Chapter 4
Occurrence of Pharmaceutical Residues in Sewage, River, Ground, and Drinking Water in Greece and Berlin (Germany) Downloaded by PENNSYLVANIA STATE UNIV on July 28, 2012 | http://pubs.acs.org Publication Date: July 30, 2001 | doi: 10.1021/bk-2001-0791.ch004
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Th. Heberer , B. Fuhrmann , K. Schmidt-Baumler , D. Tsipi , V. Koutsouba , and A. Hiskia 2
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Institute of Food Chemistry, Technical University of Berlin, Sekr. TIB 4/3-1, Gustav-Meyer-Allee 25,13355 Berlin, Germany General Chemical State Laboratory, 16, An. Tsoha, 11521, Athens, Greece Institute of Physical Chemistry,NCSRDemokritos,15310,Athens,Greece 2
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A number of pharmaceuticals used in human medical care are not completely eliminated in the municipal sewage treatment works. They are discharged as persistent contaminants into the aquatic environment. Due to their polar structures, some of these residues are not significantly adsorbed in the subsoil and may, under unfavorable conditions, also leach into the groundwater aquifers from the contaminated surface waters. Especially in conurbations such as Berlin (Germany), with high municipal sewage water outputs and low surface water flows, there is a potential risk of drinking water contamination when groundwater recharge is used in drinking water produc tion. In 1998 and 1999, in the framework of a GermanHellenic project, the occurrence of drug residues in the aquatic environment in Berlin and in different cities in Greece was in vestigated and compared. The results demonstrate the extent and variety of surface water contamination by drug residues in the aquatic environment.
© 2001 American Chemical Society
In Pharmaceuticals and Care Products in the Environment; Daughton, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001.
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Downloaded by PENNSYLVANIA STATE UNIV on July 28, 2012 | http://pubs.acs.org Publication Date: July 30, 2001 | doi: 10.1021/bk-2001-0791.ch004
Introduction When applying pharmaceuticals to humans or livestock, many of these compounds are excreted without being metabolized in the target organism. They are excreted only slightly transformed or even unchanged and often conjugated to polar molecules (e.g., as glucoronides). Considering human pharmaceuticals, the excreted drugs and drug metabolites are passed into the sewage system and will be processed by municipal sewage treatment works (STWs). In the STWs the drug conjugates are easily cleaved and then discharged into the receiving waters (1-9). Due to their polar structures, many of these persistent residues are not significantly adsorbed in the subsoil (10,11). In case of influent conditions, they may also leach into the ground water aquifers from the contaminated sur face waters (12-15). Especially in conurbations such as Berlin (Germany) with high municipal sewage water outputs and low surface water flows, there is a potential risk of drinking water contamination when groundwater recharge is used in drinking water production (13-15). In 1992, the drug metabolite clofibric acid (2-(4)-chlorophenoxy-2-methyl propionic acid) was first found in Berlin groundwater samples and in ground water samples collected from former sewage irrigation fields near Berlin (10,11,14,16). Clofibric acid is the active metabolite of the drugs clofibrate, etofyllin clofibrate, and etofibrate, which are used as blood lipid regulators in medical care. Meanwhile, the occurrence and fate of pharmaceutical residues in the aquatic environment has become a subject of public concern (1,2,4,5). More than 40 pharmaceuticals have been identified in sewage effluents and surface waters up to the μg/L-level (1-6,9), and a few pharmaceutical residues also show up in ground and drinking water (13-15). Most investigations concerning pharmaceutical residues have been carried out in Germany, but recently several findings have also been reported from Bra zil, Canada, Denmark, Italy, Switzerland, The Netherlands, and the U S A (2,8,14,17-23). In the terms of a Hellenic-German Scientific Cooperation enti tled "Investigation and Determination of New Environmental Contaminants in Greek Surface Water" (24), the occurrence of several drug residues in the aquatic system in different regions in Greece and in Berlin (Germany) was in vestigated and compared. Additionally, in the years between 1994 and 1999, sewage, surface water, ground water, and drinking water samples from the Ber lin area were analyzed for several drug residues. Over the years, the spectrum of the target compounds was extended to more than 30 pharmaceutical residues (25). Several results from these investigations are presented here. They show the impact of sewage discharges on the surface water quality of large conurba tions such as Berlin. Moreover, the results show that several pharmaceutical compounds are cycled from human application via human excretions, STWs, surface waters, ground water recharge, and back to human drinking water.
In Pharmaceuticals and Care Products in the Environment; Daughton, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2001.
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Downloaded by PENNSYLVANIA STATE UNIV on July 28, 2012 | http://pubs.acs.org Publication Date: July 30, 2001 | doi: 10.1021/bk-2001-0791.ch004
Discharges of Persistent Drug Residues from Municipal Sewage Treatment Plants in Greece and Berlin In terms of a German-Hellenic cooperation (24), the occurrence of drug residues in influents and effluents of STWs from different regions in Greece and in Berlin was investigated and compared. This survey was the first study of the occurrence of drug residues in sewage effluents in Greece. Sometimes it was difficult to encourage the operators of the sewage treatment plants to participate in this study. Thus, only random sewage effluent samples were provided and for the second major survey in 1999 only three Greek STWs supplied us with sam ples. Nevertheless, the analyses of these samples gave some interesting results and indications. Table I. Results from the first screening of influents and effluents of several STWs in Greece for clofibric acid, diclofenac and propyphenazone in 1998.
STWs influent/ (date ofsampling) effluenf Psittalia (Athens) 11/09/98 Psittalia (Athens) 11/11/98 Metamorphossi 11/16/98 Metamorphossi 11/17/98 Thessaloniki 11/18/98 Thessaloniki 11/19/98 a
clofibric acid diclofenac propyphenazone ng/L ng/L ng/L
in out in out in out in out in out in out
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n.d. n.d. n.d. n.d. n.d. n.d. n.d. 5 n.d. n.d. n.d. n.d.
85 100 115 80 560 10 35 50 105 100 120 365
n.d. n.d. n.d. n.d. 10
n.d. n.d.
