Samples were analyzed by an Agilent 7890 gas chromatograph (GC) coupled with an Agilent 7010B triple quadrupole mass spectrometer fitted with an EI source (70 eV) and collision cell (Agilent Technologies, Santa Clara, CA, USA). Two GC-columns were coupled in series through a purged ultimate union. Samples (1 µL) were injected at 310 °C splitless and carried by high purity helium at a constant flow (1.2 mL/min). The temperature started at 40 °C and increased in intervals until reaching 330 °C when the first column was back-flushed. N2 was used as collision gas and helium was used as a quench gas. Target PAHs were identified by two unique multiple reaction monitoring transitions and quantified by the most intense peak94. Alkyl PAH clusters were determined by multiple reaction monitoring using transitions from the molecular ion94. Parent PAH compounds were quantified by quadratic regression of a 12-level calibration curve (0.01–250 ng/mL), while alkyl PAH groups were quantified by the response factor calculated for a methyl-substituted PAH reference compound. Standards were run for each of the 12 sample injections. The level of detection is reported in Table S1 for each PAH and ranged from 0.0001 to 1.75 ng/L (mean 0.143 ng/L). Concentrations are described using total PAHs (tPAHs) as clusters of alkylated homologs.

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