Abstract
An aqueous chemical model has been combined with an entraining updraft model to predict cloudwater composition above cloud base. Meteorological factors such as liquid water content, entrainment, pressure and temperature were allowed to vary as they might in a cloudy environment. Chemical reactions producing sulphuric acid, formic acid and hydrogen peroxide (H2O2) are extremely sensitive to the microphysical, dynamical, and radiative properties within a cloud. Several sulphate production pathways are sensitive to cloudwater pH, which is largely determined by sulphate aerosol concentration and cloud liquid water content. Hydrogen peroxide production may occur in both the gas and aqueous phase, and is sensitive to the amount of light available to initiate photochemical reactions. Near cloud base, H2O2 may be rapidly destroyed by SO2 in polluted areas. At higher cloud levels, where light intensities are higher and SO2 concentrations are usually lower, H2O2 may be produced at rates of up to 0.5 ppb h~l. Vertical or horizontal variations in meteorological factors alone will produce significant changes in cloudwater composition. Entrainment of cleaner mid-tropospheric air, pressure reductions, and increases in liquid water content lead to a decrease in solute concentrations in cloudwater. In contrast, reductions in temperature and aqueous-phase acid generation cause solute concentrations to increase in cloudwater. At high altitude sites, the composition of cloudwater will vary significantly with altitude. Near cloud base, concentrations of sulphate and nitrate in cloudwater will probably be highest, although cloud liquid water contents and droplet sizes will be lower. At higher elevations above cloud base, liquid water contents and drop sizes are larger, while solute concentrations may be lower. These model estimates suggest that several chemical, cloud-dynamical and cloud-microphysical parameters must be well characterised in order to predict cloudwater composition.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Adams, G.E. and Boag, J.W. 1964. ’Spectroscopic studies of the OH radical’. Proc. Chem Soc. 112.
Anbar, M. and Neta, P. 1967. ’A compilation of specific bimolecular rate constants for the reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals with inorganic and organic compounds in aqueous solution’. Int. J. Appl. Rad. Isotopes 18, 493–523.
Behar, D., Czapski, G. and Duchovny, I. 1970. ’Carbonate radical flash photolysis and pulse radiolosis of aqueous carbonate solutions’. J. Physc. Chem. 74, 2206–2210.
Berdnikov, V.M. and Bazhin, N.M. 1970. ’Oxidation-reduction potentials of certain inorganic radicals in aqueous solutions’. Russian J. Phys. Chem. 44, 395–398.
Bielski, B.H.J. 1978. ’Re-evaluation of the spectral and linetic properties of HO2 and 02-free radicals’. Photochem. Photobiol. 28, 645–649.
Boyce, S.D. and Hoffmann, M.R. 1984. ’Kinetics and mechanism of the formation of hydroxymethanesulphonic acid at low pH’. J. Phys. Chem. 88, 4740–4746.
Chameides, W.L. 1984. ’The photochemistry of a remote marine stratiform cloud’. J. Geophys. Res. 89, 4739–4755.
Chameides, W.L. 1986. ’Possible role of NO3 in the night-time chemistry of a cloud’. J. Geophys. Res. 91, 5331–5337.
Christensen, H., Sehested, K. and Corfitzen, H. 1982. Reactions of hydroxyl radical with hydrogen peroxide at ambient and elevated temperatures’. J. Phys. Chem. 86, 1588–1590.
Clegg, S.L. and Brimblecombe, P. 1985. ’Potential degassing of hydrogen chloride from acidified sodium chloride droplets’. Atmos. Environ. 19, 465–470.
Frahataziz, and Ross, A.B. 1977. ’Selected specific rates of reactions of transients from water in aqueous solution. III. Hydroxy radical and perhydroxyl radical and their radical ions. Rept. # NSRDS-NBS-59, National Bureau of Standards Washington DC, USA.
Graedel, T.E. and Goldberg, K.I. 1983. ’Kinetic studies of raindrop chemistry. 1: Inorganic and organic processes’. J. Geophys. Res. 88, 10865–10882.
Hagesawa, K. and Neta, P. 1978. ’Rate constants and mechanisms of reaction for CI2 radicals’. J.Phys. Chem. 82, 854–857.
Hayon, E., Treinin, A. and Wilf, J. 1972. ’Electronic spectra, photochemistry and autoxidation mechanism of the sulphite-bisulphite pyrosulphite systems: The SO2, SO3, SO4 and SO5 radicals’. J. Am. Chem. Soc. 94, 47–57.
Hill, T.A. and Choularton, T.W. 1985. ‘An airborne study of the microphysical structure of cumulus clouds’. Quart. J. R. Met. Soc. 111, 517–544.
Huie, R.E. and Neta, P. 1984. ’Chemical behaviour of SO3’ and SO5- radicals in aqueous solutions’. J. Phys. Chem. 88, 5665–5669.
Jacob, D.J. 1986. ‘The chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulphate’. J. Geophys. Res. 91, in press.
Jacob, D. and Hoffmann, M.R. 1983. ‘A dynamic model for the production of H+, NO3” and S04= in urban fog’. J. Geophys. Res. 88, 6611–6621
Jayson, G.G., Parsons, B.J. and Swallow, A.J. 1973. ’Some simple, highly reactive, inorganic chlorine derivatives in aqueous solution’. J. Chem. Soc. Faraday Trans. 69, 1597–1607.
Leaitch, W.R., Strapp, R.J.W., Wiebe, A. and Isaac, G.A. 1983. ’Measurements of scavenging and transformation of aerosol inside cumulus. Precipitation Scavenging, Dry Deposition and Resuspension. Vol. 1 Elsevier, 53–69.
Lebury, W. and Blair, E.W. 1925. ’The partial formaldehyde vapour pressure of aqueous solutions of formaldehyde II’. J. Chem. Soc., 2832–2839.
Le Henaff, P. 1966. ’Methodes d’etude et propreites des hydrates, hemiacetals et hemithioacetals derives des aldehydes et des cetones’. Bull. Soc. Chim. France, 4687–4700.
Lind, J.A., Kok, G.L. 1986. ’Henry’s law determinations for hydrogen peroxide, methylhydroperoxide and peroxyacetic acid ’. J. Geophys. Res. 91, 7889–7895.
Lind, J., Lazrus, A.L. and Kok, G.L. 1986. ’Aqueous-phase oxidation of S(IV) by hydrogen peroxide, methy Hydroperoxide and peroxyacetic acid’. J. Geophys. Res. 91, in press.
Maahs, H.G. 1982. ’Sulphur dioxide/water equilibria between 0° and 50°C. An examination of data at low concentrations’. In: Heterogeneous Atmospheric Chemistry, Schreyer, D.R. ed. Amer. Geophys Union, Washington DC, 187–195.
Martin, L.R. and Damschen, D.E. 1981. ’Aqueous oxidation of sulphur dioxide by hydrogen peroxide at low pH’. Atmos. Environ. 15, 1615–1621.
Maruthamuthu, P. and Neta, P. 1978. ’Spectra, acid-base equilibria, and reactions with inorganic compounds’. J. Phys. Chem. 82, 710–713.
McElroy, W.J. 1986. ’The aqueous oxidation of SO2 by OH radicals’. Atmos. Environ. 20, 323–330.
Munger, J.W., Jacob, D.J., Waldman, J.M. and Hoffmann, M.R. 1983. ’Fogwater chemistry in an urban atmosphere’. J. Geophys. Res. 88, 5109–5121.
National Bureau of Standards, 1965. ’Selected values of chemical thermodynamic properties’. NBS Tech note # 270–1, 124 pp.
Nenadovic, M.T., Draganic, Z.D. and Kidric, B. 1972. ’Radiolosis of formic acid-oxygen solution of pD 1.3–13 and the yields of primary product in a-radiolosis of heavy water’. Proc. Tihany. Symp. Radiat. Che. 3, 1269–1280.
Paluch, I.R. 1979. ’The entrainment mechanism in Colorado cumuli’. J. Atmos. Sci. 36, 2467–2478.
Ross, A.B. and Neta, P. 1979. ’Rate constants for reactions of inorganic radicals in aqueous solution’. Rept. # NSRDS-NBS-65, US Department of Commerce, Washington DC, USA.
Schwartz, S.E. 1984. ’Gas and aqueous chemistry of HC2 in liquid water clouds’. J. Geophys. Res. 89, 11589–11598.
Schwartz, S.E. and White, W.H. 1981. ’Solubility equilibria of the nitrogen oxides and oxyacids in dilute aqueous solution’. Adv. Env. Sci. Eng 4, 1–45.
Sehested, K., Rasmussen, O.L. and Fricke, H. 1968. ’Rate constants of OH with HO2, O2” and H202+ from hydrogen peroxide formation in pulse-irradiated oxygenated water’. J. Phys. Chem. 72, 626–631.
Sehested, K., Holeman, J. and Hart, E.J. 1983. ’Rate constants and products of the reactions of eaq~, O2” and H with ozone in aqueous solutions’. J. Phys. Chem. 87, 1951–1954.
Smith, R.M. and Martell, A.E. 1976. Critical Solubility Constants. Vol. 4: Inorganic Complexes. Plenum Press, New York. 257 pp.
Walcek, C.J. and Taylor, G.R. 1986. ’A theoretical method for computing vertical distributions of acidity and sulphate production within cumulus clouds’. J. Atmos. Sci. 43, 339–355.
Warner, J. 1970. ’On steady-state one-dimensional models of cumulus convection’. J. Atmos. Sci. 27, 1035–1040.
Weast, R.C. (ed.) 1978. Handbook of Chemistry and Physics, 59th edition. Chemical Rubber Company, Cleveland Ohio.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1988 Kluwer Academic publishers
About this chapter
Cite this chapter
Walcek, C.J. (1988). Meteorological and Chemical Factors Influencing Cloudwater Composition in a Non-Precipitating, Liquid-Water Updraft. In: Unsworth, M.H., Fowler, D. (eds) Acid Deposition at High Elevation Sites. NATO ASI Series, vol 252. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3079-7_2
Download citation
DOI: https://doi.org/10.1007/978-94-009-3079-7_2
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-7883-2
Online ISBN: 978-94-009-3079-7
eBook Packages: Springer Book Archive