How does deposition of gas phase species affect pH at frozen salty interfaces?

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Abstract

Chemical processes occurring on snow and ice surfaces play an important role in controlling the oxidative capacity of the overlying atmosphere. However, efforts to gain a better, mechanistic understanding of such processes are impeded by our poor understanding of the chemical nature of the air-ice interface. Here we use glancing-angle laser induced fluorescence in conjunction with harmine-a surface-active, pH-sensitive fluorescent dye-to investigate how the nature of the ice, whether frozen freshwater, salt water or seawater, influences pH changes at the surface. Deposition of HCl(g) leads to a very different pH response at the frozen freshwater surface than at the frozen salt water surface indicating that these two surfaces present different chemical environments. Importantly, the sea ice surface is buffered against pH changes arising from deposition of gas phase species. These results have important implications for understanding pH-sensitive processes occurring at the air-ice boundary, such as bromine activation. © 2012 Author(s).

Figures

  • Fig. 1. (a) Harmine excitation spectra acquired at the frozen freshwater surface (red traces) and at the frozen salt water (0.5 M NaCl) surface (green traces) for strongly basic pre-freezing pH∼9.8 (solid traces) and near-neutral pre-freezing pH (dashed traces). Spectra were collected by scanning the excitation wavelength in 5 nm steps while monitoring harmine fluorescence at ∼430 nm. (b) The harmine 290/320 intensity ratio measured at the frozen freshwater surface (red circles) and at the frozen salt water (0.5 M NaCl) surface (green triangles) as a function of pre-freezing pH. Initial prefreezing pH was adjusted with NaOH(aq) or HCl(aq) and measured with a commercial pH electrode.
  • Fig. 2. Harmine fluorescence intensity (in arbitrary units) measured at 430 nm following excitation at 320 nm plotted as a function of time relative to the freezing of a freshwater sample (red circles, left axis), salt water (0.5 M NaCl) sample (green triangles, inner right axis) and artificial seawater sample (blue squares, outer right axis).
  • Fig. 3. The harmine 290/320 intensity ratio measured at the frozen freshwater surface (red circles) and at the frozen salt water (0.5 M NaCl) surface (green triangles) as a function of time. The dashed line indicates the time (t = 0) at which a 0.5 SLPM flow of 100 ppm of HCl in N2 was introduced to the chamber. The prefreezing pH of the samples was adjusted with NaOH(aq) to a pH ∼9.8. The final melted pH of the freshwater sample was∼3 and the final melted pH of the salt water sample was pH ∼2.5.
  • Fig. 4. The harmine 290/320 intensity ratio measured at the frozen salt water surface (green symbols) and at the frozen artificial seawater (blue symbols) surface as a function of time. The dashed line indicates the time (t = 0) at which a 50 sccm flow of N2 passing over a 12.75 wt % NH4OH(aq) solution held at 253 K was introduced to the chamber. The pre-freezing pH of the salt water samples was adjusted with NaOH(aq) to a pH ∼8.1, to be the same as the equilibrium pre-freezing pH of the seawater samples. The final melted pH of the salt water samples was > 10 while the final melted pH of the seawater samples was < 10. The different shapes of the symbols represent two separate trials.

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CITATION STYLE

APA

Wren, S. N., & Donaldson, D. J. (2012). How does deposition of gas phase species affect pH at frozen salty interfaces? Atmospheric Chemistry and Physics, 12(21), 10065–10073. https://doi.org/10.5194/acp-12-10065-2012

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