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Bewertung der Anwesenheit teil- oder nicht bewertbarer Stoffe im Trinkwasser aus gesundheitlicher Sicht
... In numerous cases, the German health-related indication value (HRIV) concept has proved its practicability for the assessment of drinking water relevant trace substances (Umweltbundesamt 2003). The HRIV is based on the toxicological profile of a substance. ...
... Abstract In numerous cases, the German health-related indication value (HRIV) concept has proved its practicability for the assessment of drinking water relevant trace substances (Umweltbundesamt 2003). The HRIV is based on the toxicological profile of a substance. ...
... Different approaches to assess the toxicological potential of a substance are under discussion. The German Federal Environmental Agency (UBA) has developed a recommendation for the toxicological assessment of micropollutants in drinking water (Umweltbundesamt 2003). The assessment focuses on the possible toxic potential of the substance, and a threshold value, the HRIV (Bhealth related indication value,Ĝ erman BGOW = gesundheitlicher Orientierungswert^), can be derived (Grummt et al. 2013). ...
While the relationship between carbon dioxide (CO2) emission and its determinants has been widely examined in Asia, little attention has been paid to the role played by the participation in global value chains (GVCs). Thus, this study aims to fill this research gap by investigating the relationship between participation in GVCs and CO2 emissions in eleven Asian countries along with economic growth, energy consumption, trade openness, and population density. The study covers the period 1995q1–2014q4 and employs both fully modified ordinary least square (FMOLS) and dynamic ordinary least square (DOLS) methods, as well as cointegration and causality tests to examine the dynamics between variables. The findings indicate a cointegration relationship between the variables. Moreover, both FMOLS and DOLS results show that higher participation in global value chains leads to a reduction of CO2 emissions, while economic growth and energy consumption increase CO2 emissions. The outcomes also indicate a negative relationship between trade openness and CO2 emissions. Thus, the selected Asian countries should promote policies aimed at enhancing their participation in global value chains and expanding their openness to trade. Besides, the selected countries are expected to implement energy-saving policies and promote cleaner sources of energy.
... All four matrices were spiked with isotopically labeled standards at the three concentration levels 25, 100 and 500 ng L À1 to cover a relevant magnitude including the 100 ng L À1 limit for pesticides according to Council Directive 98/83/EC. Furthermore, the German Federal Environment Agency suggests a health orientation value "for substances that cannot (or can only partially) be toxicologically assessed […]" of 100 ng L À1 [18,19]. ...
... Even for the more complex matrices in case of sample -C-and -D-, concentrations of 100 ng L À1 were sufficient to confirm all recorded standards by each model. In most instances, the health orientation value of 100 ng L À1 as suggested by the German Federal Environment Agency [18,19] is not impaired by any of the filter criteria. ...
... When disregarding the wastewater matrix, about three-quarters of the spiked standards could be detected at a concentration level of 100 ng L À1 . This indicates that for several compounds, the health orientation value of 100 ng L À1 as suggested by the German Federal Environment Agency [18,19] is difficult to be reached in the negative ionization mode which is much likely attributed to the fact that formic acid has been used as eluent additive in the negative mode as well. ...
This article focuses on the data evaluation of non-target high-resolution LC-MS profiles of water samples. Taking into account multiple technical replicates, the difficulties in peak recognition and the related problems of false positive and false negative findings are systematically demonstrated. On the basis of a combinatorial approach, different models involving sophisticated workflows are evaluated, particularly with regard to the repeatability. In addition, the improvement resulting from data processing was systematically taken into consideration where the recovery of spiked standards emphasized that real peaks of interest were barely or not removed by the derived filter criteria. The comprehensive evaluation included different matrix types spiked with up to 263 analytical standards which were analyzed repeatedly leading to a total number of more than 250 injections that were incorporated in the assessment of different models of data processing. It was found that the analysis of multiple replicates is the key factor as, on the one hand, it provides the option of integrating valuable filters in order to minimize the false positive rate and, on the other hand, allows correcting partially false negative findings occurring during the peak recognition. The developed processing strategies including replicates clearly point to an enhanced data quality since both the repeatability as well as the peak recognition could be considerably improved. As proof of concept, four different matrix types, including a wastewater treatment plant (WWTP) effluent, were spiked with 130 isotopically labeled standards at different concentration levels. Despite the stringent filter criteria, at 100 ng L-1 recovery rates of up to 93% were reached in the positive ionization mode. The proposed model, comprising three technical replicates, filters less than 5% and 2% of the standards recognized at 100 and 500 ng L-1, respectively and thus indicates the general applicability of the presented strategies.
... Instrumentarium, das vorsieht, noch nicht bewertete oder bewertbare Spurenstoffe im Trinkwasser auf < 0,1 µg L −1 zu regulieren [32]. Um die Spurenstoffkonzentrationen in Trink-und Oberŕächenwasser nicht nur regulatorisch zu beschränken, sondern die Einträge vorsorglich zu minimieren, wurde 2016 der Stakeholder-Dialog źSpurenstoffstrategie des Bundes" ins Leben gerufen [33]. ...
In this cumulative dissertation, thermoanalytical methods with evolved gas analysis were applied to current water quality control issues. It will be shown that these new analytical perspectives on solid samples can contribute to multiple knowledge gains in practical as well as for research purposes. With the finding of microplastic particles in the aquatic environment, these new microcontaminants also required new analytical techniques for detection. Unlike dissolved organic micropollutants, microplastic particles are present as solids in water. Based on an interlaboratory test for the detection of microplastic contents in a suspended matter matrix, different techniques based on thermogravimetry are introduced. Pyrolytic decomposition of a solid sample provides a demonstration of how significantly different information can be generated by different instrumental implementations. The already established TED-GC/MS proved to be the most suitable method for the detection of microplastic. However, the comparatively simpler instrument configurations TGA-FTIR, TGA-MS and MCC showed individual advantages for specific tasks. Another application is the characterization of virgin and loaded activated carbon, which is used as a solid in water treatment for the adsorptive removal of dissolved organic micropollutants. The production of activated carbon is based on pyrolysis processes, which can be exploited in analytical pyrolysis. This information is already obtained by thermogravimetric analysis and could be transferred to important properties for adsorption. Thus, correlations with carbon and oxygen content as well as with the point of zero charge were found for virgin activated carbons. Evolved gas analysis also successfully led to the qualitative and quantitative determination of six oxygen-containing functional groups for a variety of activated carbon products. The extent to which activated carbons can vary not only in their physical properties (e.g., porosity and specific surface area) but also in their chemical properties (e.g., oxygen content from 0.5% to extreme 17.6%) is demonstrated. Finally, the pyrolytic decomposition behavior of loaded activated carbon with carbamazepine was examined, which for the first time allowed conclusions to be drawn about adsorption sites and states. Adsorbates of different activated carbons also showed different decomposition products depending on their C/H ratio and sulfur content. Carbamazepine could not be completely separated by pyrolysis from the activated carbons; indirectly proportional to the carbamazepine loadings, 42% to 74% of it remained sorbed. The complementary information from the thermoanalytical methods used indicates that thermal regeneration increases the degree of graphitization of the activated carbon. This work contributes to the determination and understanding of water treatment processes for microcontaminants in water cycles.
... The action limit of 0.01 µg/L set in the guideline for the environmental assessment of medicinal products may be revised in the future to better reflect environmental exposure but it is based today on a conservative approach. Such trigger values conceptually resemble the use of the "general precautionary value" (GOW, gesundheitlicher Orientierungswert) that the German Federal Environmental Agency recommends for an initial safety assessment of pharmaceutical residues in drinking water (Umweltbundesamt, 2003), which is set at a trigger value of 0.1 µg/L. It is also analogous to the TTC/ecoTTC concept (de Wolf, 2005) (EU Scientific Committees, 2008) which is used e.g. for the health assessment of genotoxic impurities in medicinal products (EMA, 2006b). ...
A pharmaceutical medicinal product, also referred to as a medicine or medication, can be generally defined as any chemical substance - or product comprising such - intended for use in the medical diagnosis, cure, treatment, or prevention of disease. Three thousands active pharmaceutical ingredients (APIs) are currently authorised on the EU market, amongst about 4000 worldwide, with an overall consumption of about 100 000 tons or more every year.
Medicinal products are, by their very nature, biologically highly active and they are consumed in high amounts, which might pose an issue in terms of quantity and quality of emissions during their life cycle. The presence of medicinal products in the environment is a globally emerging issue. Medicinal products residues of various categories (hormones, anti-cancer, antidepressants, antibiotics, etc.) have been detected in all environmental compartments, such as surface water, groundwater, soil, air, biota and in wastewater (sewage), at concentrations ranging from sub-ng/L levels to µg/L. Such widespread occurrence obviously begs the question whether these concentrations of medicinal products in the environment might pose a risk for the exposed biota or humans.
Recent pharmacovigilance legislation in the EU acknowledges that the pollution of waters and soils with pharmaceutical residues is an emerging environmental issue3. The European Commission was asked to deliver a report on the scale of the issue, the causes, and possible policy options to mitigate such impacts. More recently, in the framework of the adoption of the Directive regarding priority substances in the field of water policy, the Commission has been asked to develop, instead of the report, a strategic approach to pollution of water by pharmaceutical substances by the end of 2015.
The main components of this study are:
An assessment of the scale and trends of the emerging issue related to the presence of medicinal products (human and veterinary)2 in the environment and their possible impacts;
Analysis of the legislative and non-legislative factors possibly influencing the issue, i.e. if and eventually how efficiently the environmental and health issues related to the presence of medicinal products in the environment are tackled by the current legislation and current practices; and
Identification of policy options to improve the current framework and discuss their feasibility.
... The health-related indicator value (HRIV) concept developed by the German Federal Environment Agency (UBA) addresses all these important aspects in a precautionary in vitro approach to assess toxicologically known and unknown single substances in drinking water regarding different endpoints: genotoxicity, neurotoxicity, and subchronical/ chronical effects (Umweltbundesamt 2003). Endocrine disruption as a major issue regarding environmental quality and human health should be included as an additional mode of action into this concept. ...
In Germany, micropollutants that (may) occur in drinking water are assessed by means of the health-related indicator value (HRIV concept), developed by the German Federal Environment Agency. This concept offers five threshold values (≤ 0.01 to ≤ 3 μg l⁻¹) depending on availability and completeness of data regarding genotoxicity, neurotoxicity, and germ cell-damaging potential. However, the HRIV concept is yet lacking integration of endocrine disruptors as one of the most prominent toxicological concerns in water bodies, including drinking water. Thresholds and proposed bioassays hence urgently need to be defined. Since endocrine disruption of ubiquitary chemicals as pharmaceuticals, industrial by-products, or pesticides is a big issue in current ecotoxicology, the aim of this study was to explore endocrine effects, i.e., estrogenic and androgenic effects, as an important, additional toxicological mode of action for the HRIV concept using a hierarchical set of well-known but improved bioassays. Results indicate that all of the 13 tested substances, industrial chemicals and combustion products (5), pharmaceuticals and medical agents (4), and pesticides and metabolites (4), have no affinity to the estrogen and androgen receptor in human U2OS cells without metabolic activation, even when dosed at their water solubility limit, while in contrast some of these substances showed estrogenic effects in the RYES assay, as predicted in pre-test QSAR analysis. Using a specifically developed S9-mix with the U2OS cells, those micropollutants, i.e., Benzo[a]pyrene, 2,4-Dichlorophenol, 3,3-Dichlorbenzidin, 3,4-Dichloranilin, and diclofenac, they show estrogenic effects at the same concentration range as for the yeast cells. Three of the drinking water-relevant chemicals, i.e., atrazine, tributyltin oxide, and diclofenac, caused effects on hormone production in the H295R assay, which can be correlated with changes in the expression of steroidogenic genes. One chemical, 17α-Ethinylestradiol, caused an estrogenic or anti-androgenic effect in the reproduction test with Potamopyrgus antipodarum. Considering these results, a proposal for a test strategy for micropollutants in drinking water regarding potential endocrine effects (hormonal effects on reproduction and sexual development) will be presented to enhance the existing HRIV concept.
Wasser ist die flüssige Form der Verbindung H2O. Ein Raumteil Wasser besteht aus zwei Raumteilen Wasserstoff (H) und einem Raumteil Sauerstoff (O). 100 Massenteile des chemisch reinen Wassers setzen sich aus 11,09 Massenteilen Wasserstoff und 88,01 Massenteilen Sauerstoff zusammen. Wasser zeigt im Vergleich zu anderen Flüssigkeiten eine Reihe auffallender Eigenschaften, wie z. B. ein Dichtemaximum bei 4 °C, die unter anderem im Bau des Wassermoleküls begründet sind.
In order to develop a test battery based on a variety of neurological systems in fish, three sensory systems (vision, olfaction, and lateral line) as well as nerve transmission (acetylcholine esterase) were analyzed in zebrafish (Danio rerio) embryos with respect to their suitability as a model for the screening of neurotoxic trace substances in aquatic ecosystems. As a selection of known or putative neurotoxic compounds, amidotrizoic acid, caffeine, cypermethrin, dichlorvos, 2,4-dinitrotoluene, 2,4-dichlorophenol, 4-nonylphenol, perfluorooctanoic acid, and perfluorooctane sulfonic acid were tested in the fish embryo test (OECD test guideline 236) to determine EC10 values, which were then used as maximum test concentration in subsequent neurotoxicity tests. Whereas inhibition of acetylcholinesterase was investigated biochemically both in vivo and in vitro (ex vivo), the sensory organs were studied in vivo by means of fluorescence microscopy and histopathology in 72- or 96-h-old zebrafish embryos, which are not regarded as protected developmental stages in Europe and thus — at least de jure — represent alternative test methods. Various steps of optimization allowed this neurotoxicity battery to identify neurotoxic potentials for five out of the nine compounds: Cypermethrin and dichlorvos could be shown to specifically modulate acetylcholinesterase activity; dichlorvos, 2,4-dichlorophenol, 4-nonylphenol, and perfluorooctane sulfonic acid led to a degeneration of neuromasts, whereas both vision and olfaction proved quite resistant to concentrations ≤ EC10 of all of the model neurotoxicants tested. Comparison of neurotoxic effects on acetylcholinesterase activity following in vivo and in vitro (ex vivo) exposure to cypermethrin provided hints to a specific enzyme-modulating activity of pyrethroid compounds. Enhancement of the neuromast assay by applying a simultaneous double-staining procedure and implementing a 4-scale scoring system (Stengel et al. 2017) led to reduced variability of results and better statistical resolution and allowed to differentiate location-dependent effects in single neuromasts. Since acetylcholinesterase inhibition and neuromast degeneration can be analyzed in 72- and 96-h-old zebrafish embryos exposed to neurotoxicants according to the standard protocol of the fish embryo toxicity test (OECD TG 236), the fish embryo toxicity test can be enhanced to serve as a sensitive neurotoxicity screening test in non-protected stages of vertebrates.
In the present study, a mixture of treated wastewater and surface water was used to rewet a degraded fen peatland site during a three-year rewetting experiment. We studied the behavior and effects of micropollutants by means of hydrological, physico-chemical, microbiological and ecotoxicological monitoring. The highest concentrations of micropollutants in the treated wastewater were found for the pharmaceuticals carbamazepine and diclofenac, some metabolites, the sweetener acesulfame, tolyl- and benzotriazole and diatrizoate. In the underlying, shallow groundwater where treated wastewater application for rewetting had been expected to have the greatest impact due to seeping and evapotranspiration processes, only a sporadic occurrence of micropollutants was found. The influence of dilution by groundwater movements was examined by applying a geohydrological model. The sorption of micropollutants onto the peaty soil also played a role, as found for carbamazepine. Further processes such as photolysis, microbial decay under low redox conditions and plant uptake can be assumed to be relevant for the removal of many substances. Ecotoxicity tests with the soil before and after rewetting did not indicate any negative impact on the soil habitat quality by wastewater application, but clearly pointed at ecotoxicologically relevant geogenic arsenic concentrations at the study site. Although a positive effect on receiving surface water systems is expected if wastewater is applied on land instead of discharged to water bodies, the rewetted soil may turn into a sink for micropollutants in the long term. Hence, the findings of the present field study encourage further investigations in order to identify the governing processes in the elimination of micropollutants in rewetted peatlands flooded with treated wastewater.
Lebensmittelwarengruppen
• Trinkwasser
• Tafel-, Quell- und Mineralwasser
• Heilwasser
Zusammenfassung
Die Bewertung von Risiken für die Trinkwasserversorgung erfordert eine grundlegende hydrogeologische Modellvorstellung des Einzugsgebiets. Aufgrund der großen Heterogenität ist in Kluft- und Karstgrundwasserleitern die Anwendung ergänzender hydrogeochemischer Methoden unumgänglich. Die Aussagekraft und Anwendbarkeit der üblicherweise genutzten künstlichen Markierungsstoffe, Umwelttracer oder stabilen Isotope ist häufig limitiert. Eine Vielzahl von Studien belegt die Anwesenheit von anthropogenen organischen Verbindungen wie Pestiziden, Arzneimitteln, Rostschutzmitteln oder auch Koffein im Nano- bis Mikrogramm-pro-Liter-Bereich im Grundwasser. Dieser Beitrag zeigt beispielhaft, wie das Vorkommen sowie die Konzentrationsverteilung organischer Spurenstoffe die hydrogeologischen Eigenschaften von Grundwasserleitern reflektieren und diese damit für die Beantwortung bestimmter hydrogeologischer Fragestellungen herangezogen werden können.
Wasser ist die flüssige Form der Verbindung H2O. 1 Raumteil Wasser besteht aus 2 Raumteilen Wasserstoff (H) und 1 Raumteil Sauerstoff (O). 100 Massenteile des chemisch reinen Wassers setzen sich aus 11,09 Massenteilen Wasserstoff und 88,01 Massenteilen Sauerstoff zusammen.
Wasser ist eine elementare Ressource, ohne die das Leben auf unserem Planeten nicht möglich wäre. Aufgrund seiner Molekülstruktur besitzt Wasser eine Reihe von Eigenschaften, die es zu einem besonderen Stoff machen und die für viele Vorgänge auf der Erde von entscheidender Bedeutung sind. So ist Wasser die einzige Verbindung, die auf der Erde in allen drei Aggregatzuständen vorkommt: als festes Eis, als flüssiges Wasser und als gasförmiger Wasserdampf. Wasser ist aufgrund seines Dipol-Charakters ein exzellentes Lösemittel für Salze und es besitzt eine hohe Wärmekapazität sowie eine hohe Verdampfungsenthalpie.
The issue of pharmaceuticals in the environment has caused increasing concern in the recent years and various strategies have been proposed to tackle this problem. This work describes a Bayesian network (BN)-based socio-ecological impact assessment of a set of measures aimed at reducing the entry of pharmaceuticals in the aquatic environment. The measures investigated were selected across three sectors: public health market, environmental politics and drug design innovation. The BN model was developed for two drugs, Metformin and Metoprolol, and it models the distribution of the Predicted Environmental Concentration (PEC) values as a function of different measures. Results show that the sensitivity of the PEC for the two drugs to the measures investigated reflects the distinct drug characteristics, suggesting that in order to ensure the successful reduction of a broad range of substances, a spectrum of measures targeting the entire lifecycle of a pharmaceutical should be implemented. Furthermore, evaluation of two scenarios reflecting different emission management strategies highlights that the integrated implementation of a comprehensive set of measures across the three sectors results in a more extensive reduction of the contamination. Finally, the BN provides an initial forecasting tool to model the PEC of a drug as a function of a combination of measures in a context-specific manner and possible adaptations of the model are proposed.
Copyright © 2015 Elsevier B.V. All rights reserved.
The application of hydraulic fracturing during exploration and exploitation of unconventional natural gas reservoirs is currently under intense public discussion. On behalf of the German Federal Environment Agency we have investigated the potential water-related environmental risks for human health and the environment that could be caused by employing hydraulic fracturing in unconventional gas reservoirs in Germany. Here we provide an overview of the present situation and the state of the debate in Germany and summarize main results of the conducted risk assessment.
We propose a concept for a risk assessment considering the site-specific analysis of the geosystem, the relevance of possible impact pathways and the hazard potential of the fracking fluids employed. The foundation of a sound risk analysis is a description of the current system, the relevant impact pathways and their interactions. An evaluation of fracking fluids used in Germany shows that several additives were employed even in newer fluids that exhibit critical properties or for which an assessment of their behaviour and effects in the environment is not possible or limited due to lack of current knowledge. The authors propose an assessment method that allows for the estimation of the hazard potential of specific fracking fluids, formation water, and the flowback based on legal thresholds and guidance values as well as on human- and eco-toxicologically predicted no-effect concentrations. The assessment of a previously employed and a prospectively planed fracking fluids shows that these fluids exhibit a high hazard potential. The flowback containing fracking fluid, formation water, and possibly reaction products can also exhibit serious hazard potentials, requiring environmentally acceptable techniques for its treatment and disposal.
The risk analysis must be conducted always site-specifically and consider regional groundwater flow conditions. The study concludes that currently missing knowledge and data prevent a profound assessment of the risks and their technical controllability in Germany. Missing knowledge and information includes data on the properties of the deep geosystem and of the behaviour and effects of the deployed chemical additives. In this setting the authors propose several recommendations for further action and procedures regarding the application of hydraulic fracturing in unconventional gas reservoirs in Germany.
In der vorliegenden Arbeit wird das Auftreten organischer Spurenstoffe in zwei hinsichtlich der geologischen Verhältnisse und der Flächennutzung unterschiedlichen Karstgebieten diskutiert.
In einem urban geprägten, moderat verkarsteten Quelleinzugsgebiet mit einer hohen Anzahl lokaler Eintragsquellen (beispielsweise Altlasten, Kanalleckagen) ist gegenüber einem landwirtschaftlich dominierten Gebiet das Spektrum der gefundenen Stoffe breiter. Die Konzentrationen der meisten dieser Stoffe nehmen auf der Fließstrecke zu den Quellaustritten bis unter die Bestimmungsgrenzen ab und können daher nur über ein flächendeckendes Messstellennetz erfasst werden. In den Quellen finden sich vorwiegend Stoffe, die entweder durch eine weite rezente Anwendungsverbreitung oder hohe Persistenz charakterisiert sind.
In der Quelle eines stärker verkarsteten und somit höher durchlässigen Grundwasserfließsystems werden zeitlich variierend auch biologisch leicht abbaubare Substanzen detektiert. Aufgrund hoher Fließgeschwindigkeiten erfordern Untersuchungen dieses Fließsystems ein zeitlich hochaufgelöstes Monitoring organischer Spurenstoffe.
Somit haben neben den jeweiligen Stoffeigenschaften auch die hydrogeologischen Systemcharakteristika erheblichen Einfluss auf das Spektrum der nachweisbaren Stoffe.
Antineoplastic drugs are important in the treatment of cancer. Some interact directly with the deoxyribonucleic acid (DNA) and are of utmost importance in terms of risk. As highly active compounds, antineoplastics and their metabolites are largely excreted into wastewater and are found in the aquatic environment up to the lower μg/L range. Their predicted environmental concentrations are often below the action limit set in the European Medicines Agency (EMA) guideline. An in-depth risk assessment regarding their presence and effects in the aquatic environment is often not performed, and there is a lack of knowledge. This study considered whether there is an underestimation of possible risks associated with the presence of antineoplastic drugs with regard to trigger value stated in the EMA and FDA guidelines. In a balance, we identified a total of 102 active pharmaceutical ingredients of the ATC-group L01 (antineoplastic agents), which are environmentally relevant. In Germany, 20.7 t of antineoplastic agents was consumed in 2012. The share of drugs with DNA-damaging properties increased within the last 6 years from 24 up to 67 %. Solely, capecitabine and 5-fluorouracil amount together 8 t-which corresponds to 39 % of the total antineoplastic consumption. Around 80 % of the total mass consumed could be attributed to prescriptions issued by office-based practitioners and is mostly excreted at home. Based on the different mode of actions, a case-by-case evaluation of the risk connected to their presence in the environment is recommended. DNA-damaging drugs should be assessed independently as no action limit can be assumed.
Options were explored for fulfilling the legally required safety assessment for a widely applied epoxy/amine coating used for restoring corroded domestic drinking water supply systems. The coating was made up of two components mixed shortly before application, the first mainly consisting of bisphenol A diglycidyl ether (BADGE), the second of various amines. The analytically identified starting substances were all authorized, but only constituted a small proportion of the low molecular mass material left after curing and potentially migrating into water. Reaction products synthesized from constituents of the starting components (expected oligomers) could not be eluted from GC even after derivatization, indicating that standard GC-MS screening would miss most potential migrants. They were detectable by size exclusion chromatography (SEC) after acetylation. HPLC with MS or fluorescence detection was possible for constituents including a BADGE moiety, but phenalkamines could not be detected with adequate sensitivity. Possibilities for determining long-term migration relevant for chronic toxicity are discussed. Analysis in water shortly after application of the coating overestimates migration if migration decreases over time and requires detection limits far out of reach. Analysis of a solvent extract of the coating is easier and provides an upper estimate of what could migrate into the drinking water over the years. However, to satisfy the regulatory requirements, components of the complex mixture need to be identified at lower proportions than those accessible. In vitro testing of the whole mixture for genotoxicity is expected to fail because of the required sensitivity and the glycidyl functions probably wrongly resulting in positive tests. The difficulties in dealing with this situation are discussed.
http://www.umweltbundesamt.de/uba-info-medien/4346.html
Nitroverbindungen sind gut bekannte und wichtige Industriechemikalien mit unterschiedlichsten Anwendungsbereichen. Sie können herstellungs- oder anwendungsbedingt in die Umwelt gelangen und damit zu Kontaminanten von Trinkwasser-Ressourcen werden. Als solche wurde eine Reihe aromatischer und cycloaliphatischer Nitroverbindungen während der vergangenen 15–20 Jahre der Öffentlichkeit dadurch bekannt, dass Untersuchungen von Altstandorten der chemischen Rüstungsproduktion teilweise massive Verunreinigungen des Grundwassers und der Oberflächengewässer mit Nitroverbindungen aufdeckten. Das einstige Bundesgesundheitsamt (BGA) stützte sich 1980 mangels Verfügbarkeit toxikologisch bewertbarer Stoffdaten bei seiner ersten Beurteilung altlastenbürtiger Nitroverbindungen in Trinkwasser auf die bekannte Kanzerogenität einiger aromatischer Amine aus dem Arbeitsplatzbereich und empfahl für die Metaboliten mit Aminogruppe(n) einen Summen-Leitwert von 0,1 µg/l in Roh- und Trinkwasser. BGA-Bewertungskonzepte von Anfang bis Mitte der 90er-Jahre beruhten auf individuellen Substanzbewertungen, gingen allerdings (noch) nicht von tolerablen/akzeptablen Körperdosen aus, sondern von standardisierten Bewertungen des toxischen Potenzials der Nitroverbindungen. Die vorliegende Arbeit stellt die Ableitung neuer, gesundheitlich basierter Trinkwasser-Leitwerte für relevante Nitroverbindungen (Nitroaromaten, Aminonitroaromaten, Nitramine und Nitratester) auf neuester Datenbasis vor. Die Ableitung der Trinkwasser-Leitwerte von Nichtkanzerogenen erfolgt auf der Basis gesundheitlich tolerabler, aus Tierversuchen auf den Menschen extrapolierter Körperdosen (TDI-Ansatz). Bei Stoffen ohne Wirkungsschwelle werden bevorzugt als belastbar bewertete Schätzungen des Krebsrisikos (UR+) nach oraler Aufnahme zur Ableitung der Trinkwasser-Leitwerte verwendet.
Diese Publikation beschäftigt sich mit der gesundheitlichen Bewertung zulassungsrechtlich nicht relevanter Metabo¬lite (nrM) landwirtschaftlich genutzter Pestizide. Ein Trinkwasser, in dem die Gesundheitlichen Orientierungswerte der nrM-Empfehlung des UBA vom April 2008 eingehalten oder unterschritten sind, ist nicht nur frei von nrM in toxiko¬logisch relevanter Konzentration, sondern enthält sehr wahrscheinlich auch keine Transformationsprodukte von nrM aus der oxidativen Trinkwasseraufbereitung oberhalb einer solchen Konzentration. Je nach Struktur möglicherweise anwesender nrM und abhängig vom Aufbereitungsverfahren empfiehlt das UBA jedoch, von Fall zu Fall die Abwe¬senheit gentoxischer oder anderer hochtoxischer Reaktions-/Transformationsprodukte in standardisierten Kurzzeit-Wirkungstests experimentell abzusichern – insbesondere dann, wenn die nrM-Werte 10 µg/l oder sogar mehr erreichen und das Trinkwasser mit Ozon ohne nachfolgende Aktivkohlefiltration aufbereitet wird. Mittel- bis langfristig sind standardisierte Tests zu entwickeln, die bereits während des Zulassungsprozesses eine Prognose darüber erlauben, welcher Wirkstoff möglicherweise einen oder mehrere nrM bildet, die sich mit oxidativen Aufbereitungschemikalien im Trinkwasser zu toxikologisch relevanten Transformationsprodukten umsetzen.
One of the most concerning xenobiotics currently under discussion by regulators and
treatment experts is N-Nitrosodimethylamine (NDMA). NDMA is a carcinogen known to
induce cancer in a variety of animals, causing DNA damage at low doses. Human
exposure occurs through cigarettes, food, personal care products and drinking water, in
addition to endogenous formation in the stomach.
The daily tolerable limit for intake has been identified to be 4.0 - 9.3 ng/kg.day (Fitzgerald
and Robinson 2007). Water at the WHO proposed guideline value of 100 ng/L would
contribute about 2.9 ng/kg.day of this intake, while intake from food varies from 5.7 – 44.2
ng/kg.day. Smoking and workplace are additional exposure routes. This outlines that the
exposure is often higher than tolerable limits. In the food and drinks industry this has in
recent decades resulted in improved manufacturing processes.
Awareness of NDMA in drinking water is a relatively recent issue. NDMA stems from
precursors in raw water and can be generated during treatment. Generally removal of
precursors is more achievable than the removal of NDMA itself. For example, the potent
NDMA precursor dimethylamine is rapidly removed in biological pre-treatment, while many
other precursor amines are more persistent. These precursor amines include some ion
exchange resins and coagulants, used in water treatment processes, which have been
shown to generate NDMA during chlorination. Ozonation has also been shown to produce
NDMA in treatment. UV oxidation is the preferred method for removal of NDMA in water
treatment, although reverse osmosis membranes are possible alternatives if effective
retention can be achieved.
Ongoing pollution and improving analytical techniques reveal more and more anthropogenic substances in drinking water sources, and incidentally in treated water as well. In fact, complete absence of any trace pollutant in treated drinking water is an illusion as current analytical techniques are capable of detecting very low concentrations. Most of the substances detected lack toxicity data to derive safe levels and have not yet been regulated. Although the concentrations in treated water usually do not have adverse health effects, their presence is still undesired because of customer perception. This leads to the question how sensitive analytical methods need to become for water quality screening, at what levels water suppliers need to take action and how effective treatment methods need to be designed to remove contaminants sufficiently. Therefore, in the Netherlands a clear and consistent approach called 'Drinking Water Quality for the 21st century (Q21)' has been developed within the joint research program of the drinking water companies. Target values for anthropogenic drinking water contaminants were derived by using the recently introduced Threshold of Toxicological Concern (TTC) approach. The target values for individual genotoxic and steroid endocrine chemicals were set at 0.01 μg/L. For all other organic chemicals the target values were set at 0.1 μg/L. The target value for the total sum of genotoxic chemicals, the total sum of steroid hormones and the total sum of all other organic compounds were set at 0.01, 0.01 and 1.0 μg/L, respectively. The Dutch Q21 approach is further supplemented by the standstill-principle and effect-directed testing. The approach is helpful in defining the goals and limits of future treatment process designs and of analytical methods to further improve and ensure the quality of drinking water, without going to unnecessary extents.
More than 2500 chemically defined substances are approved as drugs in Germany. Unlike agricultural pesticides, these biologically active structures are not used in open environmental compartments and therefore their environmental toxicological data base is not nearly as complete. Nevertheless, some of them become environmental contaminants after their intended use. Therefore, from the viewpoint of environmental health protection, there are gaps in their health-related environmental risk assessment. Organic trace compounds that lack an adequate toxicological database, and their mixtures, in drinking water can be safely regulated and provisionally assessed by combining the "similar joint action" addition rule with the recommendation of the Federal Environment Agency of March 2003 "Assessing the presence of substances in drinking water without (adequate) toxicological database from the health point of view". The general precautionary value (Gesundheitlicher Orientierungswert GOW1 = 0.10 μg/l), which is a recommendation for weakly to not genotoxic compounds, re presents a workable compromise between preventive health protection, water management considerations and aesthetic quality claims (purity). Compliance with this value in the long term will only be possible if the chemical and biological degradation of pharmaceuticals and their metabolites in waste water and waste water treatment plants is effectively improved. Alternatively, there is the risk of drinking water degener- ating into a sink for highly mobile, polar and persistent compounds. Their elimination at a stage as late as technical drinking water treatment would be neither close to the initial cause nor justifiable in terms of technical effectiveness. The risk assessment of their byproducts would give rise to further uncertainties. Possible conflicts with the therapeutic quality must be solved by developing substitute products which are environmentally sound.
Die Verknüpfung der Vorschriften der Trinkwasserverordnung (TrinkwV) 2001 mit dem umfangreichen Technischen Regelwerk sowie
mit den Empfehlungen des Umweltbundesamtes (UBA) und der Trinkwasserkommission hat sich prinzipiell bewährt. Die TrinkwV 2001
beinhaltet aber auch einige Passagen, die eine Novellierung angezeigt erscheinen lassen. Vom Verordnungsgeber wird an ihre
Überarbeitung gedacht. Dabei werden eigene Erkenntnisse sowie Erfahrungen der Länder und der Wasserversorger beim Vollzug
der Verordnung zu berücksichtigen sein. Es ist vorgesehen, Verbesserungen sowie weitere Vereinfachungen zum Bürokratieabbau
vorzunehmen, ohne dabei vom existierenden hohen Schutzniveau für das Trinkwasser in Deutschland abzuweichen.
The current regulatory approach in Germany combines regulations defined in the Drinking Water Ordinance with a comprehensive
catalogue of technical rules as well as with guidelines and recommendations by the Federal Environment Agency and the Drinking
Water Commission. This approach has proven successful in practice. Some parts would benefit from revision. The regulator is
currently contemplating some revision in order to take experience of federal, state and local authorities as well as of water
suppliers with implementation of the current Ordinance into account. The intention is improvement particularly towards reducing
bureaucracy without compromising the current high level of public health protection through drinking water hygiene in Germany.
Challenging tasks, increasing demands, and new generations of powerful analytical instruments initiated considerable progress in aquatic environmental analysis and led to a considerable improvement of analytical performance during the last few years. The ever growing number of emerging pollutants is tackled by specific and highly sensitive analytical methods with detection limits of a few nanogram per liter and even lower. Wide-scope monitoring techniques and multiclass and multiresidue analysis allow for the simultaneous determination of hundreds of compounds. The high mass resolution capability and mass accuracy of advanced mass spectrometric instruments, i.e., time-of-flight (TOF) MS or Fourier transform (FT)-Orbitrap MS, enable combined target and non-target analysis, including the identification of metabolites and abiotic degradation products. This minireview highlights some of the most recent developments in the trace analysis of important organic water pollutants and focuses on some specific groups of emerging contaminants, i.e., pharmaceuticals, flame retardants, disinfection by-products, surfactants, per- and polyfluorinated compounds, benzotriazoles, and benzothiazoles, as well as on the identification of transformation products and on non-target analysis. References were selected according to their exemplary and innovative character and to their practical relevance.
Die vorliegende Arbeit beschäftigt sich mit der Analytik zweier Stoffgruppen anthropogenen Ursprungs in der aquatischen Umwelt, einerseits mit einer Auswahl antibiotisch wirkender Substanzen als Rückstände aus Arzneimittelanwendungen (Umweltproblem: bakterielle Resistenzen), andererseits mit der Stoffgruppe der perfluorierten Tenside (PFT) als Rückstände industrieller Verarbeitungs- und Veredelungsprozesse (Umweltproblem: Persistenz und Bioakkumulation). Der erste Schwerpunkt der Untersuchungen lag dabei auf der Entwicklung und Optimierung der Extraktions- und Anreicherungsmethoden in erster Linie aus wässrigen Matrizes sowie der Identifizierung und Quantifizierung dieser Substanzen mittels Kopplung von hochleistungsflüssig-chromatographischen Trenn- und massenspektrometrischen Detektionsverfahren. Das Untersuchungsspektrum ergab sich für die Antibiotika aus Datenerhebungen zum Antibiotikaeinsatz im Universitätsklinikum Bonn und aus der dokumentierten Verordnungspraxis innerhalb der gesetzlichen Krankenversicherung in Deutschland, für die perfluorierten Tenside (perfluorierte Alkylcarbonsäuren und perfluorierte Sulfonsäuren) anhand ihrer Leitsubstanzen PFOA (Perfluoroctansäure) und PFOS (Perfluoroctansulfonsäure) und deren kürzer- bzw. längerkettigen Homologen. Mit den jeweiligen Multikomponenten-Methoden (29 Antibiotika und 12 Perfluortenside) konnten Nachweis- und Bestimmungsgrenzen im ein- bis niedrigen zweistelligen ng/L-Bereich erreicht werden. Die Methoden wurden im Rahmen mehrerer, zum Teil bundesweiter Laborvergleichsuntersuchungen erfolgreich validiert. Den zweiten Schwerpunkt der Arbeit bildete die Anwendung der neuen Methoden bei der Untersuchung von Realproben: Im Bereich der Antibiotika wurde das Abwasser des Universitätsklinikums Bonn vom Ort seiner Entstehung über die Kläranlage bis in den Rhein untersucht. Zusätzliche Datenerhebungen erfolgten für weitere Kläranlagen und Oberflächengewässer in Nordrhein-Westfalen, ebenso wurden ein Talsperrenwasser (zur Trinkwassergewinnung) und einige oberflächenwasser-beeinflusste Roh- und Trinkwässer untersucht. Im gesammelten Abwasser des Universitätsklinikums konnten große Mengen der dort verordneten Antibiotika bestimmt werden. Die Antibiotikagehalte reduzierten sich bis in den Rhein durch Abbau, Adsorption an Feststoffe und Verdünnung um mehrere Zehnerpotenzen. Analoge Daten konnten für andere Kläranlagen und Oberflächenwässer ermittelt werden. Im Trinkwasser konnten keine Antibiotika nachgewiesen werden, nur die beiden Antibiotika Erythromycin und Sulfamethoxazol gelangten bis ins Rohwasser, konnten aber durch anschließende Trinkwasseraufbereitungstechniken entfernt werden. Die Substanz Sulfamethoxazol kann hier als Tracer dienen, um rechtzeitig eine Trinkwasserbelastung mit Antibiotikarückständen zu erkennen. Im Bereich der perfluorierten Tenside konnte im Rhein eine durchgehend niedrige Belastung des Wassers ermittelt werden, die Perfluorbutansulfonsäure (PFBS) bildete dabei die Hauptkomponente. Die Ruhr zeigte flussaufwärts stark ansteigende Belastungen mit perfluorierten Tensiden, wobei PFOA mit ca. 80% die Hauptkomponente bildete. Annähernd gleich hohe PFOA-Gehalte wurden auch im Trinkwasser gefunden, das durch künstliche Grundwasseranreicherung mit Ruhr-Wasser gewonnen wird. Durch diese Befunde wurden die Behörden auf eine illegale Industrieabfallentsorgung auf landwirtschaftlichen Flächen am Oberlauf der Möhne (Zufluss der Ruhr) aufmerksam, die zur Verunreinigung des Oberflächen- und des Trinkwassers führte, in deren Folge Konzentrationsobergrenzen für PFT beschlossen wurden, eine Nachrüstung der betroffenen Wasserwerke mit zusätzlichen Aufbereitungsschritten begonnen wurde und eine bundesweit Untersuchungstätigkeit auf perfluorierte Tenside ausgelöst wurde. Die Entdeckung der PFT-Belastung im Trinkwasser an der Ruhr führte zu einer weiteren Optimierung der Anreicherungsmethodik und einem beginnenden Normungsverfahren auf Basis dieser Methode. Durch die vorliegende Arbeit konnten zwei leistungsfähige Multikomponenten-Methoden zur Bestimmung von Antibiotika und perfluorierten Tensiden in wässrigen Matrizes entwickelt werden, mit deren Hilfe eine Belastung der Bevölkerung durch PFOA-kontaminiertes Trinkwasser erkannt und zur Behebung dieses Problems beigetragen werden konnte. The present work deals with the chemical analysis of two groups of anthropogenic compounds in the aquatic environment. The first group is a selection of antibiotic substances as residues of pharmaceuticals (environmental problem: bacterial resistances). The second group includes a number of perfluorinated surfactants as residues from industrial processing and refining processes (environmental problem: persistence and bioaccumulation). The first focus of this study was on the development and optimisation of extraction and enrichment methods, primarily of aqueous matrices, as well as on the identification and quantification of these anthropogenic compounds by high-performance liquid chromatography coupled with mass spectrometric detection (HPLC-MS/MS). The investigated group of antibiotics was a result of the data collection on the use of these antibiotics at the Bonn University Hospital and a result of the documented prescribing practices within the statutory health insurance in Germany. The group of perfluorinated surfactants (perfluorinated carboxylic acids and perfluorinated sulphonic acids) was composed of a selection of substances based on their major compounds PFOA (perfluorooctanoic acid) and PFOS (perfluorooctanesulfonic acid) and their short- or long chain homologues. Limits of detection (LOD) and quantitation (LOQ) in single-digit to lower double-digit ng/L-range were achieved with the help of these new multi-component methods (29 antibiotics and 12 perfluorinated surfactants). The methods were successfully validated in several, partly nationwide, inter-laboratory tests. The second focus of the study was on the application of these new methods in the investigation of real samples: In the field of antibiotics, waste water of the Bonn University Hospital was analyzed from the place of origin, via the sewage treatment plant to the Rhine River. Additional data collection was made for further sewage treatment plants and surface waters in North Rhine-Westphalia. The water from a reservoir (for drinking water purposes) and some raw and drinking waters affected by surface water were also analysed. The great amount of antibiotics prescribed at the University Hospital was detected in the collected wastewater. The antibiotics concentrations were reduced in the Rhine River due to degradation, adsorption on sludge and dilution by several orders of magnitude. Analogue data could be determined for other sewage treatment plants and surface waters. No antibiotics were detected in drinking water, except of two antibiotics, erythromycin and sulfamethoxazole, which reached raw waters, but were removed by subsequent drinking water treatment technologies. The substance sulfamethoxazole can serve as a tracer to timely identify drinking water contamination with antibiotic residues. In the field of perfluorinated surfactants, a consistently low contamination of water was identified in the Rhine River, as the perfluorobutanesulfonic acid (PFBS) formed the main component. The Ruhr River showed a strong upstream contamination with perfluorinated surfactants, whereas PFOA with about 80% formed the main component. Nearly the same high level of PFOA was also found in the local drinking water. The drinking water stems from the Ruhr River water, after it underwent bank filtration or artificial recharge. These findings called attention of authorities to an illegal industrial waste disposal on agricultural areas on the upper reaches of the Moehne River (tributary of the Ruhr River) which led to contamination of surface and drinking water. This has resulted in agreed upper limit values for both PFOA and PFOS concentrations, refitting of the relevant water works with additional treatment steps and started a nationwide investigation on perfluorinated surfactants. The detection of the PFOA contamination in drinking water in the Ruhr catchment area led to further optimisation of the enrichment method as well as standardisation procedures in Germany on the basis of this method. With the help of this study, two powerful multi-component methods were developed for the determination of antibiotics and perfluorinated surfactants in aqueous matrices. It also helped to detect a burden for the population through drinking water contaminated by PFOA and has contributed to its elimination.
In a gasoline-contaminated site in Düsseldorf, Germany a two-year monitoring program was carried out to determine the presence, behavior, and fate of 12 gasoline additives in a total of 96 samples from 14 groundwater wells. The origin of contamination was suspected to be a gasoline spill at a gas station. Target compounds were methyl-tert-butyl ether (MTBE), its main degradation products, tert-butyl alcohol (TBA) and tert-butyl formate (TBF); other gasoline additives, oxygenate dialkyl ethers: Ethyl-tert-butyl ether (ETBE), tert-amyl methyl ether (TAME) and diisopropyl ether (DIPE); aromatics: Benzene, toluene, ethylbenzene and xylenes (BTEX), and other compounds causing odor problems: Dicyclopentadiene and trichloroethylene. Purge and trap coupled with gas chromatography-mass spectrometry permitted detection of ng/L concentrations. Ninety of the 96 samples analyzed contained MTBE at levels varying between 0.01 to 645 microg/L. Five contaminated hot spots were identified with levels up to U.S. Environmental Protection Agency (U.S. EPA) drinking water advisory values (20-40 microg/L) and one of them doubling Danish suggested toxicity level of 350 microg/L at a depth of 11 m. No significant natural attenuation was found in MTBE degradation, although samples with high levels of MTBE contained 0.1 to 440 microg/L of TBA. These levels were attributed to its presence in the contamination source more than MTBE degradation. tert-Butyl alcohol was found to be recalcitrant in groundwater. In all cases, BTEX were at low concentrations or not detected, showing less persistence than MTBE. The monitoring of the contamination plume showed that the distribution of the MTBE and TBA in the aquifer formed a similar vertical concentration profile that was influenced by the groundwater flow direction.
For assessing the safety of drinking water supplies suffering cyanobacterial blooms in their water source, a methodology is proposed which relates the performance of their current treatment train to the quality of the raw water. The approach considers that different treatment trains can remove algal toxins with different efficiency. Maximum Tolerable (MT-) values of the raw water expressed by cell counts or by biovolumes of cyanobacteria were calculated. Three MT-categories were identified by colours; high risk (red), moderate risk (yellow) and no risk (green). Two treatment facilities using a conventional (1) and polishing train (2) were assessed using this methodology. For most of the time during an algal bloom the water quality could be classified as yellow which means short term higher toxin levels in comparison to the guide line in clear water were found. However, the red classification, indicating a high risk for drinking water quality was never reached. The model proposed can be understood as supplement of the common alert level framework, ALF-concept (Chorus and Bartram, Situation Assessment, Planning and Management. London and New York: E & FN Spon. 1999; House et al., Management Strategies for Toxic Blue Green Algae: Literature Review. Australia: CRC for Water Quality and Treatment. 2004).
In May 2006 the first serious German perfluorinated compounds (PFC) case of contamination became evident. Industrial waste with high concentrations of PFC was manufactured into a soil improver by a recycling company and spread by farmers on agricultural land of the rural area Sauerland, and led to substantial environmental pollution. In parts of the affected area, perfluorooctanoic acid (PFOA) concentrations in drinking water were > 0.5 microg/L. The German Drinking Water Commission assessed PFC in drinking water and set a health-based guidance value for safe lifelong exposure of all population groups at 0.3 microg/L (sum of perfluorooctane sulfonate [PFOS] and PFOA). The Ministry of Environment together with regional institutions initiated monitoring measurements and actions to minimize further contamination. A human biomonitoring study with mother-child pairs and men revealed that increased PFOA exposure via drinking water led to about four- to eightfold higher PFOA levels in plasma compared to nonexposed groups. Analysis of PFC in breast milk showed comparatively low levels, which seemed not to pose a risk for lactating infants. Due to high levels of PFOS in fish from contaminated lakes and rivers, recommendations for anglers to reduce fish consumption were initiated. Remediation of the affected area is ongoing and PFC levels in various matrices are still above background levels.
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