Oxidative potential apportionment of atmospheric PM₁: a new approach combining high-sensitive online analysers for chemical composition and offline OP measurement technique

Abstract

Source apportionment models were widely used to successfully assign highly time-resolved aerosol data to specific emissions and/or atmospheric chemical processes. These techniques are necessary for targeting the sources affecting air quality and for designing effective mitigation strategies. Moreover, evaluation of the toxicity of airborne particulate matter is important since the classically measured particulate matter (PM) concentrations appear insufficient for characterizing the impact on human health. Oxidative potential (OP) measurement has recently been developed to quantify the capability of PM to induce an oxidative imbalance in the lungs. As a result, this measurement unit could be a better proxy than PM mass concentration to represent PM toxicity. In the present study, two source apportionment analyses were performed using positive matrix factorization (PMF) from organic aerosol (OA) mass spectra measured at a 15 min time resolution using a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) and from 19 trace elements measured on an hourly basis using an online metal analyser (Xact 625i). The field measurements were carried out in summer 2018. While it is common to perform PMF studies individually on ACSMs and more recently on Xact datasets, here we used a two-step methodology leading to a complete PM1 source apportionment. The outputs from both OA PMF and Xact PMF, the inorganic species concentrations from the ACSM, and the black carbon (BC) fractions (fossil fuel and wood burning) measured using an Aethalometer (AE33) were gathered into a single dataset and subjected to a combined PMF analysis. Overall, eight factors were identified, each of them corresponding to a more precise source than performing single PMF analyses. The results show that besides the high contribution of secondary ammonium sulfate (28 %) and organic nitrate (19 %), about 50 % of PM1 originated from distinct combustion sources, including emissions from traffic, shipping, industrial activities, cooking, and biomass burning. Simultaneously, PM1 filters were collected during the experimental period on a 4 h sampling basis. On these filters, two acellular OP assays were performed (dithiothreitol; OPDTT and ascorbic acid; OPAA) and an inversion method was applied on factors issued from all PMFs to assess the contribution of the PM sources to the OP. This work highlights the sensitivity of OPAA to industrial and dust resuspension sources and those of OPDTT to secondary ammonium sulfate, shipping, and biomass burning.