Multi-Class Organic Pollutants in Atmospheric Particulate Matter (PM2.5) From a Southwestern Europe Industrial Area: Levels, Sources and Human Health Risk

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] The occurrence of 50 multi-class pollutants comprising 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 12 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols was studied in atmospheric particulate matter (PM2.5) samples collected at an industrial area focused on automotive manufacturing located at the Southwestern Atlantic European region (Vigo city, Spain) during 1-year period. Among all quantitated pollutants in PM2.5 samples, bisphenol A (BPA) was the most predominant with an average concentration of 6180 pg m−3, followed by PAHs comprising benzo(b+j)fluoranthene (BbF + BjF) and benzo(g,h,i)perylene (BghiP), accounting for 546 pg m−3 and 413 pg m−3 respectively. In addition, two OPFRs concerning tris(chloropropyl) phosphate (TCPP) and triphenyl phosphine oxide (TPPO) were the next following the concentration order, accounting for 411 pg m−3 and 367 pg m−3 respectively; being butyl benzyl phthalate (BBP) the most profuse PAE (56.1 pg m−3 by average). High relative standard deviations (RSDs) were observed during the whole sampling period, while statistically significant differences were only observed for PAHs concentrations during cold and warm seasons. Furthermore, some water-soluble ions and metal(oid)s were analysed in PM2.5 samples to be used as PM source tracers, whose concentrations were quite below the target levels set in the current legislation. Data obtained from principal component analysis (PCA) and PAHs molecular indices suggested a pyrogenic and petrogenic origin for PAHs, whereas occurrence of the remaining compounds seems to be attributed to resources used in the automotive industrial activity settled in the sampling area. Moreover, although a substantial anthropogenic source to PM2.5 in the area was observed, marine and soil resuspension contributions were also accounted. Finally, carcinogenic and non-carcinogenic risks posed by PM2.5-bound pollutants inhalation were assessed, being both averages within the safe level considering the whole period.This work was supported by the Ministerio de Ciencia, Innovación y Universidades (MCIU), the Agencia Estatal de Investigación (AEI) and the European Regional Development Fund (ERDF) (Programa Estatal de I + D + i Orientada a los Retos de la Sociedad, ref: RTI 2018-101116-B-I00), the Xunta de Galicia (Programa de Consolidación y Estructuración de Unidades de Investigación Competitivas, refs: ED431C 2017/28 (2017–2020) and ED431C 2021/56 (2021–2024)) and ERDF-Ministerio de Economía y Empresa (MINECO) (UNLC15-DE-3097, financed together (80/20%) with the Xunta de Galicia). Joel Sánchez-Piñero acknowledges the Xunta de Galicia and the European Union (European Social Fund - ESF) for a predoctoral grant (ED481A-2018/164). Natalia Novo-Quiza acknowledges the Ministerio de Ciencia e Innovación and the European Union (ESF) for a predoctoral grant (PRE2019-088744). The Laboratorio de Medio Ambiente de Galicia (LMAG) of the Subdirección Xeral de Meteoroloxía e Cambio Climático (Xunta de Galicia) is also acknowledged for providing the samples used in the present research work. Funding for open access charge: Universidade da Coruña/CISUGXunta de Galicia; ED431C 2017/28Xunta de Galicia; ED431C 2021/56Xunta de Galicia; ED481A-2018/16

Inhalation Bioaccessibility of Multi-Class Organic Pollutants Associated to Atmospheric PM2.5: Correlation with PM2.5 Properties and Health Risk Assessment

[Abstract] Inhalation exposure to fine particulate matter (PM2.5) represents a global concern due to the adverse effects in human health. In the last years, scientific community has been adopted the assessment of the PM2.5-bound pollutant fraction that could be released (bioaccessible fraction) in simulated lung fluids (SLFs) to achieve a better understanding of PM risk assessment and toxicological studies. Thus, bioaccessibility of 49 organic pollutants, including 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 11 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols in PM2.5 samples was evaluated. The proposed method consists of a physiologically based extraction test (PBET) by using artificial lysosomal fluid (ALF) to obtain bioaccessible fractions, followed by a vortex-assisted liquid-liquid microextraction (VALLME) and a final analysis by programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS). The highest inhalation bioaccessibility ratio was found for bisphenol A (BPA) with an average of 83%, followed by OPFRs, PAEs and PAHs (with average bioaccessibilities of 68%, 41% and 34%, respectively). Correlations between PM2.5 composition (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) and bioaccessibility ratios were also assessed. Principal Component Analysis (PCA) suggested that PAHs, PAES and OPFRs bioaccessibility ratios could be positively correlated with PM2.5 carbonaceous content. Furthermore, both inverse and positive correlations on PAHs, PAEs and OPFRs bioaccessibilites could be accounted for some major ions and metal (oid)s associated to PM2.5, whereas no correlations comprising considered PM2.5 major ions and metal (oid)s contents and BPA bioaccessibility was observed. In addition, health risk assessment of target PM2.5-associated PAHs via inhalation was assessed in the study area considering both total and bioaccessible concentrations, being averaged human health risks within the safe carcinogenic and non-carcinogenic levels.This work was supported by the Ministerio de Ciencia, Innovación y Universidades (MCIU), the Agencia Estatal de Investigación (AEI) and the Fondo Europeo de Desarrollo Regional (FEDER)501100008530 (Programa Estatal de I + D + i Orientada a los Retos de la Sociedad, ref: RTI 2018-101116-B-I00), the Xunta de Galicia (Programa de Consolidación y Estructuración de Unidades de Investigación Competitivas, refs: ED431C 2017/28 (2017–2020) and ED431C 2021/56 (2021–2024)) and FEDER501100008530-MINECO (UNLC15-DE-3097, financed together (80/20%) with the Xunta de Galicia). Joel Sánchez-Piñero acknowledges the Xunta de Galicia and the European Union (European Social Fund - ESF) for a predoctoral grant (ED481A-2018/164). Natalia Novo-Quiza acknowledges the Ministerio de Ciencia e Innovación and the European Union (European Social Fund - ESF) for a predoctoral grant (PRE 2019-088744). The Laboratorio de Medio Ambiente de Galicia (LMAG) of the Subdirección Xeral de Meteoroloxía e Cambio Climático (Xunta de Galicia) is also acknowledged for providing the samples used in the present research workXunta de Galicia; ED431C 2017/28Xunta de Galicia; ED431C 2021/56Xunta de Galicia; ED481A-2018/16