Section S1. Description of MI-SPI-TOF-MS Section S2. Description of FT-ICR-MS Section S3. Analysis of FT-ICR-MS aqueous phase products based on DBE vs carbon number iso-abundance plot Section S4. Reaction mechanism of the aqueous phase product compounds Section S5. Tables, Figures and Scheme Number of Pages: 47 Number of Tables: 6 Number of Figures: 16 Number of Schemes: 1 S3 C16H8-(8H,9H)-8,9-(cyclo-OS(=O)2O) -1314.61 C16H9-8-(OS(=O)2OH) -1314.66 C16H8-(1H,2H)-1,2-(cyclo-OS(=O)2O) -1314.62 S11

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... Table S3 : Calculated Gibbs free energies for all molecules employed in the derivation of aqueous-phase reaction Gibbs energies in transformation process initiated by 3 PHE* and 3 PYR*, arranged in the order of increasing molecular mass. Chemical Formula or Name Gm Θ /Hartree Phenathrene -539.34 ( 3 Σ)Phenathrene -539.26 Pyrene -615.56 ( 3 Σ)Pyrene -615.48 C14H8-(2H,3H)-2,3-(cyclo-OS(=O)O) -1163.17 C14H8-(9H,10H)-9,10-(cyclo-OS(=O)O) -1163.20 E-C10H6-1-(CH=CHCH=CH2)-2-(OS(=O)OH) -1164.35 C12H8-2-(CH=CH2)-2'-OS(=O)OH -1164.36 C14H8-(2H,3H)-2,3-(cyclo-OS(=O)2O) -1238.40 C14H9-3-(OS(=O)2OH) -1238.46 C14H8-(9H,10H)-9,10-(cyclo-OS(=O)2O) -1238.44 C14H9-9-(OS(=O)2OH) -1238.46 E-C10H6-1-(CH=CHCH=CH2)-2-(OS(=O)2OH) -1239.59 C12H8-2-(CH=CH2)-2'-OS(=O)2OH -1239.60 C16H8-(2H,3H)-2,3-(cyclo-OS(=O)O) -1239.38 C16H8-(4H,5H)-4,5-(cyclo-OS(=O)O) -1239.43 E-C13H7-1H-1-(=CHCH=CH2)-9-(OS(=O)OH) -1240.56 C14H8-4-(OS(=O)OH)-5-(CH=CH2) -1240.56 C14H8-2-OH-3-(OS(=O)2OH) -1313.69 C14H8-9-OH-10-(OS(=O)2OH) -1313.68 E-C10H6-1-(CH=CHCH2CHO)-2-(OS(=O)2OH) -1314.83 C12H8-2-(CH2CHO)-2'-OS(=O)2OH -1314.84 C16H8-(2H,3H)-2,3-(cyclo-OS(=O)2O) -1314.61 C16H9-2-(OS(=O)2OH) -1314.66 C16H8-(4H,5H)-4,5-(cyclo-OS(=O)2O) -1314.66 C16H9-4-(OS(=O)2OH) -1314.68 E-C13H7-1H-1-(=CHCH=CH2)-9-(OS(=O)2OH) -1315.79 C14H8-4-(OS(=O)2OH)-5-(CH=CH2) -1315.80 C16H8-1-OH-2-(OS(=O)2OH) -1389.91 C16H8-2-(OS(=O)2OH)-5-OH -1389.90