Helping WWTP managers to address the volatile methylsiloxanes issue–Behaviour and complete mass balance in a conventional plant

Volatile methylsiloxanes (VMSs) are a group of additives employed in different consumer products that can affect the quality of the biogas produced in wastewater treatment plants (WWTPs). The main objective of this study is to understand the fate of different VMSs along the treatment process of a WWTP located in Aveiro (Portugal). Thus, wastewater, sludge, biogas, and air were sampled in different units for two weeks. Subsequently, these samples were extracted and analyzed by different environment-friendly protocols to obtain their VMS (L3-L5, D3-D6) concentrations and profiles. Finally, considering the different matrix flows at every sampling moment, the mass distribution of VMSs within the plant was estimated. The levels of ∑VMSs were similar to those showed in the literature (0.1–50 μg/L in entry wastewater and 1–100 μg/g dw in primary sludge). However, the entry wastewater profile showed higher variability in D3 concentrations (from non detected to 49 μg/L) than found in previous studies (0.10–1.00 μg/L), likely caused by isolated releases of this compound that could be related to industrial sources. Outdoor air samples showed a prevalence of D5, while indoor air locations were characterized by a predominance of D3 and D4. Differences in sources and the presence of an indoor air filtration system may explain this divergence. Biogas was characterized by ∑VMSs concentrations (8.00 ± 0.22 mg/m3) above the limits recommended by some engine manufacturers and mainly composed of D5 (89%). Overall, 81% of the total incoming mass of VMSs is reduced along the WWTP, being the primary decanter and the secondary treatment responsible for the highest decrease (30.6% and 29.4% of the initial mass, respectively). This reduction, however, is congener dependant. The present study demonstrates the importance of extending sampling periods and matrices (i.e., sludge and air) to improve sample representativity, time-sensitivity, and the accuracy of mass balance exercises. [Display omitted] •Environment-friendly methodologies were used to study levels of VMSs in a WWTP.•Entry wastewater presented a high variability in VMS levels and profiles.•D5 represented more than 70% of total VMSs in sludge, biogas and outdoor air.•D3 was prevalent in entry water, while D3 and D4 were predominant in indoor air.•81% of incoming VMS mass is reduced along the WWTP, mainly due to volatilization.