ALBERT

Description: The evaporation flux Jev(H2O) of H2O from HCl-doped typically 1.5 µm or so thick vapor-deposited ice films has been measured in a combined quartz crystal microbalance (QCMB)–residual gas mass spectrometry (MS) experiment. Jev(H2O) has been found to show complex behavior and to be a function of the average mole fraction χHCl of HCl in the ice film ranging from 6×1014 to 3×1017 molecule cm−2 s−1 at 174–210 K for initial values χHCl0 ranging from 5×10-5 to 3×10-3 at the start of the evaporation. The dose of HCl on ice was in the range of 1 to 40 formal monolayers and the H2O vapor pressure was independent of χHCl within the measured range and equal to that of pure ice down to 80 nm thickness. The dependence of Jev(H2O) with increasing average χHCl was correlated with (a) the evaporation range rb∕e parameter, that is, the ratio of Jev(H2O) just before HCl doping of the pure ice film and Jev(H2O) after observable HCl desorption towards the end of film evaporation, and (b) the remaining thickness dD below which Jev(H2O) decreases to less than 85 % of pure ice. The dependence of Jev(H2O) with increasing average χHCl from HCl-doped ice films suggests two limiting data sets, one associated with the occurrence of a two-phase pure ice/crystalline HCl hydrate binary phase (set A) and the other with a single-phase amorphous HCl∕H2O binary mixture (set B). The measured values of Jev(H2O) may lead to significant evaporative lifetime extensions of HCl-contaminated ice cloud particles under atmospheric conditions, regardless of whether the structure corresponds to an amorphous or crystalline state of the HCl∕H2O aggregate.

Description: Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Description: The ion composition at high altitude (3454 m a.s.l.) was measured with an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) during a period of 9 months, from August 2013 to April 2014. The negative mass spectra were dominated by the ions of sulfuric, nitric, malonic, and methanesulfonic acid (MSA) as well as SO5−. The most prominent positive ion peaks were from amines. The other cations were mainly organic compounds clustered with a nitrogen-containing ion, which could be either NH4+ or an aminium. Occasionally the positive spectra were characterized by groups of compounds each differing by a methylene group. In the negative spectrum, sulfuric acid was always observed during clear sky conditions following the diurnal cycle of solar irradiation. On many occasions we also saw a high signal of sulfuric acid during nighttime when clusters up to the tetramer were observed. A plausible reason for these events could be evaporation from particles at low relative humidity. A remarkably strong correlation between the signals of SO5− and CH3SO3− was observed for the full measurement period. The presence of these two ions during both the day and the night suggests a non-photochemical channel of formation which is possibly linked to halogen chemistry. Halogenated species, especially Br− and IO3−, were frequently observed in air masses that originated mainly from the Atlantic Ocean and occasionally from continental areas based on back trajectory analyses. We found I2O5 clustered with an ion, a species that was proposed from laboratory and modeling studies. All halogenated ions exhibited an unexpected diurnal behavior with low values during daytime. New particle formation (NPF) events were observed and characterized by (1) highly oxygenated molecules (HOMs) and low sulfuric acid or (2) ammonia–sulfuric acid clusters. We present characteristic spectra for each of these two event types based on 26 nucleation episodes. The mass spectrum of the ammonia–sulfuric acid nucleation event compares very well with laboratory measurements reported from the CLOUD chamber. A source receptor analysis indicates that NPF events at the Jungfraujoch take place within a restricted period of time of 24–48 h after air masses have had contact with the boundary layer. This time frame appears to be crucial to reach an optimal oxidation state and concentration of organic molecules necessary to facilitate nucleation.

Description: The ion composition at high-altitude (3450 m a.s.l.) was measured with an Atmospheric Pressure interface Time of Flight mass spectrometer (APi-TOF) during a period of nine months. The negative mass spectra were dominated by the ions of sulfuric, nitric, malonic and methanesulfonic acid (MSA) as well as SO5−. The most prominent positive ion peaks were from amines. The other cations were mainly organic compounds clustered with a nitrogen-containing ion, which could be either NH4+ or an aminium. Occasionally the positive spectra were characterized by groups of compounds each differing by a methylene group. In the negative spectrum, sulfuric acid was always observed during clear sky conditions following the diurnal cycle of sun irradiation. We also measured many events during night time where the signal of sulfuric acid was high and clusters up to the tetramer were observed. A plausible reason for these events could be evaporation from particles at low relative humidity. A remarkably strong correlation between the signals of SO5− and CH3SO3− was observed for the full measurement period. The presence of these two ions during both the day and the night suggests a non-photochemical channel of formation which is possibly linked to halogen chemistry. Halogenated species, especially Br− and IO3−, were frequently observed in air masses that originated mainly from the Atlantic Ocean and occasionally from continental areas based on back trajectory analyses. We measured I2O5 clustered with an ion, a species that was proposed from laboratory and modelling studies. All halogenated species exhibited an unexpected diurnal behaviour with low values during day time. New particle formation (NPF) events were observed and characterized by 1) highly oxygenated molecules (HOMs) and low sulfuric acid or 2) ammonia-sulfuric acid clusters. We present characteristic spectra for each of these two event types based on 26 nucleation episodes. The mass spectrum of the ammonia-sulfuric acid nucleation event compares very well with laboratory measurements reported from the CLOUD chamber. A source receptor analysis indicates that new particle formation events at the Jungfraujoch take place within a restricted period of time of 24–48 hours after air masses have had contact with boundary layer. This time frame appears to be crucial to reach an optimal oxidation state and concentration of organic molecules necessary to facilitate nucleation.

Description: Anthropogenic volatile organic compounds (AVOC) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHC), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g. from handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Despite their recognized importance as atmospheric reactants, the formation of highly oxygenated molecules (HOMs) in the gas phase leading to (extremely) low volatility compounds has not been studied in the past. Here we show that oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHC (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHC (naphthalene and biphenyl). We present the identified compounds, differences in the observed oxidation patterns and discuss mechanistic pathways. We hypothesize that AVOC may contribute substantially to new particle formation events that have been detected in urban areas.

Description: Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas- as well as the condensed phase has been simultaneously investigated under stratospheric temperature conditions in the range 175–200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 micron or so typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat where the optical element was the only cold point in the deposition system. FTIR absorption spectrometry in transmission as well as partial and total pressure measurement using residual gas MS and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed gas admission and continuous monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial formation of α-NAT followed by the gradual transformation of α → β-NAT starting at 185 K. NAD was formed at once at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports the formation of α-NAT proceeded without prior formation of an amorphous HNO3/H2O layer and always resulted in β-NAT. For α- and β-NAT the temperature dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3/H2O in order to afford thermochemical control of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and standard heats of evaporation ΔHev0 of H2O and HNO3 for α- and β-NAT, respectively, led to an estimate for the relative standard enthalpy difference between α- and β-NAT of −6.0 ± 20 kJ/mol in favor of β-NAT, as expected, despite a significantly larger value of Eev for HNO3 in α-NAT. This in turn implies a substantial activation energy for HNO3 accommodation in α- compared to β-NAT where Eacc(HNO3) is essentially zero. The kinetic (α(HCl), Jev(HCl)) and thermodynamic (Peq(HCl)) parameters of HCl-doped α – and β-NAT have been determined under the assumption that HCl adsorption did not significantly affect α(H2O) and α(HNO3) as well as the evaporation flux Jev(H2O). Jev(HCl) and Peq(HCl) on both α- and β-NAT are larger than the corresponding values for HNO3 across the investigated temperature range but significantly smaller than the values for pure H2O ice. This means that once contaminated with HCl the "impurity" HCl will persist along with HNO3 upon complete evaporation of the atmospheric ice particle. We comment on recent laboratory results involving the HNO3/H2O system using Chilled Mirror Hygrometers (CMH) in light of the present kinetic results.

Description: The evaporation flux Jev(H2O) of H2O from HCl-doped typically 1.5μm or so thick vapor-deposited ice films has been measured in a combined quartz crystal microbalance (QCMB) – residual gas mass spectrometry (MS) experiment. Jev(H2O) has been found to show complex behaviour and to be a function of the average mole fraction χ(HCl) of HCl in the ice film ranging from 6×1014 to 3×1017 molecule cm−2s−1 at 174–210K for initial values χ0(HCl) ranging from 5×10−5 to 3×10−3 at the start of the evaporation. The dose of HCl on ice was in the range of 1 to 40 formal monolayers and the H2O vapor pressure was independent of χ(HCl) within the measured range and equal to that of pure ice down to 80 nm thickness. The temporal dependence of Jev(H2O) was correlated with (a) the evaporation range rb/e as the ratio of Jev(H2O) just before HCl-doping of the pure ice film and Jev(H2O) after observable HCl desorption towards the end of film evaporation, and (b) the remaining thickness dD below which Jev(H2O) decreases to less than 85% of pure ice. The time dependence of Jev(H2O) from HCl-doped ice films suggests two limiting data sets, one associated with the occurrence of a two-phase pure ice/crystalline HCl hydrate binary phase (set A), and the other with a single phase amorphous HCl/H2O binary mixture (set B). The measured values of Jev(H2O) may lead to significant evaporative life-time extensions of HCl - contaminated ice cloud particles under atmospheric conditions, regardless of whether the structure corresponds to an amorphous or crystalline state of the HCl/H2O aggregate.

Description: Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR) in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175–200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered) compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR) absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS) and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate) followed by the gradual transformation of α- to β-NAT at T 〉 185 K. Nitric acid dihydrate (NAD) was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 ∕ H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O) and α(HNO3), the evaporation flux Jev(H2O) and Jev(HNO3) and the resulting saturation vapor pressure Peq(H2O) and Peq(HNO3) were measured and compared to binary phase diagrams of HNO3 ∕ H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation energies for evaporation (Eev) and standard heats of evaporation ΔHev0 of H2O and HNO3 for α- and β-NAT, respectively, led to an estimate for the relative standard enthalpy difference between α- and β-NAT of −6.0 ± 20 kJ mol−1 in favor of β-NAT, as expected, despite a significantly larger value of Eev for HNO3 in α-NAT. This in turn implies a substantial activation energy for HNO3 accommodation in α- compared to β-NAT where Eacc(HNO3) is essentially zero. The kinetic (α(HCl), Jev(HCl)) and thermodynamic (Peq(HCl)) parameters of HCl-doped α- and β-NAT have been determined under the assumption that HCl adsorption did not significantly affect α(H2O) and α(HNO3) as well as the evaporation flux Jev(H2O). Jev(HCl) and Peq(HCl) on both α- and β-NAT are larger than the corresponding values for HNO3 across the investigated temperature range but significantly smaller than the values for pure H2O ice at T