Determination of polar pharmaceuticals in sewage water of Greece by gas chromatography–mass spectrometry☆
Introduction
Over the past decade, findings have been reported for drugs and drug metabolites of various therapeutical classes, used in human and veterinary medicine in effluents of wastewater treatments plants, surface, and groundwater in Europe and in the USA (Daughton and Ternes, 1999; Kolpin et al., 2002).
Pharmaceuticals are released in the environment mainly through human wastes by excretion of unmetabolized parent compounds and metabolites. Portions of the free excreted drugs and metabolites can escape elimination in the sewage treatment process (via wastewater treatment plants, or domestic septic systems) and enter the aquatic environment in sewage effluents (Daughton, 2001). Despite their continuous discharge in the environment, few data exists about the biodegradation, toxicity and environmental fate of pharmaceuticals (Halling-Sørensen et al., 1998).
Due to the polar structure of most pharmaceutical compounds they are not significantly adsorbed in the subsoil and may leach into the groundwater aquifers from the contaminated surface water (Heberer et al., 1997). Clofibric acid is the first prescription drug metabolite ever reported in sewage influent and effluent (Kansas City, USA in 1976) (Hignite and Azaznoff, 1977) and still the most frequently detected in sewage effluents, groundwater, surface and drinking water all over the world (Stan and Linkerhanger, 1992; Stan et al., 1994; Heberer and Stan, 1997; Buser et al., 1998a; Stumpf et al., 1999). Diclofenac and ibuprofen are used in human medical care belonging to the group of the nonsteroidal anti-inflammatory drugs. They are used worldwide with a production volume estimated to be in the hundreds of tons annually. These drugs have been detected in sewage effluents, surface and groundwater in Germany (Heberer et al., 1998; Ternes, 1998), in Swiss (Buser et al., 1998b, Buser et al., 1999) and effluent sewage waters in Brazil (Stumpf et al., 1999). The analgesics phenazone and propyphenazone have been detected in Berlin sewage treatment works (Heberer et al., 1997; Ternes, 1998). Analgesics of the phenazone type, including propyphenazone, were also determined in soil and groundwater below the main municipal solid wast landfill of the city of Zagreb, Croatia (Ahel and Jelicic, 2001).
Various multi-residue analytical methods for the determination of polar drug residues in aqueous solutions have been described in literature using gas chromatography–mass spectrometry (GC–MS) detection after derivatization by diazomethane (Ternes et al., 1998; Ollers et al., 2001). However, preparation and use of diazomethane carries some risk and reasonably skilled technicians can carry out these procedures safety. Recently, alternative methods involving liquid chromatography–mass spectrometry (LC–MS) have been developed for the analysis of polar drugs in aqueous environmental samples (Farre et al., 2001; Ternes, 2001; Miao et al., 2002). However, LC–MS are costly instruments therefore their use is not always available for routine analysis.
In this study the occurrence of five polar pharmaceuticals, namely clofibric acid, diclofenac, ibuprofen, phenazone and propyphenazone was investigated in treated and untreated sewage, in Greece within a Hellenic-German joint project (Hellenic-German Scientific Cooperation, 1997–1999).
Although prescription numbers of the investigated drugs were unavailable, as they can be purchased in a pharmacy without prescription, it can be estimated that the annual consumption is high, due to their intensive use and the relatively high therapeutical dosages (Buser et al., 1998a, Buser et al., 1998b, Buser et al., 1999).
The analytical method performed, involves solid phase extraction (SPE) of the target analytes and determination by capillary GC–MS with selected ion monitoring (SIM), after derivatization with pentafluorobenzyl bromide (PFBBr). The method initially developed for the determination of acidic herbicides and related polar contaminants (Butz et al., 1994; Heberer et al., 1994) has been extended to pharmaceuticals and its potential is demonstrated in heavily polluted sewage samples.
The aim of this work was to obtain a first overview of possible contamination of sewage water of Greece from pharmaceuticals.
Section snippets
Materials
All drugs (clofibric acid, diclofenac, ibuprofen, phenazone, propyphenazone) and 2,4-dichlorobenzoic acid (Fig. 1) were with purity 99%, purchased from Sigma (St. Louis, MO, USA), Ferak (Berlin, Germany) and Promochem (Wesel, Germany). 3,4-Dichlorophenoxyacetic acid (3,4-D) was donated by the Technical University of Berlin, Institute of Food Chemistry, Germany. Pesticide grade (pestiscan) acetone, methanol and toluene were provided by Lab-scan (Dublin, Ireland). PFBBr and triethylamine were
Determination
The pentafluorobenzyl (PFB) derivatives of target compounds, i.e. phenazone, clofibric acid, propyphenazone, 2,4-dichlorobenzoic acid (internal standard, ISTD), ibuprofen, 3,4-D (surrogate standard) and diclofenac were determined by capillary GC ion trap-mass spectrometry in EI mode of operation.
Typical chromatograms are shown in Fig. 2 for a sewage sample, spiked from 500 to 1000 ng l−1 per analyte, using full-scan conditions (B) and time-scheduled SIM (C) under EI mode. As compiled in Table 1,
Conclusion
The results of our monitoring indicated that all sewage influent and effluent water samples were found contaminated with diclofenac, at concentration in the range of those reported in other European countries. The occurrence of diclofenac in all municipal sewage treatment plant influents, points to human usage and has no correlation to industrial discharges. As we found diclofenac in every effluent sample, we assume that it is not completely eliminated during passage through the sewage
Acknowledgements
This study was conducted within the activities related to the Joint Project GRI-161-97. The authors wish to thank the Hellenic-German Scientific Cooperation for supporting this field.
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Part of this work was presented in the 219th American Chemical Society National Meeting, San Francisco (CA) 26-31/3/2000.