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Study of PM2.5-bound polycyclic aromatic hydrocarbons and anhydro-sugars in ambient air near two Spanish oil refineries: Covid-19 effects

Abstract:

We report the results from a 12 month-long study of the organic compounds associated to PM<inf>2.5</inf> samples collected around two petroleum refineries (4 samples/month/site) in two complex industrial zones reporting atmospheric pollution issues in the past (Estuary of Huelva and Bay of Algeciras, Spain). Sampling campaign was done from March 2020 when a Covid-19 lockdown was established at Spain to March 2021. Concentrations of fine particulate polycyclic aromatic hydrocarbons (PAHs) and anhydrosugars were separately measured using gas chromatography-mass spectrometry (GC-MS) and ion chromatography-amperometric detection (IC-PAD). The annual average abundances of PM<inf>2.5</inf>-bound benzo[a]pyrene (BaP) are 0.024 and 0.013 ng˖m−3 at La Rábida and Puente Mayorga monitoring stations, while both sites have annual average concentrations of levoglucosan in PM<inf>2.5</inf> of 14.98 and 9.78 ng˖m−3, respectively. Seasonal variations are observed for concentrations of ƩPAHs and total anhydrosugars in both sampling sites. For PAHs, the highest concentrations averaging c. a. 0.400 (La Rábida) and 0.350 ng m−3 (Puente Mayorga) are reported in cold months during December 2020-Febraury 2021 (post-lockdown period), compared to the lowest levels averaging 0.111 and 0.211 ng˖m−3, respectively, in temperate months from mid-March 2020 to early June 2020 (0.284 and 0.321 ng m−3 on average annually), coinciding with the confinement and relaxation periods in Spain. Similarly, total anhydrosugars show the highest values of 81.80 ng˖m−3 (La Rábida) and 53.52 ng˖m−3 (Puente Mayorga) in winter and lowest values of 2.71 ng˖m−3 and 3.30 ng˖m−3 into the lockdown period (22.51 and 14.09 ng˖m−3 on average annually). Except phenanthrene, PAHs are present in PM<inf>2.5</inf> principally as result of motor vehicle exhausts. Levoglucosan, a tracer for biomass burning, peaked in December 2020 and January 2021, during the high residential wood-burning season. In addition, multivariate analysis was used to assess the origin of organic components of PM<inf>2.5</inf> samples. The two principal components are characterized by the grouping of heavy PAHs associated to vehicular traffic, and anhydrosugars indicating biomass burning emissions, respectively.