacteria. Microbiological analyses indicate that of the 38 samples analyzed the FC failure rate (positive samples) was 63.2% according to the limit set by the 98/83 directive of the European Union. The 36.8% of the source water samples was found in conformity with WHO guidelines, 42.1% of low risk, 21.1% of intermediate risk while there was not found samples of high or very high risk. Failure rates displayed a seasonal trend being greater during the winter, decreased during spring and autumn and lower during summer. This observation was explained partially by a significant positive relationship with the rainfall amount (r(Spearmann)=0.890, P=0.001). The sanitary inspection score was found 5/10 during the whole survey period that corresponds to an intermediate risk of source contamination. The color-code classification for FC contamination was found 36.8% A (blue, no risk), 42.1% B (green, low risk) and 21.1% C (yellow, intermediate risk). The previous risks were combined for the assessment of waterborne risk, which was determined as intermediate to high; therefore there is a need for high action priority. The potential remedial actions were also suggested in order to improve the source protection of such supplies.