Humanpharmakawirkstoffe in der Umwelt: Einträge, Vorkommen und der Versuch einer Bestandsaufnahme

Background

The presence of a large spectrum of pharmaceutical agents has been reported for aquatic environments (surface—and groundwater) and other aquatic media (influents and effluents of sewage treatment plants) in Germany and beyond, including their occurrence in drinking water. Considering the large number of pharmaceuticals produced for human use and released into the environment, various authors (Sattelberger 1999, Hanisch et al. 2004, Castiglioni et al. 2006, IWW 2006, Stockholm County Council 2006) tried to compile ‘priority lists’ focusing on those substances with environmental relevance. The following agents are included in all lists: ciprofloxacine, clarythromycine (antibiotics), carbamazepine (anti-epileptic agent), bezafibrate (lipid reducer), clofibric acid (lipid reducer metabolite), ethinylestradiol (sex hormone) and cylophosfamide (cytostatic agent). The agents erythromycine and sulfamethoxazole (antibiotics), ibuprofen, indometacine, propyphenazone (analgesics), atenolol (beta-blocker) and ifosfamide (cytostatic agent) can be found in three of four priority lists.

Results

Pharmaceuticals mainly enter the aquatic environment via effluent water, coming from wastewater treatment plants (including hospital and household sewerage), untreated discharges (e.g, secondary transfer of active agents into ground- and surface waters via sewage sludge application in agriculture and via landfill leachate) and leakages in the municipal sewer network.

Discussion

Potential activities towards a reduced release of pharmaceuticals into the environment should consider primarily the origin of the exposure to allow a separation of drug containing flows already at the source. Following the latter it would be possible to minimize the contamination of spring-, ground- and surface waters which serve as raw water resources for drinking water supply. However, considering the actual water pollution with pharmaceuticals and other substances, ‘end-of pipe’ techniques in the sewage and drinking water treatment are absolutely essential.

Conclusions

Sustainability criteria (e.g. protection of drinking water resources, habitats and biocoenoses, recycling and economizing use of resources) and economic aspects of modern sewage disposal concepts require a useful choice and combination of technical measures as components of centralized and decentralized sewage and drinking water treatment methods. It is though not realistic to cover and eliminate all pharmaceutical agents of environmental relevance equally effective even if a catalogue of potential technical treatment methods is elaborated thoroughly. Therefore, a concentration of efforts on selected drug agents, at least following initially some of the priority lists, is recommended.

Recommendations and Perspectives

The contamination of the water cycle with pharmaceuticals is nevertheless not exclusively to be solved via the application of technical methods. The BMBF (Federal Ministry for Education and Research) funded project start (Management Strategies for Pharmaceuticals in Drinking Water, www.start-project.de) therefore tries by implementation of a transdisciplinary approach to integrate technical-, behavioral-, and agent-orientated management strategies towards a more comprehensive and sustainable problem solution.     

Abschätzung der Reduzierung der Luftschadstoffkonzentrationen

The UN ECE Göteborg Protocol from 1. December 1999 (c.f.http://www.unece.org und SENGER, 2000) to abate acidification, eutrophication and ground-level ozone demands distinct reductions of air pollutants in different countries. In this contribution the reduction of different components of air pollutants between the years 1990 and 2010 were estimated for the German federal states of Hesse and North Rhine-Westphalia. The estimated reduction for NO_x, SO₂ and NM-VOC, and CO meet the demands set up by the UN ECE Göteborg Protocol. For O₃ a reduction could only be predicted for rural areas and, for CO₂, a steady increase in its global concentration has to be assumed.     

Probabilistische Schätzung der inhalativen Exposition vs. Punktschätzung, dargestellt am Beispiel der Freisetzung von Xylol aus Farben

Estimations of consumer exposure by inhalation have been calculated taking point estimates and were compared to estimates from a probabilistic approach using Monte Carlo analysis. The calculation is based on a model in which the liberation of the highly volatile substance, xylene is only limited by the velocity of administration. The loss of the substance is limited by the air exchange rate. It is also assumed that the substance is used in a single room. Other compartments were not considered. The distribution of xylene in solvent based paints was evaluated by probability analysis of the BgVV product data base. In the products there were xylene concentrations in a range between ～1 and 44% with a median concentration of 11,2%. For “normal-case” assumptions the exposure estimate differed between single-point and probabilistic calculations: The peak concentration in a room was 0,99 g/m³ taking the single-point and 0,49 g/m³ taking the distribution. The average concentration during duration of use was 0,16 g/m³ and 0,083 g/m³, respectively. Interestingly, comparison with calculations taking the EPA-SCIES programme revealed similar concentrations showing that models are comparable.     

Probabilistische Modelle der Expositionsabschätzung

Probabilistic exposure and risk assessment can show and help to explicate the uncertainties of deterministic single-point estimates. Heterogeneity in population and exposure parameters (variability) is a part of probabilistic models which makes use of distributions for the main influential factors. The distributions of the target variables are calculated as a model-based combination of all influence factors by Monte Carlo-simulation methods. The differences between classical and probabilistic exposure assessment are demonstrated using a residential area with soil contamination as an example. The estimated arsenic exposure due to soil and dust is calculated by deterministic single-point estimates and probabilistic exposure assessment. The results are compared to the biomonitoring results of an epidemiological study. A criteria catalogue for exposure model validation is given and discussed for this example. In this scenario, the probabilistic exposure prognosis fits the empirical data better than that of a deterministic, single-point assessment. Both approaches seem to overestimate exposure with respect to empirical data.     

Abschätzung der Einträge von polyzyklischen aromatischen Kohlenwasserstoffen in deutsche Gewässer

Background, aim, and scope Polycyclic aromatic hydrocarbons (PAH) result from incomplete combustion of almost every organic materials, e.?g. due to forest fires, residential heating, combustion engines, grilling, or smoking. PAH are predominantly distributed over the air-path. Their usage in products (e.?g. moth-balls) has been limited strictly or completely forbidden in the past. In the context of the EU Water Framework Directive (WFD), the single substances anthracene, fluoranthene and naphthalene, as well as PAHs as group of substances, are listed as “priority” substances. Background of this work is a first compilation of sources of PAH emissions, and in this context, the collection of all relevant data and information to calculate the total emissions into surface waters in Germany. Materials and methods Within the scope of diverse research projects, funded by the German Environmental Agency, the available data material concerning PAH input in surface waters has been analyzed by the Fraunhofer Institute for Systems and Innovation Research. On the basis of the collected data, a first evaluation of relevance of the different sources has been conducted using the model MONERIS. Results As a result of the atmospheric deposition, PAHs enter, to a large extent, surface waters directly or indirectly through surface runoff (e.?g. urban areas, wastewater treatment plants, erosion). Discussion Although there is still additional research need for some of the covered PAH sources, a noticeable distribution pattern of relevance emerges. Conclusions The scenarios, based on the currently known sources, show that the implementation or the neglect of emission reduction measures in the field of diffuse air-borne PAHs are crucial for the further development of the deposition of PAHs in surface waters. More far-reaching studies are necessary, e.?g. concerning emissions from inland navigation/motor boats, the inhomogeneous source “products”, or the path “erosion”. Recommendations and perspectives According to the EU-WFD, all depositions, emissions and losses of “priority hazardous” classified substances, such as the group of PAHs, have to be stopped or gradually finished in the long term. Until the year 2015, environmental quality standards (EQS) have to be met for all “priority substances”. Presently, the EQS often are not completely fulfilled for many substances of the PAH group, including benzo(a)pyrene. Reduction measures are necessary within diverse areas, especially concerning diffuse atmospheric emissions (e.?g. “residential heating”).     

Einschätzung der Konzentrationsprofile polyzyklischer aromatischer Kohlenwasserstoffe (PAK) in Böden des Biosphärenreservates Spreewald

To work out background values, the information of concentration profiles of PAHs in soils of uncontaminated territories is indispensable. This investigation shows PAH concentrations of different soil samples like agricultural soils, grassland, forest and litter from the biosphere reserve in Spreewald, Germany. The mean values of the soil samples are about 460 μg Σ-PAK/kg d.m. A top value of 7.2 mg Σ-PAK/kg d.m. shows a sample of a flooded grassland area. The relation of the concentrations in the litter, forest, grassland and agricultural soil samples is about 5∶3∶2∶1. Compared to the other samples, the litter samples contain a higher amount of low molecular PAHs. Increasing distance to the former power plants Lübbenau and Vetschau (brown coal) lead to decreasing PAH contents in the soil samples of forests from 2190.9 after 4 km to 294.8 Σ-PAK/kg d.m. after 16 km. In comparison to results obtained in Nordrhein-Westfalen and Bayern, the PAH measurements indicate Spreewald to be an uncontaminated and rural area.     

Das Biologische System der Elemente (BSE): Eine modelltheoretische Betrachtung zur Essentialität von chemischen Elementen

The correlation of data on the elements obtained by instrumental chemical analysis of highly representative plant samples led to the establishment of a first Biological System of Elements (BSE) in 1994. Including other physiological parameters like availability of chemical elements, transport, storage, etc. it is clear, that aside from the bioinorganic aspects of coordination chemistries of given elements, features of essentiality or toxicity depend on their interference with enzymatic processes. Notably, the latter are not to be considered as purely catalytic transformations, but are instead related to the reproduction of organisms in a direct or indirect manner — as autocatalytic: a process whereby a protein containing some metal or burdened in function by its presence is indirectly involved in its own reproduction. Stoichiometric Network Analysis (SNA) explicitly deals with the general dynamics of such autocatalytic systems. Given there is a relationship between the kinds of metal or metalloid species and the key biological/biochemical transformations to be promoted using them — a relationship which is the topic of bioinorgnaic chemistry-, and that biochemistry is in effect about systems which can reproduce and thus behave autocatalytically, one can expect SNA to yield statements on the basic features of biology and biochemistry as well.     

Schnelle Elementanalytik zur Abschätzung von Dioxinbelastungen: Ein neues Werkzeug zur Untersuchung von Brandschäden?

A car and a railway coach with an InterCityExpress interior were combusted in a tunnel. The deposition of pollutants could be detected by passive sampling devices over the distance of several hundred meters. Cotton passive collectors were analyzed for the elements Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Sn, V and Zn. A comparison with analytical results of PCDD/F and PAH (US EPA) showed a close similarity between the concentration profiles of some elements and the organic pollutants. As one outcome, Cd, Cu, Pb, Sb, Sn and Zn could be used as indicators for the estimation of surface contamination with PCDD/F or PAH in the event of such fires, thereby providing the advantages of faster results and lower costs.     

Bewertung der Umweltgefährlichkeit von Stoffen

By sending a questionnaire to all companies of the pulp and paper, textile finishing and leather industries in Germany a study ascertained wastewater data concerning the general situation, treatment processes and specific amounts. With these data standard figures used in the EU for the assessment of chemical substances were checked. The volume flows of the industrial sewage treatment were determined for the facilities of all three branches which discharge their wastewater directly to the receiving waters. The 10 percentile score of these facilities amounted to only a quarter of the EU standard figure of 2,000 m³/d. This value is related to a standardised waste water treatment plant within the EU, which treated the wastewater of 200 l/d from 10,000 inhabitants. The analyses of the entire branch in each case yield dilution factors of 20–70% of the EU standard value of 10. Only the full tanning leather companies yielded a dilution factor of 10. The volume flows of the sewage treatment plants of the facilities discharging to the sewer system exceeds 2,000 m³/d in call cases.     

Umweltrelevanz von Diphenylamin — Ein Stoff der 3. EU-Altstoffprioritätenliste

Diphenylamine (DPA), the simplest secondary aromatic amine, is a compound from the third European Union (EU) list of priority pollutants. It was assigned to Germany to assess and control its environmental risks. DPA is most commonly used as a stabilizer agent in nitrocellulose-containing explosives and propellants, in the perfumery, and as an antioxidant in the rubber and elastomer industry. DPA is also widely used to prevent the post-harvest deterioration of apple and pear crops. It is a parent compound of many derivatives which are used for the production of dyes, pharmaceuticals, photography chemicals and further small-scale applications. At the beginning of the eighties, the estimated world production of DPA was ?40,000 tons per year (in Germany ?4,000 tons per year). The compound is still produced world-wide by the chemical industries. Recently published reports showed that DPA was found in soil and groundwater (within the ppb to ppm range). Some ecotoxicological reports demonstrated the potential hazard of various diphenylamines to the aquatic environment and to bacteria and animals as well. Studies on the biodegradability of DPA and its derivatives are very sparse. Therefore, further investigations are required to determine the complete dimensions of the potential environmental hazard and to introduce possible (bio)remediation techniques for sites that are contaminated with this compound or its derivatives. This review summarizes the environmental relevance of DPA as has been published in the literature thus far. It may possibly support the German authorities in their assessment of the risks of this priority pollutant.     

Photometrische Bestimmung der Zytotoxizität von Chemikalien

Two test methods are presented to assess the cytotoxicity of chemicals. On one hand the protozoonTetrahymena pyriformis and on the other the bacteriumPseudomonas aeruginosa is cultured in defined media containing the test chemicals. Test parameter is the quantity of living cells surviving exposure. The conversion of the tetrazolium salt MTT into formazan is equivalent to cell viability. A mixture of detergent and isopropanol is used to dissolve the blue formazan which is not soluble in water, prior to photometric measurement. For cetyltrimethylammonium bromide, benzyldimethyldodecylammonium chloride, dodecylbenzenesulfonic acid sodium salt, potassium dichromate, 4-toluenesulfonic acid sodium salt, and 4-nitrophenol the EC50-values (mol/l) in theTetrahymena pyriformis- (Pseudomonas aeruginosa) test system were: 10^?5,81 (10^?5,08); 10^?4,68) (10^?3,80; 10^?4,50 (10^?4,14); 10^?3,97 (10^?5,11); 10^?2,71 (10^?2,50) and 10^?4,00 (10^?3,64). — With the assays described here it is possible to measure a large number of samples by quick and simple means.     

Bakterielle Biotestverfahren zur Bestimmung der Toxizität von Abfällen

For a risk assessment of wastes, fast and sensitive screening methods are required to detect possible toxic effects. In this study, different leachability methods (DIN 38414, part 4; EPA 1310; EPA 1320) were used to prepare aqueous leachates from different wastes; these leachates were rested in different bacterial toxicity test systems for possible toxic effects. As bacterial toxicity tests, the luminescent bacteria test and the growth inhibition test with activated sludge bacteria were used. The test systems showed a good agreement of the results from the different leaching methods, thereby indicating the reliability of the test systems used. The luminescent bacteria inhibition test showed a higher sensitivity than the growth inhibition test which is in good accordance with literature data. We conclude that both test systems are well suited to assess the toxic potential of aqueous waste leachates.     

Bewertung der potenziellen Grundwasserbelastung von deponierten Hochofengasschlämmen

Goal and Scope

Blast-furnace sludge is a waste originating from pig-iron production and contains contaminants such as lead, zinc, fluoride and cyanide assumably contaminating the groundwater by leaching.

Methods

We investigated the chemical composition of 27 samples of landfilled blast-furnace sludge in pore waters which were obtained by the centrifugation of fresh material and elution with water according to DIN 38414 part 4 (S 4).

Results

The pore waters as well as the eluates were neutral to alkaline (pH 7.3 to 10.7) and were dominated by alkali and alkaline-earth metals as well as sulphate and nitrate. The concentrations of all elements and compounds investigated were mostly clearly larger in the pore waters than in the eluates. The average concentrations of environmentally relevant constituents such as lead (0,18 mg?1), zinc (1,5 mg l?1), fluoride (10,6 mg l?1), and total cyanide (1.8 mg l?1) in the pore waters were distinctly larger than the inspection value of the German Federal soil Protection Ordinance for the pathway soil-groundwater. Lead, zinc, and total cyanide concentrations in the pore waters were largely underestimated by the eluates, as these concentrations were 70 to 90% lower in the eluates compared to the pore waters.

Conclusion

In the case of landfilled blast-furnace sludge, eluates according to DIN 38414 part 4 (S 4) provide low concentrations which are unrealistic to forecast concentrations in the seepage water.     

Untersuchung von Abfällen mit biologischen Testverfahren zur Bewertung der Wassergefährdung

Wastes from three different types of waste treatment facilities (slag from a municipal waste incineration plant, slag granules from a pilot plant combining carbonization and incineration, mechanical and biological treated wastes) were examined to determine their hazard potential to different waters sites. The process temperature is seen to be the main difference between the three treatment processes. The wastes were extracted with water according to the German standard DIN 38414 S 4 and additionally at a constant pH value of 4. The leachates were investigated in a battery of aquatic bioassays and characterised physically and chemically. Every leachate revealed in a toxic effect at least in one test. The toxicity of the leachates prepared at a pH of 4 was significantly higher than the toxicity of the leachates prepared by extraction with water without pH adjustment. The leachates of the slag granules showed the lowest toxicity. On the basis of these experimental results, a scheme to derive Water Hazard Classes of wastes, which is presented in part II of this publication, was developed.     

Untersuchung von Abfällen mit biologischen Testverfahren zur Bewertung der Wassergefährdung

Wastes from three different types of waste treatment facilities were examined with bioassays to determine their hazard potential to waters (→Part I). All examined wastes showed toxic effects and have to be classified as hazardous to waters according to section 19g of the German Federal Water Management Act. The toxicity is probably caused by heavy metals in the leachates, especially copper. An evaluation pattern to classify wastes in the German system of Water Hazard Classes is presented. According to this proposal, a classification of the examined wastes into Water Hazard Class 1 seems to be appropriate. This classification does not describe the hazards resulting from the regular disposal on a landfill or from the utilisation of the treated wastes.     

Prüfung der Auswirkungen von Pflanzenschutzmitteln auf Laufkäfer

The testing procedure for the effects of pesticides on carabid beetles is described and examples are given for important factors, e.g. temperature, type of soil, testing method and physiology of the test animal, which can influence the results of such tests. Risk assessment for pesticides, therefore, has to be carried out by experts. Additionally, a monitoring of effects should be carried out after the registration process in certain cases.     

Abschätzung des umweltchemischen und ökotoxikologischen Verhaltens von Stoffen durch computergestützte Analyse von Struktur und Verhalten sowie von Struktur und Wirkung

Risk assessment of chemicals requires comprehensive data material, which often is not available. To provide substitutes for the lacking experimental ecotoxicological and physico-chemical data, a software-system (SAR-System) has been developed comprising more than 90 estimation models for relevant endpoints. The approach is based on quantitative structure-activity relationships (QSAR). Two major aspects characterize the SAR-System:

1. The implemented models were tested for their validity and application range.
2. The QSARs are accessible by a menu-driven programme package.

The following endpoints are included: Thysico-Chemical Data: 1-Octanol/water-partition-coefficient log P_ow, vapour pressure, water solubility, pK_a-value, boiling point Biological Data: Toxicity towards fish, daphnia, tetrahymenae, algae, bacteria and mammals, mutagenicity. Distribution: soil sorption, bioconcentration, Henry-Constant, Mackay (Level I). Degradation: photodegradation, biodegradability.