Environ. Sci. Technol. 2010, 44, 1728–1735
Antiviral Drugs in Wastewater and Surface Waters: A New Pharmaceutical Class of Environmental Relevance? C A R S T E N P R A S S E , †,‡ ¨ SENER,† MICHAEL P. SCHLU RALF SCHULZ,‡ AND T H O M A S A . T E R N E S * ,† Federal Institute of Hydrology (BfG), Koblenz, Germany, and Institute for Environmental Sciences, University of Koblenz-Landau, Landau, Germany
Received October 22, 2009. Revised manuscript received January 7, 2010. Accepted January 11, 2010.
An analytical method was developed for the determination of nine antiviral drugs (acyclovir, abacavir, lamivudine, nevirapine oseltamivir, penciclovir, ribavirin, stavudine, zidovudine) and one active metabolite (oseltamivir carboxylate) in raw and treated wastewater as well as in surface water using LC/ESI tandem MS detection. Relative recoveries exceeded 80% and limits of quantification ranged between 0.2 and 10 ng L-1. Matrix effects were compensated by the use of stable isotope labeled surrogate standards and optimized chromatographic separation on a Hydro-RP column. All antiviral drugs, except ribavirin, were detected in raw wastewater. A significant reduction in concentrations was observed for acyclovir, lamivudine, and abacavir in treated wastewater indicating a substantial removal, while nevirapine, zidovudine and oseltamivir were found in similar concentrations in raw and treated wastewater. Concentrations in river waters were in the lower ng L-1range, with a maximum of 190 and 170 ng L-1 for acyclovir and zidovudine, respectively in the Hessian Ried. Estimated total compound loads in the Ruhr river ranged between 99%. With the exception of zidovudine, similar removal rates were calculated for WWTP1, although only grab samples were taken. Elevated concentrations of zidovudine in the effluents of WWTP2 might be caused by the cleavage of glucuronide conjugates known to be excreted by humans up to 70% (35). There are no reasonable explanations for the elevated nevirapine concentrations in the WWTP effluent. However, it cannot be excluded that the confidence interval calculated underestimates the real statistical uncertainties of the nevirapine concentrations, and thus the increase is artificial. Hessian Ried. In rivers and streams from the Hessian Ried, maximum concentrations were found for acyclovir and zidovudine with concentrations up to 190 ng L-1 (Erlenbach; HR_11) and 170 ng L-1 (Bieber; HR_09), respectively (Figure 1). Ribavirin and lamivudine were not detected at all, penciclovir was determined with concentrations close to the LOQ in the Landgraben (HR_03), and abacavir was present only in the Erlenbach (HR_11). These results are in good agreement with results from the two WWTPs with penciclovir, lamivudine, stavudine and abacavir being present in WWTP influents but not detected in WWTP effluents. Probably due to the limited biological transformation (e.g., during wastewater treatment and in rivers) oseltamivir and its active metabolite, oseltamivir carboxylate, were detected in almost all of the surface water samples collected in the Hessian Ried VOL. 44, NO. 5, 2010 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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FIGURE 1. Occurrence of antiviral drugs in rivers and streams in the Hessian Ried Region, south of Frankfurt am Main, Germany (LOQ: limit of quantification). Mean concentrations [ng L-1] are given together with 95% confidence intervals (n ) 3).
TABLE 3. Antiviral Drugs in Influents and Effluents of Sampled WWTPs. Statistical Uncertainties: 95% Confidence Intervals (n = 3) WWTP1
WWTP2
(grab samples)
(24 h composite samples)
concentration [ng L-1] analyte
influent
effluent
ribavirin acyclovir penciclovir lamivudine stavudine abacavir nevirapine oseltamivir oseltamivir carboxylate zidovudine
