Ecotoxicological mixture risk assessment of 35 pharmaceuticals in wastewater effluents following post-treatment with ozone and/or granulated activated carbon.

Reducing the risk posed by mixtures of pharmaceuticals is a goal of current initiatives such as the European Green Deal to reduce anthropological environmental impacts. Wastewater effluent typically contains large numbers of active pharmaceutical ingredients (APIs). For some APIs, existing technology such as conventional activated sludge (CAS) wastewater treatment plants (WWTPs) have removal rates below 20 %, thus the WWTP discharges are adding to the toxic burden of receiving waters. We present an environmental risk assessment of mixtures of 35 APIs in effluent samples from 82 Northern European WWTPs using the concentration addition model, and identify the respective risk-driving APIs. This is then compared to a corresponding mixture risk assessment of effluent samples from the Danish Hillerød WWTP subjected to post-treatment with varying specific ozone doses (0.15-1.05 mgO/mgDOC) and/or granulated activated carbon (GAC). All 82 WWTP effluent samples exceeded risk thresholds by at least a factor of 30, with a median RQ of 92.9, highlighting the need for effluent post-treatment and/or a substantial dilution in the recipient waters. Antibiotics, analgesics and anti-depressants were among the top risk drivers with 99 % of the average mixture risk attributable to azithromycin, diclofenac, venlafaxine, clarithromycin and mycophenolic acid. Effluent mixture risk was reduced by ozonation in a concentration-dependent manner, decreasing below threshold levels to a median RQ of 0.83 following treatment with 0.65 mgO/mg DOC. Fresh GAC was also effective at reducing the mixture risk both alone and with ozone treatment, with median RQ of 0.04 and 0.07 respectively. To our knowledge, this is the first study to present a risk assessment of pharmaceutical mixtures in effluent comparing "conventional" WWTP processes with additional post-treatment with ozone and/or GAC for reducing the joint risks of pharmaceutical mixtures for recipient waters. We demonstrate the need for additional WWTP treatment technologies, and the efficacy of GAC and ozonation in decreasing the risk to the aquatic environment from pharmaceutical mixtures to below acceptable threshold limits.