Temperature and wavelength dependence of nitrite photolysis in frozen and aqueous solutions.
While the photolysis of nitrite is an important source of hydroxyl radical (*OH) in some natural waters, its wavelength and temperature dependence have not been fully described in solution. In addition, there are no studies of this reaction on ice, although there is evidence of nitrite production in snow. To address these gaps, we have measured the wavelength and temperature dependence of the quantum yields of *OH from the photolysis of frozen and aqueous NO2-. From our solution and ice results, we derive a master equation that describes the *OH quantum yield from NO2 photolysis as a function of both temperature (240-295 K) and illumination wavelength (302-390 nm): phi(NO1- -->OH*)(T,lamda) = (Y0 + a/(1 + exp((lamda-c)/b)))exp-(((e lamda) + f)/R) x (1/295 - 1/T)) where Y0 = 0.0204 +/- 0.0010, a = 0.0506 +/- 0.0022, b = 11.2 +/- 1.2, c = 332 +/- 1, e = 20.5 +/- 3.2, f = 7553 +/- 1204, uncertainties represent 1 standard error, Tis the temperature (K), Ris the gas constant (8.314 J mol(-1) K(-1)), and lamda is the wavelength (nm). Using these results we predict the pseudo-steady-state concentrations of nitrite on sunlit polar snow grains and compare the relative importance of the photolysis of nitrite, nitrate, and hydrogen peroxide as sources of snow-grain *0H.
Chu
Liang
L
Atmosphere Science Program, Department of Land, Air, and Water Resources, University of California, One Shields Avenue, Davis, California 95616-8627, USA.
Anastasio
Cort
C
D000042:Absorption; D000864:Antarctic Regions; D001110:Arctic Regions; D019277:Entropy; D005615:Freezing; D006863:Hydrogen-Ion Concentration; D017665:Hydroxyl Radical / Q000737:chemistry; D007053:Ice; D009573:Nitrites / Q000737:chemistry*; D009994:Osmolar Concentration; D010782:Photolysis; D011789:Quantum Theory; D012996:Solutions / Q000737:chemistry; D013696:Temperature
D007053:Ice; D009573:Nitrites; D012996:Solutions; D017665:Hydroxyl Radical