Table I: Summary of the parameters and reactions included in CAPRAM 3.0 Gas phase initial concentration of organic compounds [ppb]:

Transcription

1 Table I: Summary of the parameters and reactions included in CAPRAM 3.0 Gas phase initial concentration of organic compounds [ppb]: Compound Urban Remote Marine C 2 H 5 OCHO Estimated CH 2 CH 2 CH 2 C(O)NCH Estimated Initial concentration of organic compounds in the aqueous phase [µm]: Phase transfer of organic compounds: Compound Urban Remote Marine HOOCCH 2 COO Averaged from several aerosol measurements and scaled to the C 2 O 2-2 concentration HOOCC 2 H 4 COO At ph 0 most of malonic acid and succinic acid dissociates to the monoanionic form Compound K H 298, - H / R, M atm -1 K Lit. α Lit. D g [10 5 m 2 s -1 ] 1-PrOH (Jayne et al., 1991) (Jayne et al., 1,96 (Fuller) 1991) 2-PrOH (Jayne et al., 1991) (Jayne et al., 1,96 (Fuller) 1991) 1-BuOH (Snider and Dawson, 1985) BuOH (Snider and Dawson, 1985) Trend: Smaller α with bigger compounds CH 3 CH 2 CHO (Zhou and Mopper, 1990) 0,03 = α(ch 3 CHO) 2,02 Fuller, 1986 Butanal (Zhou and Mopper, 1990) = α(propanal) Propanoic Acid 5710 (Khan et al., 1995) Butyric Acid 4700 (Khan et al., 1995) = α(ora3) CH 3 C(O)CHO 1.4 (Betterton and Hoffmann, 0.03 = α(ch 3 CHO) 1.95 (Fuller) 1988) CH 3 C(O)CH (Betterton, 1991) (Schutze and Herrmann, 2004) 2,02 (Fuller) CH 3 C(O)CH 2 CH (Zhou and Mopper, 1990) (Schutze and Herrmann, 2004) Lit (Fuller) 2

2 Compound K H 298, - H / R, M atm -1 K Lit. α Lit. D g [10 5 m 2 s -1 ] HKET 129 Meylan and Howard, = α(aceton) 1 (Fuller) CH 3 C(O)CH 2 OH DCB Estimated after the effective = α(glyoxal) 1 (Fuller) OHCCH=CHCHO Henry constant of Glyoxal CH 3 C(O)CH 2 CH(CH 3 ) (Kim et al., 2000) 0.01 Estimated 0.71 (Fuller) C 2 H 5 OCHO 2.59 Bocek, Estimated 0.93 (Fuller) CH 2 CH 2 CH 2 C(O)NCH (Kim et al., 2000) 0.01 Estimated 0.78 (Fuller) Lit. CH 2 OHCH 2 OH (Bone et al., 1983) 0.04 (Jayne et al., 1991) 1.06 (Fuller) Reaction k 298 K [M -1 s -1 ] - E A /R [K] Comments C 2 Compounds 1 OH + CH(OH) 2 COO - H 2 O + C(OH) 2 COO - 2, (Ervens et al., 2003) 2 NO 3 + CH(OH) 2 COO - C(OH) 2 COO - + NO H Calculated (Herrmann and Zellner, 3 C(OH) 2 COO - + O 2 O 2 C(OH) 2 COO Estimated like CH 2 OH + O O 2 C(OH) 2 COO - 2 CO CO H 2 O Estimated in analogy to O 2 CH 2 COO O 2 C(OH) 2 COO - 4 CO 2 + H 2 O OH Estimated in analogy to O 2 CH 2 COO O 2 C(OH) 2 COO - 2 H 2 O + 2 CO CO 2 + O Estimated in analogy to O 2 CH 2 COO O 2 C(OH) 2 COO - 2 H 2 O + CO CO 2 + O Estimated in analogy to O 2 CH 2 COO - Oxidation of 1-Propanol 8 OH + C 3 H 7 OH C 3 H 6 OH + H 2 O 3, (Ervens et al., 2003) 3

3 9 NO 3 + C 3 H 7 OH C 3 H 6 OH + NO H (Herrmann et al., 1994) 10 C 3 H 6 OH + O 2 O 2 C 3 H 6 OH Estimated after (von Sonntag, 1987) 11 O 2 C 3 H 6 OH + OH - - C 2 H 5 CH(O) + H 2 O + O Since O 2 CH 2 OH: and O 2 C 2 H 4 OH: C 3 -Radical assumedly slower (Factor 2??) 12 O 2 C 3 H 6 OH C 2 H 5 CH(O) + HO 2 52 As the C 2 -compound Oxidation of Propionaldehyde 13 OH + C 2 H 5 CH(O) C 2 H 5 C(O) + H 2 O Hesper and Herrmann, NO 3 + C 2 H 5 CH(O) C 2 H 5 C(O) + NO H In CH 3 CN (Ito et al., 1989a) 15 C 2 H 5 C(O) + O 2 C 2 H 5 C(O)O Estimated after (von Sonntag, 1987) 16 2 C 2 H 5 C(O)O 2 2 C 2 H 5 C(O)O + O Estimated after the ACO 3 recombination, (Herrmann et al., 1999) 17 C 2 H 5 C(O)O C 2 H 5 + CO (Hilborn and Pincock, 1991) 18 C 2 H 5 + O 2 ETHP Estimated after (von Sonntag, 1987) Oxidation of Propionaldehyde (hydrated form) 19 OH + C 2 H 5 CH(OH) 2 C 2 H 5 C(OH) 2 + H 2 O Hesper and Herrmann, NO 3 + C 2 H 5 CH(OH) 2 C 2 H 5 C(OH) 2 + NO H In CH 3 CN (Ito et al., 1989a) 21 C 2 H 5 C(OH) 2 + O 2 C 2 H 5 CO 2 (OH) Estimated after (von Sonntag, 1987) 22 C 2 H 5 CO 2 (OH) 2 HO 2 + C 2 H 5 COOH 1000 Estimated after (von Sonntag, 1987) Oxidation of Propanoic acid 23 OH + C 2 H 5 COOH CH 3 CHCOOH + H 2 O 3, (Ervens et al., 2003) 24 NO 3 + C 2 H 5 COOH CH 3 CHCOOH + NO H Calculated (Herrmann and Zellner, 25 CH 3 CHCOOH + O 2 CH 3 CH(O 2 )COOH Estimated after (von Sonntag, 1987) 26 2 CH 3 CH(O 2 )COOH 2 CO ETHP 1, analog to ACO 3 -Rekombination Oxidation of Propionate 27 OH + C 2 H 5 COO - CH 3 CHCOO - + H 2 O 7, (Ervens et al., 2003) 28 NO 3 + C 2 H 5 COO - CH 3 CHCOO - + NO H Calculated (Herrmann and Zellner, 4

4 29 CH 3 CHCOO - + O 2 CH 3 CH(O 2 )COO Estimated after (von Sonntag, 1987) 30 2 CH 3 CH(O 2 )COO - 2 CH 3 C(O)COO - + H 2 O Estimated in analogy to O 2 CH 2 COO CH 3 CH(O 2 )COO - CH 3 C(O)COO - + CH 3 CH(OH)COO - + O 2 1, α-hydroxy-propanoic acid: No sinks Estimated in analogy to O 2 CH 2 COO CH 3 CH(O 2 )COO H 2 O 2 CH 3 CH(O) + 2 CO OH - + H 2 O 2 1, Estimated in analogy to O 2 CH 2 COO CH 3 CH(O 2 )COO OH - + O 2 2 CH 3 C(O)COO H 2 O O 2 7, Estimated in analogy to O 2 CH 2 COO - Oxidation of 2-Propanol 34 OH + CH 3 CH(OH)CH 3 H 2 O + CH 3 C(OH)CH 3 2, (Elliot and Simsons, 1984) 35 NO 3 + CH 3 CH(OH)CH 3 CH 3 C(OH)CH 3 + NO H (Herrmann et al., 1994) 36 CH 3 C(OH)CH 3 + O 2 CH 3 C(O 2 )(OH)CH 3 1, Estimated 37 CH 3 C(O 2 )(OH)CH 3 HO 2 + CH 3 C(O)CH Estimated after (von Sonntag, 1987) Oxidation of Acetone 38 OH + CH 3 C(O)CH 3 CH 3 C(O)CH 2 + H 2 O Average of measurements within the MOST project 39 NO 3 + CH 3 C(O)CH 3 CH 3 C(O)CH 2 + NO H (Herrmann et al., 1994) 40 CH 3 C(O)CH 2 + O 2 CH 3 C(O)CH 2 OO 3, (Zegota et al., 1986) 41 2 CH 3 C(O)CH 2 OO CH 3 C(O)CHO + CH 3 C(O)CH 2 (OH) + O (Zegota et al., 1986) branching ratios after measurements within MOST by Poulain et al., 42 2 CH 3 C(O)CH 2 OO 2 CH 3 C(O)CH 2 O + O (Zegota et al., 1986)branching ratios after measurements within MOST by Poulain et al., 43 2 CH 3 C(O)CH 2 OO 2 CH 3 C(O)CHO + H 2 O (Zegota et al., 1986)branching ratios after measurements within MOST by Poulain et al., 44 CH 3 C(O)CH 2 O HCHO + CH 3 CO Estimated from the gas phase Oxidation of Hydroxy Acetone 45 CH 3 C(O)CH 2 (OH) + OH CH 3 C(O)CH(OH) + H 2 O Gligorovski and Herrmann (In Preparation) 46 NO 3 + CH 3 C(O)CH 2 (OH) CH 3 C(O)CH(OH) + NO H Calculated (Herrmann and Zellner, 47 CH 3 C(O)CH(OH) + O 2 CH 3 C(O)CH(OH)OO Estimated after (von Sonntag, 1987) 5

5 48 CH 3 C(O)CH(OH)OO CH 3 C(O)CHO + HO Estimated after OOCHOHCHOHCH 2 OH, (Bothe et al., 1978) 49 2 CH 3 C(O)CH(OH)OO H 2 O CH 3 C(O)COOH Estimated after the decay of CH 3 CH(OH)OO, (Bothe et al., 1983) Oxidation of Methylglyoxal (hydrated form) 50 CH 3 C(O)CH(OH) 2 + OH CH 3 C(O)C(OH) 2 + H 2 O Average of measurements within the MOST project 51 NO 3 + CH 3 C(O)CH(OH) 2 CH 3 C(O)C(OH) 2 + NO H Estimated 52 CH 3 C(O)C(OH) 2 + O 2 CH 3 C(O)C(OH) 2 OO Estimated after (von Sonntag, 1987) 53 CH 3 C(O)C(OH) 2 OO CH 3 C(O)COOH + HO In analogy with glyoxal, (Buxton et al., 1997)(approximation) Oxidation of Malonic acid 54 OH + CH 2 (COOH) 2 H 2 O + HOOCCHCOOH (Walling and Eltaliaw.Gm, 1973) 55 NO 3 + CH 2 (COOH) 2 HOOCCHCOOH + NO H Calculated (Herrmann and Zellner, 56 HOOCCHCOOH + O 2 HOOCCHO 2 COOH Estimated after (von Sonntag, 1987) 57 2 HOOCCHO 2 COOH HOOCC(O)COOH + HOOCCH(OH)COOH + O 2 1, Estimated in analogy to O 2 CH 2 COO HOOCCHO 2 COOH 2 HOOCC(O)COOH + H 2 O Estimated in analogy to O 2 CH 2 COO HOOCCHO 2 COOH + 2 H 2 O 2 CH(OH) 2 COOH + 2 CO 2 + H 2 O 2 1, Estimated in analogy to O 2 CH 2 COO HOOCCHO 2 COOH + 2 OH - + O 2 2 HOOCC(O)COOH + 2 O H 2 O 7, Estimated in analogy to O 2 CH 2 COO - Oxidation of Malonate (dianion) 61 OH + CH 2 (COO - ) 2 H 2 O + - OOCCHCOO - 2, (Logan, 1989) 62 NO 3 + CH 2 (COO - ) 2 - OOCCHCOO - + NO H Calculated (Herrmann and Zellner, 63 - OOCCHCOO - + O 2 - OOCCH(O 2 )COO Estimated after (von Sonntag, 1987) 6

6 1, No sinks for mesoxalate and tartronate Reaction k 298 K [M -1 s -1 ] - E A /R [K] Comments OOCCH(O 2 )COO - - OOCC(O)COO OOCCH(OH)COO - + O 2 Estimated in analogy to O 2 CH 2 COO OOCCH(O 2 )COO OOCC(O)COO - + H 2 O Estimated in analogy to O 2 CH 2 COO OOCCH(O 2 )COO H 2 O 2 CH(OH) 2 COO CO 2 + H 2 O OH - 1, Estimated in analogy to O 2 CH 2 COO OOCCH(O 2 )COO OH - + O OOCC(O)COO O H 2 O 7, Estimated in analogy to O 2 CH 2 COO - Oxidation of Malonate (monoanion) 68 OH + - OOCCH 2 COOH H 2 O + - OOCCHCOOH 3, (Ervens et al., 2003) 69 NO OOCCH 2 COOH - OOCCHCOOH + NO H Calculated (Herrmann and Zellner, 70 - OOCCHCOOH + O 2 - OOCCH(O 2 )COOH Estimated after (von Sonntag, 1987) No sinks for mesoxalate and tartronate OOCCH(O 2 )COOH - OOCC(O)COOH + - OOCCH(OH)COOH + O 2 Estimated in analogy to O 2 CH 2 COO OOCCH(O 2 )COOH 2 - OOCC(O)COOH + H 2 O Estimated in analogy to O 2 CH 2 COO OOCCH(O 2 )COOH + 4 H 2 O 2 CH(OH) 2 COOH + 2 CO 2 + H 2 O OH - 1, Estimated in analogy to O 2 CH 2 COO OOCCH(O 2 )COOH + 2 OH - + O OOCC(O)COOH + 2 O H 2 O 7, Estimated in analogy to O 2 CH 2 COO - Oxidation of Pyruvic acid 75 OH + CH 3 C(O)COOH CH 2 C(O)COOH + H 2 O 1, (Ervens et al., 2003) 76 NO 3 + CH 3 C(O)COOH CH 2 C(O)COOH + NO H Calculated (Herrmann and Zellner, 77 CH 2 C(O)COOH + O 2 O 2 CH 2 C(O)COOH Estimated after (von Sonntag, 1987) 78 2 O 2 CH 2 C(O)COOH OCHC(O)COOH + HOCH 2 C(O)COOH Estimated in analogy to O 2 CH 2 COO - O O 2 CH 2 C(O)COOH 2 OCHC(O)COOH + H 2 O Estimated in analogy to O 2 CH 2 COO O 2 CH 2 C(O)COOH + 2 H 2 O 2 CH 3 CHO + H 2 O CO O Estimated in analogy to O 2 CH 2 COO - 7

7 Reaction k 298 K [M -1 s -1 ] - E A /R [K] Comments 81 2 O 2 CH 2 C(O)COOH + 2 OH O 2 2 OHCC(O)COOH + 2 O H 2 O Estimated in analogy to O 2 CH 2 COO - Oxidation of Pyruvate 82 CH 3 C(O)COO - + OH CH 2 C(O)COO - + H 2 O (Ervens et al., 2003) 83 NO 3 + CH 3 C(O)COO - CH 2 C(O)COO - + NO H Calculated (Herrmann and Zellner, 84 CH 2 C(O)COO - + O 2 OOCH 2 C(O)COO Estimated after (von Sonntag, 1987) 85 2 OOCH 2 C(O)COO - O 2 + OCHC(O)COO - + HOCH 2 C(O)COO Estimated in analogy to O 2 CH 2 COO OOCH 2 C(O)COO - H 2 O OCHC(O)COO Estimated in analogy to O 2 CH 2 COO OOCH 2 C(O)COO H 2 O 2 CH 3 CHO + 2 CO 2 + 2O 2 + Estimated in analogy to O 2 CH 2 COO - H 2 O OH OOCH 2 C(O)COO OH - + O 2 2 O OCHC(O)COO H 2 O Estimated in analogy to O 2 CH 2 COO - Oxidation of Succinic acid 89 OH + CH 2 CH 2 (COOH) 2 CHCH 2 (COOH) 2 + H 2 O 1, (Ervens et al., 2003) 90 NO 3 + CH 2 CH 2 (COOH) 2 CHCH 2 (COOH) 2 + NO H Calculated (Herrmann and Zellner, 91 CHCH 2 (COOH) 2 + O 2 O 2 CHCH 2 (COOH) Estimated after (von Sonntag, 1987) 92 2 O 2 CHCH 2 (COOH) 2 HOOCC(O)CH 2 COOH + HOOCCH(OH)CH 2 COOH + O Estimated in analogy to O 2 CH 2 COO O 2 CHCH 2 (COOH) 2 2 HOOCC(O)CH 2 COOH + H 2 O Estimated in analogy to O 2 CH 2 COO O 2 CHCH 2 (COOH) 2 2 CH(O)CH 2 COOH + 2 CO 2 + H 2 O Estimated in analogy to O 2 CH 2 COO O 2 CHCH 2 (COOH) OH - + O 2 2 O HOOCC(O)CH 2 COOH + 2 H 2 O Estimated in analogy to O 2 CH 2 COO - 96 OH + CH(OH) 2 CH 2 COOH C(OH) 2 CH 2 COOH + H 2 O Estimated after Glycolic acid 97 NO 3 + CH(OH) 2 CH 2 COOH C(OH) 2 CH 2 COOH + NO H Estimated after Glycolic acid 98 C(OH) 2 CH 2 COOH + O 2 CH(OH) 2 O 2 CH 2 COOH Estimated after (von Sonntag, 1987) 99 CH(OH) 2 O 2 CH 2 COOH HOOCCH 2 COOH + HO Estimated after (von Sonntag, 1987) Oxidation of Succinate (dianion) 100 OH + CH 2 CH 2 (COO - ) 2 CHCH 2 (COO - ) 2 + H 2 O (Ervens et al., 2003) 8

8 101 NO 3 + CH 2 CH 2 (COO - ) 2 CHCH 2 (COO - ) 2 + NO H Calculated (Herrmann and Zellner, 102 CHCH 2 (COO - ) 2 + O 2 O 2 CHCH 2 (COO - ) Estimated after (von Sonntag, 1987) O 2 CHCH 2 (COO - ) 2 - OOCC(O)CH 2 COO OOCCH(OH)CH 2 COO - + O Estimated in analogy to O 2 CH 2 COO O 2 CHCH 2 (COO - ) 2 2 OOCC(O)CH 2 COO - + H 2 O Estimated in analogy to O 2 CH 2 COO O 2 CHCH 2 (COO - ) 2 + 2H 2 O 2 CH(O)CH 2 COO CO 2 + H 2 O OH - 1, Estimated in analogy to O 2 CH 2 COO O 2 CHCH 2 (COO - ) 2 + O OH OOCC(O)CH 2 COO O H 2 O 7, Estimated in analogy to O 2 CH 2 COO OH + CH(OH) 2 CH 2 COO - C(OH) 2 CH 2 COO - + H 2 O Estimated after Glycolate 108 NO 3 + CH(OH) 2 CH 2 COO - C(OH) 2 CH 2 COO - + NO H Estimated after Glycolate 109 C(OH) 2 CH 2 COO - + O 2 CH(OH) 2 O 2 CH 2 COO Estimated after (von Sonntag, 1987) 110 CH(OH) 2 O 2 CH 2 COO - HOOCCH 2 COO - + HO Estimated after (von Sonntag, 1987) Oxidation of Succinate (monoanion) 111 OH + HOOCCH 2 CH 2 COO - HOOCCHCH 2 COO - + H 2 O estimated: k Dianion = k Monoanion Calculated (Herrmann and Zellner, 112 NO 3 + HOOCCH 2 CH 2 COO - HOOCCHCH 2 COO - +NO H HOOCCHCH 2 COO - + O 2 HOOCCH(O 2 )CH 2 COO Estimated after (von Sonntag, 1987) HOOCCH(O 2 )CH 2 COO - HOOCC(O)CH 2 COO - + HOOCCH(OH)CH 2 COO - + O Estimated in analogy to O 2 CH 2 COO HOOCCH(O 2 )CH 2 COO - 2 HOOCC(O)CH 2 COO - + H 2 O 2 1, Estimated in analogy to O 2 CH 2 COO HOOCCH(O 2 )CH 2 COO H 2 O 2 CH(O)CH 2 COOH + 2 CO 2 + H 2 O OH - 1, Estimated in analogy to O 2 CH 2 COO HOOCCH(O 2 )CH 2 COO - + 2OH - + O 2 2 HOOCC(O)CH 2 COO O H 2 O 7, Estimated in analogy to O 2 CH 2 COO - Oxidation of Lactic acid 118 OH + CH 3 CHOHCOOH CH 3 COHCOOH + H 2 O 4, (Adams et al., 1965) 9

9 119 NO 3 + CH 3 CHOHCOOH CH 3 COHCOOH + NO H Calculated (Herrmann and Zellner, 120 CH 3 COHCOOH + O 2 CH 3 CO 2 OHCOOH Estimated after (von Sonntag, 1987) 121 CH 3 CO 2 OHCOOH CH 3 C(O)COOH + HO Estimated after Isopropanol (von Sonntag, 1987) Oxidation of Lactate 122 OH + CH 3 CHOHCOO - CH 3 COHCOO - + H 2 O (Logan, 1989) 123 NO 3 + CH 3 CHOHCOO - CH 3 COHCOO - + NO H Calculated (Herrmann and Zellner, 124 CH 3 COHCOO - + O 2 CH 3 CO 2 OHCOO Estimated after (von Sonntag, 1987) 125 CH 3 CO 2 OHCOO - CH 3 C(O)COO - + HO Estimated after Isopropanol (von Sonntag, 1987) Oxidation of Glycolic acid 126 CH 2 OHCOOH + OH CHOHCOOH + H 2 O (Scholes and Willson, 1967) 127 NO 3 + CH 2 OHCOOH CHOHCOOH + NO H Calculated (Herrmann and Zellner, 128 CHOHCOOH + O 2 O 2 CHOHCOOH Estimated after (von Sonntag, 1987) 129 O 2 CHOHCOOH + H 2 O HO 2 + CH(OH) 2 COOH 52 Estimated after Ethanol, (von Sonntag, 1987) Oxidation of Glycolate 130 CH 2 OHCOO - + OH CHOHCOO - + H 2 O (Logan, 1989) 131 NO 3 + CH 2 OHCOO - CHOHCOO - + NO H Calculated (Herrmann and Zellner, 132 CHOHCOO - + O 2 O 2 CHOHCOO Estimated after (von Sonntag, 1987) 133 O 2 CHOHCOO - + H 2 O HO 2 + CH(OH) 2 COO - 52 Estimated after Ethanol, (von Sonntag, 1987) Reactions of the peroxyl radical formed from acetic acid 134 O 2 CH 2 COOH + HO 2 HO 2 CH 2 COOH + O = k (HO 2 + HO 2 ) (Bielski et al., 1985) 10

10 135 - O 2 CH 2 COOH + O 2 + H + HO 2 CH 2 COOH + O = k (HO 2 + O - 2 ) (Bielski et al., 1985) 136 O 2 CH 2 COOH + HSO HO 2 CH 2 COOH + SO = k (CH 3 O 2 + HSO - 3 ) (Herrmann et al., 1999) 137 O 2 CH 2 COO - + HO 2 HO 2 CH 2 COO - + O = k(ho 2 + O - 2 ) (Bielski et al., 1985) 138 O 2 CH 2 COO - + O H + HO 2 CH 2 COO - + O = k (HO 2 + O 2 - ) (Bielski et al., 1985) 139 O 2 CH 2 COO - + HSO - 3 HO 2 CH 2 COO SO = k (CH 3 O 2 + HSO - 3 ) (Herrmann et al., 1999) Oxidation of Acetic acid hydroxyperoxide 140 HO 2 CH 2 COOH + OH O 2 CH 2 COOH + H 2 O = k (OH + H 2 O 2 ) 141 NO 3 + HO 2 CH 2 COOH HO 2 CHCOOH + NO H Calculated (Herrmann and Zellner, 142 HO 2 CH 2 COOH + Fe 2+ + H 2 O Fe 3+ + CH 2 (OH)COOH + OH + 50 = k (Fe 2+ + H 2 O 2 ) OH - Oxidation of acetate hydroxyperoxide 143 HO 2 CH 2 COO - + OH O 2 CH 2 COO - + H 2 O = k (OH + H 2 O 2 ) 144 NO 3 + HO 2 CH 2 COO - O 2 CH 2 COO - NO H = k ( NO 3 + H 2 O 2 ) 145 HO 2 CH 2 COO - + Fe 2+ Fe 3+ + CH 2 (OH)COO - + OH + OH - 50 = k (Fe 2+ + H 2 O 2 ) Oxidation of 1-Butanol 146 OH + CH 3 CH 2 CH 2 CH 2 OH H 2 O + CH 3 CH 2 CH 2 CHOH Hesper and Herrmann, (Shastri and Huie, 1990) 147 NO 3 + CH 3 CH 2 CH 2 CH 2 OH CH 3 CH 2 CH 2 CHOH + NO H CH 3 CH 2 CH 2 CHOH + O 2 CH 3 CH 2 CH 2 CHO 2 OH Estimated after (von Sonntag, 1987) 149 CH 3 CH 2 CH 2 CHO 2 OH CH 3 CH 2 CH 2 CHO + HO Estimated after (von Sonntag, 1987) Oxidation of Butyraldehyde 150 CH 3 CH 2 CH 2 CHO + OH CH 3 CH 2 CH 2 CO + H 2 O Hesper and Herrmann, NO 3 + CH 3 CH 2 CH 2 CHO CH 3 CH 2 CH 2 CO + NO H Calculated (Herrmann and Zellner, 152 CH 3 CH 2 CH 2 CO + O 2 CH 3 CH 2 CH 2 COO Estimated after (von Sonntag, 1987) CH 3 CH 2 CH 2 COO 2 2 CH 3 CH 2 CH 2 C(O)O + O Estimated after the ACO 3 recombination, (Herrmann et al., 1999) 11

11 154 CH 3 CH 2 CH 2 C(O)O CH 3 CH 2 CH 2 + CO Estimated after CH 3 CH 2 C(O)O (Hilborn and Pincock, 1991) 155 CH 3 CH 2 CH 2 + O 2 CH 3 CH 2 CH 2 O Estimated after (von Sonntag, 1987) CH 3 CH 2 CH 2 O 2 2 CH 3 CH 2 CH 2 O + O Estimated after ETHP, (Herrmann et al., 1999) 157 CH 3 CH 2 CH 2 O + O 2 C 2 H 5 CH(O) + HO Estimated CH 3 CH 2 CH 2 O 2 C 2 H 5 CH(O) + C 3 H 7 OH + O Estimated after ETHP, (Herrmann et al., 1999) Oxidation of Butyraldehyde (hydrated form) 159 CH 3 CH 2 CH 2 CH(OH) 2 + OH CH 3 CH 2 CH 2 C (OH) Hesper and Herrmann, Calculated (Herrmann and Zellner, 160 NO 3 + CH 3 CH 2 CH 2 CH(OH) 2 CH 3 CH 2 CH 2 C (OH) 2 + NO H CH 3 CH 2 CH 2 C (OH) 2 + O 2 CH 3 CH 2 CH 2 CO 2 (OH) Estimated after (von Sonntag, 1987) 162 CH 3 CH 2 CH 2 CO 2 (OH) 2 CH 3 CH 2 CH 2 COOH + HO Estimated after (von Sonntag, 1987) Oxidation of Butyric acid 163 CH 3 CH 2 CH 2 COOH + OH CH 3 CH 2 CHCOOH + H 2 O 2, (Scholes and Willson, 1967) 164 NO 3 + CH 3 CH 2 CH 2 COOH CH 3 CH 2 CHCOOH + NO H Calculated (Herrmann and Zellner, 165 CH 3 CH 2 CHCOOH + O 2 CH 3 CH 2 CHO 2 COOH Estimated after (von Sonntag, 1987) CH 3 CH 2 CHO 2 COOH 2 CH 3 CH 2 C(O)COOH + H 2 O Estimated in analogy to O 2 CH 2 COO CH 3 CH 2 CHO 2 COOH CH 3 CH 2 C(O)COOH + CH 3 CH 2 CHOHCOOH + O Estimated in analogy to O 2 CH 2 COO CH 3 CH 2 CHO 2 COOH 2 CH 3 CH 2 CHO + 2 CO 2 + H 2 O Estimated in analogy to O 2 CH 2 COO CH 3 CH 2 CHO 2 COOH + 2 OH - + O 2 2 CH 3 CH 2 C(O)COOH + 2 O H 2 O Estimated in analogy to O 2 CH 2 COO - Oxidation of Butyrate 170 CH 3 CH 2 CH 2 COO - + OH CH 3 CH 2 CHCOO - + H 2 O (Anbar et al., 1966) 171 NO 3 + CH 3 CH 2 CH 2 COO - CH 3 CH 2 CHCOO - + NO H Calculated (Herrmann and Zellner, 12

12 172 CH 3 CH 2 CHCOO - + O 2 CH 3 CH 2 CHO 2 COO Estimated after (von Sonntag, 1987) CH 3 CH 2 CH(O 2 )COO - 2 CH 3 CH 2 C(O)COO - + H 2 O Estimated in analogy to O 2 CH 2 COO CH 3 CH 2 CH(O 2 )COO - CH 3 CH 2 C(O)COO - + CH 3 CH 2 CHOHCOO - + O Estimated in analogy to O 2 CH 2 COO CH 3 CH 2 CH(O 2 )COO H 2 O 2 CH 3 CH 2 CHO + 2 CO OH - + H 2 O Estimated in analogy to O 2 CH 2 COO CH 3 CH 2 CH(O 2 )COO OH - + O 2 2 CH 3 CH 2 C(O)COO O H 2 O Estimated in analogy to O 2 CH 2 COO - Oxidation of 2-Butanol 177 CH 3 CH 2 CHOHCH 3 + OH CH 3 CH 2 COHCH 3 + H 2 O Hesper and Herrmann, NO 3 + CH 3 CH 2 CHOHCH 3 CH 3 CH 2 COHCH 3 + NO H Calculated (Herrmann and Zellner, 179 CH 3 CH 2 COHCH 3 + O 2 CH 3 CH 2 C(O 2 )(OH)CH Estimated after (von Sonntag, 1987) 180 CH 3 CH 2 C(O 2 )(OH)CH 3 HO 2 + CH 3 C(O)CH 2 CH (vonsonntag et al., 1997) Oxidation of Methyl Ethyl Ketone 181 CH 3 C(O)CH 2 CH 3 + OH CH 3 C(O)CHCH 3 + H 2 O Average of measurements within the MOST project 182 CH 3 C(O)CH 2 CH 3 + OH CH 2 C(O)CH 2 CH 3 + H 2 O Average of measurements within the MOST project 183 NO 3 + CH 3 C(O)CH 2 CH 3 CH 3 C(O)CHCH 3 + NO H Calculated (Herrmann and Zellner, 184 NO 3 + CH 3 C(O)CH 2 CH 3 CH 2 C(O)CH 2 CH 3 + NO H Calculated (Herrmann and Zellner, 185 CH 3 C(O)CHCH 3 + O 2 CH 3 C(O)CH(OO)CH (Glowa et al., 2000) CH 3 C(O)CH(OO)CH 3 O CH 3 C(O)CHOCH (Glowa et al., 2000) branching ratios after measurements within MOST by Poulain et al., CH 3 C(O)CH(OO)CH 3 H 2 O CH 3 C(O)C(O)CH (Glowa et al., 2000) branching ratios after measurements within MOST by Poulain et al., 13

13 188 CH 3 C(O)CHOCH 3 CH 3 CHO + CH 3 CO 1.3E Estimated after gas phase rate const. (Baldwin et al., 1977) Oxidation of 2,3-Butanedione 189 CH 3 C(O)C(O)CH 3 + OH CH 3 C(O)C(O) CH 2 + H 2 O k(298) after Gligorovski and Herrmann, 2004 Branching ratio estimated based on the gas phase reaction (Christensen et al., 190 CH 3 C(O)C(O)CH 3 + OH CH 3 COOH + CH 3 CO k(298) after Gligorovski and Herrmann, 2004 Branching ratio estimated based on the gas phase reaction (Christensen et al., 191 CH 3 C(O)C(O)CH 3 + NO 3 CH 3 C(O)C(O) CH 2 + NO H Calculated (Herrmann and Zellner, 192 CH 3 C(O)C(O)CH 3 + NO 3 CH 3 C(O)NO 3 + CH 3 CO Calculated (Herrmann and Zellner, 193 CH 3 C(O)C(O) CH 2 + O 2 CH 3 C(O)C(O) CH 2 OO Estimated after (von Sonntag, 1987) CH 3 C(O)C(O) CH 2 OO 2 CH 3 C(O)C(O)CH 2 O + O k(298) estimated after the CH 3 C(O)OO recombination 195 CH 3 C(O)C(O) CH 2 OO + CH 3 C(O)OO CH 3 C(O)O + CH 3 C(O)C(O)CH 2 O + O k(298) estimated after the CH 3 C(O)OO recombination 196 CH 3 C(O)C(O)CH 2 O CH 3 CO + HCHO + CO 1.3E k 1st estimated after reac CH 2 C(O)CH 2 CH 3 + O 2 OOCH 2 C(O)CH 2 CH By analogy with acetone OOCH 2 C(O)CH 2 CH 3 O OCH 2 C(O)CH 2 CH By analogy with acetone 199 OCH 2 C(O)CH 2 CH 3 HCHO + C(O)CH 2 CH 3 1.3E By analogy with reac C(O)CH 2 CH 3 + H 2 O C(OH) 2 CH 2 CH By analogy with CH 3 CO (Schuchmann and Vonsonntag, 1988) 201 C(OH) 2 CH 2 CH 3 C(O)CH 2 CH 3 + H 2 O 3E+4 By analogy with CH 3 C(OH) 2 (Schuchmann and Vonsonntag, 1988) 202 C(OH) 2 CH 2 CH 3 + O 2 OOC(OH) 2 CH 2 CH 3 2E+9 Estimated after (von Sonntag, 1987) 203 C(O)CH 2 CH 3 + O 2 OOC(O)CH 2 CH 3 2E+9 Estimated after (von Sonntag, 1987) 204 OOC(OH) 2 CH 2 CH 3 CH 3 CH 2 C(O)OH + HO 2 1E+6 Estimated 14

14 Oxidation of 1,4-Dioxo Butene 205 OH + OHCCH=CHCHO OHCCH(OH)CH CHO = k (Maleic acid), (Cabelli and Bielski, 1985) 206 OHCCH(OH)CH CHO + O 2 OHCCH(OH)CHO 2 CHO Estimated after (von Sonntag, 1987) OHCCH(OH)CHO 2 CHO OHCCHOHC(O)CHO + OHCCHOHCHOHCHO + O 2 Oxidation of 2-Hydroxy, 3,4-Dioxo Butyraldehyde 208 OHCCH(OH)C(O)CHO + OH OC CH(OH)C(O)CHO + H 2 O 209 OHCCH(OH)C(O)CHO + NO 3 OC CH(OH)C(O)CHO NO H Formation of keto and hydroxy species = k (2 ETHP) Estimated after Glyoxal, (Buxton et al., 1997) Calculated (Herrmann and Zellner, 210 OC CH(OH)C(O)CHO + O 2 OCO 2 CH(OH)C(O)CHO Estimated after (von Sonntag, 1987) 211 OCO 2 CH(OH)C(O)CHO + H 2 O HOOCCH(OH)C(O)CHO + HO 2 Oxidation of 2-Hydroxy, 3,4-Dioxo Butyric acid 212 HOOCCH(OH)C(O)CHO + OH HOOCCH(OH)C(O)C O + H 2 O 1000 Estimated after (von Sonntag, 1987) 3, = k (Glyoxylic acid), (Ervens et al., 2003) k(298) is eventually overestimated, because k was set according to the fully hydrated form Calculated, (Herrmann and Zellner, 213 HOOCCH(OH)C(O)CHO + NO 3 HOOCCH(OH)C(O)C O + NO H HOOCCH(OH)C(O)C O + O 2 HOOCCH(OH)C(O)C(O)O Estimated after (von Sonntag, 1987) 215 HOOCCH(OH)C(O)C(O)O 2 + H 2 O 1000 Estimated after (von Sonntag, 1987) HOOCCH(OH)C(O)COOH + HO HOOCCHOHC(O)COOH CO 2 + CH 2 OHC(O)COOH Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) Oxidation of 2-Hydroxy, 3,4-Dioxo Butyrate OOCCH(OH)C(O)CHO + OH - OOCCH(OH)C(O)C O = k (Glyoxylate), (Ervens et al., 2003) H 2 O OOCCH(OH)C(O)CHO + NO 3 - OOCCH(OH)C(O)C O = k (Glyoxylate) NO H OOCCH(OH)C(O)C O + O 2 - OOCCH(OH)C(O)C(O)O Estimated after (von Sonntag, 1987) 15

15 220 - OOCCH(OH)C(O)C(O)O 2 + H 2 O - OOCCH(OH)C(O)COOH Estimated after (von Sonntag, 1987) HO OOCCHOHC(O)COOH CO 2 + CH 2 OHC(O)COO Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) Oxidation of 2,3-Dihydroxy, 4-Oxo Butyraldehyde 222 OHCCH(OH)CH(OH)CHO + OH OC CH(OH)CH(OH)CHO + H 2 O Estimated after Glyoxal, (Buxton et al., 1997) 223 OHCCH(OH)CH(OH)CHO + NO 3 OC CH(OH)CH(OH)CHO + NO H Calculated (Herrmann and Zellner, 224 OC CH(OH)CH(OH)CHO + O 2 OCO 2 CH(OH)CH(OH)CHO Estimated after (von Sonntag, 1987) 225 OCO 2 CH(OH)CH(OH)CHO + H 2 O 1000 Estimated after (von Sonntag, 1987) HOOCCH(OH)CH(OH)CHO + HO 2 Oxidation of 2,3-Dihydroxy, 4-Oxo Butyric acid 226 HOOCCH(OH)CH(OH)CHO + OH HOOCCH(OH)CH(OH)C O + H 2 O Estimated after Malic acid (Gligorovski and Herrmann 2004) 227 HOOCCH(OH)CH(OH)CHO + NO 3 HOOCCH(OH)CH(OH)C O + NO H Calculated (Herrmann and Zellner, 228 HOOCCH(OH)CH(OH)C O + O Estimated after (von Sonntag, 1987) HOOCCH(OH)CH(OH)C(O)O HOOCCH(OH)CH(OH)C(O)O 2 + H 2 O 1000 Estimated after (von Sonntag, 1987) HOOCCH(OH)CH(OH)COOH + HO 2 Oxidation of 2,3-Dihydroxy, 4-Oxo Butyrate OOCCH(OH)CH(OH)CHO + OH OOCCH(OH)CH(OH)C O + H 2 O Estimated after Malate (Gligorovski and Herrmann 2004) OOCCH(OH)CH(OH)CHO + NO 3 - OOCCH(OH)CH(OH)C O + NO H = BDE (Malonate) Calculated (Herrmann and Zellner, OOCCH(OH)CH(OH)C O + O 2 - OOCCH(OH)CH(OH)C(O)O Estimated after (von Sonntag, 1987) OOCCH(OH)CH(OH)C(O)O 2 + H 2 O - OOCCH(OH)CH(OH)COOH + HO 2 Oxidation of Ethylene Glycol 1000 Estimated after (von Sonntag, 1987) 16

16 234 CH 2 OHCH 2 OH + OH C HOHCH 2 OH + H 2 O 1, Source for Hydroxyacetaldehyde (Adams et al., 1965) 235 CH 2 OHCH 2 OH + NO 3 C HOHCH 2 OH + NO H (Ito et al., 1989b) 236 C HOHCH 2 OH + O 2 O 2 CH(OH)CH 2 OH Estimated after (von Sonntag, 1987) 237 O 2 CH(OH)CH 2 OH OHCCH 2 OH + HO (von Sonntag, 1987) Oxidation of Glycolaldehyde 238 OHCCH 2 OH + OH CH 2 OHC O + H 2 O = k (CH 3 CHO) (Schuchmann and Vonsonntag, 1988) 239 OHCCH 2 OH + NO 3 CH 2 OHC O + NO H Estimated 240 CH 2 OHC O + O 2 CH 2 OHCO 2 O Estimated after (von Sonntag, 1987) 241 CH 2 OHCO 2 O + H 2 O CH 2 OHCOOH + HO Estimated after Ethylene Glycol (von Sonntag, 1987) Oxidation of Glycolaldehyde (hydrated form) 242 (OH) 2 CHCH 2 OH + OH (OH) 2 C CH 2 OH = k (CH 3 CH(OH) 2 ) (Schuchmann and Vonsonntag, 1988) 243 OHCCH 2 OH + NO 3 CH 2 OHC O + NO H Estimated 244 (OH) 2 C CH 2 OH + O 2 (OH) 2 CO 2 CH 2 OH Estimated after (von Sonntag, 1987) 245 (OH) 2 CO 2 CH 2 OH OC(OH)CH 2 OH + HO Estimated after Ethylene Glycol (von Sonntag, 1987) Oxidation of 3-Hydroxy Pyruvic acid 246 HOCH 2 C(O)COOH + OH HOC HC(O)COOH + H 2 O 5, =k (Glycolic acid), (Scholes and Willson, 1967) 247 HOCH 2 C(O)COOH + NO 3 HOC HC(O)COOH + NO H Calculated (Herrmann and Zellner, 248 HOC HC(O)COOH + O 2 HOCO 2 HC(O)COOH Estimated after (von Sonntag, 1987) 249 HOCO 2 HC(O)COOH OHCC(O)COOH + HO Estimated after Isopropanol, (von Sonntag, 1987) 250 OHCC(O)COOH + H 2 O CH 3 CH(O) + CO 2 + O Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) Oxidation of 3-Hydroxy Pyruvate 251 HOCH 2 C(O)COO - + OH HOC HC(O)COO - + H 2 O =k (Glycolate), (Logan, 1989) 17

17 252 HOCH 2 C(O)COO - + NO 3 HOC HC(O)COO - + NO H = BDE (Glycolate) Calculated (Herrmann and Zellner, 253 HOC HC(O)COO - + O 2 HOCO 2 HC(O)COO Estimated after (von Sonntag, 1987) 254 HOCO 2 HC(O)COO - OHCC(O)COO - + HO Estimated after Isopropanol, (von Sonntag, 1987) 255 OHCC(O)COO - + H 2 O CH(O)CH(O) + CO 2 + OH Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) Oxidation of 3-Oxo, Pyruvic acid 256 OHCC(O)COOH + OH OC C(O)COOH + H 2 O 3, = k (Glyoxylic acid) (Ervens et al., 2003) Additional source of mesoxalic acid 257 OHCC(O)COOH + NO 3 OC C(O)COOH + NO H Calculated (Herrmann and Zellner, 258 OC C(O)COOH + O 2 OCO 2 C(O)COOH Estimated after (von Sonntag, 1987) 259 OCO 2 C(O)COOH + H 2 O HOOCC(O)COOH + HO Estimated after Isopropanol, Von Sonntag, 1987 Oxidation of 3-Oxo, Pyruvate 260 OHCC(O)COO - + OH OC C(O)COO - + H 2 O = k (Glyoxylate) (Ervens et al., 2003) Additional source of mesoxalate 261 OHCC(O)COO - + NO 3 OC C(O)COO - + NO H = BDE (Glyoxylate) Calculated (Herrmann and Zellner, 262 OC C(O)COO - + O 2 OCO 2 C(O)COO Estimated after (von Sonntag, 1987) 263 OCO 2 C(O)COO - + H 2 O HOOCC(O)COO - + HO Estimated after Isopropanol, Von Sonntag, 1987 Oxidation of Malic acid 264 HOOCCH(OH)CH 2 COOH + OH HOOCC (OH)CH 2 COOH Gligorovski and Herrmann, H 2 O 265 HOOCCH(OH)CH 2 COOH + NO HOOCC (OH)CH 2 COOH + NO H + Calculated, Herrmann and Zellner HOOCC (OH)CH 2 COOH + O 2 HOOCCO 2 (OH)CH 2 COOH Estimated after (von Sonntag, 1987) 18

18 267 HOOCCO 2 (OH)CH 2 COOH HOOCC(O)CH 2 COOH + HO Estimated after (von Sonntag, 1987) Oxidation of Malate 268 HOOCCH(OH)CH 2 COO - + OH HOOCC (OH)CH 2 COO Gligorovski and Herrmann, 2004 H 2 O 269 HOOCCH(OH)CH 2 COO - + NO 3 HOOCC (OH)CH 2 COO - + NO H Calculated (Herrmann and Zellner, 270 HOOCC (OH)CH 2 COO - + O 2 HOOCCO 2 (OH)CH 2 COO Estimated after (von Sonntag, 1987) 271 HOOCCO 2 (OH)CH 2 COO - HOOCC(O)CH 2 COO - + HO Estimated after (von Sonntag, 1987) Oxidation of Oxalacetic acid 272 HOOCC(O)CH 2 COOH + OH HOOCC(O)CH COOH + H 2 O = k ( C 2 H 4 (COOH) 2 ) (Ervens et al., 2003) 273 HOOCC(O)CH 2 COOH + NO 3 HOOCC(O)CH COOH + NO H Calculated (Herrmann and Zellner, 274 HOOCC(O)CH COOH + O 2 HOOCC(O)CH(O 2 )COOH Estimated after (von Sonntag, 1987) HOOCC(O)CH(O 2 )COOH HOOCC(O)CH(OH)COOH + HOOCC(O)C(O)COOH + O 2 1, Formation from Keto- und Hydroxyacids = k (2 ETHP) 276 HOOCC(O)C(O)COOH CO 2 + OHCC(O)COOH Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) 277 HOOCC(O)CH(OH)COOH CO 2 + OHCCH(OH)COOH Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) 278 OH + OHCCH(OH)COOH OHCC(OH)COOH Estimated after Lactic acid Estimated after Lactic acid 279 NO 3 + OHCCH(OH)COOH OHCC(OH)COOH + NO H OHCC(OH)COOH + O 2 OHCC(OH)O 2 COOH Estimated after (von Sonntag, 1987) 281 OHCC(OH)O 2 COOH OHCC(O)COOH + HO Estimated after (von Sonntag, 1987) Oxidation of Oxalacetate 282 HOOCC(O)CH 2 COO - + OH HOOCC(O)CH COO - + H 2 O = k ( C 2 H 4 (COO - ) 2 ) (Ervens et al., 2003) 283 HOOCC(O)CH 2 COO - + NO 3 HOOCC(O)CH COO NO = k (HOOCCH 2 CH 2 COO - ) + H HOOCC(O)CH COO - + O 2 HOOCC(O)CH(O 2 )COO Estimated after (von Sonntag, 1987) 19

19 285 2 HOOCC(O)CH(O 2 )COO - HOOCC(O)CH(OH)COO - + HOOCC(O)C(O)COO - + O 2 1, Formation from Keto- und Hydroxyacids = k (2 ETHP) 286 HOOCC(O)C(O)COO - CO 2 + OHCC(O)COO Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) 287 HOOCC(O)CH(OH)COO - CO 2 + OHCCH(OH)COO Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) 288 OH + OHCCH(OH)COO - OHCC(OH)COO - + H 2 O Estimated after Lactate 289 NO 3 + OHCCH(OH)COO - OHCC(OH)COO - + NO H Estimated after Lactate 290 OHCC(OH)COO - + O 2 OHCC(OH)O 2 COO Estimated after (von Sonntag, 1987) 291 OHCC(OH)O 2 COO - OHCC(O)COO - + HO Estimated after (von Sonntag, 1987) Oxidation of Tartronic acid 292 HOOCCH(OH)COOH + OH HOOCC (OH)COOH + H 2 O (Schuchmann et al., 1995) Calculated (Herrmann and Zellner, HOOCCH(OH)COOH + NO 3 HOOCC (OH)COOH + NO 3 + H HOOCC (OH)COOH + O 2 HOOCCO 2 (OH)COOH Estimated after (von Sonntag, 1987) 295 HOOCCO 2 (OH)COOH HOOCC(O)COOH + HO Estimated after Isopropanal (von Sonntag, 1987) 296 HOOCC(O)COOH + H 2 O CO 2 + CH(OH) 2 COOH Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) Oxidation of Tartronate 297 HOOCCH(OH)COO - + OH HOOCC (OH)COO - + H 2 O (Schuchmann et al., 1995) = k (HOOCCH COO - ) 298 HOOCCH(OH)COO - + NO 3 HOOCC (OH)COO - + NO H HOOCC (OH)COO - + O 2 HOOCCO 2 (OH)COO Estimated after (von Sonntag, 1987) 300 HOOCCO 2 (OH)COO - HOOCC(O)COO - + HO Estimated after Isopropanal (von Sonntag, 1987) 301 HOOCC(O)COO - + H 2 O CO 2 + CH(OH) 2 COO Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) Oxidation of Methyl Isobutyl Ketone 302 CH 3 C(O)CH 2 CH(CH 3 ) 2 + OH CH 3 C(O)CHCH(CH 3 ) 2 + H 2 O Average of measurements within the MOST project 303 CH 3 C(O)CH 2 CH(CH 3 ) 2 + OH CH 3 C(O)CH 2 C(CH 3 ) 2 + H 2 O Average of measurements within the MOST project 20

20 304 NO 3 + CH 3 C(O)CH 2 CH(CH 3 ) 2 CH 3 C(O)CHCH(CH 3 ) NO H + Calculated (Herrmann and Zellner, Calculated (Herrmann and Zellner, 305 NO 3 + CH 3 C(O)CH 2 CH(CH 3 ) 2 CH 3 C(O)CH 2 C(CH 3 ) 2 + NO H CH 3 C(O)CHCH(CH 3 ) 2 + O 2 CH 3 C(O)CH(OO)CH(CH 3 ) Estimated after (von Sonntag, 1987) CH 3 C(O)CH(OO)CH(CH 3 ) 2 O CH 3 C(O)CHOCH(CH 3 ) Estimated after CH 3 C(O)CH 2 OO; branching ratios after measurements within MOST by Poulain et al., CH 3 C(O)CH(OO)CH(CH 3 ) 2 H 2 O CH 3 C(O)C(O)CH(CH 3 ) CH 3 C(O)CH(OO)CH(CH 3 ) 2 O 2 + CH 3 C(O)C(O)CH(CH 3 ) 2 + CH 3 C(O)CH(OH)CH(CH 3 ) Estimated after CH 3 C(O)CH 2 OO; branching ratios after measurements within MOST by Poulain et al., Estimated after CH 3 C(O)CH 2 OO; branching ratios after measurements within MOST by Poulain et al., 310 CH 3 C(O)CHOCH(CH 3 ) 2 CH 3 CO + H(O)CCH(CH 3 ) By analogy with acetone and with the gas phase (Mellouki et al., ) 311 CH 3 C(O)CH 2 C(CH 3 ) 2 + O 2 CH 3 C(O)CH 2 C(OO)(CH 3 ) Estimated after (von Sonntag, 1987) CH 3 C(O)CH 2 C(OO)(CH 3 ) 2 O CH 3 C(O)CH 2 CO(CH 3 ) Estimated 313 CH 3 C(O)CH 2 CO(CH 3 ) 2 CH 3 C(O)CH 3 + CH 3 COCH By analogy with the gas phase, (Mellouki et al., ) By analogy with t-butanol 314 CH 3 C(O)CH 2 CO(CH 3 ) 2 CH 2 C(O)CH 2 C(OH)(CH 3 ) By analogy with the gas phase, (Mellouki et al., ) 315 CH 2 C(O)CH 2 C(OH)(CH 3 ) 2 + O 2 OOCH 2 C(O)CH 2 C(OH)(CH 3 ) By analogy with acetone OOCH 2 C(O)CH 2 C(OH)(CH 3 ) 2 H 2 O By analogy with acetone H(O)CC(O)CH 2 C(OH)(CH 3 ) OOCH 2 C(O)CH 2 C(OH)(CH 3 ) 2 O By analogy with acetone H(O)CC(O)CH 2 C(OH)(CH 3 ) 2 + CH 2 (OH)C(O)CH 2 C(OH)(CH 3 ) OOCH 2 C(O)CH 2 C(OH)(CH 3 ) 2 O By analogy with acetone OCH 2 C(O)CH 2 C(OH)(CH 3 ) OCH 2 C(O)CH 2 C(OH)(CH 3 ) 2 H(O)CC(O)CH 2 C(OH)(CH 3 ) 2 + CH 2 (OH)C(O)CH 2 C(OH)(CH 3 ) By analogy with acetone 21

21 320 OCH 2 C(O)CH 2 C(OH)(CH 3 ) 2 HCHO + C(O)CH 2 C(OH)(CH 3 ) By analogy with acetone By analogy with the gas phase (Mellouki et al.) 321 C(O)CH 2 C(OH)(CH 3 ) 2 OHCCH 2 C(OH)CH 3 CH By analogy with CH 3 C(O)CH 2 CO(CH 3 ) OHCCH 2 C(OH)CH 3 CH 2 + O 2 OHCCH 2 C(OH)CH 3 CH 2 O Estimated after (von Sonntag, 1987) OHCCH 2 C(OH)CH 3 CH 2 O 2 OHCCH 2 C(OH)CH 3 CH 2 OH Estimated after OHCCH 2 C(OH)CH 3 CHO + O 2 OOCH 2 C(O)CH 2 C(OH)(CH 3 ) C 2 H 5 OCHO + H 2 O C 2 H 5 OH + HCOOH (Mata-Segreda, 2000) 325 C 2 H 5 OCHO + H 3 O + C 2 H 5 OH + HCOOH + H (Mata-Segreda, 2000) Oxidation of Ethyl Formate 326 C 2 H 5 OCHO + OH C 2 H 5 OC (O) + H 2 O Average of measurements within the MOST project 327 C 2 H 5 OCHO + OH CH 3 CHOCHO + H 2 O Average of measurements within the MOST project 328 NO 3 + C 2 H 5 OCHO C 2 H 5 OC (O) + NO H Calculated (Herrmann and Zellner, 329 NO 3 + C 2 H 5 OCHO CH 3 CHOCHO + NO H Calculated (Herrmann and Zellner, 330 C 2 H 5 OC (O) + O 2 C 2 H 5 OC(O)OO Estimated after (von Sonntag, 1987) 331 C 2 H 5 OC(O)OO + H 2 O C 2 H 5 OH + CO 2 + HO Estimated after reaction C 2 H 5 OC(O)OO + H 3 O + C 2 H 5 OH + CO 2 + HO 2 + H Estimated after reaction C 2 H 5 OC(O)OO C 2 H 5 OC(O)O + ½ O Estimated based on product studies carried out within MOST by Poulain et al., 334 CH 3 CH 2 OC(O)O C 2 H 5 O + CO Wang CH 3 CH 2 OC(O)O CH 2 CH 2 OC(O)OH Estimated CH 3 CH(OO )OH H 2 O CH 3 C(O)OH (Neta et al., 1990) 337 CH 2 CH 2 OC(O)OH + O 2 OOCH 2 CH 2 OC(O)OH Estimated OOCH 2 CH 2 OC(O)OH 2 OCH 2 CH 2 OC(O)OH + O Estimated 339 OCH 2 CH 2 OC(O)OH HCHO + CH 2 OC(O)OH Estimated in analogy with CH 3 C(O)CH 2 O 340 CH 2 OC(O)OH HCHO + COOH Estimated in analogy with CH 3 C(O)CH 2 O 341 CH 3 C HOCHO + O 2 CH 3 CH(OO )OCHO Estimated after (von Sonntag, 1987) 22

22 342 CH 3 CH(OO )OCHO + H 2 O CH 3 CH(OO )OH + HCOOH In analogy with Ethyl Formate, (Mata-Segreda, 2000) 343 CH 3 CH(OO )OCHO + H 3 O + CH 3 CH(OO )OH + HCOOH + H In analogy with Ethyl Formate, (Mata-Segreda, 2000) Oxidation of N Methyl Pyrrolidinone 344 CH 2 CH 2 CH 2 C(O)NCH 3 + OH CH 2 CH 2 C(O)NCH 3 CH + H 2 O Average of measurements within the MOST project 345 CH 2 CH 2 CH 2 C(O)NCH 3 + OH CH 2 CH 2 CH 2 C(O)NC H 2 + H 2 O Average of measurements within the MOST project 346 NO 3 + CH 2 CH 2 CH 2 C(O)NCH 3 CH 2 CH 2 C(O)NCH 3 CH + NO H Calculated (Herrmann and Zellner, 347 NO 3 + CH 2 CH 2 CH 2 C(O)NCH 3 CH 2 CH 2 CH 2 C(O)NC H 2 + NO H Calculated (Herrmann and Zellner, 348 CH 2 CH 2 C(O)NCH 3 CH + O 2 CH 2 CH 2 C(O)NCH 3 CHO Estimated after (von Sonntag, 1987) CH 2 CH 2 C(O)NCH 3 CHO 2 2 CH 2 CH 2 C(O)NCH 3 CHO + O k(298) estimated after the ethyl peroxy radical (Herrmann et al., 1999) 350 CH 2 CH 2 C(O)NCH 3 CHO + O 2 CH 2 CH 2 C(O)NCH 3 C(O) + HO k(298) estimated after the reaction CH3CH2O + O2 (214 in CAPRAM 2.4) 351 CH 2 CH 2 C(O)NCH 3 C(O) + OH CH 2 CH 2 C(O)NC H 2 C(O) Estimated after NMP H 2 O 352 NO 3 + CH 2 CH 2 C(O)NCH 3 C(O) CH 2 CH 2 C(O)NC H 2 C(O) NO H + Calculated (Herrmann and Zellner, in (Gligorovski and Herrmann, 2004) (3) 353 CH 2 CH 2 C(O)NC H 2 C(O) + O 2 CH 2 CH 2 C(O)NCH 2 OO C(O) Estimated after (von Sonntag, 1987) CH 2 CH 2 C(O)NCH 2 OO C(O) + O 2 2 CH 2 CH 2 C(O)NHC(O) k(298) estimated after the ethyl peroxy 2 CO 2 + H 2 O 2 radical (Herrmann et al., 1999) 355 CH 2 CH 2 CH 2 C(O)NC H 2 + O 2 CH 2 CH 2 CH 2 C(O)NCH 2 O Estimated after (von Sonntag, 1987) CH 2 CH 2 CH 2 C(O)NCH 2 O 2 + O 2 2 CH 2 CH 2 C(O)NHCH k(298) estimated after the ethyl peroxy CO 2 + H 2 O 2 radical (Herrmann et al., 1999) 357 CH 2 CH 2 C(O)NHCH 2 + OH CH 2 CH 2 C(O)NHC H + H 2 O Estimated after NMP Estimated after NMP 358 NO 3 + CH 2 CH 2 C(O)NHCH 2 CH 2 CH 2 C(O)NHC H + NO H CH 2 CH 2 C(O)NHC H + O 2 CH 2 CH 2 C(O)NHCHO Estimated after (von Sonntag, 1987) 23

23 360 2 CH 2 CH 2 C(O)NHCHO 2 2 CH 2 CH 2 C(O)NHCHO + O k(298) estimated after the ethyl peroxy radical (Herrmann et al., 1999) 361 CH 2 CH 2 C(O)NHCHO + O 2 CH 2 CH 2 C(O)NHC(O) + HO k(298) estimated after the reaction CH3CH2O + O2 (214 in CAPRAM 2.4) HO 2 elimination from CH 3 C(OH) 2 O CH 3 C(OH) 2 O 2 CH 3 COOH + HO Estimated after (von Sonntag, 1987) Remarks: (1) : Contribution of H-abs back calculated using correlation for the reaction of NO 3 with aliphatic compounds in aqueous solution (Herrmann and Zellner, where the BDEs were derived from the correlation reported in (Gligorovski and Herrmann, 2004) for the reaction of OH with organic compounds. (2) : Calculated using the correlation for the reaction of NO3 with aliphatic compounds in aqueous solution (Herrmann and Zellner,. The BDEs determined with Benson s incremental method. (3) : Contribution of H-abs back calculated using correlation for the reaction of NO 3 with aliphatic compounds in aqueous solution (Herrmann and Zellner, where the BDEs were derived from the correlation (gas-phase) reported in (Gligorovski and Herrmann, 2004) for the reaction of OH with organic compounds. Equilibrium reactions: Equilibrium K Ea/R k for k back Comments E1 HOOCCH 2 COO - H + + CH 2 (COO - ) 2 2, , Lit.: Handb. Of Org. Comp. T-dependency between 0 and 30 C E2 CH 3 C(O)COOH H + + CH 3 C(O)COO - 3, , Lit.: Handb. Of Org. Comp. E3 CH 3 CH 2 COOH H + + CH 3 CH 2 COO - 1, , T-dependency between 5 and 20 C E4 CH 3 C(O)CHO + H 2 O CH 3 C(O)CH(OH) , (Betterton and Hoffmann, 1988) k hin as for Glyoxal E5 C 2 H 4 (COOH) 2 H +- + OOCC 2 H 4 COOH 6, , OOCC 2 H 4 COOH H +- + C 2 H 4 (COO - ) 2 2, , , E6 E7 CH 3 CHOHCOOH CH 3 CHOHCOO - + H , α-hydroxy-propionate is formed by the recombination of the propionate peroxy radical. No sinks implemented until now for α-hydroxy- Propionate = K, k (Propanoic acid) E8 CH 2 OHCOOH CH 2 OHCOO - + H + 1, , (Lide, 1995) E9 CH 3 CH 2 CH 2 COOH CH 3 CH 2 CH 2 COO - + 1, , (Lide, 1995)

24 Estimated after the second step dissociation Estimated after oxalacetic acid (Lide, 1995) Equilibrium K Ea/R k for k back Comments H + E10 ACO 3 + H 2 O CH 3 C(OH) 2 O Estimated in analogy with the acetyl radical E11 HO 2 CH 2 COOH HO 2 CH 2 COO - + H Estimated after acetic acid (Lide, 1995) E12 HOOCCH(OH)C(O)CHO - OOCCH(OH)C(O)CHO + H + constant of tartaric acid (Lide, 1995) E13 HOOCCHOHC(O)COOH - OOCCHOHC(O)COOH + H + E14 CH 2 OHC(O)COOH CH 2 OHC(O)COO Estimated after pyruvic acid (Lide, 1995) + H + E15 HOOCCH(OH)CH(OH)CHO Estimated after the second step dissociation - OOCCH(OH)CH(OH)CHO + H + constant of tartaric acid (Lide, 1995) E16 HOOCCH(OH)CH(OH)COOH (Lide, 1995) - OOCCH(OH)CH(OH)COOH + H (Lide, 1995) E17 OHCC(O)COOH OHCC(O)COO - + H Estimated after pyruvic acid (Lide, 1995) E18 HOOCC(O)COOH HOOCC(O)COO - + H (Albalat et al., 1989) E19 HOOCCH(OH)CH 2 COOH (Lide, 1995) HOOCCH(OH)CH 2 COO - + H + E20 HOOCCH(OH)CH 2 COO - - OOCCH(OH)CH 2 COO - + H + E21 HOOCC(O)CH 2 COOH (Lide, 1995) HOOCC(O)CH 2 COO - + H + E22 HOOCC(O)CH 2 COO (Lide, 1995) - OOCC(O)CH 2 COO - E23 HOOCC(O)C(O)COOH HOOCC(O)CH 2 COO - + H + E24 HOOCCH(OH)COOH HOOCCH(OH)COO - + H + E25 HOOCCH(OH)COO OOCCH(OH)COO - + H Estimated after mesoxalic acid (Albalat et al., 1989) (Campi, 1963) (Campi, 1963) E26 HOOCCH 2 COOH HOOCCH 2 COO - + H Smith and Marthell, 1989 E27 CH 3 CH 2 C(O)COOH CH 3 CH 2 C(O)COO Ojelund and Wadso, H + E28 OHCCH(OH)COOH Estimated after Propanoic acid OHCCH(OH)COO - + H + E29 OHCCH 2 COOH OHCCH 2 COO - + H Estimated after Propanoic acid E30 C 2 H 5 CH(O) + H 2 O C 2 H 5 CH(OH) Xu et al., 1992 k back estimated after acetaldehyde E31 CH 3 CH 2 CH 2 CHO + H 2 O CH 3 CH 2 CH 2 CH(OH) Xu et al., 1992 k back estimated after acetaldehyde

25 Equilibrium K Ea/R k for k back Comments E32 OHCCH 2 OH + H 2 O (OH) 2 CHCH 2 OH Betterton and Hoffmann 1988 k back estimated after acetaldehyde E33 OHCCH 2 COOH + H 2 O Estimated after acetaldehyde CH(OH) 2 CH 2 COOH E34 OHCCH 2 COO - + H 2 O CH(OH) 2 CH 2 COO Estimated after acetaldehyde Photolysis rates: Reaction j max Reference P1 HO 2 CH 2 COOH OH + OCH 2 COOH 7, Photochemical rate constant estimated equal to J(H 2 O 2 ) References: Adams, G.E., Boag, J.W., Currant, J. and Michael, B.D., Absolute rate constants for the reaction of the hydroxyl radical with organic compounds. In: M. Ebert, J.P. Keen, A.J. Swallow and J.H. Baxendale (Editors), Pulse Radiolysis. Academic Press, London, pp Albalat, R., Claret, J., Gomez, E., Muller, C. and Sarret, M., Electrocatalytic Oxidation of Mesoxalic Acid on a Polycrystalline Platinum-Electrode in Acid- Medium. Electrochimica Acta, 34(5): Anbar, M., Meyerste.D and Neta, P., Reactivity of Aliphatic Compounds Towards Hydroxyl Radicals. Journal of the Chemical Society B-Physical Organic(8): 742-&. Baldwin, A.C., Barker, J.R., Golden, D.M. and Hendry, D.G., Photochemical Smog - Rate Parameter Estimates and Computer Simulations. Journal of Physical Chemistry, 81(25): Betterton, E.A., The Partitioning of Ketones between the Gas and Aqueous Phases. Atmospheric Environment Part a-general Topics, 25(8): Betterton, E.A. and Hoffmann, M.R., Henry Law Constants of Some Environmentally Important Aldehydes. Environmental Science & Technology, 22(12): Bielski, B.H.J., Cabelli, D.E., Arudi, R.L. and Ross, A.B., Reactivity of Ho2/O-2 Radicals in Aqueous-Solution. Journal of Physical and Chemical Reference Data, 14(4): Bone, R., Cullis, P. and Wolfenden, R., Solvent Effects on Equilibria of Addition of Nucleophiles to Acetaldehyde and the Hydrophilic Character of Diols. Journal of the American Chemical Society, 105(5): Bothe, E., Schuchmann, M.N., Schultefrohlinde, D. and Vonsonntag, C., Ho2 Elimination from Alpha-Hydroxyalkylperoxyl Radicals in Aqueous-Solution. Photochemistry and Photobiology, 28(4-5): Bothe, E., Schuchmann, M.N., Schultefrohlinde, D. and Vonsonntag, C., Hydroxyl Radical-Induced Oxidation of Ethanol in Oxygenated Aqueous-Solutions - a Pulse-Radiolysis and Product Study. Zeitschrift Fur Naturforschung Section B-a Journal of Chemical Sciences, 38(2): Butler, J.A.V. and Ramchandani, C.N., Solubility of nonelectrolytes. II. Effect of the polar group on the free energy of hydration of aliphatic compounds. Journal of the Chemical Society: Buxton, G.V., Malone, T.N. and Salmon, G.A., Oxidation of glyoxal initiated by (OH)-O-. in oxygenated aqueous solution. Journal of the Chemical Society- Faraday Transactions, 93(16): Cabelli, D.E. and Bielski, B.H.J., A Pulse-Radiolysis Study of Some Dicarboxylic-Acids of the Citric-Acid Cycle - the Kinetics and Spectral Properties of the Free-Radicals Formed by Reaction with the Oh Radical. Zeitschrift Fur Naturforschung Section B-a Journal of Chemical Sciences, 40(12):

26 Campi, E., Ann. Chim., 53: 96. Christensen, L.K. et al., Kinetics and mechanism of the reactions of 2,3-butadione with F and Cl atoms, UV absorption spectra of CH3C(O)C(O)CH2 center dot and CH3C(O)C(O)CH2O2 center dot radicals, and atmospheric fate of CH3C(O)C(O)CH2O center dot radicals. Journal of Physical Chemistry A, 102(45): Elliot, A.J. and Simsons, A.S., Rate Constants for Reactions of Hydroxyl Radicals as a Function of Temperature. Radiation Physics and Chemistry, 24(2): Ervens, B., Gligorovski, S. and Herrmann, H., Temperature-dependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solutions. Physical Chemistry Chemical Physics, 5(9): Fuller, E.N., Diffusion Coefficients for Binary Gas Systems at Low Pressures: Empirical Correlations. Mc Graw Hill, New York, 587 pp. Gligorovski, S. and Herrmann, H., Glowa, G., Driver, P. and Wren, J.C., Irradiation of MEK - II: A detailed kinetic model for the degradation under of 2-butanone in aerated aqueous solutions steady-state gamma-radiolysis conditions. Radiation Physics and Chemistry, 58(1): Guthrie, J.P., Uncatalyzed and amine catalyzed decarboxylation of acetoacetic acid: An examination in terms of no barrier theory. Bioorganic Chemistry, 30(1): Guthrie, J.P. and Jordan, F., Amine-Catalyzed Decarboxylation of Acetoacetic Acid - Rate Constant for Decarboxylation of Beta-Imino Acid. Journal of the American Chemical Society, 94(26): Herrmann, H., Exner, M. and Zellner, R., Reactivity Trends in Reactions of the Nitrate Radical (No3) with Inorganic and Organic Cloudwater Constituents. Geochimica Et Cosmochimica Acta, 58(15): Herrmann, H., Reese, A., Ervens, B., Wicktor, F. and Zellner, R., Laboratory and modelling studies of tropospheric multiphase conversions involving some C1 and C2 peroxyl radicals. Physics and Chemistry of the Earth Part B-Hydrology Oceans and Atmosphere, 24(3): Herrmann, H. and Zellner, R., Reactions of NO 3 - radicals in aqueous solution. In: Z.B. Alfassi (Editor), N-Centered Radicals. Wiley, New York, pp Hilborn, J.W. and Pincock, J.A., Rates of Decarboxylation of Acyloxy Radicals Formed in the Photocleavage of Substituted 1-Naphthylmethyl Alkanoates. Journal of the American Chemical Society, 113(7): Ito, O., Akiho, S. and Iino, M., 1989a. Kinetics for Reactions of the Nitrate Radical (No3.) with Aldehydes in Acetonitrile. Journal of Physical Chemistry, 93(10): Ito, O., Akiho, S. and Iino, M., 1989b. Kinetic-Study for Reactions of Nitrate Radical (No3.) with Alcohols in Solutions. Bulletin of the Chemical Society of Japan, 62(5): Jayne, J.T. et al., Uptake of Gas-Phase Alcohol and Organic-Acid Molecules by Water Surfaces. Journal of Physical Chemistry, 95(16): Khan, I., Brimblecombe, P. and Clegg, S.L., Solubilities of Pyruvic-Acid and the Lower (C-1-C-6) Carboxylic-Acids - Experimental-Determination of Equilibrium Vapor-Pressures above Pure Aqueous and Salt-Solutions. Journal of Atmospheric Chemistry, 22(3): Kim, B.R., Kalis, E.M., DeWulf, T. and Andrews, K.M., Henry's law constants for paint solvents and their implications on volatile organic compound emissions from automotive painting. Water Environment Research, 72(1): Lide, D.R., Handbook of Chemistry and Physics. Lide, D. R., Boca Raton. Logan, S.R., Redox Reactions of Organic Radicals with Ferrocene Ferricenium Species in Aqueous-Solution.1. Radicals Derived from Carboxylic-Acids. Journal of the Chemical Society-Perkin Transactions 2(7): Mata-Segreda, J.F., Spontaneous hydrolysis of ethyl formate: Isobaric activation parameters. International Journal of Chemical Kinetics, 32(1): Neta, P., Huie, R.E. and Ross, A.B., Rate Constants for Reactions of Peroxyl Radicals in Fluid Solutions. Journal of Physical and Chemical Reference Data, 19(2): Saxena, P. and Hildemann, L.M., Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds. Journal of Atmospheric Chemistry, 24(1): Scholes, G. and Willson, R.L., Gamma-Radiolysis of Aqueous Thymine Solutions - Determination of Relative Reaction Rates of Oh Radicals. Transactions of the Faraday Society, 63(540P): 2983-&. 27