Uncertainties in monitoring of SVOCs in air caused by within-sampler degradation during active and passive air sampling

•O3 and NOx pass through SVOC air samplers at the same levels as in outdoor air.•Within-sampler degradation of particle-bound PAHs can occur during air sampling.•Persistent compounds (PCBs, OCPs, PBDEs) do not show significant degradation.•Degradation may occur during passive air sampling at conventional deployment times.•Denuders may remove polar compounds from sampled air.

Degradation of semivolatile organic compounds (SVOCs) occurs naturally in ambient air due to reactions with reactive trace gases (e.g., ozone, NOx). During air sampling there is also the possibility for degradation of SVOCs within the air sampler, leading to underestimates of ambient air concentrations. We investigated the possibility of this sampling artifact in commonly used active and passive air samplers for seven classes of SVOCs, including persistent organic pollutants (POPs) typically covered by air monitoring programs, as well as SVOCs of emerging concern. Two active air samplers were used, one equipped with an ozone denuder and one without, to compare relative differences in mass of collected compounds. Two sets of passive samplers were also deployed to determine the influence of degradation during longer deployment times in passive sampling. In active air samplers, comparison of the two sampling configurations suggested degradation of particle-bound polycyclic aromatic hydrocarbons (PAHs), with concentrations up to 2× higher in the denuder-equipped sampler, while halogenated POPs did not have clear evidence of degradation. In contrast, more polar, reactive compounds (e.g., organophosphate esters and current use pesticides) had evidence of losses in the sampler with denuder. This may be caused by the denuder itself, suggesting sampling bias for these compounds can be created when typical air sampling apparatuses are adapted to limit degradation. Passive air samplers recorded up to 4× higher concentrations when deployed for shorter consecutive sampling periods, suggesting that within-sampler degradation may also be relevant in passive air monitoring programs.