Appendix B: Aqueous chemistry and gas-phase halogen chemistry

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1 1 Appendix B: Aqueous chemistry and gasphase halogen chemistry SANFORD SILLMAN, FRANK MARSIK, KHALID I. ALWALI, GERALD J. KEELER AND MATTHEW S. LANDIS* Department of Atmospheric, Oceanic and Space Sciences University of Michigan Ann Arbor, Michigan *Office of Research and Development, USEPA, Research Triangle Park, NC The tables listed here give the reactions used to represent aqueous and halogen chemistry in the model described by Sillman et al. [2007] (Reactive mercury in the troposphere: Model formation and results for Florida, the northeastern U.S. and the Atlantic Ocean, submitted to J. Geophys. Res., 2006). Reactions for atmospheric mercury are not included here. They are described separately (Appendix C). The mechanism for gasphase photochemistry (other than mercury or halogens) is described in Appendix A of Ito et al. [2006]. The reactions and rates included here are taken from compilations by Jacob et al. [1986], Pandis and Seinfeld [1989], Lelieveld et al. [1990], Liu et al. [1997], Sander and Crutzen [1996] and Sander et al. [2003]. These studies are cited as references for the individual rates. Readers are referred there for the primary sources. Appendix B includes the following tables: Table B1: Henry s law coefficients Table B2: Aqueous equilibrium coefficients. Table B3: Aqueous reactions. Table B4: Gasphase reactions involving halogens.

2 2 Table B1 Henry s Law coefficients Values here represent the physical Henry constants (K H ) and do not take into account enhanced solubilities due to dissociation equilibria. Abbreviations and units: K H298 =Henry s law coefficient at 298 K, expresed in M atm 1. ΔH = enthalpy of solution, expressed as ΔH/R (where R represents the gas constant) in units K. The temperature dependence is represented by K H = K H298 exp[δh/r(1/t 1/298)] for temperature T in K. Species K H298 ΔH/R Reference CO 2 3.4E Pandis, 1989 H 2 O E JPL, 2003 OH 2.5E Jacob, 1986 HO 2 2.0E Jacob, 1986 O E JPL, 2003 NO 2 1.0E Pandis, 1989 NO 1.9E Pandis, 1989 HNO 3 2.1E Lelieveld, 1991, Sander, 1996 HONO 5.1E Pandis, 1989 NH 3 7.5E Pandis, 1989 PAN 2.9E Pandis, 1989 CH 3 CO 3 1.0E Pandis, 1989 CH 3 C(O)OOH 4.73E Pandis, 1989 CH 3 O 2 6.0E Pandis, 1989 CH 3 OOH (MP) 2.27E Pandis, 1989 HCHO 6.3E Pandis, 1989 CH 3 CHO 1.14E Hermann, 2000

3 3 CH 3 OH 2.2E Pandis, 1989 CH 3 COOH 5.5E Hermann, 2000 (Acetic acid) 1 H 2 SO 4 1.0E See note 1 HCl 1.1E Sander, 1996 Cl 2 9.2E02 0. Sander, 1996 HOCl 4.8E Sander, 1996 HBr 7.2E Sander, 1996 HOBr 4.8E Sander, H 2 SO 4 and other species that form soluble aerosols are represented by a gasphase pseudospecies with a very high Henry constant, which insures rapid incorporation into the aqueous phase. This is used in model calculations that do not include explicit treatment of aerosols.

4 4 Table B2 Aqueous equilibrium coefficients K aq represents the equilibrium constant for reactions with the form C<=>A+B, with format Kaq = [A][B]/[C], in M. Abbreviations and units: K aq298 =equilibrium constant at 298 K, in M. ΔH = reaction enthalpy, expressed as ΔH/R (where R represents the gas constant) in units K. The temperature dependence is represented by K aq = K aq298 exp[δh/r(1/t 1/298)] for temperature T in K. Reaction K aq298 ΔH/R Reference CO 2 H + +HCO E Pandis, 1989 HCO 3 H + 2 +CO E Pandis, 1989 SO 2 H + +HSO E Pandis, 1989 HSO 3 H + 2 +SO E Sander, 1996 H 2 SO 4 H + +HSO 4 1.0E+03 Pandis, 1989 HSO 4 H + 2 +SO E Pandis, 1989 H 2 O 2 H + +HO 2 2.2E Pandis, 1989 HO 2 H + +O 2 1.6E05 0. Sander, 1996 HNO 3 H + +NO E Pandis, 1989 HONO H + +NO 2 5.1E Pandis, 1989 NH 3 OH + +NH 4 1.7E Pandis, 1989 HCHO+H 2 O H 2 C(OH) E Pandis, 1989, Sander, 2004 HCOOH H + +HCOO 1.78E Pandis, 1989 HOCH 2 SO 3 (HMS) H + 2 +OCH 2 SO 3 2.0E12 Jacob et al., 1986

5 5 CH 3 C(O)OOH 1.78E04 0. assumed equal to HCOOH H + +CH 3 C(O)OO CH 3 COOH H + +CH 3 COO 1.75E05 0. Hermann, 2000 HCl H + +Cl 1.74E Sander, 1996 Cl H + +ClOH 6.19E08 0. Pandis, 1989, Sander, see note 1 HOCl H + +OCl 3.2E08 0. Sander, 1996 HBr H + +Br 1.0E Sander, 1996 HOBr H + +OBr 2.100E09 0. Sander, 1996 Cl 2 Cl+Cl 5.26E06 Sander, 1996 Br 2 Br+Br 9.1E06 Sander, 1996 Notes: 1. This equilibrium coefficient is derived from the rates reported by Pandis and Seinfeld [1989] and Sander and Crutzen [1996] for the reactions Cl H + +ClOH and H + +ClOH Cl.

6 6 Table B3 Aqueous reactions Units are M s 1 for reactions involving two species, M 2 s 1 for reactions involving three species and s 1 for reactants involving a single species. Abbreviations: k 0 =equilibrium constant at 0 K, in M. E a = activation energy, expressed as E a /R (where R represents the gas constant) in units K. The temperature dependence is represented by k T = k 298 exp[e a /R(1/T 1/298)] for temperature T in K. Reaction k 298 E a /R References OH+ HO 2 7.0E Pandis, 1989 OH+ O 2 OH 1.0E Pandis, 1989 OH+ H 2 O 2 HO 2 2.7E Pandis, 1989 HO 2 + HO 2 H 2 O 2 8.6E Pandis, 1989 HO 2 + O 2 H 2 O 2 +OH 1.0E Pandis, 1989 O 2 + O 2 H 2 O 2 + 2OH 3.0E01 0. Pandis, 1989 HO 2 + H 2 O 2 OH 5.0E01 Pandis, 1989 O 2 + H 2 O 2 OH 1.3E01 Pandis, 1989 OH+ O 3 HO 2 2.0E+09 Pandis, 1989 HO 2 + O 3 OH 1.0E+04 Pandis, 1989 O 2 + O 3 OH+OH 1.5E Pandis, 1989 OH + O 3 HO 2 + O 2 7.0E+01 Pandis, 1989 HO 2 + O 3 OH+ O 2 2.8E Pandis, 1989 HCO 3 + OH CO 3 1.5E Pandis, 1989 HCO 3 + O 2 CO 3 +HO 2 1.5E Pandis, 1989 CO 3 + O 2 HCO 3 +OH 4.0E Pandis, 1989 CO 3 + H 2 O 2 HCO 3 +HO 2 8.0E Pandis, 1989

7 7 HCO 3 + OH CO 3 1.4E Pandis, 1989 Cl + HOCl+H + Cl 2 1.8E Sander, Cl 2 Cl +HOCl 1.1E Sander, 1996 Cl 2 +HO 2 2Cl +H + 4.5E Sander, 1996 Cl 2 + O 2 2Cl 1.0E Sander, 1996 Cl 2 +H 2 O 2 2Cl + HO 2 +H + 1.4E Pandis, 1989 Cl 2 + OH 2Cl +OH 7.3E Pandis, 1989 Cl+HO 2 Cl +H + 3.1E Pandis, 1989 Cl+H 2 O 2 Cl + HO 2 +H + 4.5E Pandis, 1989 Cl + OH ClOH 4.3E Pandis, 1989, Sander, 1996 ClOH Cl + OH 6.1E Pandis, 1989, Sander, 1996 SO 4 +Cl SO = 4 +Cl 2.0E Pandis, 1989 NO 3 +Cl NO 3 +Cl 1.0E Pandis, 1989 Br 2 +HO 2 2Br +H + 4.4E Sander, 1996, 2004 Br 2 + O 2 2Br 1.7E Sander, 1996 Br 2 +H 2 O 2 2Br +HO 2 +H + 1.0E Sander, 2004 Br 2 + OH 2Br +OH 1.1E Sander, 2004 HOBr+HO 2 Br 1.0E Sander, 2004 HOBr+O 2 Br 3.5E Sander, 2004 SO 4 +Br SO 4 +Br 3.5E Sander, 1996 NO 3 +Br NO 3 +Br 4.0E Sander, 1996, 2004 NO+NO 2 2NO 2 +H + 2.0E Pandis, 1989 NO 2 +NO 2 NO 2 +NO 3 1.0E Pandis, H + NO+OH NO 2 +H + 2.0E Pandis, 1989 NO 2 +OH NO 3 +H + 1.3E Pandis, 1989 HONO+OH NO 2 1.0E Pandis, 1989 NO 2 +OH NO 2 +OH 1.0E Pandis, 1989

8 8 NO 2 +O 3 NO 3 NO 2 +NO 3 NO 2 +NO 3 5.0E Pandis, E Pandis, 1989 NO 3 +HO 2 NO 3 +H + 1.2E Jacob, 1986 NO 3 +O 2 NO 3 1.0E Jacob, 1986 NO 3 +H 2 O 2 NO 3 +HO 2 +H + 1.0E Pandis, 1989 NO 2 +CO 3 NO 2 +CO E Pandis, 1989 NO 2 +Cl 2 NO 2 +2Cl 2.5E Pandis, 1989 NO 2 +Br 2 NO 2 +2Br 1.7E Sander, 2004 H 2 C(OH) 2 +OH HCOOH+HO 2 2.0E Pandis, 1989 HCOOH+OH CO 2 +HO 2 1.6E Pandis, 1989 HCOO +OH CO 2 +HO 2 +OH 2.5E Pandis, 1989 HCOOH+NO 3 2.1E Pandis, 1989 NO 3 +CO 2 +HO 2 +H + HCOO +NO 3 NO 3 +CO 2 +HO 2 6.0E Jacob, 1986 HCOOH+O 3 CO 2 +HO 2 +OH 5.0E Pandis, 1989 HCOO +O 3 CO 2 +O 2 +OH 1.0E Pandis, 1989 HCOO +CO 3 1.1E Pandis, 1989 HCO 3 +CO 2 +HO 2 +OH HCOOH+Cl 2 6.7E Pandis, 1989 CO 2 +HO 2 +2Cl +H + HCOO +Cl 2 CO 2 +HO 2 +2Cl 1.9E Pandis, 1989 CH 3 O 2 +HO 2 CH 3 OOH 4.3E Jacob, 1986 CH 3 O 2 +O 2 CH 3 OOH+OH 5.0E Jacob, 1986 CH 3 OOH+OH CH 3 O 2 2.7E Jacob, 1986 CH 3 OOH+OH HCHO+OH 1.9E Jacob, 1986 CH 3 OH+OH HCHO+HO 2 4.5E Pandis, 1989 CH 3 OH+CO 3 HCHO+HO 2 +HCO 3 CH 3 OH+Cl 2 2.6E Pandis, 1989 HCHO+HO 2 +2Cl +H + 3.5E Pandis, 1989

9 9 CH 3 OH+NO 3 1.0E Pandis, 1989 HCHO+HO 2 +NO 3 +H + CH 3 CO 3 +O 2 CH 3 C(O)OO 1.0E CH 3 C(O)OOH+CH 3 CHO 1.5E CH 3 COOH+2H + SO 2 +O 3 H 2 SO 4 2.4E Pandis, 1989 HSO 3 +O 3 HSO 4 SO 3 2 +O 3 SO E Pandis, E Pandis, 1989 SO 2 +H 2 O 2 H 2 SO 4 1.3E Pandis, 1989 HSO 3 +H 2 O 2 HSO 4 HSO 3 +OH SO 5 5.2E Sander, E Pandis, 1989 SO 3 2 +OH SO 5 +OH 4.6E Pandis, 1989 SO 5 +HSO 3 SO 5 +HSO 5 SO 5 +SO 3 2 SO 4 2 +SO 4 3.0E Pandis, E Jacob, 1986 (1.0E07) SO 5 +O 2 HSO 5 +OH 1.0E Jacob, 1986 SO 5 +HCOOH HSO 5 +CO 2 +HO 2 SO 5 +HCOO HSO 5 +CO 2 +O 2 SO 5 +SO 5 2SO 4 HSO 5 +OH SO 5 2.0E Jacob, E Jacob, E Jacob, E Jacob, 1986 HSO 5 +SO 4 SO 5 +SO 4 2 +H + 1.0E Jacob, 1986 HSO 5 +NO 2 HSO 4 +NO 3 3.1E Jacob, 1986 SO 4 +HSO 3 SO 5 +SO 4 2 +H + 1.3E Jacob, 1986 SO 4 +SO 3 2 SO 5 +SO E Jacob, 1986 SO 4 +HO 2 SO 4 2 +H + 5.0E Jacob, 1986 SO 4 +O 2 SO E Jacob, 1986 SO 4 +OH SO 4 2 +OH 8.0E Jacob, 1986 SO 4 +H 2 O 2 SO 4 2 +HO 2 +H + 1.2E Pandis, 1989 SO 4 +NO 2 SO 4 2 +NO 2 8.8E Jacob, 1986

10 10 SO 4 +HCO 3 SO 4 2 +CO 3 +H + 9.1E Pandis, 1989 SO 4 +HCOO SO 4 2 +CO 2 +HO 2 1.7E Jacob, 1986 SO 4 +HCOOH 1.4E Jacob, 1986 SO 2 4 +CO 2 +HO 2 +H + SO 2 +HO 2 H 2 SO 4 +OH 1.0E Pandis, 1989 SO 4 +CH 3 OH 2.5E Pandis, 1989 SO 2 4 +HCHO+HO 2 +H + SO 4 +Cl 2 SO Cl +H + 3.4E Pandis, 1989 SO 3 +Cl 2 SO 5 +2Cl 1.6E Pandis, 1989 H 2 O 2 (aq)+ hν 2 OH(aq) same as gasphase H 2 O 2 +hν 2OH O 3 (aq) + hν H 2 O 2 (aq) same as gasphase O 3 + hν O( 1 D) HONO(aq) + hν NO+OH same as gasphase HONO+hν NO+OH HNO 2 + hν NO+OH same as gasphase HONO+hν NO+OH NO 3 + hν NO 2 +OH+OH same as gasphase HNO 3 + hν NO 3 + hν NO same as gasphase NO 3 + hν NO Sander, 1996 Pandis, 1989, Sander, 1996 Pandis, 1989 Pandis, 1989 Pandis, 1989 Pandis, 1989

11 11 CH 3 OOH+ hν 5.0E04*j NO2 Pandis, 1989 HCHO+OH+HO 2 1. Sander and Crutzen [1996] give this reaction as a H + +Cl +HOCL. We have converted this into an equivalent reaction for HCl+HOCl, with a rate equal to k s *K e, where k s is the rate from Sander and Crutzen [1996] and Ke is the equilibrium constant for HCl H + +Cl.

12 12 Table B4 Gasphase reactions: Halogens Units are molec. cm 3 s 1 for reactions involving two species and s 1 for reactants involving a single species. Abbreviations: k 0 =equilibrium constant at 0 K, in M. E a = activation energy, expressed as E a /R (where R represents the gas constant) in units K. The temperature dependence is represented by k T = k 0 exp[e a /R(1/T)] for temperature T in K. Reaction k 0 E a /R References Cl 2 + OH HOCl 1.4E JPL, 2003 HCl+ OH Cl 2.6E JPL, 2003 HOCl+ OH ClO 3.0E JPL, 2003 Cl+ HO 2 HCl 1.8E JPL, 2003 Cl+ HO 2 OH+ClO 4.1E JPL, 2003 ClO+ HO 2 HOCl 2.7E JPL, 2003 ClO+ NO Cl+NO 2 6.4E JPL, 2003 ClO+ OH Cl+HO 2 7.4E JPL, 2003 ClO+ OH HCl 6.0E JPL, 2003 Cl+ H 2 O 2 HCl+HO 2 1.1E JPL, 2003 Cl+ NO 3 ClO+NO 2 2.4E11 0. JPL, 2003 Cl+ H 2 HCl+HO 2 3.7E JPL, 2003 Cl+ CH 4 HCl+CH 3 O 2 9.6E JPL, 2003 Cl+ O 3 ClO 2.3E JPL, 2003 Br 2 + OH HOBr+Br 4.2E11 JPL, HBr + OH Br 1.1E11 0. JPL, 2003

13 13 HOBr + OH BrO 3.0E assumed equal to HOCl+OH ClO Br + HO 2 HBr 1.5E JPL, 2003 BrO+ HO 2 HOBr 3.4E rate from JPL, 2003, products from Sander, 1996 BrO+ NO Br +NO 2 8.8E JPL, 2003 Br + NO 3 Br 2 +NO 2 1.6E11 0. JPL, 2003 Br + HCHO 1.7E JPL, 2003 HBr +HO 2 +CO Br+ O 3 BrO 1.7E JPL, 2003 Br+ HO 2 HBr 1.5E JPL, 2003 Cl 2 + hν 2 Cl 0.267*j NO2 Sander, 1996 Br 2 + hν 2 Br 4.444*j NO2 Sander, 1996

14 14 References Evans, M. J., A. Fiore, and D. J. Jacob, (2003) The GEOSCHEM chemical mechanism version 5078, Harvard University, Cambridge, MA, USA. Available at CHEM/geoschem_mech.pdf. Hermann, H., B. Ervens, H. W. Jacobi, R. Wolke, P. Nowacki and R. Zellner, CAPRAM2.3: A Chemical aqueous phase radical mechanism for tropospheric chemistry. J. Atmos. Chem. 36, , Jacob, D. J., Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate, J. Geophy. Res. 91, , Lelieveld, J. and P. J. Crutzen, Influences of cloud photochemical processes on tropospheric ozone. Nature. 343, , Lelieveld, J., and P. J. Crutzen, The role of clouds in tropospheric photochemistry, J. Atmos. Chem., 12, , Liu, X., G. Mauersberger and Moeller D., The effects of cloud processes on the tropopheric photochemistry: an improvement of the EURAD model with a coupled gaseous and aqueous chemical mechanism. Atmospheric Environment. 31, , Pandis, S. N., and J. H. Seinfeld, Sensitivity analysis of a chemical mechanism for aqeuousphase atmospheric chemistry. Journal of Geophysical Research. 94, , Sander, R and P. J. Crutzen, Model study indicating halogen activation and ozone destruction in polluted air masses transported to the sea, J. Geophys. Res., 101, , Sander, S. P., Friedl R. R., D. M. Golden, M. J. Kurylo, R. E. Huie, V. L. Orkin, G. K. Moortgaat, A. R. Ravishankara, C. E. Kolb,M. J. Molina, and B. J. FinlaysonPitts. Chemical kinetics and photochemical data for use in stratospheric modeling, Evaluation No. 14. JPL 0225, Jet Propulsion Laboratory, NASA, 2003, available from (Abbrev: JPL 2003). Sander,R., A. Kerkweg, P. J ockel, and J. Lelieveld, Technical Note: The new comprehensive atmospheric chemistry module MECCA. Atmos. Chem. Phys. Discuss., 4, , 2004

Reference M atm -1 H / R,

Reference M atm -1 H / R, Table 1a: Henry's Law Constants of halogen containing compounds Species K H 298, M atm 1 H / R, K 1 BrO 48 K H 1 =K H 4 2 ClO 926 K H 2 =K H 5 3 HBr 0.72 6077 Sander and Crutzen, 1996 4 HOBr 48 Sander