Medium- and long-chain chlorinated paraffins in air: A review of levels, physicochemical properties, and analytical considerations

Chlorinated paraffins (CPs) are synthetic chemicals that are produced at high volumes and have a global presence. CPs are generally divided into three groups based on their carbon chain lengths: short-chain CPs (SCCPs, C10-13), medium-chain CPs (MCCPs, C14-17), and long-chain CPs (LCCPs, C≥18). SCCPs have been formally recognized as persistent organic pollutants (POPs) and have been listed under the Stockholm Convention on POPs. Concerns about increases in MCCP and LCCP production as replacements for SCCP products are rising, given their similar properties to SCCPs and the fact that they remain relatively understudied with only a few reported measurements in air. Passive air samplers with polyurethane foam disks (PUF-PAS), which have been successfully applied to SCCPs, provide an opportunity to expand the existing body of data on MCCP and LCCP air concentrations, as they are inexpensive and require little maintenance. The uptake of MCCPs and LCCPs by PUF disk samplers is characterized in this paper based on newly derived PUF-air partitioning coefficients using COSMOtherm. The ability of PUF disk samplers to capture both gas-phase and particle fractions is important because MCCPs and LCCPs have reduced volatility compared to SCCPs and therefore are mainly associated with particulate matter in air. In addition, due to their use as additives in plastics and rubber products, they are associated with micro- and nanoplastics, which are considered to be potential vectors for the long-range atmospheric transport (LRAT) of these chemicals. The review has highlighted other limitations to reporting of MCCPs and LCCPs in air, including the lack of suitable analytical standards and the requirement for advanced analytical methods to detect and resolve these complex mixtures. Overall, this review indicates that further research is needed in many areas for medium- and long-chain chlorinated paraffins in order to better understand their occurrence, transport and fate in air.