Insecticide fipronil and its transformation products in human blood and urine: Assessment of human exposure in general population of China

Abstract

Fipronil (FP) is widely used as a highly effective insecticide worldwide, thereby raising concern about environmental contamination and risk for human health. However, data on the occurrence of FP and its transformation products (FPs) in human blood and urine are limited. In this study, 39 pairs of serum, plasma, blood cells (BCs), and urine samples were collected from adults in Wuhan, central China (2020), in order to characterize the concentration profiles of FPs in different matrices. FPs were also determined in serum samples (n = 226, including 57, 56, 56, and 57 samples for Wuhan, Huangshi, Nanjing, and Zhenjiang, respectively) collected from four cities of China (2015) to characterize the exposure levels of FPs among the general population and potential spatial variations. Fipronil sulfone (FP-SFO) was 100% detectable in blood samples, and it was the predominant metabolite (accounting for 86–95% of the cumulative concentrations of FPs [ΣFPs]), with the median concentrations (ng/mL) of 0.17, 0.16, and 0.03 in serum (range: 0.07–1.53), plasma (range: 0.06–1.41), and BCs (range: 0.01–0.24), respectively. The compositional profiles of FPs in serum, plasma, and BCs were similar; very strong positive correlations were observed between different blood matrices for FP-SFO (r = 0.94–0.97, p < 0.01) but not between blood and urine. The median ΣFPs (ng/mL) in the serum (0.20; range: 0.09–1.56) and the plasma samples (0.19; range: 0.09–1.43) was higher than that in BCs samples (0.04; range: 0.01–0.24). In the urine samples, only the major metabolite FP-SFO was detectable in approximately 10% of the samples. Additionally, the highest median ΣFPs (ng/mL) in the serum samples was found in Nanjing (0.56; range: 0.13–1.88), followed by Wuhan (0.34; range: 0.06–1.02), Huangshi (0.10; range: 0.03–0.60), and Zhenjiang (0.08; range: 0.02–0.42). The level of ΣFPs seemed to increase with city sizes and urbanization scale, though further studies are needed to confirm the variations with larger sample size. The estimated daily intake of ΣFPs based on the median concentration of samples from Nanjing (18.5 ng/kg-bw/d) was higher than that of Wuhan (11.3), Huangshi (3.40), and Zhenjiang (2.80). Dietary intake should be the major exposure route for the general population, while water or indoor dust accounted for <1% of the ΣFPs intake. This pilot study provided the first data on the profiles of FPs in paired human serum, plasma, BCs, and urine samples, and potential spatial variations of ΣFPs in China. FP-SFO and FP desulfinyl should be considered among priority substances worthy to be bio-monitored in China due to its moderated persistence and ubiquitous occurrence in human blood.