Development and Calibration of the Polar Organic Chemical Integrative Sampler (POCIS) for Neonicotinoid Pesticides

Abstract

Neonicotinoid pesticides are highly hydrophilic systemic insecticides that have been extensively used worldwide. To evaluate their environmental risks, the concentrations of these pesticides in the aquatic environment must be monitored. Although the polar organic chemical integrative sampler (POCIS) has proved to be a suitable passive sampler for many highly hydrophilic compounds, Oasis HLB (Waters) POCIS has shown limitations for the monitoring of neonicotinoid pesticides, such as short linear uptake ranges. In the present study we optimized POCIS for neonicotinoid pesticides by selecting suitable adsorbents and filters. The ENVI‐Carb (Supelco) nonporous carbon‐based adsorbent demonstrated a good balance between strong sorption and high recovery. Static renewal experiments showed that the our POCIS device using ENVI‐Carb with a polyethersulfone membrane filter had a 3 d (dinotefuran) to 28 d (clothianidin, imidacloprid, acetamiprid, and thiacloprid) linear range, which is longer than that of HLB POCIS (≤1 [dinotefuran] to 14 d). The POCIS using ENVI‐Carb with a polytetrafluoroethylene membrane had higher sampling rates (0.270 L/d [clothianidin] to 0.686 [imidacloprid] L/d) than those of the HLB POCIS for short‐term deployment. The time‐weighted average concentrations in actual river water measured by the new POCIS were in good agreement with those obtained by repeated grab sampling, within 30%. Moreover, POCIS detected 2 neonicotinoid pesticides that were not detected by grab sampling. Thus, the proposed POCIS is a promising tool for the monitoring of neonicotinoid pesticides. Environ Toxicol Chem 2020;39:1325–1333. © 2020 SETAC

Characterization of the Permeation Properties of Membrane Filters and Sorption Properties of Sorbents Used for Polar Organic Chemical Integrative Samplers

“…Three types of calibration experiments have been conducted in previous laboratory-based studies: static renewal, tank, and static experiments. In previous static renewal experiments, a single POCIS device was deployed for certain periods (typically 1-28 d) in a 1 L glass beaker with solutions containing contaminants, and was refreshed every 1-2 days to avoid changes in contaminant concentrations (1,5,6,8,9,13,14). In tank experiments, POCIS devices were deployed in a tank filled with solution (typically 50-100 L) for certain periods (15)(16)(17)(18).…”

“…The obtained samples were then pretreated prior to gas chromatography-triple quadrupole mass spectrometry analysis (GC-MS/MS analysis) and liquid chromatography-triple quadrupole mass spectrometry analysis (LC-MS/MS analysis). POCIS devices with PES membranes have previously been used to detect PPPs and neonicotinoid herbicides (6,9,10); whereas, POCIS devices with PTFE membranes have previously been used to detect neonicotinoid herbicides and LAS (5,34). Thus, PES membranes were tested for and neonicotinoid herbicides.…”

“…S3). The ks values of this study should reflect the actual sorption kinetics for the POCIS uptake because the adsorption experiments were conducted under a similar flow velocity condition as the calibrations of the POCIS devices (5,6,34).…”

“…This implies that the adsorption rate may depend on other characteristics (i.e., particle size) of the sorbent besides the capacity. The elevated ks values of Oasis HLB may have resulted in the high Rs values for neonicotinoid herbicides compared to ENVI-Carb (Table 1) (5,6). Therefore, the sorption rate can be a parameter to predict the Rs values of highly hydrophilic compounds (log Kow<2) such as neonicotinoid herbicides.…”

Development and Evaluation of the Performance of the Polar Organic Chemical Integrative Sampler for Linear Alkylbenzene Sulfonate

“…However, passive sampling methods have not yet been applied in the detection of LASs given that they may absorb on membranes, making their permeation to sorbents difficult. In addition, in previous studies, target chemicals of POCIS devices were not chosen based on their abundance, but on their toxicity or measurability using conventional devices (Kaserzon et al 2012;Noro et al 2020;Rosen et al 2018, Yabuki et al 2018. Therefore, no POCIS device has been developed to monitor LASs, which have relatively low toxicity in aquatic environments.…”