TOWARDS A MORE DETAILED DESCRIPTION OF TROPOSPHERIC AQUEOUS PHASE ORGANIC CHEMISTRY: CAPRAM 3.0 ELECTRONIC SUPPLEMENTAL MATERIAL (ESM)

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1 TWARDS A MRE DETAILED DESRIPTIN F TRPSPERI AQUEUS PASE RGANI EMISTRY: APRAM 30 errmann 1 *, A Tilgner 1, P Barzaghi 1, Z Majdik 1, S Gligorovski 1, L Poulain 2 and A Monod 2 1 Leibniz Institut für Troposphärenforschung, Permoserstraße 15, Leipzig, Germany 2 Laboratoire de himie et Environnement, Université de Provence, Place Victor ugo 3, Marseille cedex 3, France *orresponding author Leibniz Institut für Troposphärenforschung, Permoserstr 15, Leipzig, Germany Tel: ; fax: ELETRNI SUPPLEMENTAL MATERIAL (ESM) 1

2 Table I: Summary of the parameters and reactions included in APRAM 30 Gas phase initial concentration of organic compounds [ppb]: ompound Urban Remote Marine Estimated ()N Estimated Initial concentration of organic compounds in the aqueous phase [µm]: Phase transfer of organic compounds: ompound Urban Remote Marine Averaged from several aerosol measurements and scaled to the concentration At p 0 most of malonic acid and succinic acid dissociates to the monoanionic form ompound K 298, - / R, M atm -1 K Lit α Lit D g [10 5 m 2 s -1 ] 1-Pr (Jayne et al, 1991) 0011 (Jayne et al, 1,96 (Fuller) 1991) 2-Pr (Jayne et al, 1991) 0013 (Jayne et al, 1,96 (Fuller) 1991) 1-Bu (Snider and Dawson, 1985) Bu (Snider and Dawson, 1985) Trend: Smaller α with bigger compounds (Zhou and Mopper, 1990) 0,03 = α( 3 ) 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(ra3) 3 () 14 (Betterton and offmann, 003 = α( 3 ) 195 (Fuller) 1988) 3 () (Betterton, 1991) (Schutze and errmann, 2004) 2,02 (Fuller) 3 () (Zhou and Mopper, 1990) (Schutze and errmann, 2004) Lit 087 (Fuller) 2

3 ompound K 298, - / R, M atm -1 K Lit α Lit D g [10 5 m 2 s -1 ] KET 129 Meylan and oward, = α(aceton) 1 (Fuller) 3 () 2 DB Estimated after the effective 0023 = α(glyoxal) 1 (Fuller) = enry constant of Glyoxal 3 () 2 ( 3 ) (Kim et al, 2000) 001 Estimated 071 (Fuller) Bocek, Estimated 093 (Fuller) ()N (Kim et al, 2000) 001 Estimated 078 (Fuller) Lit (Bone et al, 1983) 004 (Jayne et al, 1991) 106 (Fuller) Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments 2 ompounds 1 + () () 2-2, (Ervens et al, 2003) 2 N 3 + () 2 - () N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 3 () () Estimated like () Estimated in analogy to () Estimated in analogy to () Estimated in analogy to () Estimated in analogy to xidation of 1-Propanol , (Ervens et al, 2003) 3

4 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments 9 N N (errmann et al, 1994) Estimated after (von Sonntag, 1987) () Since 2 2 : and : Radical assumedly slower (Factor 2??) () As the 2 -compound xidation of Propionaldehyde () 2 5 () esper and errmann, N () 2 5 () + N In 3 N (Ito et al, 1989a) () () Estimated after (von Sonntag, 1987) () () Estimated after the A 3 recombination, (errmann et al, 1999) () (ilborn and Pincock, 1991) ETP Estimated after (von Sonntag, 1987) xidation of Propionaldehyde (hydrated form) () () esper and errmann, N () () 2 + N In 3 N (Ito et al, 1989a) () () Estimated after (von Sonntag, 1987) () Estimated after (von Sonntag, 1987) xidation of Propanoic acid , (Ervens et al, 2003) 24 N N alculated (errmann and Zellner, ( 2 ) Estimated after (von Sonntag, 1987) ( 2 ) ETP 1, analog to A 3 -Rekombination xidation of Propionate , (Ervens et al, 2003) 28 N N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 4

5 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments ( 2 ) Estimated after (von Sonntag, 1987) ( 2 ) () Estimated in analogy to ( 2 ) - 3 () () , α-ydroxy-propanoic acid: No sinks Estimated in analogy to ( 2 ) () , Estimated in analogy to ( 2 ) () , Estimated in analogy to xidation of 2-Propanol () () 3 2, (Elliot and Simsons, 1984) 35 N () 3 3 () 3 + N (errmann et al, 1994) 36 3 () ( 2 )() 3 1, Estimated 37 3 ( 2 )() () Estimated after (von Sonntag, 1987) xidation of Acetone () 3 3 () Average of measurements within the MST project 39 N () 3 3 () 2 + N (errmann et al, 1994) 40 3 () () 2 3, (Zegota et al, 1986) () 2 3 () + 3 () 2 () (Zegota et al, 1986) branching ratios after measurements within MST by Poulain et al, () () (Zegota et al, 1986)branching ratios after measurements within MST by Poulain et al, () () (Zegota et al, 1986)branching ratios after measurements within MST by Poulain et al, 44 3 () Estimated from the gas phase xidation of ydroxy Acetone 45 3 () 2 () + 3 ()() Gligorovski and errmann (In Preparation) 46 N () 2 () 3 ()() + N alculated (errmann and Zellner, 47 3 ()() ()() Estimated after (von Sonntag, 1987) 5

6 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments 48 3 ()() 3 () Estimated after 2, (Bothe et al, 1978) ()() () Estimated after the decay of 3 (), (Bothe et al, 1983) xidation of Methylglyoxal (hydrated form) 50 3 ()() ()() Average of measurements within the MST project 51 N ()() 2 3 ()() 2 + N Estimated 52 3 ()() ()() Estimated after (von Sonntag, 1987) 53 3 ()() 2 3 () In analogy with glyoxal, (Buxton et al, 1997)(approximation) xidation of Malonic acid () (Walling and EltaliawGm, 1973) 55 N () 2 + N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) Estimated after (von Sonntag, 1987) () + () + 2 1, Estimated in analogy to () Estimated in analogy to () , Estimated in analogy to () , Estimated in analogy to xidation of Malonate (dianion) ( - ) , (Logan, 1989) 62 N ( - ) N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ( 2 ) Estimated after (von Sonntag, 1987) 6

7 1, No sinks for mesoxalate and tartronate Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments ( 2 ) - - () () Estimated in analogy to ( 2 ) () Estimated in analogy to ( 2 ) () , Estimated in analogy to ( 2 ) () , Estimated in analogy to xidation of Malonate (monoanion) , (Ervens et al, 2003) 69 N N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ( 2 ) Estimated after (von Sonntag, 1987) No sinks for mesoxalate and tartronate ( 2 ) - () + - () + 2 Estimated in analogy to ( 2 ) 2 - () Estimated in analogy to ( 2 ) () , Estimated in analogy to ( 2 ) () , Estimated in analogy to xidation of Pyruvic acid () 2 () + 2 1, (Ervens et al, 2003) 76 N () 2 () + N alculated (errmann and Zellner, 77 2 () () Estimated after (von Sonntag, 1987) () () + 2 () Estimated in analogy to () 2 () Estimated in analogy to () Estimated in analogy to 2 2-7

8 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments () () Estimated in analogy to xidation of Pyruvate 82 3 () () (Ervens et al, 2003) 83 N () - 2 () - + N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 84 2 () () Estimated after (von Sonntag, 1987) () () () Estimated in analogy to () () Estimated in analogy to () Estimated in analogy to () () Estimated in analogy to xidation of Succinic acid () 2 2 () , (Ervens et al, 2003) 90 N () 2 2 () 2 + N alculated (errmann and Zellner, 91 2 () () Estimated after (von Sonntag, 1987) () 2 () 2 + () Estimated in analogy to () 2 2 () Estimated in analogy to () 2 2 () Estimated in analogy to () () Estimated in analogy to () 2 2 () Estimated after Glycolic acid 97 N 3 + () 2 2 () N Estimated after Glycolic acid 98 () () Estimated after (von Sonntag, 1987) 99 () Estimated after (von Sonntag, 1987) xidation of Succinate (dianion) ( - ) 2 2 ( - ) (Ervens et al, 2003) 8

9 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments 101 N ( - ) 2 2 ( - ) 2 + N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ( - ) ( - ) Estimated after (von Sonntag, 1987) ( - ) 2 - () () Estimated in analogy to ( - ) 2 2 () Estimated in analogy to ( - ) () , Estimated in analogy to ( - ) () , Estimated in analogy to () () Estimated after Glycolate 108 N 3 + () () N Estimated after Glycolate 109 () () Estimated after (von Sonntag, 1987) 110 () Estimated after (von Sonntag, 1987) xidation of Succinate (monoanion) estimated: k Dianion = k Monoanion alculated (errmann and Zellner, 112 N N in (Gligorovski and errmann, 2004) (1) ( 2 ) Estimated after (von Sonntag, 1987) ( 2 ) 2 - () () Estimated in analogy to ( 2 ) 2-2 () , Estimated in analogy to ( 2 ) () , Estimated in analogy to ( 2 ) () , Estimated in analogy to xidation of Lactic acid , (Adams et al, 1965) 9

10 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments 119 N N alculated (errmann and Zellner, Estimated after (von Sonntag, 1987) () Estimated after Isopropanol (von Sonntag, 1987) xidation of Lactate (Logan, 1989) 123 N N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) Estimated after (von Sonntag, 1987) () Estimated after Isopropanol (von Sonntag, 1987) xidation of Glycolic acid (Scholes and Willson, 1967) 127 N N alculated (errmann and Zellner, Estimated after (von Sonntag, 1987) () 2 52 Estimated after Ethanol, (von Sonntag, 1987) xidation of Glycolate (Logan, 1989) 131 N N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) Estimated after (von Sonntag, 1987) () 2-52 Estimated after Ethanol, (von Sonntag, 1987) Reactions of the peroxyl radical formed from acetic acid = k ( ) (Bielski et al, 1985) 10

11 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments = k ( ) (Bielski et al, 1985) S S = k ( S - 3 ) (errmann et al, 1999) = k( ) (Bielski et al, 1985) = k ( ) (Bielski et al, 1985) S S = k ( S - 3 ) (errmann et al, 1999) xidation of Acetic acid hydroxyperoxide = k ( ) 141 N N alculated (errmann and Zellner, Fe Fe () = k (Fe ) - xidation of acetate hydroxyperoxide = k ( ) 144 N N = k ( N ) Fe 2+ Fe () = k (Fe ) xidation of 1-Butanol esper and errmann, (Shastri and uie, 1990) 147 N N Estimated after (von Sonntag, 1987) Estimated after (von Sonntag, 1987) xidation of Butyraldehyde esper and errmann, N N alculated (errmann and Zellner, Estimated after (von Sonntag, 1987) () Estimated after the A 3 recombination, (errmann et al, 1999) 11

12 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments () Estimated after 3 2 () (ilborn and Pincock, 1991) Estimated after (von Sonntag, 1987) Estimated after ETP, (errmann et al, 1999) () Estimated () Estimated after ETP, (errmann et al, 1999) xidation of Butyraldehyde (hydrated form) () () esper and errmann, alculated (errmann and Zellner, 160 N () () 2 + N () () Estimated after (von Sonntag, 1987) () Estimated after (von Sonntag, 1987) xidation of Butyric acid , (Scholes and Willson, 1967) 164 N N alculated (errmann and Zellner, Estimated after (von Sonntag, 1987) () Estimated in analogy to () Estimated in analogy to Estimated in analogy to () Estimated in analogy to xidation of Butyrate (Anbar et al, 1966) 171 N N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 12

13 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments Estimated after (von Sonntag, 1987) ( 2 ) () Estimated in analogy to ( 2 ) () Estimated in analogy to ( 2 ) Estimated in analogy to ( 2 ) () Estimated in analogy to xidation of 2-Butanol esper and errmann, N N alculated (errmann and Zellner, ( 2 )() Estimated after (von Sonntag, 1987) ( 2 )() () (vonsonntag et al, 1997) xidation of Methyl Ethyl Ketone () () Average of measurements within the MST project () () Average of measurements within the MST project 183 N () () 3 + N alculated (errmann and Zellner, 184 N () () N alculated (errmann and Zellner, () ()() (Glowa et al, 2000) ()() () (Glowa et al, 2000) branching ratios after measurements within MST by Poulain et al, ()() ()() (Glowa et al, 2000) branching ratios after measurements within MST by Poulain et al, 13

14 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments () E Estimated after gas phase rate const (Baldwin et al, 1977) xidation of 2,3-Butanedione ()() ()() k(298) after Gligorovski and errmann, 2004 Branching ratio estimated based on the gas phase reaction (hristensen et al, ()() k(298) after Gligorovski and errmann, 2004 Branching ratio estimated based on the gas phase reaction (hristensen et al, ()() 3 + N 3 3 ()() 2 + N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ()() 3 + N 3 3 ()N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ()() ()() Estimated after (von Sonntag, 1987) ()() ()() k(298) estimated after the 3 () recombination ()() () 3 () + 3 ()() k(298) estimated after the 3 () recombination ()() E k 1st estimated after reac () () By analogy with acetone () () By analogy with acetone () () E By analogy with reac () () By analogy with 3 (Schuchmann and Vonsonntag, 1988) 201 () () E+4 By analogy with 3 () 2 (Schuchmann and Vonsonntag, 1988) 202 () () E+9 Estimated after (von Sonntag, 1987) 203 () () 2 3 2E+9 Estimated after (von Sonntag, 1987) 204 () () + 2 1E+6 Estimated 14

15 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments xidation of 1,4-Dioxo Butene = () = k (Maleic acid), (abelli and Bielski, 1985) 206 () + 2 () Estimated after (von Sonntag, 1987) () 2 () xidation of 2-ydroxy, 3,4-Dioxo Butyraldehyde 208 ()() + ()() ()() + N 3 ()() N Formation of keto and hydroxy species = k (2 ETP) Estimated after Glyoxal, (Buxton et al, 1997) alculated (errmann and Zellner, 210 ()() ()() Estimated after (von Sonntag, 1987) ()() + 2 ()() + 2 xidation of 2-ydroxy, 3,4-Dioxo Butyric acid 212 ()() + ()() 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 alculated, (errmann and Zellner, 213 ()() + N 3 ()() + N ()() + 2 ()()() Estimated after (von Sonntag, 1987) 215 ()()() Estimated after (von Sonntag, 1987) ()() () () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) xidation of 2-ydroxy, 3,4-Dioxo Butyrate ()() + - ()() = k (Glyoxylate), (Ervens et al, 2003) ()() + N 3 - ()() = k (Glyoxylate) N ()() ()()() Estimated after (von Sonntag, 1987) 15

16 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments ()()() ()() Estimated after (von Sonntag, 1987) () () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) xidation of 2,3-Dihydroxy, 4-xo Butyraldehyde 222 ()() + ()() Estimated after Glyoxal, (Buxton et al, 1997) 223 ()() + N 3 ()() + N alculated (errmann and Zellner, 224 ()() ()() Estimated after (von Sonntag, 1987) ()() Estimated after (von Sonntag, 1987) ()() + 2 xidation of 2,3-Dihydroxy, 4-xo Butyric acid 226 ()() + ()() Estimated after Malic acid (Gligorovski and errmann 2004) 227 ()() + N 3 ()() + N alculated (errmann and Zellner, 228 ()() Estimated after (von Sonntag, 1987) ()()() ()()() Estimated after (von Sonntag, 1987) ()() + 2 xidation of 2,3-Dihydroxy, 4-xo Butyrate ()() + ()() Estimated after Malate (Gligorovski and errmann 2004) ()() + N 3 - ()() + N = BDE (Malonate) alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ()() ()()() Estimated after (von Sonntag, 1987) ()()() ()() + 2 xidation of Ethylene Glycol 1000 Estimated after (von Sonntag, 1987) 16

17 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments , Source for ydroxyacetaldehyde (Adams et al, 1965) N N (Ito et al, 1989b) () Estimated after (von Sonntag, 1987) () (von Sonntag, 1987) xidation of Glycolaldehyde = k ( 3 ) (Schuchmann and Vonsonntag, 1988) N N Estimated Estimated after (von Sonntag, 1987) Estimated after Ethylene Glycol (von Sonntag, 1987) xidation of Glycolaldehyde (hydrated form) 242 () () = k ( 3 () 2 ) (Schuchmann and Vonsonntag, 1988) N N Estimated 244 () () Estimated after (von Sonntag, 1987) 245 () () Estimated after Ethylene Glycol (von Sonntag, 1987) xidation of 3-ydroxy Pyruvic acid () + () + 2 5, =k (Glycolic acid), (Scholes and Willson, 1967) () + N 3 () + N alculated (errmann and Zellner, 248 () () Estimated after (von Sonntag, 1987) () () Estimated after Isopropanol, (von Sonntag, 1987) 250 () () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) xidation of 3-ydroxy Pyruvate () - + () =k (Glycolate), (Logan, 1989) 17

18 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments () - + N 3 () - + N = BDE (Glycolate) alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 253 () () Estimated after (von Sonntag, 1987) () - () Estimated after Isopropanol, (von Sonntag, 1987) 255 () ()() Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) xidation of 3-xo, Pyruvic acid 256 () + () + 2 3, = k (Glyoxylic acid) (Ervens et al, 2003) Additional source of mesoxalic acid 257 () + N 3 () + N alculated (errmann and Zellner, 258 () () Estimated after (von Sonntag, 1987) () + 2 () Estimated after Isopropanol, Von Sonntag, 1987 xidation of 3-xo, Pyruvate 260 () - + () = k (Glyoxylate) (Ervens et al, 2003) Additional source of mesoxalate 261 () - + N 3 () - + N = BDE (Glyoxylate) alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 262 () () Estimated after (von Sonntag, 1987) () () Estimated after Isopropanol, Von Sonntag, 1987 xidation of Malic acid 264 () 2 + () Gligorovski and errmann, () 2 + N () 2 + N alculated, errmann and Zellner () () Estimated after (von Sonntag, 1987) 18

19 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments () 2 () Estimated after (von Sonntag, 1987) xidation of Malate 268 () () Gligorovski and errmann, () N 3 () N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 270 () () Estimated after (von Sonntag, 1987) () 2 - () Estimated after (von Sonntag, 1987) xidation of xalacetic acid 272 () 2 + () = k ( 2 4 () 2 ) (Ervens et al, 2003) 273 () 2 + N 3 () + N alculated (errmann and Zellner, 274 () + 2 ()( 2 ) Estimated after (von Sonntag, 1987) ()( 2 ) ()() + ()() + 2 1, Formation from Keto- und ydroxyacids = k (2 ETP) 276 ()() 2 + () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) 277 ()() 2 + () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) () () Estimated after Lactic acid Estimated after Lactic acid 279 N 3 + () () + N () + 2 () Estimated after (von Sonntag, 1987) 281 () 2 () Estimated after (von Sonntag, 1987) xidation of xalacetate 282 () () = k ( 2 4 ( - ) 2 ) (Ervens et al, 2003) 283 () N 3 () N = k ( ) () ()( 2 ) Estimated after (von Sonntag, 1987) 19

20 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments ()( 2 ) - ()() - + ()() , Formation from Keto- und ydroxyacids = k (2 ETP) 286 ()() () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) 287 ()() () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) () - () Estimated after Lactate 289 N 3 + () - () - + N Estimated after Lactate 290 () () Estimated after (von Sonntag, 1987) 291 () 2 - () Estimated after (von Sonntag, 1987) xidation of Tartronic acid 292 () + () (Schuchmann et al, 1995) alculated (errmann and Zellner, () + N 3 () + N () () Estimated after (von Sonntag, 1987) () () Estimated after Isopropanal (von Sonntag, 1987) 296 () () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) xidation of Tartronate 297 () - + () (Schuchmann et al, 1995) = k ( - ) 298 () - + N 3 () - + N () () Estimated after (von Sonntag, 1987) () - () Estimated after Isopropanal (von Sonntag, 1987) 301 () () Estimated after (Guthrie, 2002) and (Guthrie and Jordan, 1972) xidation of Methyl Isobutyl Ketone () 2 ( 3 ) ()( 3 ) Average of measurements within the MST project () 2 ( 3 ) () 2 ( 3 ) Average of measurements within the MST project 20

21 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments 304 N () 2 ( 3 ) 2 3 ()( 3 ) N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) alculated (errmann and Zellner, 305 N () 2 ( 3 ) 2 3 () 2 ( 3 ) 2 + N in (Gligorovski and errmann, 2004) (1) ()( 3 ) ()()( 3 ) Estimated after (von Sonntag, 1987) ()()( 3 ) ()( 3 ) Estimated after 3 () 2 ; branching ratios after measurements within MST by Poulain et al, ()()( 3 ) ()()( 3 ) ()()( 3 ) ()()( 3 ) ()()( 3 ) Estimated after 3 () 2 ; branching ratios after measurements within MST by Poulain et al, Estimated after 3 () 2 ; branching ratios after measurements within MST by Poulain et al, ()( 3 ) ()( 3 ) By analogy with acetone and with the gas phase (Mellouki et al, ) () 2 ( 3 ) () 2 ()( 3 ) Estimated after (von Sonntag, 1987) () 2 ()( 3 ) () 2 ( 3 ) Estimated () 2 ( 3 ) 2 3 () By analogy with the gas phase, (Mellouki et al, ) By analogy with t-butanol () 2 ( 3 ) 2 2 () 2 ()( 3 ) By analogy with the gas phase, (Mellouki et al, ) () 2 ()( 3 ) () 2 ()( 3 ) By analogy with acetone () 2 ()( 3 ) By analogy with acetone ()() 2 ()( 3 ) () 2 ()( 3 ) By analogy with acetone ()() 2 ()( 3 ) ()() 2 ()( 3 ) () 2 ()( 3 ) By analogy with acetone 2 () 2 ()( 3 ) () 2 ()( 3 ) 2 ()() 2 ()( 3 ) ()() 2 ()( 3 ) By analogy with acetone 21

22 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments () 2 ()( 3 ) 2 + () 2 ()( 3 ) By analogy with acetone By analogy with the gas phase (Mellouki et al) 321 () 2 ()( 3 ) 2 2 () By analogy with 3 () 2 ( 3 ) () () Estimated after (von Sonntag, 1987) () () Estimated after 2 () () 2 ()( 3 ) (Mata-Segreda, 2000) (Mata-Segreda, 2000) xidation of Ethyl Formate () Average of measurements within the MST project Average of measurements within the MST project 328 N () + N alculated (errmann and Zellner, 329 N N alculated (errmann and Zellner, () () Estimated after (von Sonntag, 1987) () Estimated after reaction () Estimated after reaction () 2 5 () + ½ Estimated based on product studies carried out within MST by Poulain et al, () Wang () 2 2 () Estimated ( ) () (Neta et al, 1990) () () Estimated () () Estimated () + 2 () Estimated in analogy with 3 () () Estimated in analogy with 3 () ( ) Estimated after (von Sonntag, 1987) 22

23 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments ( ) ( ) In analogy with Ethyl Formate, (Mata-Segreda, 2000) ( ) ( ) In analogy with Ethyl Formate, (Mata-Segreda, 2000) xidation of N Methyl Pyrrolidinone ()N ()N Average of measurements within the MST project ()N ()N Average of measurements within the MST project 346 N ()N ()N 3 + N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) 347 N ()N ()N 2 + N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (1) ()N ()N Estimated after (von Sonntag, 1987) ()N ()N k(298) estimated after the ethyl peroxy radical (errmann et al, 1999) ()N ()N 3 () k(298) estimated after the reaction (214 in APRAM 24) ()N 3 () ()N 2 () Estimated after NMP N ()N 3 () 2 2 ()N 2 () N alculated (errmann and Zellner, in (Gligorovski and errmann, 2004) (3) ()N 2 () ()N 2 () Estimated after (von Sonntag, 1987) ()N 2 () ()N() k(298) estimated after the ethyl peroxy radical (errmann et al, 1999) ()N ()N Estimated after (von Sonntag, 1987) ()N ()N k(298) estimated after the ethyl peroxy radical (errmann et al, 1999) ()N ()N Estimated after NMP Estimated after NMP 358 N ()N ()N + N ()N ()N Estimated after (von Sonntag, 1987) 23

24 Reaction k 298 K [M -1 s -1 ] - E A /R [K] omments ()N ()N k(298) estimated after the ethyl peroxy radical (errmann et al, 1999) ()N ()N() k(298) estimated after the reaction (214 in APRAM 24) 2 elimination from 3 () () Estimated after (von Sonntag, 1987) Remarks: (1) : ontribution of -abs back calculated using correlation for the reaction of N 3 with aliphatic compounds in aqueous solution (errmann and Zellner, where the BDEs were derived from the correlation reported in (Gligorovski and errmann, 2004) for the reaction of with organic compounds (2) : alculated using the correlation for the reaction of N3 with aliphatic compounds in aqueous solution (errmann and Zellner, The BDEs determined with Benson s incremental method (3) : ontribution of -abs back calculated using correlation for the reaction of N 3 with aliphatic compounds in aqueous solution (errmann and Zellner, where the BDEs were derived from the correlation (gas-phase) reported in (Gligorovski and errmann, 2004) for the reaction of with organic compounds Equilibrium reactions: Equilibrium K Ea/R k for k back omments E ( - ) 2 2, , Lit: andb f rg omp T-dependency between 0 and 30 E2 3 () () - 3, , Lit: andb f rg omp E , , T-dependency between 5 and 20 E4 3 () ()() , (Betterton and offmann, 1988) k hin as for Glyoxal E5 2 4 () , , ( - ) 2 2, , , E6 E , α-ydroxy-propionate is formed by the recombination of the propionate peroxy radical No sinks implemented until now for α-ydroxy- Propionate = K, k (Propanoic acid) E , , (Lide, 1995) E , , (Lide, 1995)

25 Estimated after the second step dissociation Estimated after oxalacetic acid (Lide, 1995) Equilibrium K Ea/R k for k back omments + E10 A () Estimated in analogy with the acetyl radical E Estimated after acetic acid (Lide, 1995) E12 ()() - ()() + + constant of tartaric acid (Lide, 1995) E13 () - () + + E14 2 () 2 () Estimated after pyruvic acid (Lide, 1995) + + E15 ()() Estimated after the second step dissociation - ()() + + constant of tartaric acid (Lide, 1995) E16 ()() (Lide, 1995) - ()() (Lide, 1995) E17 () () Estimated after pyruvic acid (Lide, 1995) E18 () () (Albalat et al, 1989) E19 () (Lide, 1995) () E20 () () E21 () (Lide, 1995) () E22 () (Lide, 1995) - () 2 - E23 ()() () E24 () () E25 () () Estimated after mesoxalic acid (Albalat et al, 1989) (ampi, 1963) (ampi, 1963) E Smith and Marthell, 1989 E () 3 2 () jelund and Wadso, E28 () Estimated after Propanoic acid () E Estimated after Propanoic acid E () () Xu et al, 1992 k back estimated after acetaldehyde E () Xu et al, 1992 k back estimated after acetaldehyde

26 Equilibrium K Ea/R k for k back omments E () Betterton and offmann 1988 k back estimated after acetaldehyde E Estimated after acetaldehyde () 2 2 E () Estimated after acetaldehyde Photolysis rates: Reaction j max Reference P , Photochemical rate constant estimated equal to J( 2 2 ) References: Adams, GE, Boag, JW, urrant, J and Michael, BD, 1965 Absolute rate constants for the reaction of the hydroxyl radical with organic compounds In: M Ebert, JP Keen, AJ Swallow and J Baxendale (Editors), Pulse Radiolysis Academic Press, London, pp Albalat, R, laret, J, Gomez, E, Muller, and Sarret, M, 1989 Electrocatalytic xidation of Mesoxalic Acid on a Polycrystalline Platinum-Electrode in Acid- Medium Electrochimica Acta, 34(5): Anbar, M, MeyersteD and Neta, P, 1966 Reactivity of Aliphatic ompounds Towards ydroxyl Radicals Journal of the hemical Society B-Physical rganic(8): 742-& Baldwin, A, Barker, JR, Golden, DM and endry, DG, 1977 Photochemical Smog - Rate Parameter Estimates and omputer Simulations Journal of Physical hemistry, 81(25): Betterton, EA, 1991 The Partitioning of Ketones between the Gas and Aqueous Phases Atmospheric Environment Part a-general Topics, 25(8): Betterton, EA and offmann, MR, 1988 enry Law onstants of Some Environmentally Important Aldehydes Environmental Science & Technology, 22(12): Bielski, BJ, abelli, DE, Arudi, RL and Ross, AB, 1985 Reactivity of o2/-2 Radicals in Aqueous-Solution Journal of Physical and hemical Reference Data, 14(4): Bone, R, ullis, P and Wolfenden, R, 1983 Solvent Effects on Equilibria of Addition of Nucleophiles to Acetaldehyde and the ydrophilic haracter of Diols Journal of the American hemical Society, 105(5): Bothe, E, Schuchmann, MN, Schultefrohlinde, D and Vonsonntag,, 1978 o2 Elimination from Alpha-ydroxyalkylperoxyl Radicals in Aqueous-Solution Photochemistry and Photobiology, 28(4-5): Bothe, E, Schuchmann, MN, Schultefrohlinde, D and Vonsonntag,, 1983 ydroxyl Radical-Induced xidation of Ethanol in xygenated Aqueous-Solutions - a Pulse-Radiolysis and Product Study Zeitschrift Fur Naturforschung Section B-a Journal of hemical Sciences, 38(2): Butler, JAV and Ramchandani, N, 1935 Solubility of nonelectrolytes II Effect of the polar group on the free energy of hydration of aliphatic compounds Journal of the hemical Society: Buxton, GV, Malone, TN and Salmon, GA, 1997 xidation of glyoxal initiated by ()-- in oxygenated aqueous solution Journal of the hemical Society- Faraday Transactions, 93(16): abelli, DE and Bielski, BJ, 1985 A Pulse-Radiolysis Study of Some Dicarboxylic-Acids of the itric-acid ycle - the Kinetics and Spectral Properties of the Free-Radicals Formed by Reaction with the h Radical Zeitschrift Fur Naturforschung Section B-a Journal of hemical Sciences, 40(12):

27 ampi, E, 1963 Ann him, 53: 96 hristensen, LK et al, 1998 Kinetics and mechanism of the reactions of 2,3-butadione with F and l atoms, UV absorption spectra of 3()()2 center dot and 3()()22 center dot radicals, and atmospheric fate of 3()()2 center dot radicals Journal of Physical hemistry A, 102(45): Elliot, AJ and Simsons, AS, 1984 Rate onstants for Reactions of ydroxyl Radicals as a Function of Temperature Radiation Physics and hemistry, 24(2): Ervens, B, Gligorovski, S and errmann,, 2003 Temperature-dependent rate constants for hydroxyl radical reactions with organic compounds in aqueous solutions Physical hemistry hemical Physics, 5(9): Fuller, EN, Diffusion oefficients for Binary Gas Systems at Low Pressures: Empirical orrelations Mc Graw ill, New York, 587 pp Gligorovski, S and errmann,, 2004 Glowa, G, Driver, P and Wren, J, 2000 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 hemistry, 58(1): Guthrie, JP, 2002 Uncatalyzed and amine catalyzed decarboxylation of acetoacetic acid: An examination in terms of no barrier theory Bioorganic hemistry, 30(1): Guthrie, JP and Jordan, F, 1972 Amine-atalyzed Decarboxylation of Acetoacetic Acid - Rate onstant for Decarboxylation of Beta-Imino Acid Journal of the American hemical Society, 94(26): errmann,, Exner, M and Zellner, R, 1994 Reactivity Trends in Reactions of the Nitrate Radical (No3) with Inorganic and rganic loudwater onstituents Geochimica Et osmochimica Acta, 58(15): errmann,, Reese, A, Ervens, B, Wicktor, F and Zellner, R, 1999 Laboratory and modelling studies of tropospheric multiphase conversions involving some 1 and 2 peroxyl radicals Physics and hemistry of the Earth Part B-ydrology ceans and Atmosphere, 24(3): errmann, and Zellner, R, 1998 Reactions of N 3 - radicals in aqueous solution In: ZB Alfassi (Editor), N-entered Radicals Wiley, New York, pp ilborn, JW and Pincock, JA, 1991 Rates of Decarboxylation of Acyloxy Radicals Formed in the Photocleavage of Substituted 1-Naphthylmethyl Alkanoates Journal of the American hemical Society, 113(7): Ito,, Akiho, S and Iino, M, 1989a Kinetics for Reactions of the Nitrate Radical (No3) with Aldehydes in Acetonitrile Journal of Physical hemistry, 93(10): Ito,, Akiho, S and Iino, M, 1989b Kinetic-Study for Reactions of Nitrate Radical (No3) with Alcohols in Solutions Bulletin of the hemical Society of Japan, 62(5): Jayne, JT et al, 1991 Uptake of Gas-Phase Alcohol and rganic-acid Molecules by Water Surfaces Journal of Physical hemistry, 95(16): Khan, I, Brimblecombe, P and legg, SL, 1995 Solubilities of Pyruvic-Acid and the Lower (-1--6) arboxylic-acids - Experimental-Determination of Equilibrium Vapor-Pressures above Pure Aqueous and Salt-Solutions Journal of Atmospheric hemistry, 22(3): Kim, BR, Kalis, EM, DeWulf, T and Andrews, KM, 2000 enry's law constants for paint solvents and their implications on volatile organic compound emissions from automotive painting Water Environment Research, 72(1): Lide, DR, 1995 andbook of hemistry and Physics Lide, D R, Boca Raton Logan, SR, 1989 Redox Reactions of rganic Radicals with Ferrocene Ferricenium Species in Aqueous-Solution 1 Radicals Derived from arboxylic-acids Journal of the hemical Society-Perkin Transactions 2(7): Mata-Segreda, JF, 2000 Spontaneous hydrolysis of ethyl formate: Isobaric activation parameters International Journal of hemical Kinetics, 32(1): Neta, P, uie, RE and Ross, AB, 1990 Rate onstants for Reactions of Peroxyl Radicals in Fluid Solutions Journal of Physical and hemical Reference Data, 19(2): Saxena, P and ildemann, LM, 1996 Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds Journal of Atmospheric hemistry, 24(1): Scholes, G and Willson, RL, 1967 Gamma-Radiolysis of Aqueous Thymine Solutions - Determination of Relative Reaction Rates of h Radicals Transactions of the Faraday Society, 63(540P): 2983-& 27

28 Schuchmann, MN, Schuchmann, P and Vonsonntag,, 1995 xidation of ydroxymalonic Acid by h Radicals in the Presence and in the Absence of Molecular- xygen - a Pulse-Radiolysis and Product Study Journal of Physical hemistry, 99(22): Schuchmann, MN and Vonsonntag,, 1988 The Rapid ydration of the Acetyl Radical - a Pulse-Radiolysis Study of Acetaldehyde in Aqueous-Solution Journal of the American hemical Society, 110(17): Schuchmann, MN, Zegota, and Vonsonntag,, 1985 Acetate Peroxyl Radicals, 2ch2co2(-) - a Study on the Gamma- Radiolysis and Pulse-Radiolysis of Acetate in xygenated Aqueous-Solutions Zeitschrift Fur Naturforschung Section B-a Journal of hemical Sciences, 40(2): Schutze, M and errmann,, 2004 Uptake of acetone, 2-butanone, 2,3-butanedione and 2- oxopropanal on a water surface Physical hemistry hemical Physics, 6(5): Shastri, LV and uie, RE, 1990 Rate onstants for ydrogen Abstraction Reactions of No3 in Aqueous-Solution International Journal of hemical Kinetics, 22(5): Snider, JR and Dawson, GA, 1985 Tropospheric Light Alcohols, arbonyls, and Acetonitrile - oncentrations in Southwestern United-States and enry Law Data Journal of Geophysical Research-Atmospheres, 90(ND2): von Sonntag,, 1987 The chemical Basis of Radiation Biology Taylor und Francis, London vonsonntag, et al, 1997 The fate of peroxyl radicals in aqueous solution Water Science and Technology, 35(4): 9-15 Walling, and EltaliawGm, 1973 Fentons Reagent 2 Reactions of arbonyl-ompounds and Alpha,Beta-Unsaturated Acids Journal of the American hemical Society, 95(3): Yaffe, D, ohen, Y, Espinosa, G, Arenas, A and Giralt, F, 2003 A fuzzy ARTMAP-based quantitative structure-property relationship (QSPR) for the henry's law constant of organic compounds Journal of hemical Information and omputer Sciences, 43(1): Zegota,, Schuchmann, MN, Schulz, D and Vonsonntag,, 1986 Acetonylperoxyl Radicals, h3coch2o2 - a Study on the Gamma- Radiolysis and Pulse-Radiolysis of Acetone in xygenated Aqueous-Solutions Zeitschrift Fur Naturforschung Section B-a Journal of hemical Sciences, 41(8): Zhou, XL and Mopper, K, 1990 Apparent Partition-oefficients of 15 arbonyl-ompounds between Air and Seawater and between Air and Fresh-Water - Implications for Air Sea Exchange Environmental Science & Technology, 24(12):

29 Table II: lassification of the diurnal behaviors of the organics compounds considered in APRAM 30 for the three different scenarios (remote, urban and marine) ompound Remote Urban Marine 1,2-dioxo 4-hydroxy isohexane A (1) A A 1,4-dihydroxy 2-oxo isohexane A A A 2-buten-1,4-dial B1 (2) B1 B1 1-butanol B2 (3) A A 1-propanol B2 A B1 2,3-butanedione A A A 2,3-dihydroxy 4-oxo butyraldehyde B1 A B1 2,3-dihydroxy 4-oxo butyric acid B1 A B1 2,3-dioxo isohexane A A A 2-butanol B2 A A 2-hydroxy 3,4-dioxo butyraldehyde B1 A B1 2-hydroxy 3,4-dioxo butyric acid B1 A B1 2-hydroxy 3-oxo propanoic acid B1 A B2 2-hydroxy 3-oxo succinic acid B1 B1 B2 2-oxo 3-hydroxy isohexane A A A 2-propanol B2 A A 2-pyrrolidinone (4) 3-hydroxy pyruvic acid B1 A B2 3-oxo propanoic acid A 3-oxo pyruvic acid B1 A Acetic acid hydroperoxide B1 B1 A Acetone A A A Butyraldehyde B (5) A D (6) Butyric acid A A D Dioxo succinic acid D D A Ethyl formate D D D Ethylene glycol B1 B1 D Glycolaldehyde B1 A D ydroxy acetone A A ydroxy butyric acid A A A Lactic acid A A D Malic acid B 29

30 ompound Remote Urban Marine Malonic acid D D D Methyl ethyl ketone A A A Mesoxalic acid A A A Methylglyoxal B Methyl isobutyl ketone A A A N-methylsuccinimide N-methylpyrrolidinone xalacetic acid A xo butyric acid A A A xo isobutane A A A Propanoic acid A A D Propionaldehyde B A D Pyruvic acid A Succinic acid D D D Succinimide D A D Tartaric acid A A A Tartronic acid A D omments to the table: (1) : A: Increasing concentration throughout the simulation time (2) : B1: oncentration having a strong diurnal variation with an increasing daily peak concentration (3) : B2: oncentration having a strong diurnal variation with a decreasing daily peak concentration (4) : : Decreasing concentration profile after a reached maximum concentration (5) : B: oncentration having a strong diurnal variation without a clear increase or decrease in time (6) : D: Diurnal concentration profiles which could not be included in either of the above described cases 30

31 Acetone (remote scenario) 3,00e-8 2,50e-8 conc [moles / l] 2,00e-8 1,50e-8 1,00e-8 5,00e-9 0, time [h] Figure I: Aqueous phase concentration of acetone for the standard scenario (remote) MEK (remote scenario) 6,00e-9 5,00e-9 conc [moles / l] 4,00e-9 3,00e-9 2,00e-9 1,00e-9 0, time [h] Figure II: Aqueous phase concentration of MEK for the standard scenario (remote) 31

32 MIBK (remote scenario) 2,50e-10 2,00e-10 conc [moles / l] 1,50e-10 1,00e-10 5,00e-11 0, time [h] Figure III: Aqueous phase concentration of MIBK for the standard scenario (remote) Mesoxalic acid (remote scenario) 5,00e-6 4,00e-6 conc [moles / l] 3,00e-6 2,00e-6 1,00e-6 0, time [h] Figure IV: Aqueous phase concentration of mesoxalic acid for the standard scenario (remote) 32

33 Tartaric acid (remote scenario) 1,00e-5 8,00e-6 conc [moles / l] 6,00e-6 4,00e-6 2,00e-6 0, time [h] Figure V: Aqueous phase concentration of tartaric acid for the standard scenario (remote) 2-hydroxy 3,4-dioxo butyric acid (remote scenario) 1,00e-6 8,00e-7 conc [moles / l] 6,00e-7 4,00e-7 2,00e-7 0, time [h] Figure VI: Aqueous phase concentration of 2-hydroxy-3,4-butyric acid for the standard scenario (remote) 33

34 Propionaldehyde (remote scenario) 3,00e-10 2,50e-10 conc [moles / l] 2,00e-10 1,50e-10 1,00e-10 5,00e-11 0, time [h] Figure VII: Aqueous phase concentration of propionaldehyde for the standard scenario (remote) Butyraldehyde (remote scenario) 1,80e-10 1,60e-10 1,40e-10 conc [moles / l] 1,20e-10 1,00e-10 8,00e-11 6,00e-11 4,00e-11 2,00e-11 0, time [h] Figure VIII: Aqueous phase concentration of butyraldehyde for the standard scenario (remote) 34

35 2-buten-1,4-dial (remote scenario) 5,00e-7 4,00e-7 conc [moles / l] 3,00e-7 2,00e-7 1,00e-7 0, time [h] Figure XIX: Aqueous phase concentration of 2-buten-1,4-dial for the standard scenario (remote) NMP (remote scenario) 1,60e-6 1,40e-6 1,20e-6 conc [moles / l] 1,00e-6 8,00e-7 6,00e-7 4,00e-7 2,00e-7 0, time [h] Figure X: Aqueous phase concentration of NMP for the standard scenario (remote) 35

36 N-methylsuccinimide (remote scenario) 8,00e-7 6,00e-7 conc [moles / l] 4,00e-7 2,00e-7 0, time [h] Figure XI: Aqueous phase concentration of N-methylsuccinimide for the standard scenario (remote) Tartronic acid (remote scenario) 1,40e-8 1,20e-8 1,00e-8 conc [moles / l] 8,00e-9 6,00e-9 4,00e-9 2,00e-9 0, time [h] Figure XII: Aqueous phase concentration of tartronic acid for the standard scenario (remote) 36

37 xalacetic acid (remote scenario) 2,50e-8 2,00e-8 conc [moles / l] 1,50e-8 1,00e-8 5,00e-9 0, time [h] Figure XIII: Aqueous phase concentration of oxalacetic acid for the standard scenario (remote) 37

38 Ȯ Ȯ Ȯ Fe Fe N N N 3 N N Scheme I: xidation pathways implemented in APRAM 30 38