Organochlorverbindungen in Eiern von Wanderfalken und anderen wild lebenden Vogelarten in Baden-Württemberg

Goal and Scope

Organochlorine pollutants such as some pesticides and polychlorinated biphenyls (PCBs), dioxins and furans (PCDD/F) are highly persistent compounds in the environment. As synthetic, man-made products they are not encountered in natural ecosystems. Due to their high lipid solubility these compounds can accumulate in animals and humans, where they may exert chronically toxic and carcinogenic effects or disrupt endocrine functions and/or interfere with reproduction. Sound environmental stewardship demands continuous monitoring of such substances, assessment of their ecotoxicological risk, and reduction of excessive risk by setting appropriate standards.

Methods

The analysis of birds’ eggs is one method for the detection of organochlorine pollutants in ecosystems. In the German state of Baden-Wuerttemberg eggs of some bird species, especially Peregrine falcons, have been collected and analysed for selected persistent organic pollutants [total DDT (dichlorodiphenyl-trichloroethane), HCB (hexachlorobenzene), HCEP (heptachloroepoxide), HCH (hexachlorocyclohexane), PCBs] since the 1970s. Long-term continuous investigations yield data concerning temporal changes and regional differences in the pollution of the bio-indicators.

Results and Conclusion

Dioxin-like PCBs and total DDT were the most prominent pollutants. The Peregrine falcon (Falco peregrinus) was the most polluted bird species within the project. During the 1970s and 1980s all of the mentioned substances showed an encouraging decrease, undoubtedly because their use was banned in Germany. Analyses for PCDD/F in a small number of Peregrine falcon eggs from the period of 2000 to 2003 revealed the high level of pollution of these samples with dioxin toxicity equivalents (WHO-TEQ) from PCB and PCDD/F, which in all eggs reached the no observed effect level (NOEL) determined in osprey chicks and surpassed this threshold fivefold in the most polluted one.. Because of their great variability the pollutant concentrations in the eggs were difficult to interprete in some cases. Based on the results for the Peregrine falcon eggs of the years 2001 to 2003 a statement concerning the regional distribution of DDT and PCBs in Baden-Wuerttemberg could be made and depicted on the map. Because of their high lipid content, birds’ eggs are generally well suited as bio-indicators for the accumulation of persistent and lipophilic compounds.

Recommendations and Perspective

In spite of the significant decline of the organochlorine concentrations in the eggs of the birds investigated, the present situation is still alarming. Too many of the analytical data continue to exceed the respective national and EU-wide limit values for food and feed, and in the case of dioxin equivalents even lie above the assumed action threshold in the indicator organism. Therefore it is necessary to continue the bio-monitoring in Baden-Wuerttemberg in order to be able to recommend reduction measures where appropriate.     

Levels and trends of industrial chemicals (PCBs, PFCs, PBDEs) in archived herring gull eggs from German coastal regions

Background

Polychlorinated biphenyls [PCBs], perfluorinated compounds, and polybrominated diphenyl ethers [PBDEs] were retrospectively analyzed in archived herring gull (Larus argentatus) eggs from the North and the Baltic Sea over the last 20 years. The aim was to assess temporal trends and effects of regulatory measures.

Results

PCBs (sum of 7 congeners) were highest in eggs from the North Sea island Trischen, i.e., 3,710 to 20,760 ng/g lipid weight [lw] compared to 2,530 to 11,650 ng/g lw on the North Sea island Mellum and 4,840 to 9,190 ng/g lw on the Baltic Sea island Heuwiese. During the study period, PCBs decreased significantly. Concentrations of PFOS ranged between 46 and 170 ng/g wet weight [ww] at Trischen, 39 to 99 ng/g ww at Mellum, and 20 to 159 ng/g ww at Heuwiese. Since 2000 and 2003, concentration levels decreased in eggs from Mellum and Heuwiese, respectively. Perfluorooctanoic acid was the dominant perfluorinated carboxylic acid in the North Sea eggs (Trischen 2.0 to 74 ng/g ww; Mellum 2.6 to 118 ng/g ww), whereas perfluoroundecanoate [PFUnA] and perfluorodecanoate [PFDA] (means 3.9 ± 3.6 ng/g and 2.9 ± 2.3 ng/g ww, respectively) dominated in the Baltic Sea eggs. At all three locations, longer-chained perfluorinated carboxylic acids (perfluorononanoate, PFDA, PFUnA, perfluorododecanoate) increased during the monitoring period. PBDE concentrations (sum of 35 congeners) in eggs were in the ranges of 282 to 2,059 ng/g lw (Mellum), 116 to 1,722 ng/g (Trischen), and 232 to 2,021 ng/g lw (Heuwiese). Congeners associated with commercial Penta- and Octa-BDE formulations decreased during the study period. No decrease was observed for technical Deca-BDE.

Conclusion

Effects of regulatory measures were apparent for PCBs and Penta- and Octa-BDE, while no consistent trend is noticeable for PFOS.     

Dioxinähnliche polychlorierte Biphenyle (PCB) in der Umwelt

Goal and Scope

The state of the art on sources, transport and environmental fate, human exposure and toxicological risk assessment of dioxin-like polychlorinated biphenyls (PCB), and non dioxin-like PCB is described and summarized with focus on Germany and neighbouring countries.

Methods

Presentations and discussions of a two-days symposium in Germany are the primary source of information. The significance of dioxin-like PCB is evaluated in relation to polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). For that purpose, toxicity equivalent concentrations (TEQ) of both groups of contaminants in environmental matrices are compared.

Results and Conclusions

TEQ values of dioxin-like PCB are comparable to those of PCDD/PCDF in many environmental media; in food of animal origin PCB-TEQ is even higher. In most media, the non-ortho substituted PCB 126 has by far the highest contribution to the PCB-TEQ due to its high toxicity equivalency factor of 0.1. Atmospheric (long-range) transport obviously plays the major role for the diffuse PCB contamination of the environment. The transfer atmosphere-plant is apparently the key process for the entrance of dioxin-like PCB into terrestrial food chains.

Recommendation and Perspective

In spite of the decline of environmental contamination with PCB and PCDD/PCDF, a significant part of the general population in Germany and other European countries currently exceeds the tolerable intake of dioxin-like substances. However, also the results of a new toxicological risk assessment of non dioxin-like PCB implicate the need of further reduction of PCB exposure.     

Reviewing the relevance of dioxin and PCB sources for food from animal origin and the need for their inventory,control and management

Background

In the past, cases of PCDD/F and PCB contamination exceeding limits in food from animal origin (eggs, meat or milk) were mainly caused by industrially produced feed. But in the last decade, exceedances of EU limit values were discovered more frequently for PCDD/Fs or dioxin-like(dl)-PCBs from free range chicken, sheep, and beef, often in the absence of any known contamination source.

Results

The German Environment Agency initiated a project to elucidate the entry of PCBs and PCDD/Fs in food related to environmental contamination. This paper summarizes the most important findings. Food products from farm animals sensitive to dioxin/PCB exposure—suckling calves and laying hens housed outdoor—can exceed EU maximum levels at soil concentrations that have previously been considered as safe. Maximum permitted levels can already be exceeded in beef/veal when soil is contaminated around 5 ng PCB-TEQ/kg dry matter (dm). For eggs/broiler, this can occur at a concentration of PCDD/Fs in soil below 5 ng PCDD/F–PCB-TEQ/kg dm. Egg consumers—especially young children—can easily exceed health-based guidance values (TDI). The soil–chicken egg exposure pathway is probably the most sensitive route for human exposure to both dl-PCBs and PCDD/Fs from soil and needs to be considered for soil guidelines. The study also found that calves from suckler cow herds are most prone to the impacts of dl-PCB contamination due to the excretion/accumulation via milk. PCB (and PCDD/F) intake for free-range cattle stems from feed and soil. Daily dl-PCB intake for suckler cow herds must in average be less than 2 ng PCB-TEQ/day. This translates to a maximum concentration in grass of 0.2 ng PCB-TEQ/kg dm which is less than 1/6 of the current EU maximum permitted level. This review compiles sources for PCDD/Fs and PCBs relevant to environmental contamination in respect to food safety. It also includes considerations on assessment of emerging POPs.

Conclusions

The major sources of PCDD/F and dl-PCB contamination of food of animal origin in Germany are (1) soils contaminated from past PCB and PCDD/F releases; (2) PCBs emitted from buildings and constructions; (3) PCBs present at farms. Impacted areas need to be assessed with respect to potential contamination of food-producing animals. Livestock management techniques can reduce exposure to PCDD/Fs and PCBs. Further research and regulatory action are needed to overcome gaps. Control and reduction measures are recommended for emission sources and new listed and emerging POPs to ensure food safety.

     

Coplanare polychlorierte Biphenyle (PCB) in den Oberböden Hamburgs

Goal and Scope

In topsoil samples of areas with different land use within the agglomeration of Hamburg, the coplanar polychlorinated biphenyls PCB 77, 126 und 169 were determined to estimate the importance of coplanar PCBs in urban soils. Proportions relative to Balischmiter-PCBs (PCB 28, 52, 101, 138, 153 and 180) and PCDD/F concentrations were examined.

Methods

Soil samples were taken from different depths (litter horizon, 0–10 cm, 0–30 cm) at 24 different sites within the State territory of Hamburg. Coplanar PCBs, Ballschmiter-PCBs and PCDD/Fs were analysed by GC-MS-coupling in the soil fraction <2 mm. Congener distributions are discussed with respect to contamination sources.

Results and Conclusion

Land use and position of soil sample areas are only of subordinate importance for coplanar PCB concentration of the soil samples. The industrial centre of Hamburg (including harbour) shows higher contamination concentrations than the suburban areas. In levels, patterns and relative proportion to PCDD/F concentrations, the samples from dredging material disposal fields differ from all other samples. Calculation of coplanar TEQs related to total TEQs shows a contribution to total TEQs of 11–32% for the background (non dredging material influenced) samples.

Recommendation and Perspective

Estimation of coplanar PCB concentrations by determining Ballschmiter-PCB concentrations in top soil samples does merely work at samples which contamination is caused by the use of commercial PCB mixtures. Rating samples by TEQ concentrations, an increase of TEQs up to 30%, due to coplanar PCBs, should be reckonned. These considerations should be reason for extending the usual PCB determinations of Ballschmiter-PCBs to coplanar PCBs in more cases than is the general practice today.     

Polychlorinated -dibenzo-p-dioxins/furans and -dioxin-like biphenyls in eggs of common terns from lime island,St. Mary's river,Michigan, USA

Population collapse of common tern (Sterna hirundo) from Lime Island in the St. Mary's River, Michigan, USA were related to the 2,3,7,8-chlorine substituted dioxins, furans, dioxin-like PCBs, and other possible factors using unhatch egg target contaminant analysis. The most toxic congeners, 2,3,7,8-TCDD/DF was found in all samples at noticeable concentrations. Magnitude of sum 2,3,7,8-PCDD/DFs were within the range of 39–93?pg/g wet wt. Dioxin-like PCBs were within the range of 360–1230?ng/g wet wt. Great Toxic Equivalent Quantity (TEQ) contributions by 2,3,7,8-TCDF, 2,3,4,7,8-PeCDF, 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, and dioxin-like PCBs such as CB-77, CB-126 and CB-105 are considered greatly due to their influence of poor embryo development and consequent damage of embryos of common terns in egg injection studies. However, other organochlorines, heavy metals, and/or synergistic effects also taken in to account. On the whole, TEQs in the tern eggs were greater than the Lowest-Observable-Adverse Effect Level (LOAEL) for bald eagle (Haliaeetus leucocephalus) embryos observed in British Columbia, Canada. Concentrations of dioxin-like PCBs, dioxins, furans in the St. Mary's River food chain are at levels for concern for nesting colonial waterbirds. Eventually, the possible movements of analyzed chemicals downstream from a man-made flood event are discussed.     

Peregrine falcon egg pollutants

The role of the peregrine falcon (Falco peregrinus) as a bioindicator for the accumulation of organohalogen compounds and other persistent organic pollutants has been established in field studies. Biometric indices for damage caused by pollutants such as the shell thickness and the shell index were determined and the egg contents were analyzed for various pollutants by gas chromatography/mass spectrometry. A wide range of chemically activated luciferase expression (CALUX®) bioassays were performed on subsamples of the eggs.

The following organohalogen compounds were found in the eggs of 2009: dichlorodiphenyltrichloroethane (DDT) and dichlorodiphenyldichloroethane, heptachlor epoxide, hexachlorobenzene, dieldrin, hexachlorocyclohexane, polychlorobiphenyls and polychlorodibenzodioxins and polychlorodibenzofurans, polybromodiphenyl ethers, hexabromocyclododecane, tetrabromobisphenyl A, perfluoro compounds, and mercury. The DDT metabolite, dichlorodiphenyldichloroethene (DDE) (11,800 ng/g dry matter), was found to be the most highly concentrated egg contaminant followed by 2,2′,4,4′,5,5′-hexachlorobiphenyl (3800 ng/g). After a past general drop in pollution level, most egg contaminants presently plateau at levels that may still exceed limit values in foods of animal origin (DDE) or even toxicological thresholds (polychlorobiphenyls + polychlorodibenzodioxins, polybromodiphenyl ethers, perfluorooctanesulfonate, methylmercury).

Accumulation of DDE could be shown in peregrine falcon eggs from the uplands of Southwest Germany with elevations up to 1500 m, presumably due to its global distribution and its cold condensation in higher altitudes. In contrast, the concentration of polychlorobiphenyls in falcon eggs decreases with elevation, indicating that these pollutants originate mainly from conurbations and local industrial sites.

Significant negative correlations were found between both shell index and thickness and the concentration of Hg. A deleterious effect is also evident from a no-observed-adverse-effect level of 120 ng MeHg per gram egg determined by other authors in chronic feeding studies with ibises, which resulted in decreased egg productivity and male homosexual nesting and courtship behavior. The average Hg concentration in the peregrine falcon eggs from 2009 is almost four times higher than this level. MeHg accounted for 82.5% of the Hg present in the eggs of 2009 and 2010.

The cell test DR CALUX® for screening of dioxin-like activities can be used to detect not only the 29 regulated dioxin-like substances but also many other persistent organic pollutants with dioxin-like potencies, such as mixed halogenated dioxins/biphenyls. In our case, the results of bioanalytical screening methods showed no additional effect of other compounds with dioxin-like activity.

Ninety-three out of 177 analytes sought could be detected in the eggs. Chlorinated paraffins, organotin compounds, some pesticides that are still in use, and phthalic esters with the exception of traces of diethylhexyl phthalate could be excluded. All pollutants found in the eggs belong to substance classes banned by the Stockholm and Minamata Conventions.     

(Persistent) Organic pollutants in Germany: results from a pilot study within the 2015 moss survey

Background

Since 1990, every 5 years, moss sampling is conducted within the European moss monitoring programme to assess the atmospheric deposition of airborne pollutants. Besides many other countries, Germany takes regularly part at these evaluations. Within the European moss monitoring 2015, more than 400 moss samples across Germany were taken according to a harmonized methodology for the assessment heavy metal and nitrogen input. In a pilot programme, eight of these sites were chosen for additional investigations on a broad range of organic contaminants to evaluate their accumulation in moss and thereby their presence in atmospheric deposition in Germany. Target compound classes comprised polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and –furans (PCDD/F), dioxin-like and non-dioxin-like polychlorinated biphenyls (dl-PCB, ndl-PCB), polyfluorinated alkyl substances, classical flame retardants as well as emerging chlorinated and brominated flame retardants. In total, 120 target compounds were analysed. For some analytes, comparisons of accumulation in moss and tree leave samples were possible.

Results

Except for certain flame retardants, PFAS, and ndl-PCB, substances of all other compound classes could be quantified in moss samples of all sites. Concentrations were highest for PAH (40–268 ng g^?1) followed by emerging flame retardants (0.5–7.7 ng g^?1), polybrominated diphenyl ethers (PBDE; 0.3–3.7 ng g^?1), hexabromocyclododecane (HBCD; 0.3–1.2 ng g^?1), dl-PCB (0.04–0.4 ng g^?1) and PCDD/F (0.008–0.06 ng g^?1).

Conclusions

Results show the widespread atmospheric distribution and deposition of organic contaminants across Germany as well as the suitability of moss as bioaccumulation monitor for most of these compound classes. Compared to nearby tree leaf samples, accumulation potential of moss appeared to be higher for pollutants of high octanol–air partition coefficient (K_OA) and octanol–water partition coefficient (K_OW).

     

GIS-basierte Modellierung von Gewässerimmissionen

Goal and Scope

Environmental assessment of aquatic micro pollutants should consider the spatial and temporal variability of emission, transport and transformation. Simulation models coupled with Geographic Information Systems (GIS) provide digital maps of concentration patterns caused by the overlay of multipoint and diffuse emissions and natural attenuation processes in river basins. The paper gives an overview on GIS-based models for river basins and demonstrates the applicability by using some illustrating examples with GREAT-ER.

Main Features

Georeferenced models have several advantages: visualization of concentration patterns, investigation of spatial and temporal concentration profiles, analysis of exceedance of environmental quality standards, embedding in integrated river basin management systems.

Results and Discussion

GIS-based models allow a more realistic assessment. Monitoring programmes should be designed to deliver appropriate measured data for the evaluation and improvement of models.

Recommendation and Perspectives

The combination of digital maps, simulation models and environmental monitoring would provide better approaches for the risk assessment and water quality management of aquatic micro pollutants.     

Entwicklung von Prüfwertempfehlungen für ausgewählte Schadstoffe zum Schutz des Bodens als Lebensraum für Bodenorganismen

Goal and Scope

In the German Federal Soil Protection and Contaminated Sites Ordinance there are no ecotoxicological trigger values for the protection of soil as a habitat for soil organisms. The objective of this study was to derive preliminary trigger values for the habitat function of soils. This was done by collecting data on the impact of priority pollutants on soil organisms and plants followed by the parallel use of the Factorial Application Method (FAME) and Distribution Based Extrapolation (DIBAEX) and a final verification of the plausibility of the calculated trigger values by means of an ecotoxicological test battery.

Methods

Data on the effects of pollutants on soil organisms and plants were recorded in a specific data base (Soil Value). Subsequently, we derived so-called ‘working trigger values’ using the extrapolation methods FAME (factorial application method) and DIBAEX (distribution based extrapolation). In the second phase of the project, we verified experimentally the plausibility of these values by means of an ecotoxicological test battery. Test substrate was a sandy soil with low sorption capacity and organic carbon content which was mixed with fresh pollutants (e.g. heavy metal salts) and polluted soil material from contaminated sites (aged contamination), respectively. Organisms tested were microorganisms, plants, earthworms, springtails and nematodes.

Results and Conclusions

We calculated working trigger values for 12 pollutants based on 900 datasets compiled in he data base. The laboratory investigations showed the freshly added contaminants to be less strongly adsorbed to the soil than those added by the use of contaminated soil material. Nevertheless, aged contaminations displayed often the same inhibitive effects as the freshly added chemicals. The results achieved in the second phase of the project were also recorded in the Soil-Value database. Based on the new data set, final trigger values were derived for the experimentally tested substances.

Outlook

The procedure described in this contribution exemplarily for copper can be used for the derivation of recommended trigger values for the pathway soil ? soil organisms. Besides copper, preliminary trigger values were derived for zinc, mercury, lead and HCH.     

Bestimmung des Ferntransports von persistenten organischen Spurenstoffen und der Umweltexposition mittels Modelluntersuchungen

Background, Aim and Scope

Many environmental pollutants are slowly degrading (persistent) and very mobile. They are semivolatile, i.e. they are partitioned between the environmental media of soil, water and air, and undergo long-range transport. The combined action of climate and substance properties determines the distributions and fate of these substances, among them as the persistent organic pollutants (POPs), other pesticides and industrial chemicals.

Main Features

Multicompartment chemistry-transport models are under development in order to study environmental exposure models.

Results

The investigation of transport and fate of some POPs on the global scale has emphasized the significance of historically explicit and geo-referenced simulations for substance distributions, persistence and long-range transport potential. Apart from the substance properties, it is the regional climate which is most important. This was illustrated by studies into the regional cycling of DDT and γ-HCH in selected tropical and extra-tropical regions.

Discussion

The isolation of individual steps of subsequent cycles of emission, transport and deposition (a so-called grasshopper effect) in model experiments shows the potential to elucidate the complex superposition of substance properties and environmental conditions, variable in time and space.

Conclusions

The results suggest that the grasshopper effect enhances the long-range transport potential, but is not required to explain an accumulation in polar regions (at least for γ-HCH).

Perspectives

A number of relevant scientific questions should be addressed by exposure modelling.     

DEHP (Di(2-ethylhexyl)phthalat)

Background, Goal and Scope

The plasticiser DEHP is suspected to affect the human reproductive system as an endocrine disruptor (Latini et al. 2004). A meta-analysis was performed to compare annual production amounts and daily uptake of DEHP.

Methods

For this purpose, production data were used from annual publications of the Federal Statistical German Agency (Statistiches Bundesamt) and daily uptake values on the basis of urinary secretion of DEHP metabolites from Wittassek et al. (2007a).

Results

It is shown that the daily uptake of DEHP by German university students is strictly and almost perfectly correlated with the industrial production of DEHP in Germany (correlation coefficient >0.9).

Discussion

The annual production amounts are reflected by the daily uptake values. When the production amount is high, the uptake increases; when the production amount is low, the uptake decreases.

Conclusions

This strict correlation allows the extrapolation of daily DEHP uptake for the 1970s years. On this basis it can be assumed that, at least for a part of the German population, the TDI of 50 μg/kg BW/day was exceeded. Because of their higher susceptibility and, therefore, higher uptake rate (Becker et al. 2004), a considerable exposure for infants might have occurred in these years.     

六溴环十二烷及其复合污染脑发育期暴露对大鼠甲状腺激素代谢过程的影响

研究六溴环十二烷（HBCD）及其复合污染对发育期幼鼠甲状腺激素代谢过程的影响。设计HBCD单一暴露剂量（10、50、100、300ttg·kg-1）,及HBCD与等浓度商用多溴联苯醚DE-71按2：1复合暴露剂量（10、50、100、300gg·kg-1）,对新生3d的SD大鼠进行为期42d的暴露,放射免疫法测定血清中甲状腺激素（TT3,TT4,FT3,FT4,TSH）水平,并分别测定肝脏和脑组织中甲状腺激素脱碘酶（D1,D2）活性及其对应基因的相对表达水平。与对照组相比较,经HBCD暴露后,大鼠血清中TT4、TT3、FT4、FT3浓度随着暴露剂量增大呈现先升高后下降的趋势,其中10μg·kg-1剂量组的FT3质量分数显著升高（P〈0．05）,300μg·kg-1剂量组的FT4质量分数显著下降（P〈0．05）;TSH则呈现下降趋势。lO、50及300μg·kg-1剂量组的TSH质量分数均显著下降（P〈0．05）。HBCD／DE-7l复合暴露后,大鼠血清中TT4、TT3、FT4、FT3浓度随着暴露剂量的增大呈升高趋势,其中50μg·kg-1剂量组TT4质量分数显著升高（P〈0．05）,50μg·kg-1及300μg·kg-1剂量组FT4质量分数显著升高（P〈0．05）,300μg·kg-1剂量组FT3质量分数显著升高（P〈0．05）。单一暴露后,D1活性及基因表达水平均呈下降趋势,300gμg·kg-1剂量组基因表达水平下降显著（P〈0．05）;D2活性及基因表达水平则均呈现下降趋势,50μg·kg-1剂量组均显著下降（P〈0．05）;HBCD／DE-71复合暴露后,D1、D2活性及其基因表达水平则均呈升高趋势,其中100μg·kg-1剂量组D1活性及基因表达水平均显著性升高（P〈0．05）,300μg·kg-1剂量组D2活性显著性升高（P〈0．05）。HBCD及HBCD／DE-71复合污染物均能通过改变甲状腺激素代谢酶的活性及mRNA表达水平进一步影响机体甲状腺激素的内稳态平衡,且HBCD单一暴露与HBCD／DE-71复合暴露对机体毒性作用途径及所产生的毒性效果存在着很大的差异。     

Elbehochwasser 2002 — Ein Rückblick

Objective

Flood sediments were investigated due to the extreme flood situation around Dresden in August 2002

Method

The samples have been analyzed by screening inorganic and organic pollutants.

Results

It was observed that As, Pb, Cd, Zn, Cu, B and other heavy metals as well as DDT, PCB and Benzo [a] pyren were significantly enriched.

Conclusion

Depending on geogenic and anthropogenic impacts, the spatial distribution of these contaminants was different. Organic compounds were dislocated down stream from Czech Republic along the Elbe River. Because of the old ore mining, samples near the Mulde and Wei\eritz Rivers showed high metal pollution.

Perspective

More detailed and systematic investigations should be undertaken in the Elbe and Mulde river systems.     

Humanarzneimittel im aquatischen Ökosystem

Goal

In the Brandenburg State Office for the Environment an approach to assess the potential risk of drug residues in aquatic ecosystems has been developed based on an investigation of the consumption amounts in 1999 to identify or to exclude a potential environmental risk of important human drugs and further to define priority substances for monitoring programs in Brandenburg in the future.

Method

This assessment approach tested with 60 drug agents is based on an exposure estimation considering the main path for the entry human—waste water—sewage plant—surface water, on a substance specific analysis of effects and on an analysis of the environmental fate as compartment distribution, bioaccumulation and persistence.

Results

In Brandenburg surface waters the drug agent concentration for eight of the considered substances is supposed to be greater than 1 μg/l and for at least 13 of the considered substanoes the PNEC in aquatic ecosystems is assumed to be lower than 1 μg/l. A potential risk for the environment can be seen for the antibiotics Ciprofloxacin-HCl and Clarithromycin, the disinfectants Benzalkonium Chloride, Cocospropylendiaminguaniacetat, Glucoprotamine, Laurylpropylenediamine and Polyvidone-iodine, the sexual hormon Ethinylestradiol, the antidiabetic Metformin-HCl, the antiepileptic Carbamazepine and the lipid regulator Clofibrinic acid on the basis of effects because their PEC:PNEC-relation is about 1 or higher. For further 19 drug agents an environmental risk is to be assumed because of their environmental behaviour without support by ecotoxicological data at present.

Conclusion

Although there is only a small base of valid ecotoxicological data, this risk assessment shows that adverse effects in the aquatic environment by some drug agents cannot be excluded. However, it should be noted that this first assessment gives only a crude orientation. Appropriate test data are necessary to refine the assessment in future.     

Distribution,seasonal variation and inhalation risks of polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins and dibenzofurans,polychlorinated biphenyls and polybrominated diphenyl ethers in the atmosphere of Beijing,China

Spatial distribution, seasonal variation and potential inhalation risks of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were investigated in the atmosphere of Beijing, using passive air samplers equipped with polyurethane foam disks. Concentrations of ΣPCDD/Fs, ΣPCBs and ΣPBDEs ranged from 8.4 to 179 fg WHO₂₀₀₅-TEQ/m³, 38.6–139 and 1.5–176 pg/m³, respectively. PCDFs showed higher air concentrations than those of PCDDs, indicating the influence of industrial activities and other combustion processes. The non-Aroclor congener, PCB-11, was detected in air (12.3–99.4 pg/m³) and dominated the PCB congener profiles (61.7–71.5% to ∑PCBs). The congener patterns of PBDEs showed signatures from both penta-BDE and octa-BDE products. Levels of PCDD/Fs, PCBs and PBDEs at the industrial and residential sites were higher than those at rural site, indicating human activities in urban area as potential sources. Higher air concentrations of PCDD/Fs, PCBs and PBDEs were observed in summer, which could be associated with atmospheric deposition process, re-volatilization from soil surface and volatilization from use of technical products, respectively. Results of inhalation exposure and cancer risk showed that atmospheric PCDD/Fs, dioxin-like PCBs and PBDEs did not cause high risks to the local residents of Beijing. This study provides further aid in evaluating emission sources, influencing factors and potential inhalation risks of the persistent organic pollutants to human health in mega-cities of China.     

Solvent effects on quantitative analysis of brominated flame retardants with Soxhlet extraction

Reliable quantifications of brominated flame retardants (BFRs) not only ensure compliance with laws and regulations on the use of BFRs in commercial products, but also is key for accurate risk assessments of BFRs. Acetone is a common solvent widely used in the analytical procedure of BFRs, but our recent study found that acetone can react with some BFRs. It is highly likely that such reactions can negatively affect the quantifications of BFRs in environmental samples. In this study, the effects of acetone on the extraction yields of three representative BFRs [i.e., decabrominated diphenyl ether (decaBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol A (TBBPA)] were evaluated in the Soxhlet extraction (SE) system. The results showed that acetone-based SE procedure had no measureable effect for the recovery efficiencies of decaBDE but could substantially lower the extraction yields for both TBBPA and HBCD. After 24 h of extraction, the recovery efficiencies of TBBPA and HBCD by SE were 93 and 78% with acetone, 47 and 70% with 3:1 acetone:n-hexane, and 82 and 94% with 1:1 acetone:n-hexane, respectively. After 72 h of extraction, the extraction efficiencies of TBBPA and HBCD decreased to 68 and 55% with acetone, 0 and 5% with 3:1 acetone/n-hexane mixtures, and 0 and 13% with 1:1 acetone/n-hexane mixtures, respectively. The study suggested that the use of acetone alone or acetone-based mixtures should be restricted in the quantitative analysis of HBCD and TBBPA. We further evaluated nine alternative solvents for the extraction of the three BFRs. The result showed that diethyl ether might be reactive with HBCD and may not be considered as the alternative to acetone used solvents for the extraction of HBCD.     

Schwermetalle in Regenwürmern Baden-Württembergs

Goal and Scope

The heavy metal burden of the soil and of earthworms from representative long-term forest observation plots has been measured since 1984 as one component of the media-embracing environmental monitoring network of the State of Baden-Wuerttemberg. These investigations are aimed at elucidating and assessing adverse effects of pollutants on the soil biocenosis

Methods

So-called characteristic curves for the metals Cd, Cu, Ni, Pb, and Zn were developed for the assessment. Earthworm toxicity data and background values in soil served as criteria. This procedure facilitates a comparative assessment of different pollutants. The mobility of the metals, which greatly influences their bioavailability and toxicity, was taken into account for the effects assessment.

Results and Conclusion

Besides inventorying the heavy metals (Part 1), the question of threshold values for toxic reactions as well as for accumulation was raised. The metal concentrations were assessed in the soil with regard to its habitat function. The ecotoxicological assessment revealed that the heavy metal burden of the investigated plots lies within the background- or precautionary range, well below the screening value established here to indicate the effect threshold in earthworms. This result means that a pollution of the forest observation plots with the metals cadmium, copper, lead, nickel, and zinc is low or absent. Only the distribution of the lead content is centered slightly above background (but clearly below the toxicity threshold). This slight lead burden of the soil of the observation plots can be explained by emissions from motor vehicles. Investigations at sites that are contaminated with either chromium or copper or cadmium showed that an accumulation of these metals in the body of the worms can be observed only above a threshold concentration of several hundred micrograms of mobile metal per kilogram in the upper layer of the soil.

Recommendations and Perspectives

The hitherto unknown threshold values for the accumulation in the body of the earthworm should be statistically validated and extended to other elements. Further research is needed in order to build a well founded basis for the ecotoxicological assessment of soil pollution. Acute and chronic earthworm effect thresholds are neither available yet for arsenic, cobalt, and mercury nor for some other elements occurring less frequently as soil pollutants. Background values depending on the kind of rock have been measured so far for total chromium only. They are lacking for the more toxic chromium (VI) which is a frequent soil pollutant but naturally occurs in traces only.     

Implikationen der landwirtschaftlichen Klärschlammverwertung Status quo und Perspektiven

Goal and Scope

At all times animal as well as human excrements have been used as organic fertilizers. Disposing of municipal sewage sludge on arable farmland means saving mineral fertilizer to conserve the exhaustible resource phosphorus; one can consider this kind of recycling management as a contribution to a sustainable regional development. However, the use of sludge implies a significant release of pollutants. Hence, in Germany as well as internationally, this is a controversial issue and therefore it needs to be re-evaluated under consideration of regional circumstances.

Methods

A material flow management framework is used to first analyse toxic, fertilizing and legal aspects of the ‘sludge metabolism’ in Schleswig-Holstein, including involved participants. Then, the treatment of waste water as well as potential and actual recycling of domestic sewage sludge are regionally compared. The study is based on a survey of the municipal waste water treatment plants which serve more than 10.000 people including population equivalence; these plants cover about 94% of the sewage sludge in Schleswig-Holstein.

Results and Conclusions

After taking the phosphorus of manure into account, the modelled potentials of recycling on the scale of districts do not correspond with the actual use of sludge in agriculture. The disposal firms recycle the sludge where they can get the highest profit. By minimizing transaction costs, lager recycling distances can be compensated. The potential of phosphorus recycling is limited. The calculated state-wide amount is not more than 10% of the total phosphorus demand of the arable land, so the benefit is less important for the national economy. On the other hand, there is a significant discharge of pollutants mainly into the soil, where apart from copper and cadmium, the charge through sewage sludge is higher than through mineral fertilizer and manure. In addition, the risk of pollutants with endocrine disrupters is difficult to estimate.

Outlook

In respect of the net ecological effects, thermal utilization of sewage sludge, e.g. in clinker works, coal-fired power stations or waste incineration plants, combined with previous or additional phosphorus recovery from cinder, meets the criteria of sustainable material flows more than its use on arable land. Even though these disposal options are still more expensive, law induced adjustment of the waste market and more strict land application regulations will reduce their price differences. This will make a middle-term change from the agricultural use to a thermal recycling of sewage sludge possible to avoid soil impacts and fulfil the requirements of a sustainable development.     

Staubfilterung und immissionshistorische Aspekte am Beispiel fassadenbegrünenden Wilden Weines (Parthenocissus tricuspidata)

Goal and Scope

At the present, air borne particulate matter is in the focus of public and scientific interest. In this context, it makes sense to remember the buffer function of vegetation for particulate air pollutants, notwithstanding technical and traffic management measures. Since trees with large and dense crowns might be able to shade windows and minimise the turbulent dilution of pollutants, natural-scientific results and socio-scientific aspects will point to the potentials of vertical greening with creeping plants.

Methods

To differentiate the endogenous and exogenous element fractions, the pollution caused by dust that covers the façade climbing creepers leaves was removed by a polyvinyl-butyrale based stripping method. The cleaning success is proven by SEM-Scans. The results of cleaned and not cleaned leaf-samples from an inner-city vertical greening for the element concentrations of Al, Cd, Co, Cr, Cu, Fe, Ni, Pb, Pt, Rh, Sb and Zn between 1991 and 1997 are shown by AAS- and ICP-MS analyses.

Results and Conclusion

The results show the increasing element concentrations during the course of the separate vegetation periods. Due to the long investigation period, it is possible to detect historical aspects concerning pollution, such as the end of the use of leaded fuel and the introduction of the catalytic converters. The comparison of dust deposition data from different cities shows the relevance of the pollution filtering by vertical greenings with Japanese Creeper. The comparison of investigation results of sycamore leaves refer to entirely different filtering characteristics of the leaf-surfaces.

Recommendation and Perspective

If appropriate planning and maintenance is assured, vertical greening can be a useful contribution for air pollution control and neighbourhood improvement. As selected results from a survey show, from the citizens point of view, the aesthetical and psychosocial aspects of well-being are of more relevant than ecological arguments. Therefore it seems to be wise to implement the combined fields of interest.