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The uptake of hydrochloric acid (HCl), ethanol (C2H5OH), 1-butanol (1-C4H9OH), formic acid HC(O)OH and trifluoroacetic (CF3C(O)OH) acid to growing ice surfaces was investigated at temperatures between 194 and 228 K. HCl displayed extensive, continuous uptake during ice growth, which was strongly dependent on the ice growth velocity, the temperature of the ice surface and the gas phase concentration of HCl. Trifluoroacetic acid was also observed to be trapped in growing ice, albeit approximately an order of magnitude less efficiently than HCl, whereas the adsorption and desorption kinetics of ethanol, 1-butanol, formic acid on ice were not measurably different to those for non-growing ice, even at very high ice growth rates. We present a parameterisation of the uptake coefficient for HCl on growing ice films (γtrap) and compare the results to an existing framework that describes the non-equilibrium trapping of trace gases on ice. The trapping of HCl in growing ice crystals in the atmosphere is assessed and compared to the gas and ice phase partitioning resulting from equilibrium surface adsorption and solubility.

The uptake of hydrochloric acid (HCl), ethanol (C2H5OH), 1-butanol (1-C4H9OH), formic acid HC(O)OH and tri-fluoro acetic (CF3C(O)OH) acid to growing ice surfaces was investigated at temperatures between 194 and 228 K. HCl displayed extensive, continuous uptake during ice growth, which was strongly dependent on the ice growth velocity, the temperature of the ice surface and the gas phase concentration of HCl. Tri-fluoro acetic acid was also observed to be trapped in growing ice, albeit approximately an order of magnitude less efficiently than HCl, whereas the adsorption and desorption kinetics of ethanol, 1-butanol, formic acid on ice was not measurably different to that for non-growing ice, even at very large ice-growth rates. We present a parameterisation of the uptake coefficient for HCl on growing ice films (gamma_trap) and compare the results to an existing framework that describes the non-equilibrium trapping of trace gases on ice. The trapping of HCl in growing ice crystals in the atmosphere is assessed and compared to the gas- and ice-phase partitioning resulting from equilibrium surface adsorption and solubility.

The interaction of hydrogen chloride (HCl) with ice surfaces at temperatures between 190 and 220 K was investigated using a coated-wall flow-tube connected to a chemical ionization mass spectrometer. Equilibrium surface coverages of HCl were determined at gas phase concentrations as low as 2 × 10(9) molecules cm(-3) (∼4 × 10(-8) Torr at 200 K) to derive Langmuir adsorption isotherms. The data are described by a temperature independent partition coefficient: KLang = (3.7 ± 0.2) × 10(-11) cm(3) molecule(-1) with a saturation surface coverage Nmax = (2.0 ± 0.2) × 10(14) molecules cm(-2). The lack of a systematic dependence of KLang on temperature contrasts the behaviour of numerous trace gases which adsorb onto ice via hydrogen bonding and is most likely related to the ionization of HCl at the surface. The results are compared to previous laboratory studies, and the equilibrium partitioning of HCl to ice surfaces under conditions relevant to the atmosphere is evaluated.

The objective of this work was to develop a method to determine the concentrations of higher organic acids in snow samples. The target species are the homologous aliphatic alpha,omega-dicarboxylic acids from C(5) to C(13), pinonic acid, pinic acid and phthalic acid. A preconcentration procedure utilizing solid phase extraction was developed and optimized using solutions of authentic standards. The influences of different parameters such as flow rate during extraction and the concentration of the eluent on the efficiency of the extraction procedure were investigated. The compounds of interest were separated by HPLC and detected by a quadrupole time-of-flight mass spectrometer (qTOF-MS). The recovery rate (extraction efficiency) of the extraction procedure was found to vary between 41% for tridecanedioic acid and 102% for adipic acid. The limits of detection were determined for all compounds and were between 0.9 nmol/L (dodecanedioic acid) and 29.5 nmol/L (pinonic acid). An exception is pinic acid, for which a considerably higher detection limit of 103.9 nmol/L was calculated. Snow samples were collected in December 2006 and January 2007 at the Fee glacier (Switzerland) from locations at heights from 3056 to 3580 m asl and from different depths within the snow layer. In total, the analysis of 61 single snow samples was performed, and the following compounds could be quantified: homologous aliphatic alpha,omega-dicarboxylic acids with 5-12 carbon atoms and phthalic acid. Tridecanedioic acid, pinonic and pinic acid were identified in the samples but were not quantified due to their low concentrations. The three most abundant acids found in the molten snow samples were glutaric acid (C(5)-di; 3.90 nmol/L), adipic acid (C(6)-di; 3.35 nmol/L) and phthalic acid (Ph; 3.04 nmol/L).

The interaction of H(2)O(2) with ice surfaces at temperatures between 203 and 233 K was investigated using a low pressure, coated-wall flow tube equipped with a chemical ionisation/electron impact mass spectrometer. Equilibrium surface coverages of H(2)O(2) on ice were measured at various concentrations and temperatures to derive Langmuir-type adsorption isotherms. H(2)O(2) was found to be strongly partitioned to the ice surface at low temperatures, with a partition coefficient, K(linC), equal to 2.1 × 10(-5) exp(3800/T) cm. At 228 K, this expression results in values of K(linC) which are orders of magnitude larger than the single previous determination and suggests that H(2)O(2) may be significantly partitioned to the ice phase in cirrus clouds. The partition coefficient for H(2)O(2) was compared to several other trace gases which hydrogen-bond to ice surfaces and a good correlation with the free energy of condensation found. For this class of trace gas a simple parameterisation for calculating K(linC)(T) from thermodynamic properties was established.