Passive sampling of very hydrophilic chemicals is challenging due to the weak adsorption affinity to commonly used sorbent phases. Here we present a technique for the passive time-integrative sampling of highly water-soluble chemicals in wastewater influent, using a new diffusion-based sampling device. The sampler is a sealed chamber covered at one end by a porous polyethylene membrane, allowing chemicals to diffuse through the water-filled pores into the receiving phase of water. When submerged, the concentration gradient drives diffusion into the sampler, increasing the concentration of analytes in the receiving phase over time. To calibrate and test sampler performance, the sampler was deployed in wastewater influent for 31 d. The accumulation of acesulfame, ethyl sulfate, methamphetamine, and benzoylecgonine into the sampler was modeled using simultaneously collected 24 h composite samples. The four chemicals are typically monitored in wastewater-based surveillance programs and ranged in log K ow from −2.49 (ethyl sulfate) to 2.22 (methamphetamine). In situ calibration showed linear increases in concentration over the deployment period, and calculated sampling rates ranged from 2.2 mL d–1 (methamphetamine) to 4.0 mL d–1 (ethyl sulfate). This technique is useful for the time-integrative sampling of a range of hydrophilic chemicals in wastewater and shows potential for other aquatic matrices.

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Passive sampling approaches to monitor licit and illicit drugs of concern in wastewater shows promise as a supplementary sampling technique to grab sampling when conventional composite autosampling may not be possible. Recent studies have assessed the applicability of passive sampling at a single wastewater treatment plant (WWTP). However, it remains unknown whether a single-site calibration can be applied to other WWTPs. This study evaluated the in situ calibration of microporous polyethylene tube passive samplers (MPTs) against simultaneously collected composite samples for 22 different WWTPs. Samples were analyzed for methylamphetamine, amphetamine, hydroxycotinine, cotinine, benzoylecgonine, 3,4-methylenedioxymethamphetamine, and noroxycodone. Estimated rates of chemical uptake (sampling rates) were calculated using the mass accumulated in the samplers, the concentration measured in composite samples, and the duration of deployment. The estimated sampling rates were consistent between WWTPs (>90% within a factor of two) and ranged from 5 mL day–1 (amphetamine) to 9 mL day–1 (noroxycodone). The samplers were effective at estimating analyte concentrations, with 77% of results having a normalized difference to 24 h composite samples of below 30%. Our study suggests that MPT passive samplers provide a tool for the spatiotemporal monitoring of drug use where automated integrative sampling techniques may not be feasible.