Determination of persistent organic pollutants in urban and peri-urban wastewater sludge: environmental and carcinogenic human risk assessment in the case of land application.

The management of digested sludge derived from treatment water plants is a problem worldwide due to the possible transfer of contamination from sludge to amended soil and, in turn, to humans. Within this work, through a chemometric experimental design, a robust GC-MS method for the simultaneous determination of two classes of micropollutants of concern (polycyclic aromatic hydrocarbons-PAHs-and polychlorinated biphenyls-PCBs-including dioxin-like compounds) was developed using microwave-assisted extraction (MAE). The method, which showed interesting greenness features in compliance with the 12 principles of Green Chemistry, allowed PCB and PAH extraction with recoveries higher than 75% (RSD < 14%) with method detection limits between 4.6 and 11.5 µg kg (PAHs) and between 6.9 and 13.7 µg kg (PCBs), without preconcentration. The matrix effect was below 20%. The validated protocol allowed the characterization of two digested sludges sampled in an urban and a peri-urban district, representative models of two scenarios of different anthropic impacts. This study highlighted higher contamination for the sludge derived from the urban area, accounted for by the 4-ring PAHs. In addition, since carcinogenic PAHs were detected, the environmental risk (by mean of the comparison of predicted vs predicted no-effect concentrations) and the carcinogenic human risk from dermal contact (through the calculation of the adsorbed lifetime average daily dose) were assessed in the case of soils amended with the sludges considered, pointing out that the measured concentrations do not pose a risk.