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The kinetics of the gas phase reaction of the Criegee intermediate CH2OO with SO2 have been studied as a function of temperature in the range 223–344 K at 85 Torr using flash photolysis of CH2I2/O2/SO2/N2 mixtures at 248 nm coupled to time-resolved broadband UV absorption spectroscopy. Measurements were performed under pseudo-first-order conditions with respect to SO2, revealing a negative temperature dependence. Analysis of experimental results using the Master Equation Solver for Multi-Energy well Reactions (MESMER) indicates that the observed temperature dependence, combined with the reported lack of a pressure dependence in the range 1.5–760 Torr, can be described by a reaction mechanism consisting of the formation of a pre-reaction complex leading to a cyclic secondary ozonide which subsequently decomposes to produce HCHO + SO3. The temperature dependence can be characterised by kCH2OO+SO2 = (3.72 ± 0.13) × 10-11 (T/298)(-2.05 ± 0.38) cm3 molecule-1 s-1. The observed negative temperature dependence for the title reaction in conjunction with the decrease in water dimer (the main competitor for the Criegee intermediate) concentration at lower temperatures means that Criegee intermediate chemistry can play an enhanced role in SO2 oxidation in the atmosphere at lower temperatures.

The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube coupled to a photo-fragmentation laser induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) × 1016 photons cm−2 s −1 (integrated between 290 and 400 nm), which is similar to values of ambient actinic flux at midday. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) × 10−4 at 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios, rather than levelling off which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ~25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no statistically significant production of HONO was seen from the illumination of pure nitrate aerosols. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

Decomposition kinetics of stabilised CH2OO and CD2OO Criegee intermediates have been investigated as a function of temperature (450–650 K) and pressure (2–350 Torr) using flash photolysis coupled with time-resolved cavity-enhanced broadband UV absorption spectroscopy. Decomposition of CD2OO was observed to be faster than CH2OO under equivalent conditions. Production of OH radicals following CH2OO decomposition was also monitored using flash photolysis with laser-induced fluorescence (LIF), with results indicating direct production of OH in the v = 0 and v = 1 states in low yields. Master equation calculations performed using the Master Equation Solver for Multi-Energy well Reactions (MESMER) enabled fitting of the barriers for the decomposition of CH2OO and CD2OO to the experimental data. Parameterisations of the decomposition rate coefficients, calculated by MESMER, are provided for use in atmospheric models and implications of the results are discussed. For CH2OO, the MESMER fits require an increase in the calculated barrier height from 78.2 kJ mol−1 to 81.8 kJ mol−1 using a temperature-dependent exponential down model for collisional energy transfer with 〈ΔE〉down = 32.6(T/298 K)1.7 cm−1 in He. The low- and high-pressure limit rate coefficients are k1,0 = 3.2 × 10−4(T/298)−5.81exp(−12 770/T) cm3 s−1 and k1,∞ = 1.4 × 1013(T/298)0.06exp(−10 010/T) s−1, with median uncertainty of ∼12% over the range of experimental conditions used here. Extrapolation to atmospheric conditions yields k1(298 K, 760 Torr) = 1.1+1.5−1.1 × 10−3 s−1. For CD2OO, MESMER calculations result in 〈ΔE〉down = 39.6(T/298 K)1.3 cm−1 in He and a small decrease in the calculated barrier to decomposition from 81.0 kJ mol−1 to 80.1 kJ mol−1. The fitted rate coefficients for CD2OO are k2,0 = 5.2 × 10−5(T/298)−5.28exp(−11 610/T) cm3 s−1 and k2,∞ = 1.2 × 1013(T/298)0.06exp(−9800/T) s−1, with overall error of ∼6% over the present range of temperature and pressure. The extrapolated k2(298 K, 760 Torr) = 5.5+9.2−5.5 × 10−3 s−1. The master equation calculations for CH2OO indicate decomposition yields of 63.7% for H2 + CO2, 36.0% for H2O + CO and 0.3% for OH + HCO with no significant dependence on temperature between 400 and 1200 K or pressure between 1 and 3000 Torr.

Laboratory studies have revealed that alkene-derived RO2 and longer chain alkane-derived RO2 (> C3) radicals rapidly convert to HO2 and then to OH in the presence of NO in a fluorescence assay by gas expansion (FAGE) detection cell (Fuchs et al., 2011). Three different FAGE cells that have been used to make ambient measurements of OH and HO2 in the University of Leeds ground-based instrument have been assessed to determine the sensitivity of each cell, when operating in HO2 detection mode, to RO2 radicals. The sensitivity to this interference was found to be highly dependent on cell design and operating parameters. Under the operating conditions employed, during fieldwork undertaken in the Borneo rainforest in 2008, an OH yield of 17% was experimentally determined for both ethene- and isoprene-derived RO2 radicals. The high pumping capacity of this system, resulting in a short residence time in the cell, coupled with poor mixing of NO into the ambient air-stream for the titration of HO2 to OH effectively minimised this potential interference. An OH yield of 46% was observed for ethene-derived RO2 radicals when a smaller detection cell was used, in which the mixing of NO into the ambient air was improved and the cell residence times were much longer. For a newly developed ROxLIF cell, used for detection of HO2 and RO2 radicals an OH yield of 95% was observed for ethene-derived RO2 radicals, when running in HO2 mode. In experiments in which conditions ensured the conversion of RO2 to OH were complete, the yields of OH from a range of different RO2 species agreed well with model predictions based on the Master Chemical Mechanism version 3.2. For ethene and isoprene-derived RO2 species, the relative sensitivity of FAGE was found to be close to that for HO2, with an OH yield of 100% and 92%, respectively. For the longer chain or cyclic alkane-derived RO2 radicals (> C3), model predicted OH yields were highly dependent upon temperature. A model predicted OH yield of 74% at 298 K and 36% at 255 K were calculated for cyclohexane-derived RO2 radicals, and an experimental yield of 38% was observed indicating that the temperature within the cell was below ambient owing to the supersonic expansion of the airstream in the low pressure cell. These findings suggest that observations of HO2 by some LIF instruments worldwide may be higher than the true value if the instruments were sensitive to these RO2 species. If this is the case, it becomes necessary to compare atmospheric chemistry model simulations to HO2* observations, where HO2* = [HO2] + Σi αi [RO2i], and αi is the mean fractional contribution of the RO2 species that interfere (RO2i). This methodology, however, relies on model simulations of speciated RO2 radicals, as instrumentation to make speciated RO2 measurements does not currently exist. Here we present an approach that enables the concentration of HO2 and RO2i to be selectively determined by varying the concentration of NO injected into a FAGE cell. Measurements of [HO2] and [RO2i] taken in London are presented.

Fast radical reactions are central to the chemistry of planetary atmospheres and combustion systems. Laser-induced fluorescence is a highly sensitive and selective technique that can be used to monitor a number of radical species in kinetics experiments, but is typically limited to low pressure systems owing to quenching of fluorescent states at higher pressures. The design and characterisation of an instrument is reported using laser-induced fluorescence detection to monitor fast radical kinetics (up to 25,000 s-1) at high temperatures and pressures by sampling from a high pressure reaction region to a low pressure detection region. Kinetics have been characterised at temperatures reaching 740 K and pressures up to 2 atm, with expected maximum operational conditions of up to ~ 900 K and ~ 5 atm. The distance between the point of sampling from the high pressure region and the point of probing within the low pressure region is critical to the measurement of fast kinetics. The instrumentation described in this work can be applied to the measurement of kinetics relevant to atmospheric and combustion chemistry.

Kinetics of CH₂OO Criegee intermediate reactions with SO₂, NO₂, NO, H₂O and CH₃CHO and CH₂I radical reactions with NO₂ are reported as a function of pressure at 295 K. Measurements were made under pseudo-first-order conditions using flash photolysis of CH₂I₂–O₂–N₂ gas mixtures in the presence of excess co-reagent combined with monitoring of HCHO reaction products by laser-induced fluorescence (LIF) spectroscopy and, for the reaction with SO₂, direct detection of CH₂OO by photoionisation mass spectrometry (PIMS). Rate coefficients for CH₂OO + SO₂ and CH₂OO + NO₂ are independent of pressure in the ranges studied and are (3.42 ± 0.42) × 10‾¹¹ cm³ s‾¹ (measured between 1.5 and 450 Torr) and (1.5 ± 0.5) × 10‾¹² cm³ s‾¹ (measured between 25 and 300 Torr), respectively. The rate coefficient for CH₂OO + CH₃CHO is pressure dependent, with the yield of HCHO decreasing with increasing pressure. Upper limits of 2 × 10−13 cm³ s‾¹ and 9 × 10−17 cm³ s‾¹ are placed on the rate coefficients for CH₂OO + NO and CH₂OO + H₂O, respectively. The upper limit for the rate coefficient for CH₂OO + H₂O is significantly lower than has been reported previously, with consequences for modelling of atmospheric impacts of CH₂OO chemistry.