Characterizing pyrethroid and fipronil concentrations in biosolids

Pesticides are prevalent in wastewater, yet few studies have measured pesticides in biosolids and aqueous media from samples collected concurrently. Seventeen California wastewater treatment plants (WWTPs) were sampled in May 2020. Biosolids samples were analyzed for 27 analytes, and paired aqueous samples (influent and effluent) were analyzed for 23 analytes. Analytes included fipronil and its transformation products (fiproles), pyrethroids, novaluron, and several other pesticides with down-the-drain transport potential. Of the 27 compounds analyzed in biosolids samples, 16 were detected in at least one sample, and 10 had a detection frequency (DF) of at least 25 %. Fipronil sulfone, fipronil sulfide, and fipronil were the most frequently detected fiproles (DF = 100 %, 94 %, and 67 %, respectively); permethrin was the most frequently detected pyrethroid (DF = 100 %), followed by bifenthrin (DF = 94 %), cyhalothrin (DF = 89 %), and etofenprox (DF = 78 %). To elucidate fipronil transformation pathways within the treatment system, data from the three sample types were compared; findings were generally consistent with transformation pathways reported previously (e.g., some fiproles were rarely detected in influent or biosolids, but frequently detected in effluent, indicating their formation during the treatment process). No correlations were found between WWTP characteristics and pesticide concentrations in biosolids. The fraction of organic carbon (f_OC) of each biosolids sample was measured, and a statistically significant negative correlation was observed between f_OC and some fiproles, but not fipronil; possible explanations are discussed. Additional analysis for two major agricultural pesticides (bifenthrin and permethrin) indicated that estimated mass loads of these pesticides in biosolids applied to land as a soil amendment are minimal (approximately 2 to 3 orders of magnitude lower) compared to inputs from agricultural applications. This study provides insight on the magnitude of pesticides entering the environment via land-applied biosolids; existing regulations surrounding agricultural pesticide applications are expected to also be protective of the relatively low inputs from biosolids.