Modelling future soil chemistry at a highly polluted forest site at Istebna in Southern Poland using the "SAFE" model

The multi-layer dynamic model SAFE was applied to the forested catchment Istebna (Southern Poland), to study recovery from acidification. Environmental pollution in the area has been historically high. The model uses data from an intensive monitoring plot established in 1999 in a spruce stand, which was planted in 1880. Observations showed that the soil was depleted of base cations. The measured base saturation in 1999 was between 5 and 8% in the different soil layers. Model predictions assuming full implementation of the UNECE 1999 Gothenburg Protocol and present day base cation deposition show that the base saturation will slowly increase to 20% by 2100. Despite large emission reductions, Istebna still suffers from the very high loads of acidifying input during the past decades. Soil recovery depends on future emissions especially on base cation deposition. The recovery will be even slower if the base cation deposition decreases further.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

PCDD/PCDF-Kontaminationen aus Kieselrot von Sport- und Spielanlagen

Surfaces of many sports fields, playgrounds and paths in Germany are covered with red slag ?Kieselrot”. Kieselrot is extremely high contaminated by polychlorinated dibenzodioxines and dibenzofurans. Mean PCDD/F-concentration in surface layers of 35 locations in Hessen is 45 500 ng I-TE/kg. PCDD/F-contents range from 1 000 to 250 ng I-TE/kg within 10 cm under surface layers and from 6 000 to 600 ng I-TE/kg in top soils of three metres wide peripheral areas. Concentration in subsoils is a function of depth (n=18, r=?0,741), concentration in topsoils of peripheral areas is a function of distance from large sports fields (n=14, r=?0,881) or small sportsfields (n=23, r=?0,742), respectively. A 15 metres wide and 10 centimetres deep peripheral area contains 0,8 g I-TE PCDD/F. The pollution of surroundings and further observations indicate that ?Kieselrot-areas” must be regarded as important dioxin sources.     

Endocrine disruption of water and sediment extracts in a non-radioactive dot blot/RNAse protection-assay using isolated hepatocytes of rainbow trout

Goal, Scope and Background In order to evaluate the estrogenic activity of sediments and XAD water extracts of selected sites of the catchment area of the River Neckar, a river system in Southern Germany, an integrative assessment approach was used to assess the ecological hazard potential of endocrine-disrupting compounds in sediment and water. Methods The approach is based on estrogen receptor-mediated vitellogenin synthesis induced in isolated hepatocytes of rainbow trout and quantified in a non-radioactive dot blot/RNAse protection-assay in parallel to comprehensive chemical analyses of estrogenic substances. Results and Discussion Numerous investigated extracts revealed an estrogen activity comparable to that of the positive control (1 nM 17?-estradiol corresponding to 270 ng/L in the test medium). Based on a concentration factor of 30 in the extracts and a recovery of XAD resins of approximately 80 %, 17?-estradiol equivalent concentrations between 20 and 26.7 ng/L could be calculated downstream of a sewage treatment plant (< 0.1 ng/L for a reference site). A comparison of the bioassay-derived Bio-TEQs (toxicity equivalents) and the Chem-TEQs revealed a high correlation with a Pearson coefficient of 0.85, indicating that the same ranking of the samples could be obtained with respect to the endocrine disrupting potential with both chemical and bioanalytical analysis. However, the TEQ concentrations computed from chemical analyses were significantly lower than the bioassay-derived TEQ concentrations. In fact, in none of the samples, more than 14 % of the vitellogenin-inducing potency could be attributed to the substances (steroids, alkylphenols, bisphenol A, diethylstilbestrol) analyzed. A comparison of the endocrine disrupting potential of sediments extracted by the solvents acetone and methanol revealed lower biological effects for acetone-extracted samples. Possible reasons may be a masking of endocrine effects in acetone extracts by cytotoxicity, a low extraction efficiency of the solvent acetone, or anti-estrogen potencies of some extracted sediment compounds. Using a mass balance approach, the contribution of the compounds analyzed chemically (Chem-TEQs) to the total endocrine activity (Bio-TEQs) was calculated. Based on the very low detection limits, particularly of the steroids with their high TEF factors, results revealed that a calculation of the Chem-TEQs is associated with considerable scale inaccuracy: Whereas only 7-15 % of the biological effectiveness (Bio-TEQs) could be explained by endocrine substances identified above the detection limits, the assumption of concentrations slightly below the given detection limits would result in a significant over estimation (137-197 %) of the Bio-TEQs. Even the interassay variation of the dot blot assay with different fish donors for primary hepatocyte (factor 2 - 2.5) is relatively low, when compared to the large range of the Chem-TEQ concentrations (factor 20) obtained when applying different modes of calculation. Conclusions and Outlook Overall, only a minor portion of the endocrine activity detected by bioassays could be linked to compounds identified by chemical analysis. In vitro assays for assessment of endocrine activities are useful as sensitive integrating methods that provide quantitative estimates of the total activity of particular receptor-mediated responses. Although discrepancies may also result from different bioanalytical approaches, it is overall likely that bioanalytical and not chemical analytical approaches give the correct estimate of endocrine disrupting potencies in environmental samples. As a conclusion, assessment of endocrine disruption based on chemical analysis alone does not appear sufficient and further research into the spectrum of substances with potential endocrine activity as well as into additive or even synergistic effects in complex environmental samples is urgently needed.     

Modeling recovery of Swedish ecosystems from acidification

Dynamic models complement existing time series of observations and static critical load calculations by simulating past and future development of chemistry in forest and lake ecosystems. They are used for dynamic assessment of the acidification and to produce target load functions, that describe what combinations of nitrogen and sulfur emission reductions are needed to achieve a chemical or biological criterion in a given target year. The Swedish approach has been to apply the dynamic acidification models MAGIC, to 133 lakes unaffected by agriculture and SAFE, to 645 productive forest sites. While the long-term goal is to protect 95% of the area, implementation of the Gothenburg protocol will protect approximately 75% of forest soils in the long term. After 2030, recovery will be very slow and involve only a limited geographical area. If there had been no emission reductions after 1980, 87% of the forest area would have unwanted soil status in the long term. In 1990, approximately 17% of all Swedish lakes unaffected by agriculture received an acidifying deposition above critical load. This fraction will decrease to 10% in 2010 after implementation of the Gothenburg protocol. The acidified lakes of Sweden will recover faster than the soils. According to the MAGIC model the median pre-industrial ANC of 107 microeq L(-1) in acid sensitive lakes decreased to about 60 microeq L(-1) at the peak of the acidification (1975-1990) and increases to 80 microeq L(-1) by 2010. Further increases were small, only 2 microeq L(-1) between 2010 and 2040. Protecting 95% of the lakes will require further emission reductions below the Gothenburg protocol levels. More than 7000 lakes are limed regularly in Sweden and it is unlikely that this practice can be discontinued in the near future without adverse effects on lake chemistry and biology.     

Bioconcentration potential (BCP) of 2,3,7,8-Tetrachlorodibenzop-dioxin (2,3,7,8-TCDD) in terrestrial organisms including humans

The bioconcentration factors (BCFs) of 2,3,7,8-TCDD in adipose tissue of rats, beef cattle and monkeys have been calculated. The bioconcentration potential of TCDD in man was calculated by two indirect methods: 1) from daily intake of TCDD and its measured concentrations in adipose tissues and 2) from measured half-life and measured concentrations in body fat at steady state using a linear one compartment pharmacokinetic model. The BCFs in humans calculated by both methods are between 104 and 206, or 153, respectively.     

The vulnerability of hydropower production in the Zambezi River Basin to the impacts of climate change and irrigation development

The Zambezi River Basin in southern Africa is relatively undeveloped from both a hydropower and irrigated agriculture perspective, despite the existence of the large Kariba and Cahora Bassa dams. Accelerating economic growth increases the potential for competition for water between hydropower and irrigated agriculture, and climate change will add additional stresses to this system. The objective of this study was to assess the vulnerability of major existing and planned new hydropower plants to changes in climate and upstream irrigation demand. Our results show that Kariba is highly vulnerable to a drying climate, potentially reducing average electricity generation by 12 %. Furthermore, the expansion of Kariba generating capacity is unlikely to deliver the expected increases in production even under a favourable climate. The planned Batoka Gorge plant may also not be able to reach the anticipated production levels from the original feasibility study. Cahora Bassa’s expansion is viable under a wetting climate, but its potential is less likely to be realised under a drying climate. The planned Mphanda Nkuwa plant can reach expected production levels under both climates if hydropower is given water allocation priority, but not if irrigation is prioritised, which is likely. For both Cahora Bassa and Mphanda Nkuwa, prioritising irrigation demand over hydropower could severely compromise these plants’ output. Therefore, while climate change is the most important overall driver of variation in hydropower potential, increased irrigation demand will also have a major negative impact on downstream plants in Mozambique. This implies that climate change and upstream development must be explicitly incorporated into both project and system expansion planning.