Combined sewer overflows to surface waters detected by the anthropogenic marker caffeine

Continuous progress in wastewater treatment technology and the growing number of households connected to wastewater treatment plants (WWTPs) have generally resulted in decreased environmental loading of many pollutants. Nonetheless, further reduction of pollutant inputs is required to improve the quality of surface waters in densely populated areas. In this context, the relative contribution of combined sewer overflows as sources of wastewater-derived contaminants has attracted more and more attention, but the quantitative importance of these overflows has barely been investigated. In this study, caffeine was successfully used as a chemical marker to estimate the fraction of sewer overflows in the catchment area of lake Greifensee, Switzerland. Caffeine is a ubiquitous compound in raw, domestic wastewater with typical per capita loads of approximate to 16 mg person(-1) d(-1). In WWTPs of the Greifensee region, caffeine is largely eliminated (> 99%), resulting in much smaller loads of <= 0.15 mg person(-1) d(-1) in treated wastewater. However, in receiving streams as in the inflows to Greifensee, caffeine loads (0.1-1.6 mg person(-1) d(-1)) were higher than those in WWTP effluents, indicating additional sources. As the loads in the streams correlated with precipitation during sampling, it was concluded that combined sewer overflows were the most likely source of caffeine. Using a mass balance approach, it was possible to determine the fraction of wastewater in dry weather equivalents discharged untreated to the receiving streams (up to 10%, annual mean, approximate to 2-3%). The concept of caffeine as a marker for combined sewer overflows was then applied to estimate phosphorus inputs to Greifensee with untreated and treated wastewater (approximate to 1.5 and 2.0 t P y(-1), respectively), which corresponded well with P inputs determined in a separate study based on hydraulic considerations. For compounds with high elimination in WWTPs such as phosphorus (96-98% in the Greifensee area), inputs from combined sewer overflows are thus of similar magnitude as inputs from treated wastewater. The study demonstrated that caffeine is a suitable marker for untreated wastewater (from combined sewer overflows, direct discharges, etc.), but its sensitivity depends on regional conditions and decreases with decreasing elimination efficiency in WWTPs.