Occurrence and distribution of trisiloxane ethoxylates in citrus orchard soils in China: Analytical challenges

Trisiloxane ethoxylates (TSEOn) are widely used as agricultural surfactants due to their significant synergism with the active ingredients of pesticides, generally, including three typical end groups which are hydroxyl (TSEOn-H), methoxy (TSEOn-CH₃), and acetoxy (TSEOn-COCH₃), respectively. However, the potential ecotoxicological and endocrine-disrupting risks of TSEOn congeners have recently attracted ever-growing concern. Above all, there is limited research on the concentration levels of TSEOn in agroecosystems. This study, simultaneous analysis of 39 TSEOn oligomers in citrus orchard soils in China was implemented by the modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The method detection limits (MDLs) and the method quantification limits (MQLs) for TSEOn were 0.003-0.07 μg/kg and 0.01-0.20 μg/kg, respectively. The recoveries for TSEOn oligomers in soils ranged from 81 % ∼ 106 % with related standard deviations (RSDs) < 7 %. This newly developed UPLC-MS/MS method with high sensitivity and stability allows us to successfully trace the occurrence of TSEOn congeners in the citrus orchard soils from 3 provinces and 1 municipality in China. The detected concentrations of TSEOn-H oligomers in the sampled soils ranged from 0.02 to 0.288 μg/kg (dry weight). The congener profiles of TSEOn-H were dominated by TSEOn-H (n = 6- 8) in the soils. Additionally, the total concentrations of TSEOn-H congeners (ΣTSEOn-H) in the soils were in the range of 0.03 to 1.49 μg/kg. A comparison of ΣTSEOn-H distribution among the different citrus orchard soils indicated a higher level of ΣTSEOn-H in the soil samples collected from Zhejiang Province. Notably, TSEOn-CH₃ or TSEOn-COCH₃ oligomers were not detected in the tested soils. To the best of our knowledge, this is the first report on the occurrence and distribution of TSEOn congeners in agricultural soils.