Field comparison of passive polyurethane foam and active air sampling techniques for analysis of gas-phase semi-volatile organic compounds at a remote high-mountain site

Polyurethane foam passive air samplers (PUF-PAS) are good candidates for the determination of gas-phase semi-volatile organic compound (SVOC) air concentrations in high-mountain areas over long periods because they do not require an energy supply. However, the harsh meteorological conditions present in such locations can increase the uncertainties inherently associated to PAS sampling rates due to the many variables involved in their calculation and to the assumptions made regarding PUF diffusive uptake mechanics, which can considerably bias the resulting concentrations. Therefore, we studied the performance of PUF-PASs in a remote location in the Pyrenees mountain range for the analysis of several SVOCs in air, including polychlorobiphenyls (PCBs), hexachlorobenzene, pentachlorobenzene, polycyclic aromatic hydrocarbons (PAHs), and the less studied emerging organophosphate flame retardants (OPFRs). An in-situ PUF-PAS calibration using Performance Reference Compounds (PRCs) provided compound- and sampler-specific sampling rates, showing mean experimental errors (12%) that adequately conformed to an estimate of their expanded theoretical uncertainties (15%). This showcases the suitability of this calibration strategy in an area with conditions beyond those typically considered in calibration efforts available to date. Moreover, gas-phase concentrations of the studied pollutants from PUF-PAS samples showed very good agreement (R2 up to 0.91, p < 0.01) when compared to those obtained using a conventional high-volume active air sampler (PUF-AAS), with some minor deviations observed for PAHs caused by the seasonality in their atmospheric concentrations. No relevant levels of pollutants preferentially bound to the particle phase were detected in the PUF-PASs, the particle infiltration efficiency of the sampler configuration used was found to be low, and compounds typically distributed between the gas and particle phases of AAS samples revealed profiles consistent with their vapor pressures, except for some OPFRs.This work was supported by the Spanish Ministry of Science and Innovation (CTM2015-71832-P and PGC2018-102288-B-I00). Raimon M. Prats also acknowledges financial support from the Spanish Ministry of Science and Innovation (BES-2016-076339).Peer reviewe