Abstract
Chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs) are persistent organic pollutants that are ubiquitous in the atmospheric environment. The sources, fate, and sinks in the atmosphere of these substances are largely unknown. One of the reasons is the lack of widely accessible analytical instrumentation. In this study, a new analytical method for ClPAHs and BrPAHs using gas-chromatography coupled with triple quadrupole mass spectrometry is presented. The method was applied to determine ClPAHs and BrPAHs in total deposition samples collected at two sites in central Europe. Deposition fluxes of ClPAHs and BrPAHs ranged 580 (272–962) and 494 (161–936) pg m−2 day−1, respectively, at a regional background site, Košetice, and 547 (351–724) and 449 (202–758) pg m−2 day−1, respectively, at a semi-urban site, Praha-Libuš. These fluxes are similar to those of PCBs and more than 2 orders of magnitude lower than those of the parent PAHs in the region. Seasonal variations of the deposition fluxes of these halogenated PAHs were found with maxima in summer and autumn, and minima in winter at Košetice, but vice versa at Praha-Libuš. The distribution of ClPAHs and BrPAHs between the particulate and dissolved phases in deposition samples suggests higher degradability of particulate BrFlt/Pyr and BrBaA than of the corresponding ClPAHs. A number of congeners were detected for the first time in the atmospheric environment.
Highlights
Polycyclic aromatic hydrocarbons (PAHs) are globally ubiquitous pollutants drawing a lot of attention as posing a risk for human health upon inhalation exposure, and for ecosystemsResponsible Editor: Philippe GarriguesEnviron Sci Pollut Res2012; Jin et al 2020a)
Gas chromatography coupled with triple quadrupole mass spectrometry (GC-MS/ MS) has been applied as an alternative to GC, coupled with high-resolution mass spectrometry (GC-HRMS) which is widely used for the analysis of POPs, namely polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) (Banerjee et al 2012; Li et al 2014; van Bavel et al 2015; Wu et al 2017)
Standards of XPAH congeners were purchased from commercial laboratories, i.e., 9,10dichloroanthracene (9,10-Cl2Ant), 2,6-dibromoanthracene (2,6-Br2Ant), 2,7-dibromophenanthrene (2,7-Br2Phe), 1,6dibromopyrene (1,6-Br2Pyr), 7-bromobenz[a]anthracene (7BrBaA), 4-bromobenz[a]anthracene (4-BrBaA), 3bromofluoranthene (3-BrFlt), and 1,8-dibromopyrene (1,8Br2Pyr) were purchased from Tokyo Chemistry Industry (TCI), Japan; 7-chlorobenz[a]anthracene (7-ClBaA), 7,12dichlorobenz[a]anthracene (7,12-Cl2BaA), and 13C6-labelled 7,12-Cl2BaA were purchased from Cambridge Isotope Laboratories, Tewksbury, USA; 1,4-dichloroanthracene (1,4Cl2Ant), 1,5-dichloroanthracene (1,5-Cl2Ant), 2,3dichloroanthracene (2,3-Cl2Ant), 9,10-dibromoanthracene (9,10-Br2Ant), 3-bromophenanthrene (3-BrPhe), 9,10dibromophenanthrene (9,10-Br2Phe), and 1-bromopyrene (1BrPyr) were purchased from Sigma Aldrich, St
Summary
Polycyclic aromatic hydrocarbons (PAHs) are globally ubiquitous pollutants drawing a lot of attention as posing a risk for human health upon inhalation exposure, and for ecosystemsResponsible Editor: Philippe GarriguesEnviron Sci Pollut Res2012; Jin et al 2020a). XPAH concentrations in many environmental matrices were reported at ultra-trace level, such as 2–3 orders of magnitude lower than PAHs in air samples (Ohura et al 2009; Jin et al 2017a) Such low concentrations render them not quantifiable by many widely available GC-MS instruments (that are commonly used for analysis of other PAHs) due to challenges with analytical sensitivity. Gas chromatography coupled with triple quadrupole mass spectrometry (GC-MS/ MS) has been applied as an alternative to GC, coupled with high-resolution mass spectrometry (GC-HRMS) which is widely used for the analysis of POPs, namely polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) (Banerjee et al 2012; Li et al 2014; van Bavel et al 2015; Wu et al 2017) In these studies, GC-MS/ MS could satisfy the methodological requirements for determination of POPs in many environmental matrices (e.g., air, soil, and human milk). The development of an analytical method for XPAH on GC-MS/ MS would provide the potential for further applications and method comparison
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