| Summary: | As a passive sampling device, the polar organic chemical integrative sampler (POCIS) has the characteristics of simple operation, safety, and reliability for assessing the occurrence and risk of persistent and emerging trace organic pollutants. The POCIS, allowing for the determination of time-weighted average (TWA) concentration of polar organic chemicals, exhibits good application prospects in aquatic environments. Before deploying the device in water, the sampling rate (<i>R<sub>s</sub></i>), which is a key parameter for characterizing pollutant enrichment, should be determined and calibrated accurately. However, the <i>R<sub>s</sub></i> values strongly depend on experimental hydrodynamic conditions. This paper provides an overview of the current situation of the POCIS for environmental monitoring of organic pollutants in an aquatic system. The principle and theory of the POCIS are outlined. In particular, the effect factors such as the ambient conditions, pollutant properties, and device features on the <i>R<sub>s</sub></i> are analyzed in detail from aspects of impact dependence and mechanisms. The calibration methods of the <i>R<sub>s</sub></i> under laboratory and in situ conditions are summarized. This review offers supplementary information on comprehensive understanding of mechanism and application of the POCIS. Nevertheless, the <i>R<sub>s</sub></i> were impacted by a combined effect of solute–sorbent–membrane–solution, and the influence extent of each variable was still unclear. On this basis, the ongoing challenges are proposed for the future application of the POCIS in the actual environment, for instance, the need for this device to be improved in terms of quantitative methods for more accurate measurement of the <i>R<sub>s</sub></i>.
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