Carl J. Percival

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 240–340u2005K. The rate coefficients k(CH2OO + CF3COOH)=(3.4±0.3)×10−10u2005cm3u2009s−1 and k((CH3)2COO + CF3COOH)=(6.1±0.2)×10−10u2005cm3u2009s−1 at 294u2005K 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 [cm3u2009s−1]=(3.8±2.6)×10−18u2005T2 exp((1620±180)/T) + 2.5×10−10 and k [cm3u2009s−1]=(4.9±4.1)×10−18u2005T2 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.

Online Chemical Characterization of Food-Cooking Organic Aerosols: Implications for Source Apportionment

Food-cooking organic aerosols (COA) are one of the primary sources of submicron particulate matter in urban environments. However, there are still many questions surrounding source apportionment related to instrumentation as well as semivolatile partitioning because COA evolve rapidly in the ambient air, making source apportionment more complex. Online measurements of emissions from cooking different types of food were performed in a laboratory to characterize particles and gases. Aerosol mass spectrometer (AMS) measurements showed that the relative ionization efficiency for OA was higher (1.56-3.06) relative to a typical value of 1.4, concluding that AMS is over-estimating COA and suggesting that previous studies likely over-estimated COA concentrations. Food-cooking mass spectra were generated using AMS, and gas and particle food markers were identified with filter inlets for gases and aerosols-chemical ionization mass spectrometer (CIMS) measurements to be used in future food cooking-source apportionment studies. However, there is a considerable variability in both gas and particle markers, and dilution plays an important role in the particle mass budget, showing the importance of using these markers with caution during receptor modeling. These findings can be used to better understand the chemical composition of COA, and they provides useful information to be used in future source-apportionment studies.

Online gas and particle phase measurements of organosulfates, organosulfonates and nitrooxyorganosulfates in Beijing utilizing a FIGAERO ToF-CIMS

A time-of-flight chemical ionization mass spectrometer (CIMS) utilizing the Filter Inlet for Gas and Aerosol (FIGAERO) was deployed at a regional site 40 km north-west of Beijing and successfully identified and measured 17 sulfur-containing organics (SCOs are organo/nitrooxy organosulfates and sulfonates) with biogenic and anthropogenic precursors. The SCOs were quantified using laboratory-synthesized standards of lactic acid sulfate and nitrophenol organosulfate (NP OS). The variation in field observations was confirmed by comparison to offline measurement techniques (orbitrap and high-performance liquid chromatography, HPLC) using daily averages. The mean total (of the 17 identified by CIMS) SCO particle mass concentration was 210± 110 ng m−3 and had a maximum of 540 ng m−3, although it contributed to only 2± 1 % of the organic aerosol (OA). The CIMS identified a persistent gasphase presence of SCOs in the ambient air, which was further supported by separate vapour-pressure measurements of NP OS by a Knudsen Effusion Mass Spectrometer (KEMS). An increase in relative humidity (RH) promoted partitioning of SCO to the particle phase, whereas higher temperatures favoured higher gas-phase concentrations. Biogenic emissions contributed to only 19 % of total SCOs measured in this study. Here, C10H16NSO7, a monoterpenederived SCO, represented the highest fraction (10 %) followed by an isoprene-derived SCO. The anthropogenic SCOs with polycyclic aromatic hydrocarbon (PAH) and aromatic precursors dominated the SCO mass loading (51 %) with C11H11SO7, derived from methyl naphthalene oxidation, contributing to 40 ng m−3 and 0.3 % of the OA mass. Anthropogenic-related SCOs correlated well with benzene, although their abundance depended highly on the photochemical age of the air mass, tracked using the ratio between pinonic acid and its oxidation product, acting as a qualitative Published by Copernicus Publications on behalf of the European Geosciences Union. 10356 M. Le Breton et al.: Online gasand particle-phase measurements of sulfur containing organics in China photochemical clock. In addition to typical anthropogenic and biogenic precursors the biomass-burning precursor nitrophenol (NP) provided a significant level of NP OS. It must be noted that the contribution analysis here is only representative of the detected SCOs. There are likely to be many more SCOs present which the CIMS has not identified. Gasand particle-phase measurements of glycolic acid suggest that partitioning towards the particle phase promotes glycolic acid sulfate production, contrary to the current formation mechanism suggested in the literature. Furthermore, the HSO4·H2SO−4 cluster measured by the CIMS was utilized as a qualitative marker for acidity and indicates that the production of total SCOs is efficient in highly acidic aerosols with high SO2− 4 and organic content. This dependency becomes more complex when observing individual SCOs due to variability of specific VOC precursors.

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.

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.

A modeling study of secondary organic aerosol formation from sesquiterpenes using the STOCHEM global chemistry and transport model: SOA FORMATION FROM SESQUITERPENES

Sesquiterpenes are one of the precursors of secondary organic aerosol (SOA) which can be an important global sources of organic aerosol (OA). Updating the chemistry scheme in the global chemistry transport model by incorporating an oxidation mechanism for β-caryophyllene (representing all sesquiterpenes), adding global sesquiterpene emissions of 29xa0Tg/yr, and revising global monoterpene emissions up to 162xa0Tg/yr [Guenther et al., 2012] led to an increase of SOA burden by 95% and SOA production rate by 106% relative to the base case described in Utembe et al. [2011]. Including the emissions of sesquiterpenes resulted in increase of SOA burden of 0.11xa0Tg and SOA production rate of 12.9xa0Tg/yr relative to the base case. The highest concentrations of sesquiterpene-derived SOA (by up to 1.2xa0μg/m3) were found over central Africa and South America, the regions having high levels of biogenic emissions with significant biomass burning. In the updated model simulation, the multigeneration oxidation products from sesquiterpenes and monoterpenes transported above the boundary layer and condensed to the aerosol phase at higher altitude led to an increase of OA by up to 30% over the tropics and northern midlatitude to higher altitude. The model evaluation showed an underestimation of model OA mostly for the campaigns dominated by regional anthropogenic pollution. The increase of SOA production from sesquiterpenes reduced the discrepancies between modeled and observed OA concentrations over the remote and rural areas. The increase of SOA concentrations by up to 200% from preindustrial to present scenarios was found over the tropical oceans.

Temperature Dependence of the Rates of Reaction of Trifluoracetic Acid with Criegee Intermediates

The rate coefficients for gas-phase reactions 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 + TFA) = (3.4 ± 0.3) × 10-10 cm3 s-1 and k((CH3)2COO + TFA) = (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.