In situ calibration of polar organic chemical integrative samplers to monitor organophosphate flame retardants in river water using polyethersulfone membranes with performance reference compounds

Abstract

Passive sampler is an innovative way of monitoring chemicals in different environmental. A modified polar organic chemical integrative sampler (m-POCIS) with a performance reference compound (PRC) was used to evaluate the concentrations of 8 organophosphate flame retardants (OPFRs) under field conditions. The m-POCIS was deployed for 15days under laboratory conditions and 21days under in situ conditions to determine the concentrations of OPFRs. The analytes were trapped in the sorbent and the microporous polyethersulfone (PES) membrane of the m-POCIS. Sampling rates (Rs) were determined for the studied compounds and ranged from 0.02±0.0003L/d (triphenylphosphine oxide, TPPO) to 0.24±0.021L/d (tripropyl phosphate, TPrP) in the laboratory. The membranes accumulation increased with usage and was correlated to the logKow. Among the tested compounds, tripentylphosphate (TPeP) and triphenylphosphate (TPhP) had the highest logKow values and were mostly detected in the membranes. This behavior resulted in a lag-phase, which was measured by extrapolating the data from the last third of the uptake phase (quasilinear) to the x-axis using a linear regression, before the compounds transferred into the sorbent. TPhP was the only compound with a lag-phase of 3.9days during the 15days experiment. Deuteratedtributyl phosphate (TBP-d27) and desisopropyl atrazine-d5 (DIA-d5) were identified through specific experiments as potential PRC. The results from the PRC calibrations suggested that DIA-d5 (ke (in situ)=0.075±0.0048day−1) can be used as a PRC for the evaluation of OPFRs using m-POCISs. The time-weighted average (TWA) concentrations estimated by the m-POCIS with or without a PRC were significantly correlated with the corresponding values determined from the grab samples. After the PRC calibration, the TWA concentrations of the tested OPFRs in an aquatic environment were lower than those estimated using the laboratory sampling rates (Rs). The m-POCIS with a PRC correction was a suitable tool for estimating OPFRs TWA concentrations in the Yangtze River.