Determination and Ecological Risk Assessment of Organophosphate Esters in Drinking and Environmental Waters by Automated Liquid–Liquid Extraction Coupled with GC-MS/MS

Organophosphate esters (OPEs) are ubiquitous in the global water environment and may pose potential risks to aquatic ecosystems and human health. Herein, we present a simple and efficient method for accurate quantification of nineteen OPEs in water based on automated liquid–liquid extraction (LLE) with dichloromethane and hexane, followed by gas chromatography–tandem mass spectrometry (GC-MS/MS) with isotope dilution calibration. This method demonstrated a negligible matrix effect, satisfactory recoveries (70–120%), and low limits of detection (0.46–2.32 ng/L). A total of 3, 9, 10, and 11 OPEs were detected in Wahaha pure water, tap water, river water, and seawater, respectively, with total OPE (∑OPE) concentration ranges of 8.23–18.5 ng/L, 159–218 ng/L, 202–623 ng/L, and 111–175 ng/L, respectively. Among the detected OPEs, tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCIPP) were the predominant compounds in four test water matrices. The risk quotient (RQ) results revealed that OPEs exhibited a low risk to algae, crustaceans and fish in the river water of Zhoushan and seawater of Sanmen Bay. Overall, the proposed method is sensitive and reliable for routine OPE analysis in drinking and environmental waters.