Part IV: Fitness for Aquatic Systems Long-term Forecast: Key to groundwater protection

Groundwater resources are at risk from pollution, climate change and land-management practices. Long-term forecast is a tool to demonstrate future development and to support decisions on measures which can be implemented, controlled and eventually corrected. As the basis for preventive action, a forecast can be viewed as a key to groundwater protection. The soil zone plays a vital role in groundwater protection. Research on soil and groundwater trends, as affected by change of climate and/or land-management practices, is on the agenda. Integrated research is necessary to develop numerical soil-water system models reflecting all relevant transport processes at various scales. Even relatively simple problems like forecasting pollutant release from contaminated materials are difficult to resolve. Batch tests may be sufficient in low-risk cases. At higher risk when contaminated substrates are chosen for deposition on a large scale, a thorough characterization of the materials is necessary covering all aspects of stability and possible changes of the environment.     

Formation and emission of chloroanisoles as indoor pollutants

GOAL, SCOPE AND BACKGROUND: Complaints by residents of frame-houses about musty odour in the houses has become an increasing problem within the last years. An additional problem is that the odour is transferred to clothes and skin. The persons themselves do not recognize the smell after a while because of adaptation. Serious social problems are the result. For a long time, the smell was explained to be from mould due to construction-based humidity problems. However, in an increasing number of houses, no indications were found for elevated levels of mould growth. METHODS: Air and material samples were taken from 5 houses, which show typical musty odours, and analysed with respect to chlorophenols and chloroanisoles. Additionally, some samples were analysed for lindane and its metabolites, because lindane was commonly used together with pentachlorophenol (PCP) for wood protection. RESULTS AND DISCUSSION: Meticulous analysis resulted in the identification of chloroanisoles, mainly 2,3,4,6-tetrachloroanisole. These substances are known from corky wines and from contamination of food from pentachlorophenol (PCP) treated pallets and result from microbiological metabolic processes. Pentachlorophenol was commonly used to protect wood from fungi in Germany mainly in the later 60s and 70s. Details of these processes, as well as effective methods to identify chloroanisoles in the problem houses, are described. CONCLUSIONS: Chloroanisoles formed by metabolism of PCP have been well known to contaminate food or wine. Here, they were identified and are probably responsible for the musty odours in the frame houses. Since it is quite clear that these substances were not components of building materials used in the houses, an explanation for chloroanisole formation is proposed. Localized dampness probably favours microbial growth associated with metabolic conversion of chlorophenols to the corresponding chloroanisoles, primarily 2,3,4,6-tetrachloroanisol, which spread throughout the buildings, resulting in the observed odours. RECOMMENDATIONS AND OUTLOOK: The group of chloroanisoles has been recognized as important indoor pollutants as they possess musty odours at extremely low concentrations, e.g. for 2,4,6-trichloroanisole in a range of 5-10 ppt in air (Staples 2000). On the basis of currently available toxicological data, exposure of the occupants to the concentrations of chloroanisoles measured is not associated with a health risk. No correlation could be observed between concentrations of chloroanisoles and PCP in house dust and indoor air. However, chloroanisoles are good indicators for possible PCP-treatment of wood in frame houses and their detection should initiate investigations on PCP contamination. Research is continuing to identify the microorganisms involved and to devise a remediation procedure for affected houses.     

Biological variation in sensitivity to N-heterocyclic PAHs; effects of acridine on seven species of micro-algae

The toxicity of the nitrogen (N) heterocyclic polyaromatic hydrocarbon (PAH) acridine was tested for seven species of microalgae: Scenedesmus acuminatus, Selenastrum capricornutum, Chlamydomonas eugametos, Staurastrum chaetoceras, Staurastrum manfeldtii, Navicula salinarum and Nitzschia sigma. The effect of acridine on the algae was studied in a 96-h growth test, in which growth rates were determined using cell numbers and biovolume. The obtained EC50 values (for growth rates based on cell numbers) ranged from 0.08 mg litre(-1) for N. sigma to 0.78 mg litre(-1) for C. eugametos and N. salinarum. Effect concentrations based on biovolume were slightly higher for most species. Metabolism of acridine was observed for one species (S. capricornutum), but this capacity did not result in a very different tolerance. Acridine toxicity was neither related to taxonomical background (green algae versus diatoms) nor to original habitat of the species (planktonic or benthic, eutrophic or oligo-mesotrophic). The presence of near-UV radiation during the incubation might explain the higher toxicity of acridine than is expected on basis of QSAR derived narcotic toxicity.     

Mercury in two fish species from the Paraná river floodplain, Paraná, Brazil

Total mercury concentrations were measured in dorsal muscle tissue of two edible fish species, Prochilodus scrofa 'curimba' and Pseudoplatystoma corruscans 'pintado', respectively detritivorous and carnivorous. Fish species were sampled monthly between February 1993 and January 1994 and bimonthly between April 1994 and February 1995 in three subsystems of Paraná river' system (Ivinhema River/Lake Patos; Baía River/Lake Guaraná and Paraná River/Cortado Channel), between Paraná and Mato Grosso do Sul. Total mercury was determined by HNO3/H2SO4/V2O5 digestion, SnCl2 reduction, and vapour generation method analysis (CGCH 900), adapted to Atomic Absorption Spectrometer (CGAA 7000 ABC). The mean mercury concentrations varied from 82.0 to 310.5 ng g(-1) and from 68 to 294.4 ng g(-1) in 'curimbas' and 'pintados', respectively. Mercury level increases in sexually mature 'curimbas'. Mercury values detected do not exceed the prevailing criteria for issuance of fish consumption advisories (< 500 ng g(-1)).     

Results from the first year of the Swedish dioxin survey

PCDD/F levels are presented for food baskets, raw and fried herring, wolf muscle and moose tallow collected from the same area, three burbot liver samples, a sediment core from the Baltic Sea and leach water from three garbage dumps. Levels in food baskets were at or below detection limits making the estimation of intake via the diet difficult. Frying herring produces no net change in PCDD/F levels. Moose have lower PCDD/F levels than wolf from the same area. Levels in burbot liver samples are much higher near industrial discharges than in a more undisturbed area. The top 4 cm of the sediment core contain the highest levels of PCDD/F. Thereafter the levels drop and reach a low level. This low level is probably caused by contamination during sampling and is not evidence of PCDD/F presence far back in time. Leach water from city dumps contains low levels of PCDD/F but that from a dump that takes industrial wastes had higher levels and a different congener pattern.     

Surface catalyzed formation of polychlorinated dibenzo-p-dioxins/dibenzofurans during municipal waste incineration

A series of reactions was carried out on different surfaces using carbon and CuCl₂, and KCl or HCl as a Cl-source. The PCDD/PCDF congener distribution was seen to vary to a great extent but the isomer distribution remained fairly constant. It is concluded that thermodynamic properties are largely responsible for the PCDD/PCDF isomer distribution. With pentachlorobenzene Cl₂ elimination, assisted by oxygen, appears to be the major pathway for PCDD/PCDF formation.     

Formation of mutagenic activity during surface water preozonization and its removal in drinking water treatment

The influence of preozonization, coagulation and double layer filtration on formation and removal of mutagenic activity was studied using XAD-8 extracts collected from neutral and acidic solutions and assaying them in the Salmonella typhimurium microsomal assay.Preozonization of surface water produced direct acting frame shift mutagens which were adsorbed on XAD-8 from neutral solutions. This phenomenon was shown to be dependent on the ozone dose applied. Coagulation with different chemicals and subsequent direct filtration partially reduced the mutagenic activity.     

Determination of metoxuron and 3-chloro-4-methoxyaniline via direct derivatization with heptafluorobutyric anhydride and GC-ECD

The phenylurea herbicide metoxuron and its main metabolite, 3-chloro-4-methoxyaniline, can be determined rapidly in aqueous samples via extraction, derivatization with heptafluorobutyric anhydride (HFBA), washing with an aqueous bufferof pH 8, and analysis by capillary GC with electron capture detection. Linear calibration curves are obtained over two orders of magnitude, and the detection limit for the HFB derivatives is about 0.5 pg. The method has successfully been applied to several types of water samples.     

Analyse statistique correlative de l'influence des proprietes des sols sur l'adsorption d'herbicides et insecticides

A statistical correlative study (simple and multiple) between 14 herbicides and insecticides and composition of 51 soil samples has been performed by considering top- and sub-soil horizons, separately. Results point out the suitability of these regression models as a predictive tool to determine quantitatively the adsorption of numerous pesticides in soils mainly the more soluble compounds.     

Analysis of Ah receptor pathway activation by brominated flame retardants

Brominated flame-retardants (BFRs) are used as additives in plastics to decrease the rate of combustion of these materials, leading to greater consumer safety. As the use of plastics has increased, the production and use of flame-retardants has also grown. Many BFRs are persistent and have been detected in environmental samples, raising concerns about the biological/toxicological risk associated with their use. Most BFRs appear to be non-toxic, however there is still some concern that these compounds, or possible contaminants in BFRs mixtures could interact with cellular receptors. In this study we have examined the interaction of decabromodiphenyl ether, Firemaster BP4A (tetrabromobisphenol A), Firemaster PHT4 (tetrabromophthalic anhydride), hexabromobenzene, pentabromotoluene, decabromobiphenyl, Firemaster BP-6 (2,2^′,4,4^′,5,5^′-hexabromobiphenyl) and possible contaminants of BFR mixtures with the Ah receptor. Receptor binding and activation was examined using the Gel Retardation Assay and increased expression of dioxin responsive genes was detected using the reporter gene based CALUX assay. The results demonstrate the ability of BFRs to activate the AhR signal transduction pathway at moderate to high concentrations as assessed using both assays. AhR-dependent activation by BFRs may be due in part to contaminants present in commercial/technical mixtures. This was suggested by our comparative analysis of Firemaster BP-6 versus its primary component 2,2^′,4,4^′,5,5^′-hexabromobiphenyl. Some technical mixtures of brominated flame-retardants contain brominated biphenyls, dioxins or dibenzofurans as contaminants. When tested in the CALUX assay these compounds were found to be equivalent to, or more active than their chlorinated analogues. Relative effective potency values were determined from dose response curves for these brominated HAHs.