Particulate matter is a component of ambient air pollution that has been linked to millions of annual premature deaths globally^1,2,3. Assessments of the chronic and acute effects of particulate matter on human health tend to be based on mass concentration, with particle size and composition also thought to play a part⁴. Oxidative potential has been suggested to be one of the many possible drivers of the acute health effects of particulate matter, but the link remains uncertain^5,6,7,8. Studies investigating the particulate-matter components that manifest an oxidative activity have yielded conflicting results⁷. In consequence, there is still much to be learned about the sources of particulate matter that may control the oxidative potential concentration⁷. Here we use field observations and air-quality modelling to quantify the major primary and secondary sources of particulate matter and of oxidative potential in Europe. We find that secondary inorganic components, crustal material and secondary biogenic organic aerosols control the mass concentration of particulate matter. By contrast, oxidative potential concentration is associated mostly with anthropogenic sources, in particular with fine-mode secondary organic aerosols largely from residential biomass burning and coarse-mode metals from vehicular non-exhaust emissions. Our results suggest that mitigation strategies aimed at reducing the mass concentrations of particulate matter alone may not reduce the oxidative potential concentration. If the oxidative potential can be linked to major health impacts, it may be more effective to control specific sources of particulate matter rather than overall particulate mass.

Many studies have demonstrated associations between exposure to ambient particulate matter (PM) and adverse health outcomes in humans that can be explained by PM capacity to induce oxidative stress in vivo. Thus, assays have been developed to quantify the oxidative potential (OP) of PM as a more refined exposure metric than PM mass alone. Only a small number of studies have compared different acellular OP measurements for a given set of ambient PM samples. Yet, fewer studies have compared different assays over a year-long period and with detailed chemical characterization of ambient PM. In this study, we report on seasonal variations of the dithiothreitol (DTT), ascorbic acid (AA), electron spin resonance (ESR) and the respiratory tract lining fluid (RTLF, composed of the reduced glutathione (GSH) and ascorbic acid (ASC)) assays over a 1-year period in which 100 samples were analyzed. A detailed PM₁₀ characterization allowed univariate and multivariate regression analyses in order to obtain further insight into groups of chemical species that drive OP measurements. Our results show that most of the OP assays were strongly intercorrelated over the sampling year but also these correlations differed when considering specific sampling periods (cold vs. warm). All acellular assays are correlated with a significant number of chemical species when considering univariate correlations, especially for the DTT assay. Evidence is also presented of a seasonal contrast over the sampling period with significantly higher OP values during winter for the DTT, AA, GSH and ASC assays, which were assigned to biomass burning species by the multiple linear regression models. The ESR assay clearly differs from the other tests as it did not show seasonal dynamics and presented weaker correlations with other assays and chemical species.

Particulate matter (PM) induces oxidative stress in vivo, leading to adverse health effects. Oxidative potential (OP) of PM is increasingly studied as a relevant metric for health impact (instead of PM mass concentration) as much of the ambient particle mass do not contribute to PM toxicity. Several assays have been developed to quantify PM oxidative potential and a widely used one is the acellular dithiothreitol (DTT) assay. However in such assays, particles are usually extracted with methanol or Milli-Q water which is unrepresentative of physiological conditions. For this purpose, OP_DTT measurements after simulated lung fluids (SLF) extraction, in order to look at the impact of simulated lung fluid constituents, were compared to Milli-Q water extraction measurements. Our major finding is a significant decrease of the OP_DTT when the artificial lysosomal fluid (ALF) solution was used. Indeed, ligand compounds are present in the SLF solutions and some induce a decrease of the OP when compared to water extraction. Our results suggest that the effect of ligands and complexation in lining fluids towards PM contaminants probably has been underestimated and should be investigated further.