Workshop of the German Environmental Specimen Bank
on monitoring of priority pollutants and emerging substances in sewage sludge Schmallenberg, Germany, June 24 to 25, 2009 Heinz Rdel & Karlheinz Weinfurtner & Jan Koschorreck
Received: 19 January 2010 / Accepted: 10 April 2010 / Published online: 28 April 2010 # Springer-Verlag 2010
1 Motivation and background
Each monitoring study examines only one fraction of the pollutants in a sample, mostly a spectrum of currently interesting compounds. Therefore, each monitoring ideally should be combined with an archiving of the samples. This would later allow a retrospective monitoring of such substances that seemed to not be relevant for the current investigations, or for which no validated analytical methods were available. Due to such considerations, an environmental specimen bank (ESB) was established in Germany (Umweltprobenbank (UPB)). It is based on a regular and standardized collection of representative samples that are archived for future investigations. Examples of retrospective monitoring investigations and the application of their results for risk assessment of chemicals are already documented for biota samples as well as for human specimens retrieved from the UPB archive. Today, major inputs into the environment occur via the wastewater path by sewage treatment plants (STP). Thus, several investigations were accomplished recently to characterize the contaminant pattern of STP sludges. Sludges may also be potential sample material for an ESB. On behalf of the UPB group of the German Federal Environment Agency (UBA), a workshop was organized to share experiences with experts from sludge monitoring programs, to balance the current state of research on the methodology H. Rdel (*) : K. Weinfurtner Fraunhofer IME, 57392 Schmallenberg, Germany e-mail: heinz.ruedel@ime.fraunhofer.de J. Koschorreck Federal Environment Agency (Umweltbundesamt), 06813 Dessau-Rosslau, Germany
and to discuss the need for sludge investigations for
chemicals risk assessment. More than 30 scientists attended the workshop at Fraunhofer IME in Schmallenberg in June 2009, and 11 participants presented their results and ideas for discussion.
2 General considerations for a sludge monitoring within
an ESB context M. Kolossa-Gehring (UBA) chaired a session that highlighted general conditions of a possible ESB sludge monitoring. J. Koschorreck (UBA) presented the conception of the German UPB that was established to compile trends for chemical safety. A network of sampling regions covers coastal regions, major rivers, and representative terrestrial ecosystems. ESBs become increasingly important, since they can support chemical risk management, e.g., in the context of REACH, the European Union (EU) chemicals management system.1 S. Hahn (Fraunhofer ITEM) gave a presentation on the application of sludge monitoring data for the evaluation of chemicals in the context of current EU regulations. So far, the assessment of environmental risks of chemicals (e.g., personal care products and washing and cleaning agents) is mainly based on modeled values. However, measured concentrations can clearly deviate, especially if models come to their borders. New EU regulations such as the Biocidal Product Directive, and 1 The US-EPA is developing an amendment to a similar system, the Toxic Substances Control Act (TSCA, called Tosca). The Toxic Substances Control Act became law on October 11, 1976 and became effective on January 1, 1977.
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REACH, affect the application of chemicals and products
in the long run. Effects of taken measures for minimizing risks (e.g., use restrictions) as well as of substitutions would become verifiable with a retrospective monitoring of archived sludges. B. M. Gawlik (EU Joint Research Centre, Italy) highlighted a monitoring concept for the determination of background levels of priority and emerging pollutants by the example of STP sludge. In the last 30 years, the EU implemented several environmentally relevant guidelines. These were accompanied by the implementation of harmonized quality standards for classical pollutants in different media. Parallel to these regulations, an infrastructure for monitoring these compounds was developed in EU member states (e.g., Water Framework Directive). However, in comparison, the information status for emerging substances permits hardly an EU-wide overview. Therefore, a nonprobabilistic concept for providing EU-wide snapshots of the occurrence of emerging substances in different matrices was developed, which is now applied to STP sludges and effluents.
3 Experiences from sludge monitoring studies
M. Oberdrfer (LANUV North Rhine-Westphalia (NRW)) reported on experiences from the sludge monitoring in NRW. Sludge from about 160 STPs was analyzed for 70 organic compounds. The evaluation revealed that ubiquitously occurring pollutants exhibited only small temporal variations in their concentrations. The characteristics of an STP catchment area, the applied STP technology, or the kind of sludge treatment process had only small influence on the pollutants' burden of the sludge. On the other hand, for some compounds, it was obvious that the procedure of sludge stabilization (aerobic/ anaerobic) is an important determining factor for pollutants' levels. T. Kupper (Swiss College of Agriculture Berne) described experiences from the sludge monitoring in Switzerland. The multi-year program investigated 20 representative STPs covering, e.g., different STP sizes as well as inputs from combined and separated sewage systems. These investigations proved that sludge contains a multiplicity of pollutants and is a suitable matrix for the observation of anthropogenic emissions (Table 1). B. Kuch (ISWA, University of Stuttgart) reported on experiences from sludge investigations in BadenWuerttemberg. So-called xenoestrogens like Bisphenol A or hydroxybiphenyls, which were quantified with an in vitro test system, were nearly always detectable. Further pollutants, so far less investigated in sludge, were phosphorus-based flame retardants like trichloroethylene
such as terbutryne and propiconazole, phenolic compounds and stabilizers (e.g., Irganox 1076), or benzophenone derivatives. The speech of M. Letzel (LfU, Bavarian Environment Agency) covered the monitoring of Bavarian STP sludges for (dioxin-like) polychlorinated biphenyls, perfluorinated compounds (PFCs) and possible substitutes, polycyclic aromatic hydrocarbons, biocides such as triclosan, organotin compounds, brominated flame retardants, DEHP, and substitutes, as well as alkylphenols. For PFCs, a broader database was compiled since sludges, which are applied on lands, are analyzed routinely. From about 800 sludge samples, approximately 6% exceeded the precautionary value for PFCs (125 g/kg dry weight).
4 Aspects of the practical implementation of an ESB
sludge monitoring The third session was conceived as basis for the discussion in working groups (WGs). U. Eckhoff (LANUV NRW) reported on sludge sampling methodology. His remark, the sampler is responsible for the digits before the decimal point, the analyst for those behind it, stressed the importance of the sampling step. Basis for the agricultural sludge utilization in Germany is a Federal Sewage Sludge Regulation. Sludge sampling has to follow the standard ISO 5667-13 (1997). Results in the context of the NRW monitoring program showed that sludge samples drawn from digestion towers were relatively homogeneous. K. Weinfurtner (Fraunhofer IME) presented the protocol for the cryogenic processing of suspended particulate
compounds like HHCB and AHTN) Polychlorinated biphenyls (sum of 7 congeners) Organochlorine pesticides (e.g., HCB and lindane) Biocides (e.g., carbendazime and tributyltin) Polybrominated flame retardants (PBDE and HBCD)
Environ Sci Pollut Res (2010) 17:11831185
matter (SPM) applied for the UPB. Since the water
content of SPM is comparable to that of sewage sludge, SPM has similar demands for sample treatment. Material collected from SPM traps is frozen directly on site as a thin layer over liquid nitrogen. Later on in the laboratory, pooled SPM samples are freeze-dried (with active cooling to reduce thermal stress). Accompanying investigations confirmed the good homogeneity of archived SPM subsamples. A presentation by H. Rdel (Fraunhofer IME) summarized the requirements for sludge monitoring in an ESB context. Important aspects are standardized sampling under similar STP operation conditions at each occasion as well as a reproducible sample processing excluding impairments of chemical information in sludges. The long-term goal would be to build up an ESB sludge archive which allows the detection of concentration trends of chemicals (e.g., ingredients from personal care products) in time series of comparable samples.
5 Working group discussions for the possible
implementation of a retrospective sludge monitoring W. Krdel (Fraunhofer IME) chaired the WG on sludge sampling aspects. The group suggested that primarily STPs in regions with existing ESB river sampling sites should be covered. A number of about ten STPs was seen as appropriate for this purpose. It was stressed that samplings should always be performed exclusively by qualified personnel. Concerning the sample matrix, the WG agreed that it may not be sufficient to only collect the sludge fraction. Instead, it was suggested that both final products should be sampled, i.e., the sludge (after anaerobic/aerobic treatment) and, if possible, also effluent waters. The WG also discussed the extent of necessary documentations of relevant parameters. For information on STP operating parameters, cooperation with the plant operators was seen as essential. The second WG, chaired by B. M. Gawlik, discussed the preparation of sludge samples in the laboratory. Participants agreed that an immediate freezing of the sludge after sampling is most recommendable because also with cooling, biological processes would continue, and a change of the chemical composition could not be
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excluded. For reduction of the water content, a cooled
freeze-drying device was recommended by the WG to reduce possible losses of semi-volatile organic materials. Requirements of sludge monitoring for use in risk management of chemicals was discussed in the WG chaired by J. Koschorreck. A sludge archive could be seen as a useful addition to the archiving of biota. Such a scheme would allow a better surveillance of the wastewater path, which currently seems to be most important for the entry of chemicals into the environment. Large benefits are expected for the risk assessment of pharmaceuticals (optimally also with coverage of STP effluents). An advantage of the STP monitoring in the context of the UPB was also seen as possibility of a non-target screening for unknown chemicals.
6 Recommendations from the workshop on sludge
monitoring After presentation of the results of the WGs, a synoptic discussion was conducted. The potential of a sludge monitoring and archiving in an ESB was acknowledged. Also, most participants agreed with the recommendation to consider not only sludge but also STP effluents. This would provide a basis for the investigation of all potential STP inputs into the environment and allow a large-scale modeling of the flow of substances (if sufficient substance data would be available). In addition, through an effluent monitoring, a more direct linkage to the UPB biota monitoring would be given. Participants emphasized that by the high concentrations of chemicals in STPs, the monitoring could also serve as an early warning system for the environmental occurrence of chemicals. Finally, the time frame for the possible implementation of a routine sludge monitoring for the UPB was discussed. Generally, a fast implementation was seen as desirable so that changes of the application pattern of chemicals (e.g., by nonregistration of compounds and substitutions by others) already caused by the REACH directive could be covered. In the concluding session, the workshop was unanimously regarded as successful. A detailed workshop report (in German) has been published at http://www. umweltprobenbank.de/en/documents/publications/12761.