M. Anwar H. Khan

Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2OO and CH3CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10−10 cm3 s−1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH3)2COO

The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10-11 cm3 s-1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10-10 cm3 s-1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10-10 to (2.29 ± 0.08) × 10-10 cm3 s-1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10-12 cm3 s-1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s-1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products.

Reaction between CH3O2 and BrO radicals: a new source of upper troposphere lower stratosphere hydroxyl radicals.

Over the last two decades it has emerged that measured hydroxyl radical levels in the upper troposphere are often underestimated by models, leading to the assertion that there are missing sources. Here we report laboratory studies of the kinetics and products of the reaction between CH3O2 and BrO radicals that shows that this could be an important new source of hydroxyl radicals:BrO + CH3O2 → products (1). The temperature dependent value in Arrhenius form of k(T) is k1 = (2.42–0.72+1.02) × 10–14 exp[(1617 ± 94)/T] cm3 molecule–1 s–1. In addition, CH2OO and HOBr are believed to be the major products. Global model results suggest that the decomposition of H2COO to form OH could lead to an enhancement in OH of up to 20% in mid-latitudes in the upper troposphere and in the lower stratosphere enhancements in OH of 2–9% are inferred from model integrations. In addition, reaction 1 aids conversion of BrO to HOBr and slows polar ozone loss in the lower stratosphere.

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

ABSTRACT Levels of the stabilized Criegee Intermediate (sCI), produced via the ozonolysis of unsaturated volatile organic compounds (VOCs), were estimated at two London urban sites (Marylebone Road and Eltham) and one rural site (Harwell) in the UK over the period of 1998–2012. The steady‐state approximation was applied to data obtained from the NETCEN (National Environmental Technology Centre) database, and the levels of annual average sCI were estimated to be in the range of 30–3000 molecules cm−3 for UK sites. A consistent diurnal cycle of sCI concentration is estimated for the UK sites with increasing levels during daylight hours, peaking just after midday. The seasonal pattern of sCI shows higher levels in spring with peaks around May due to the higher levels of O3. The ozone weekend effect resulted in higher sCI in UK urban areas during weekend. The sCI data were modeled using the information provided by the Air Quality Improvement Research Program (AQIRP) and found that the modeled production was five‐ to six‐fold higher than our estimated data, and therefore the estimated sCI concentrations in this study are thought to be lower estimates only. Compared with nighttime, 1.3‐ to 1.8‐fold higher sCI exists under daytime conditions. Using the levels of sCI estimated at Marylebone Road, globally the oxidation rates of NO2 + sCI (22.4 Gg/yr) and SO2 + sCI (37.6 Gg/yr) in urban areas can increase their effect in the troposphere and potentially further alter the oxidizing capacity of the troposphere. Further investigations of modeled sCI show that CH3CHOO (64%) and CH2OO (13%) are dominant among all contributing sCI at the UK sites.

Ground and Airborne U.K. Measurements of Nitryl Chloride: An Investigation of the Role of Cl Atom Oxidation at Weybourne Atmospheric Observatory

Nitryl Chloride (ClNO2) measurements from the Weybourne Atmospheric Observatory (WAO) are reported from March and April 2013 using a quadruple chemical ionisation mass spectrometer (CIMS) with the I- ionisation scheme. WAO is a rural coastal site with generally low NOx concentrations, a type of location poorly studied for ClNO2 production. Concentrations of ClNO2 exceeded that of the limit of detection (0.8 ppt) on each night of the campaign, as did concentrations of N2O5, which was also measured simultaneously with the Cambridge Broadband Cavity Enhanced Absorption Spectrometer (BBCEAS). A peak concentration of 65 ppt of ClNO2 is reported here. Vertical profiles of ClNO2 from early- to mid-morning flights in close proximity to WAO are also reported, showing elevated concentrations at low altitude. The photolysis of observed ClNO2 and a box model utilising the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. This model utilised numerous VOCs from the second Tropospheric ORganic CHemistry project (TORCH 2) in 2004, at the same location and time of year. From this the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes and alkynes) by OH radicals, Cl atoms and O3 is compared. Cl atom oxidation was deemed generally insignificant at this time and location for total oxidation due to the much lower concentration of ClNO2 observed, even following the night of greatest ClNO2 production.

Temperature‐Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates

Abstract The rate coefficients for gas‐phase reaction of trifluoroacetic acid (TFA) with two Criegee intermediates, formaldehyde oxide and acetone oxide, decrease with increasing temperature in the range 240–340 K. The rate coefficients k(CH2OO + CF3COOH)=(3.4±0.3)×10−10 cm3 s−1 and k((CH3)2COO + CF3COOH)=(6.1±0.2)×10−10 cm3 s−1 at 294 K exceed estimates for collision‐limited values, suggesting rate enhancement by capture mechanisms because of the large permanent dipole moments of the two reactants. The observed temperature dependence is attributed to competitive stabilization of a pre‐reactive complex. Fits to a model incorporating this complex formation give k [cm3 s−1]=(3.8±2.6)×10−18 T2 exp((1620±180)/T) + 2.5×10−10 and k [cm3 s−1]=(4.9±4.1)×10−18 T2 exp((1620±230)/T) + 5.2×10−10 for the CH2OO + CF3COOH and (CH3)2COO + CF3COOH reactions, respectively. The consequences are explored for removal of TFA from the atmosphere by reaction with biogenic Criegee intermediates.

Estimation and comparison of night-time OH levels in the UK urban atmosphere using two different analysis methods

Night-time OH levels have been determined for UK urban surface environments using two methods, the decay and steady state approximation methods. Measurement data from the UK National Environmental Technology Centre archive for four urban sites (Bristol, Harwell, London Eltham and Edinburgh) over the time period of 1996 to 2000 have been used in this study. Three reactive alkenes, namely isoprene, 1,3-butadiene and trans-2-pentene were chosen for the calculation of OH levels by the decay method. Hourly measurements of NO, NO2, O3, CO and 20 VOCs were used to determine night-time OH level using the steady state approximation method. Our results showed that the night-time OH levels were in the range of 1 x 10(5) - 1 x 10(6) molecules/cm3 at these four urban sites in the UK. The application of a t-test of these analyses indicated that except Bristol, there was no significant difference between the OH levels found from the decay and steady state approximation methods. Night-time levels of the OH radical appeared to peak in summer and spring time tracking the night-time O3 levels which also passed through a maximum at this time.

Observations of Isocyanate, Amide, Nitrate, and Nitro Compounds From an Anthropogenic Biomass Burning Event Using a ToF‐CIMS

Anthropogenic biomass burning is poorly represented in models due to a lack of observational data but represents a significant source of short-lived toxic gases. Guy Fawkes Night (bonfire night) is a regular UK-wide event where open fires are lit and fireworks are set off on 5 November. Previous gas phase studies of bonfire night focus on persistent organic pollutants primarily using off-line techniques. Here the first simultaneous online gas phase measurements of several classes of compounds including isocyanates, amides, nitrates, and nitro-organics are made during bonfire night (2014) in Manchester, UK, using a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) using iodide reagent ions. A shallow boundary layer and low wind speeds favor pollutant buildup with typical HCN, HNCO, and CH3NCO concentrations of tens of parts per thousand increasing by a factor of 13 to potentially harmful levels >1 ppb. Normalized excess mixing ratios relative to CO for a range of isocyanates and amides are reported for the first time. Using a HNCO:CO ratio of 0.1%, we distinguish emissions from flaming and smoldering combustion and report more accurate normalized excess mixing ratios for the distinct burning phases. While bonfire night is a highly polluting event, NO2 concentrations measured at this location are higher at other times, highlighting the importance of traffic as an NO2 emission source at this location. A risk communication methodology is used to equate enhancements in hourly averaged black carbon and NO2 concentrations caused by bonfire night as an equivalent of 26.1 passively smoked cigarettes.

Urban pollutant transport and infiltration into buildings using perfluorocarbon tracers

People spend the majority of their time indoors and therefore the quality of indoor air is worthy of investigation; indoor air quality is affected by indoor sources of pollutants and from pollutants entering buildings from outdoors. In this study, unique perfluorocarbon tracers were released in five experiments at a 100 m and ~2 km distance from a large university building in Manchester, UK and tracer was also released inside the building to measure the amount of outdoor material penetrating into buildings and the flow of material within the building itself. Air samples of the tracer were taken in several rooms within the building, and a CO2 tracer was used within the building to estimate air-exchange rates. Air-exchange rates were found to vary between 0.57 and 10.90 per hour. Indoor perfluorocarbon tracer concentrations were paired to outdoor tracer concentrations, and in-out ratios were found to vary between 0.01 and 3.6. The largest room with the lowest air-exchange rate exhibited elevated tracer concentrations for over 60 min after the release had finished, but generally had the lowest concentrations, the room with the highest ventilation rates had the highest concentration over 30 min, but the peak decayed more rapidly. Tracer concentrations indoors compared to outdoors imply that pollutants remain within buildings after they have cleared outside, which must be considered when evaluating human exposure to outdoor pollutants.

Global Budget and Distribution of Peroxyacetyl Nitrate (PAN) for Present and Preindustrial Scenarios

A global 3-D chemistry and transport model, STOCHEM integrated with a detailed VOC oxidation scheme (CRI v2-R5) has been employed to study the important NOx reservoir compound, peroxyacetyl nitrate (PAN). Globally, PAN is produced entirely by the reaction of acetyl peroxy radicals (CH3CO3) with NO2 and up to 2.0 ppb of PAN is found over the polluted regions of North America during June- July-August for the present scenario. The imbalances between model and measurement data are noted, with STOCHEM-CRI overestimating PAN mixing ratios relative to the measurement data by +17 and +80 pptv for the lower and upper troposphere, respectively. The inclusion of additional HOx recycling mechanisms (e.g. related to isoprene oxidation) in STOCHEM-CRI causes a decrease in PAN in a present scenario by as much as 40% over sink regions and reduces the model-measurement disagreement by 90% for the lower troposphere and 40% for the upper troposphere. The lower NOx emissions and CH3CO3 formation upon including HOx recycling in a preindustrial scenario led to a decrease in PAN formation by as much as 40%. The decrease in PAN formation results in less nitrogen being transported to remote regions which in turn leads to the greatest percentage change in O3 concentration (9% decrease) in the equatorial regions.