Mark D. Scrimshaw

Polybrominated diphenyl ether (PBDE) flame retardants.

Polybrominated diphenyl ether, PBDE, flame retardants are now a world-wide pollution problem reaching even remote areas. They have been found to bioaccumulate and there are concerns over the health effects of exposure to PBDEs, they also have potential endocrine disrupting properties. They are lipophilic compounds so are easily removed from the aqueous environment and are predicted to sorb onto sediments and particulate matter or to fatty tissue, aiding their distribution throughout the environment. PBDEs are structurally similar to PCBs and DDT and, therefore, their chemical properties, persistence and distribution in the environment follow similar patterns. Concentrations of PBDEs found in environmental samples are now higher than those of PCBs. Evidence to date demonstrates that PBDEs are a growing problem in the environment and concern over their fate and effects is warranted. The manufacture of reactive and additive flame retardants is briefly discussed and their fate and behaviour in the environment is assessed. PBDE toxicology is reviewed and methods of analysis are evaluated.

Conditions influencing the precipitation of magnesium ammonium phosphate.

Struvite precipitation in wastewater treatment works has caused substantial operational problems since the early 1960s. Struvite, magnesium ammonium phosphate hexahydrate (MgNH4PO4 6H2O), is a white inorganic crystalline mineral that precipitates in places with increased turbulence such as pumps, aerators and pipe bends. Batch experiments were conducted to examine the influence of a number of physical and chemical parameters on struvite crystallisation. This was undertaken by dosing a medium of de-ionised water with varying concentrations of Mg2+, NH4+ and PO4(3-) ions. Preliminary experiments found that struvite could be precipitated out of solution at pH 10 and increasing the ion concentration stoichiometrically could increase crystal yield. Increasing the NH4+ concentration increased purity of the precipitate. As reaction time was increased from 1 to 180 min, crystal size was found to increase from 0.1 to 3mm.

Alternative antifouling biocides

In response to increasing scientific evidence on the toxicity and occurrence of organotin residues from antifouling paints in the aquatic environment, the use of triorganotin antifouling products was banned on boats of less than 25 m length in many countries during 1987. The use of tributyltin (TBT) products on small boats was superseded by products based on copper, containing organic booster biocides to improve the efficacy of the formulation. Available information and evidence on the occurrence, fate and toxicity of these biocides is reviewed. It is concluded that increased copper concentrations in the aquatic environment, due to the increased use of copper-based antifoulants, do not have significant effects on marine ecosystems. However, lack of validated analytical methods, limited monitoring data, and very little information about the fate and toxicity of the booster biocides in the aquatic environment, make accurate risk assessments in relation to these compounds difficult. Copyright

Prediction of the bioaccumulation factors and body burden of natural and synthetic estrogens in aquatic organisms in the river systems

This study undertakes an initial prediction of the bioaccumulation factors and body burden of the steroid estrogens, estrone, estradiol, estriol and ethinylestradiol in a range of aquatic organisms (plankton, benthic and free-living invertebrates and fish) in river systems using a food-web model. These data are compared to that derived from less complex predictions based on octanol-water partition coefficient and molecular connectivity index. The model predicted that bioaccumulation of steroid estrogens occurred in all organisms, however, the values were small, and the maximum and minimum bioaccumulation factors in this study were found in the fish at the lowest trophic level with ethinylestradiol (332) and the fish at the highest trophic level with estriol (1.8), respectively. Moreover, the bioaccumulation factors were sensitive to the metabolic rates of the estrogens in the free living organisms, while the concentration of estrogens in sediment was a significant factor in determining these values in benthic invertebrates. Biomagnification contributed little to the overall bioaccumulation, but the importance increased in fish exposed to ethinylestradiol. The predicted bioaccumulation factors from the food web model were generally smaller than the calculated bioconcentration factors from the simpler octanol-water partition coefficient/molecular connectivity index based estimates. Compared to literature measured data, the predicted values for fish were approximately 1000 times less than the values observed in laboratory tests, while for invertebrates, the modeled values were less than two orders of magnitude below laboratory results. However, the model predicted a similar bioconcentration factor for plankton in relation to experimental data for Chlorella vulgaris for estrone and estriol.

Occurrence of Four Biocides Utilized in Antifouling Paints, as Alternatives to Organotin Compounds, in Waters and Sediments of a Commercial Estuary in the UK

Waters and sediments from marinas, mooring areas and coastal sites in the Blackwater Estuary, Essex, UK were collected and analysed for the occurrence of Irgarol 1051, chlorothalonil, dichlofluanid and diuron. These biocides were introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin (TBT) in 1987. Samples were collected at the end of one boating season (October 98) and the beginning of the following one (June 99). An input survey was also undertaken with the objective of identifying input sources of these biocides and quantifying the amounts used in the catchment area. The results of the monitoring exercise exhibited some agreement with the findings of the input survey. Irgarol, dichlofluanid and chlorothalonil were detected at a number of sites. Concentrations of Irgarol and dichlofluanid in waters and sediments were enhanced after the boating season and the highest ones were relatively enhanced within the marinas, implying that use in antifoulants accounted for the inputs. Contamination with chlorothalonil was more widespread, consistent with its use in agriculture.

Determination of endocrine disrupters in sewage treatment and receiving waters

The presence of numerous endocrine-disrupting compounds (EDCs) in surface waters and sediment has been primarily attributed to their incomplete removal in the sewage-treatment process. Determination of these chemicals is required in order to assess their environmental impact. An overview is given on the biological and analytical methodologies used, both individually and in combination, to determine estrogenicity and quantification for several EDCs present in sewage and surface-water matrices.

BIOTRANSFORMATION AND BIOCONCENTRATION OF STEROID ESTROGENS BY CHLORELLA VULGARIS

ABSTRACT The biotransformation and bioconcentration of natural and synthetic steroid estrogens by Chlorella vulgaris were investigated by using batch-shaking experiments with incubation for 48 h in the light or dark. Estradiol and estrone were interconvertible in both light and dark conditions; however, this biotransformation showed a preference for estrone. In the light, 50% estradiol was further metabolized to an unknown product. Apart from biotransformation, estrone, as well as hydroxyestrone, estriol, and ethinylestradiol, was relatively stable in the algal culture, whereas estradiol valerate was hydrolyzed to estradiol and then to estrone within 3 h of incubation. All of the tested estrogens exhibited a degree of partitioning to C. vulgaris; however, the concentrations of estriol, hydroxyestrone, ethinylestradiol, and estradiol valerate were always below the quantification limits. For estradiol and estrone, the partitioning of these estrogens in the algal extracts to the filtrates was <6% of the total amount present. The average concentration factor for estrone was ca. 27; however, the concentration factor for estradiol was not reported since no equilibrium was reached between the aqueous solution and that within the cells due to continuing biotransformation.

The effects of natural and synthetic steroid estrogens in relation to their environmental occurrence.

Laboratory-based acute toxicity data and physiological studies relating to natural and synthetic steroid estrogens in a range of animals and plants are reviewed. Steroid estrogens may induce adverse effects in animals that do or do not express the estrogen receptor, and in plants, and they may mimic other hormones or induce nonestrogenic effects. Although the findings of such studies should be treated with caution when extrapolated to possible environmental effects, the available data indicate that a wide range of effects may be manifested in a diversity of species. The environmental occurrence of the compounds and possible environmental exposure routes are also reviewed and discussed in relation to the laboratory-based acute toxicity data. While there are likely to be difficulties in relating some of the observed laboratory data to possible environmental effects, studies undertaken on fish are directly relevant because exposure pathways and concentrations were related to those occurring in the environment. Effects that may occur in the environment are discussed in relation to their significance to the individual and at the species level.

Future water quality monitoring - Adapting tools to deal with mixtures of pollutants in water resource management

Environmental quality monitoring of water resources is challenged with providing the basis for safeguarding the environment against adverse biological effects of anthropogenic chemical contamination from diffuse and point sources. While current regulatory efforts focus on monitoring and assessing a few legacy chemicals, many more anthropogenic chemicals can be detected simultaneously in our aquatic resources. However, exposure to chemical mixtures does not necessarily translate into adverse biological effects nor clearly shows whether mitigation measures are needed. Thus, the question which mixtures are present and which have associated combined effects becomes central for defining adequate monitoring and assessment strategies. Here we describe the vision of the international, EU-funded project SOLUTIONS, where three routes are explored to link the occurrence of chemical mixtures at specific sites to the assessment of adverse biological combination effects. First of all, multi-residue target and non-target screening techniques covering a broader range of anticipated chemicals co-occurring in the environment are being developed. By improving sensitivity and detection limits for known bioactive compounds of concern, new analytical chemistry data for multiple components can be obtained and used to characterise priority mixtures. This information on chemical occurrence will be used to predict mixture toxicity and to derive combined effect estimates suitable for advancing environmental quality standards. Secondly, bioanalytical tools will be explored to provide aggregate bioactivity measures integrating all components that produce common (adverse) outcomes even for mixtures of varying compositions. The ambition is to provide comprehensive arrays of effect-based tools and trait-based field observations that link multiple chemical exposures to various environmental protection goals more directly and to provide improved in situ observations for impact assessment of mixtures. Thirdly, effect-directed analysis (EDA) will be applied to identify major drivers of mixture toxicity. Refinements of EDA include the use of statistical approaches with monitoring information for guidance of experimental EDA studies. These three approaches will be explored using case studies at the Danube and Rhine river basins as well as rivers of the Iberian Peninsula. The synthesis of findings will be organised to provide guidance for future solution-oriented environmental monitoring and explore more systematic ways to assess mixture exposures and combination effects in future water quality monitoring.

Comparative environmental assessment of biocides used in antifouling paints.

In response to increasing scientific evidence on the toxicity and persistence of organotin residues from antifouling paints in the aquatic environment, the use of triorganotin antifouling products was banned on boats of less than 25 m length in many countries during 1987. Alternatives to tributyltin (TBT) paint are mainly copper based coatings containing organic booster biocides to improve the efficacy of the formulation, and have been utilised on small boats for the last 10 years. With policies encouraging a total ban on TBT, it is expected that these biocides will be used to a greater extent in the future. Limited data and information are available on the environmental occurrence, fate, toxicity, and persistence of these biocides, and thus any decisions on policies regulating antifoulants cannot be fully informed. In this study, a multicriteria comparison of alternative biocides, based on a general assessment of available information in the literature, provided support for the use of the precautionary principle with respect to policies on antifouling products. This assessment was validated by a more detailed comparison of four selected biocides and TBT. Results indicate that TCMS pyridine and TCMTB demonstrate environmental characteristics similar to TBT and thus detail risk assessments are needed before their use is permitted. The widespread use of the other biocides should be allowed only after research to fill the gaps in knowledge with respect to their toxicity and persistence in aquatic environments.