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Climate change is of great concern to all age groups but in particular to children. "Simple" climate models have been in place for a long time and can be used effectively with post-16 students. For younger children, modifications are required, and we describe in this paper the development and use of two such models. The first (the Granny Model) is a pictorial version of the model that has been used extensively with primary and early secondary school aged children (14 and younger). The second is an online version of the simple climate model that can be used without recourse to the underpinning mathematics and science but allows children to experiment with changing variables and how these changes affect the average surface temperature of the Earth., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society and Division of Chemical Education, Inc.)

Topics associated with the chemical sciences form a significant part of the curriculum in science at the primary school level in the U.K. In this methodology paper, we demonstrate how a wide range of research articles associated with the chemical sciences can be disseminated to an elementary school audience and how children can carry out investigations associated with cutting-edge research in the classroom. We discuss how the Primary Science Teaching Trust's (PSTT's) "I bet you did not know" (IBYDK) articles and their accompanying Teacher Guides benefit children, primary (elementary) school teachers, and other stakeholders including the researchers themselves. We define three types of research articles; ones describing how children can reproduce the research themselves without much adaptation, others where children can mirror the research using similar methods, and some where an analogy can be used to explain the research. We provide exemplars of each type and some preliminary feedback on articles written., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society and Division of Chemical Education, Inc.)

Hydrofluoroolefins are being adopted as sustainable alternatives to long-lived fluorine- and chlorine-containing gases and are finding current or potential mass-market applications as refrigerants, among a myriad of other uses. Their olefinic bond affords relatively rapid reaction with hydroxyl radicals present in the atmosphere, leading to short lifetimes and proportionally small global warming potentials. However, this type of functionality also allows reaction with ozone, and whilst these reactions are slow, we show that the products of these reactions can be extremely long-lived. Our chamber measurements show that several industrially important hydrofluoroolefins produce CHF 3 (fluoroform, HFC-23), a potent, long-lived greenhouse gas. When this process is accounted for in atmospheric chemical and transport modeling simulations, we find that the total radiative effect of certain compounds can be several times that of the direct radiative effect currently recommended by the World Meteorological Organization. Our supporting quantum chemical calculations indicate that a large range of exothermicity is exhibited in the initial stages of ozonolysis, which has a powerful influence on the CHF 3 yield. Furthermore, we identify certain molecular configurations that preclude the formation of long-lived greenhouse gases. This demonstrates the importance of product quantification and ozonolysis kinetics in determining the overall environmental impact of hydrofluoroolefin emissions., Competing Interests: Competing interests statement:The authors declare no competing interest.

All learners have a contribution to make to the development of the Chemical Sciences, be that in novel ways to teach, and their perspectives and contexts, but also in research, both in chemical education and the wider Chemical Sciences. Through four case studies, this paper explores interactions with diverse groups and how this has altered perspectives on both teaching and research. The case studies include work with visually impaired adults, a project bringing together First Peoples in Australia with academics to explore old ways (traditional science) and new ways (modern approaches), primary (elementary) school perspectives on teaching science, and a project in South Africa to connect university and township communities. Not only do these case studies demonstrate the immense value these diverse groups bring to our understanding about how to learn, but they also bring new perspectives on how to view and solve chemical problems., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society and Division of Chemical Education, Inc.)

Corona ions produced by high voltage power lines (HVPL) can alter the local atmospheric electrical environment downwind, potentially increasing electrostatic charge on airborne particulates via ion-aerosol attachment. However, previous epidemiological assessments attempting to assess this 'corona ion hypothesis' have used proxies e.g. ion concentration or distance from HVPL, rather than aerosol charge state directly, due to difficulties in modeling this quantity. We present a quasi-1D model incorporating both Gaussian plume dynamics and ion-aerosol and ion-ion interaction microphysics which could be applied to future studies of charged aerosol near HVPL. The response of the model to changes in a range of input parameters is characterized, and validation is attempted by means of comparison with previous work where ion- and aerosol concentrations and properties (including electrical mobility and electric charge states) upwind and downwind of HVPL are measured., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Corona ions from high voltage power lines (HVPL) can increase electrostatic charge on airborne pollutant particulates, possibly increasing received dose upon inhalation. To investigate the potential increased risk of childhood leukemia associated with residence near alternating current (AC) HVPL, we measured the particle charge state and atmospheric electricity parameters upwind, downwind and away from HVPL. Although we observed noticeable charge state alteration from background levels, most HVPL do not significantly increase charge magnitude. Particular HVPL types are shown to have most effect, increasing net charge to 15 times that at background. However, the magnitude of charge alteration during rainfall is comparable with the most extreme HVPL measurement. On current evidence, based on the current adult lung model, we suggest that although charge is sometimes enhanced to levels which may alter atmospheric particle dynamics, increased lung deposition is unlikely., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Honorary Scientific Director at Children with Cancer UK until December 2020 - DLH., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Ozonolysis of isoprene is considered to be an important source of formic acid (HCOOH), but its underlying reaction mechanisms related to HCOOH formation are poorly understood. Here, we report the kinetic and product studies of the reaction between the simplest Criegee intermediate (CH 2 OO) and formaldehyde (HCHO), both of which are the primary products formed in ozonolysis of isoprene. By utilizing time-resolved infrared laser spectrometry with the multifunctional dual-comb spectrometers, the rate coefficient k CH2OO+HCHO is determined to be (4.11 ± 0.25) × 10 -12  cm 3  molecule -1  s -1 at 296 K and a negative temperature dependence of the rate coefficient is observed and described by an Arrhenius expression with an activation energy of (-1.81 ± 0.04) kcal mol -1 . Moreover, the branching ratios of the reaction products HCOOH + HCHO and CO + H 2 O + HCHO are explored. The yield of HCOOH is obtained to be 37-54% over the pressure (15-60 Torr) and temperature (283-313 K) ranges. The atmospheric implications of the reaction CH 2 OO + HCHO are also evaluated by incorporating these results into a global chemistry-transport model. In the upper troposphere, the percent loss of CH 2 OO by HCHO is found by up to 6% which can subsequently increase HCOOH mixing ratios by up to 2% during December-January-February months., (© 2023. The Author(s).)

Reduced nitrogen (N) is central to global biogeochemistry, yet there are large uncertainties surrounding its sources and rate of cycling. Here, we present observations of gas-phase urea (CO(NH 2 ) 2 ) in the atmosphere from airborne high-resolution mass spectrometer measurements over the North Atlantic Ocean. We show that urea is ubiquitous in the lower troposphere in the summer, autumn, and winter but was not detected in the spring. The observations suggest that the ocean is the primary emission source, but further studies are required to understand the responsible mechanisms. Urea is also observed aloft due to long-range transport of biomass-burning plumes. These observations alongside global model simulations point to urea being an important, and currently unaccounted for, component of reduced-N to the remote marine atmosphere. Airborne transfer of urea between nutrient-rich and -poor parts of the ocean can occur readily and could impact ecosystems and oceanic uptake of carbon dioxide, with potentially important climate implications.

Traffic is a major source of particulate pollution in large cities, and particulate matter (PM) level in Bangkok often exceeds the World Health Organisation limits. While PM 2.5 and PM 10 are both measured in Bangkok regularly, the sub-micron range of PM, of specific interest in regard to possible adverse health effects, is very limited. In the study, particle number concentration (PNC) was measured on public transport in Bangkok. A travel route through Bangkok using the state railway, the mass rapid transport underground system, the Bangkok Mass Transit System (BTS) Skytrain and public buses on the road network, with walking routes between, was taken whilst measuring particle levels with a hand-held concentration particle counter. The route was repeated 19 times covering different seasons during either morning or evening rush hours. The highest particle concentrations were found on the state railway, followed by the bus, the BTS Skytrain and the MRT underground with measured peaks of 350,000, 330,000, 33,000 and 9000 cm -3 , respectively, though particle numbers over 100,000 cm -3 may be an underestimation due to undercounting in the instrument. Inside each form of public transport, particle numbers would peak when stopping to collect passengers (doors opening) and decay with a half-life between 2 and 3 min. There was a weak correlation between particle concentration on bus, train and BTS and Skytrain with carbon monoxide concentration, as measured at a fixed location in the city.

Inhalable particulate matter (PM) is a health concern, and people living in large cities such as Bangkok are exposed to high concentrations. This exposure has been linked to respiratory and cardiac diseases and cancers of the lung and brain. Throughout 2018, PM was measured in northern Bangkok near a toll road (13.87°N, 100.58°E) covering all three seasons (cool, hot and rainy). PM 10 was measured in 24- and 72-h samples. On selected dates aerodynamic size and mass distribution were measured as 3-day samples from a fixed 5th floor inlet. Particle number concentration was measured from the 5th floor inlet and in roadside survey measurements. There was a large fraction of particle number concentration in the sub-micron range, which showed the greatest variability compared with larger fractions. Metals associated with combustion sources were most found on the smaller size fraction of particles, which may have implications for associated adverse health outcomes because of the likely location of aerosol deposition in the distal airways of the lung. PM 10 samples varied between 30 and 100 μg m -3 , with highest concentrations in the cool season. The largest metal fractions present in the PM 10 measurements were calcium, iron and magnesium during the hot season with average airborne concentrations of 13.2, 3.6 and 2.0 μg m -3 , respectively. Copper, zinc, arsenic, selenium, molybdenum, cadmium, antimony and lead had large non-crustal sources. Principal component analysis (PCA) identified likely sources of the metals as crustal minerals, tailpipe exhaust and non-combustion traffic. A health risk analysis showed a higher risk of both carcinogenic and non-carcinogenic health effects in the drier seasons than the wet season due to ingestion of nickel, arsenic, cadmium and lead., (© 2022. The Author(s).)

The concentrations of benzene and 1,3-butadiene in urban, suburban, and rural sites of the U.K. were investigated across 20 years (2000-2020) to assess the impacts of pollution control strategies. Given the known toxicity of these pollutants, it is necessary to investigate national long-term trends across a range of site types. We conclude that whilst legislative intervention has been successful in reducing benzene and 1,3-butadiene pollution from vehicular sources, previously overlooked sources must now be considered as they begin to dominate in contribution to ambient pollution. Benzene concentrations in urban areas were found to be ~5-fold greater than those in rural areas, whilst 1,3-butadiene concentrations were up to ~10-fold greater. The seasonal variation of pollutant concentration exhibited a maximum in the winter and a minimum in the summer with summer: winter ratios of 1:2.5 and 1:1.6 for benzene and 1,3-butadiene, respectively. Across the period investigated (2000-2020), the concentrations of benzene decreased by 85% and 1,3-butadiene concentrations by 91%. A notable difference could be seen between the two decades studied (2000-2010, 2010-2020) with a significantly greater drop evident in the first decade than in the second, proving, whilst previously successful, legislative interventions are no longer sufficiently limiting ambient concentrations of these pollutants. The health impacts of these pollutants are discussed, and cancer impact indices were utilized allowing estimation of cancer impacts across the past 20 years for different site types. Those particularly vulnerable to the adverse health effects of benzene and 1,3-butadiene pollution are discussed.

The contribution of NO x emissions and background O 3 to the sources and partitioning of the oxidants [OX (= O 3 + NO 2 )] at the Marylebone Road site in London during the 2000s and 2010s has been investigated to see the impact of the control measures or technology changes inline with the London Mayor's Air Quality Strategy. The abatement of the pollution emissions has an impact on the trends of local and background oxidants, [OX] L and [OX] B , decreasing by 1.4% per year and 0.4% per year, respectively from 2000 to 2019. We also extend our study to three roadside sites (Din Daeng, Thonburi and Chokchai) in another megacity, Bangkok, to compare [OX] L and [OX] B and their behavioural changes with respect to the Marylebone Road site. [OX] L and [OX] B at the Marylebone Road site (0.21[NO x ] and 32 ppbv) are comparable with the roadside sites of Thailand (0.12[NO x ] to 0.26[NO x ] and 29 to 32 ppbv). The seasonal variation of [OX] B levels displays a spring maximum for London, which is due to the higher northern hemispheric ozone baseline, but a maximum during the dry season is found for Bangkok which is likely due to regional-scale long-range transport from the Asian continent. The diurnal variations of [OX] L for both London and Bangkok roadside sites confirm the dominance of the oxidants from road transport emissions, which are found to be higher throughout the daytime. WRF-Chem-CRI model simulations of the distribution of [OX] showed that the model performed well for London background sites when predicting [OX] levels compared with the measured [OX] levels suggesting that the model is treating the chemistry of the oxidants correctly. However, there are large discrepancies for the model-measurement [OX] levels at the traffic site because of the difficulties in the modelling of [OX] at large road networks in megacities for the complex sub grid-scale dynamics that are taking place, both in terms of atmospheric processes and time-varying sources, such as traffic volumes. For roadside sites in Bangkok, the trend in changes of [OX] is predicted by the model correctly but overestimated in absolute magnitude. We suggest that this large deviation is likely to be due to discrepancies in the EDGAR emission inventory (emission overestimates) beyond the resolution of the model.

Unregulated chlorocarbons, here defined as dichloromethane (CH 2 Cl 2 ), perchloroethene (C 2 Cl 4 ), chloroform (CHCl 3 ), and methyl chloride (CH 3 Cl), are gases not regulated by the Montreal Protocol. While CH 3 Cl is the largest contributor of atmospheric chlorine, recent studies have shown that growth in emissions of the less abundant chlorocarbons could pose a significant threat to the recovery of the ozone layer. Despite this, there remain many regions for which no atmospheric monitoring exists, leaving gaps in our understanding of global emissions. Here, we report on a new time series of chlorocarbon measurements from Cape Point, South Africa for 2017, which represent the first published high-frequency measurements of these gases from Africa. For CH 2 Cl 2 and C 2 Cl 4 , the majority of mole fraction enhancements were observed from the north, consistent with anthropogenically modified air from Cape Town, while for CHCl 3 and CH 3 Cl, we found evidence for both oceanic and terrestrial sources. Using an inverse method, we estimated emissions for south-western South Africa (SWSA). For each chlorocarbon, SWSA accounted for less than 1% of global emissions. For CH 2 Cl 2 and C 2 Cl 4 , we extrapolated using population statistics and found South African emissions of 8.9 (7.4-10.4) Gg yr -1 and 0.80 (0.64-1.04) Gg yr -1 , respectively.

Urban aerosol is a growing concern for people living within cities; aerosol have been implicated in many ill health conditions, including that of the lung and of the heart. Atmospheric potential gradient is a consequence of charge carried to the ionosphere through thunderstorms, and its value depends on highly electrically mobile ion concentrations, hence local conductivity of the air. Ions attach to aerosol in the atmosphere, reducing their mobility and therefore increasing the potential gradient, and so potential gradient measurements have been suggested as a proxy for aerosol measurements. Particle number count, size distribution and potential gradient were measured for two campaigns in Manchester, U.K., and one campaign in Bristol, U.K. Using a factor based on size distribution to account for preferential attachment at larger sizes provided the best relationship with potential gradient, but particle count alone showed a weaker, but similar relationship. The increase in particle count caused by annual bonfire and fireworks celebrations (November) was evidenced in both potential gradient and particle numbers. Daily regression or correlation did not show a consistent relationship. In the larger Bristol data set, increasing humidity led to a reduction of potential gradient, while increasing particle number led to an increase., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Ozonolysis of isoprene, one of the most abundant volatile organic compounds emitted into the Earth's atmosphere, generates two four-carbon unsaturated Criegee intermediates, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide). The extended conjugation between the vinyl substituent and carbonyl oxide groups of these Criegee intermediates facilitates rapid electrocyclic ring closures that form five-membered cyclic peroxides, known as dioxoles. This study reports the first experimental evidence of this novel decay pathway, which is predicted to be the dominant atmospheric sink for specific conformational forms of MVK-oxide ( anti ) and MACR-oxide ( syn ) with the vinyl substituent adjacent to the terminal O atom. The resulting dioxoles are predicted to undergo rapid unimolecular decay to oxygenated hydrocarbon radical products, including acetyl, vinoxy, formyl, and 2-methylvinoxy radicals. In the presence of O 2 , these radicals rapidly react to form peroxy radicals (ROO), which quickly decay via carbon-centered radical intermediates (QOOH) to stable carbonyl products that were identified in this work. The carbonyl products were detected under thermal conditions (298 K, 10 Torr He) using multiplexed photoionization mass spectrometry (MPIMS). The main products (and associated relative abundances) originating from unimolecular decay of anti -MVK-oxide and subsequent reaction with O 2 are formaldehyde (88 ± 5%), ketene (9 ± 1%), and glyoxal (3 ± 1%). Those identified from the unimolecular decay of syn -MACR-oxide and subsequent reaction with O 2 are acetaldehyde (37 ± 7%), vinyl alcohol (9 ± 1%), methylketene (2 ± 1%), and acrolein (52 ± 5%). In addition to the stable carbonyl products, the secondary peroxy chemistry also generates OH or HO 2 radical coproducts.

Isoprene has the highest emission into Earth's atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield from isoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jet-cooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn -conformers are observed; anti -conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn -MVK-oxide with SO 2 and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO 3 and identifying organic hydroperoxide formation from reaction with SO 2 and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model., Competing Interests: Competing interest statement: R.L.C., C.A.T., and A. R. Ravishankara are amongst numerous coauthors in the General Discussion associated with the 2017 Faraday Discussion of Atmospheric Chemistry in the Anthropocene [Faraday Discuss. 200, 353–378 (2017)].

One hydrochlorofluorocarbon and two hydrofluorocarbons (HCFC-22, HFC-125, and HFC-152a) were measured in air samples at the Cape Point observatory (CPT), South Africa, during 2017. These data represent the first such atmospheric measurements of these compounds from southwestern South Africa (SWSA). Baseline atmospheric growth rates were estimated to be 8.36, 4.10, and 0.71 ppt year -1 for HCFC-22, HFC-125, and HFC-152a, respectively. The CPT measurements were combined with an inverse model to investigate emissions from SWSA. For all three halocarbons, Cape Town was found to be the dominant source within SWSA. These estimates were extrapolated, based on population statistics, to estimate emissions for the whole of South Africa. We estimate South Africa's 2017 emissions to be 3.0 (1.6-4.4), 0.8 (0.5-1.2), and 1.1 (0.6-1.6) Gg year -1 for HCFC-22, HFC-125, and HFC-152a, respectively. For all three halocarbons, South Africa's contribution to global emissions is small (<2.5%), but future monitoring is needed to ensure South Africa's compliance with regulation set out by the Montreal Protocol and its Amendments.

Ammonia and amines are emitted into the troposphere by various natural and anthropogenic sources, where they have a significant role in aerosol formation. Here, we explore the significance of their removal by reaction with Criegee intermediates, which are produced in the troposphere by ozonolysis of alkenes. Rate coefficients for the reactions of two representative Criegee intermediates, formaldehyde oxide (CH2OO) and acetone oxide ((CH3)2COO) with NH3 and CH3NH2 were measured using cavity ring-down spectroscopy. Temperature-dependent rate coefficients, k(CH2OO + NH3) = (3.1 ± 0.5) × 10-20T2 exp(1011 ± 48/T) cm3 s-1 and k(CH2OO + CH3NH2) = (5 ± 2) × 10-19T2 exp(1384 ± 96/T) cm3 s-1 were obtained in the 240 to 320 K range. Both the reactions of CH2OO were found to be independent of pressure in the 10 to 100 Torr (N2) range, and average rate coefficients k(CH2OO + NH3) = (8.4 ± 1.2) × 10-14 cm3 s-1 and k(CH2OO + CH3NH2) = (5.6 ± 0.4) × 10-12 cm3 s-1 were deduced at 293 K. An upper limit of ≤2.7 × 10-15 cm3 s-1 was estimated for the rate coefficient of the (CH3)2COO + NH3 reaction. Complementary measurements were performed with mass spectrometry using synchrotron radiation photoionization giving k(CH2OO + CH3NH2) = (4.3 ± 0.5) × 10-12 cm3 s-1 at 298 K and 4 Torr (He). Photoionization mass spectra indicated production of NH2CH2OOH and CH3N(H)CH2OOH functionalized organic hydroperoxide adducts from CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. Ab initio calculations performed at the CCSD(T)(F12*)/cc-pVQZ-F12//CCSD(T)(F12*)/cc-pVDZ-F12 level of theory predicted pre-reactive complex formation, consistent with previous studies. Master equation simulations of the experimental data using the ab initio computed structures identified submerged barrier heights of -2.1 ± 0.1 kJ mol-1 and -22.4 ± 0.2 kJ mol-1 for the CH2OO + NH3 and CH2OO + CH3NH2 reactions, respectively. The reactions of NH3 and CH3NH2 with CH2OO are not expected to compete with its removal by reaction with (H2O)2 in the troposphere. Similarly, losses of NH3 and CH3NH2 by reaction with Criegee intermediates will be insignificant compared with reactions with OH radicals.

This paper describes the development of a new sampling and measurement method to infer methane flux using proxy measurements of CO 2 concentration and wind data recorded by Unmanned Aerial Systems (UAS). The flux method described and trialed here is appropriate to the spatial scale of landfill sites and analogous greenhouse gas emission hotspots, making it an important new method for low-cost and rapid case study quantification of fluxes from currently uncertain (but highly important) greenhouse gas sources. We present a case study using these UAS-based measurements to derive instantaneous methane fluxes from a test landfill site in the north of England using a mass balance model tailored for UAS sampling and co-emitted CO 2 concentration as a methane-emission proxy. Methane flux (and flux uncertainty) during two trials on 27 November 2014 and 5 March 2015, were found to be 0.140 kg s -1 (±61% at 1σ), and 0.050 kg s -1 (±54% at 1σ), respectively. Uncertainty contributing to the flux was dominated by ambient variability in the background (inflow) concentration (>40%) and wind speed (>10%); with instrumental error contributing only ∼1-2%. The approach described represents an important advance concerning the challenging problem of greenhouse gas hotspot flux calculation, and offers transferability to a wide range of analogous environments. This new measurement solution could add to a toolkit of approaches to better validate source-specific greenhouse emissions inventories - an important new requirement of the UNFCCC COP21 (Paris) climate change agreement., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The reaction of perfluorooctanoic acid with the smallest carbonyl oxide Criegee intermediate, CH 2 OO, has been measured and is very rapid, with a rate coefficient of (4.9 ± 0.8) × 10 -10 cm 3 s -1 , similar to that for reactions of Criegee intermediates with other organic acids. Evidence is shown for the formation of hydroperoxymethyl perfluorooctanoate as a product. With such a large rate coefficient, reaction with Criegee intermediates can be a substantial contributor to atmospheric removal of perfluorocarboxylic acids. However, the atmospheric fates of the ester product largely regenerate the initial acid reactant. Wet deposition regenerates the perfluorocarboxylic acid via condensed-phase hydrolysis. Gas-phase reaction with OH is expected principally to result in formation of the acid anhydride, which also hydrolyzes to regenerate the acid, although a minor channel could lead to destruction of the perfluorinated backbone.

Methanol is a benchmark for understanding tropospheric oxidation, but is underpredicted by up to 100% in atmospheric models. Recent work has suggested this discrepancy can be reconciled by the rapid reaction of hydroxyl and methylperoxy radicals with a methanol branching fraction of 30%. However, for fractions below 15%, methanol underprediction is exacerbated. Theoretical investigations of this reaction are challenging because of intersystem crossing between singlet and triplet surfaces - ∼45% of reaction products are obtained via intersystem crossing of a pre-product complex - which demands experimental determinations of product branching. Here we report direct measurements of methanol from this reaction. A branching fraction below 15% is established, consequently highlighting a large gap in the understanding of global methanol sources. These results support the recent high-level theoretical work and substantially reduce its uncertainties.

The OH initiated oxidation of HNO3 in the UT/LS plays an important role in controlling the O3 budget, removing HOx radicals whilst driving NOx/y partitioning chemistry by yielding NO3 radicals: OH + HNO3 → H2O + NO3. In this paper, k1(T, P) was measured using OH (A ← X) Laser Induced Fluorescence (LIF) and the data was modelled over the 223-298 K temperature and 25-750 Torr pressure ranges, using the modified Lindemann-Hinshelwood expression , where k0 = 5.2 × 10-14 exp(200/T) cm3 s-1, k2 = 8.4 × 10-17 exp(1900/T) cm3 s-1 and k3 = 1.6 × 10-34 exp(1745/T) cm3 s-1. A significant source of experimental uncertainty derives from accurate determination of HNO3 concentration, which is impacted by heterogeneous uptake of the low volatility HNO3 onto cold surfaces of the reactors. Our results represent the determination of k1(T, P) using two different in situ [HNO3] measurements: VUV absorption and a new two photon Photolysis Induced Fluoresence (PIF). Experimental results are discussed along with a computational master equation calculation (MESMER), which highlight the need for further theoretical study into the OH + HNO3 mechanism and potential energy surface. The atmospheric impact of these new rate constants were modelled using the STOCHEM-CRI chemistry transport global model, which have shown a small reduction in global budgets of key atmospheric species, with more significant changes in the NOx/HNO3 ratio, peaking in the tropical upper troposphere regions.

Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. This work investigates the reactions of the smallest Criegee intermediate, CH2OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-α (10.2 eV) radiation for photoionization. CH2OO was produced via pulsed laser photolysis of CH2I2 in the presence of excess O2. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH2OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH2OO + MVK) = (5.0 ± 0.4) × 10-13 cm3 s-1 and k(CH2OO + MACR) = (4.4 ± 1.0) × 10-13 cm3 s-1, where the stated ±2σ uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH2OO + CO reaction and for the reaction of CH2OO with CF3CHCH2 at 300 K and 4 Torr. For CH2OO + CO, no reaction is observed and an upper limit is determined: k(CH2OO + CO) < 2 × 10-16 cm3 s-1. For CH2OO + CF3CHCH2, an upper limit of k(CH2OO + CF3CHCH2) < 2 × 10-14 cm3 s-1 is obtained.

Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 10 4 cm -3 to 1 × 10 5 cm -3 , which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found to be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (e.g. hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO 2 to form SO 3 , which can go on to form a significant amount of H 2 SO 4 which is a key atmospheric nucleation species and therefore vital to the formation of clouds. The sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.

The reactions of Criegee intermediates with NO 2 have been proposed as a potentially significant source of the important nighttime oxidant NO 3 , particularly in urban environments where concentrations of ozone, alkenes and NO x are high. However, previous efforts to characterize the yield of NO 3 from these reactions have been inconclusive, with many studies failing to detect NO 3 . In the present work, the reactions of formaldehyde oxide (CH 2 OO) and acetaldehyde oxide (CH 3 CHOO) with NO 2 are revisited to further explore the product formation over a pressure range of 4-40 Torr. NO 3 is not observed; however, temporally resolved and [NO 2 ]-dependent signal is observed at the mass of the Criegee-NO 2 adduct for both formaldehyde- and acetaldehyde-oxide systems, and the structure of this adduct is explored through ab initio calculations. The atmospheric implications of the title reaction are investigated through global modelling.

The rapid reaction of the smallest Criegee intermediate, CH 2 OO, with water dimers is the dominant removal mechanism for CH 2 OO in the Earth's atmosphere, but its products are not well understood. This reaction was recently suggested as a significant source of the most abundant tropospheric organic acid, formic acid (HCOOH), which is consistently underpredicted by atmospheric models. However, using time-resolved measurements of reaction kinetics by UV absorption and product analysis by photoionization mass spectrometry, we show that the primary products of this reaction are formaldehyde and hydroxymethyl hydroperoxide (HMHP), with direct HCOOH yields of less than 10%. Incorporating our results into a global chemistry-transport model further reduces HCOOH levels by 10-90%, relative to previous modeling assumptions, which indicates that the reaction CH 2 OO + water dimer by itself cannot resolve the discrepancy between the measured and predicted HCOOH levels.

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 O 3 . 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 NO 2 + sCI (22.4 Gg/yr) and SO 2 + 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 CH 3 CHOO (64%) and CH 2 OO (13%) are dominant among all contributing sCI at the UK sites.

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(CH 2 OO + CF 3 COOH)=(3.4±0.3)×10 -10  cm 3  s -1 and k((CH 3 ) 2 COO + CF 3 COOH)=(6.1±0.2)×10 -10  cm 3  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 [cm 3  s -1 ]=(3.8±2.6)×10 -18  T 2 exp((1620±180)/T) + 2.5×10 -10 and k [cm 3  s -1 ]=(4.9±4.1)×10 -18  T 2 exp((1620±230)/T) + 5.2×10 -10 for the CH 2 OO + CF 3 COOH and (CH 3 ) 2 COO + CF 3 COOH reactions, respectively. The consequences are explored for removal of TFA from the atmosphere by reaction with biogenic Criegee intermediates., (© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

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.

The Criegee intermediate acetone oxide, (CH 3 ) 2 COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O 2 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 SO 2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10 -11 cm 3 s -1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10 -10 cm 3 s -1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH 3 CHOO with SO 2 , 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 N 2 from cavity ring-down decay of the ultraviolet absorption of (CH 3 ) 2 COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10 -10 to (2.29 ± 0.08) × 10 -10 cm 3 s -1 . Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, k H /k D = (0.53 ± 0.06), for reactions with SO 2 , which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD 3 ) 2 COO with NO 2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10 -12 cm 3 s -1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH 3 CHOO with NO 2 . 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 (CH 3 ) 2 COO 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 (CH 3 ) 2 COO with SO 2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH 3 ) 2 COO with NO 2 and with SO 2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products.

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.

Criegee intermediates are important species formed during the ozonolysis of alkenes. Reaction of stabilized Criegee intermediates with various species like SO2 and NO2 may contribute significantly to tropospheric chemistry. In the laboratory, self-reaction can be an important loss pathway for Criegee intermediates and thus needs to be characterized to obtain accurate bimolecular reaction rate coefficients. Cavity ring-down spectroscopy was used to perform kinetic measurements for various reactions of CH2OO at 293 K and under low pressure (7 to 30 Torr) conditions. For the reaction CH2OO + CH2OO (8), a rate coefficient k8 = (7.35 ± 0.63) × 10(-11) cm(3) molecule(-1) s(-1) was derived from the measured CH2OO decay rates, using an absorption cross section value reported previously. A rate coefficient of k4 = (3.80 ± 0.04) × 10(-11) cm(3) molecule(-1) s(-1) was obtained for the CH2OO + SO2 (4) reaction. An upper limit for the unimolecular CH2OO loss rate coefficient of 11.6 ± 8.0 s(-1) was deduced from studies of reaction (4). SO2 catalysed CH2OO isomerization or intersystem crossing is proposed to occur with a rate coefficient of (3.53 ± 0.32) × 10(-11) cm(3) molecule(-1) s(-1).

Criegee intermediates are formed in the ozonolysis of alkenes and play an important role in indoor chemistry, notably as a source of OH radicals. Recent studies have shown that these Criegee intermediates react very quickly with NO2 , SO2 , and carbonyls, and in this study, steady-state calculations are used to inspect the potential impact of these data on indoor chemistry. It is shown that these reactions could accelerate NO3 formation and SO2 removal in the indoor environment significantly. In addition, reaction between Criegee intermediates and halogenated carbonyls could provide a significant loss process indoors, where currently one does not exist., (© 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2 OO and CH3 CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3 COOH), 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)  cm(3)  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., (© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.)

Absorption cross-sections and quantum yields for NO2 production (ΦNO2) are reported for gaseous methyl, ethyl, n-propyl, and isopropyl nitrate at 294 K. Absorption cross-sections in the wavelength range of 240-320 nm agree well with prior determinations. NO2 quantum yields at photoexcitation wavelengths of 290, 295, and 315 nm are unity within experimental uncertainties for all of the alkyl nitrates studied and are independent of bath gas (N2) pressure for total sample pressures in the range of 250-700 Torr. When averaged over all wavelengths and sample pressures, values of ΦNO2 are 1.03 ± 0.05 (methyl nitrate), 0.98 ± 0.09 (ethyl nitrate), 1.01 ± 0.04 (n-propyl nitrate), and 1.00 ± 0.05 (isopropyl nitrate), with uncertainties corresponding to 1 standard deviation. Absorption cross-sections for ethyl nitrate, isopropyl nitrate, and two unsaturated dinitrate compounds, but-3-ene-1,2-diyl dinitrate and (Z)-but-2-ene-1,4-diyl dinitrate in acetonitrile solution, are compared to gas-phase values, and over the wavelength range of 260-315 nm, the gas-phase values are well-reproduced by dividing the liquid-phase cross-sections by 2.0, 1.6, 1.7, and 2.2, respectively. Reasonable estimates of the gas-phase absorption cross-sections for low-volatility organic nitrates can therefore be obtained by halving the values for acetonitrile solutions. The quantum yield for NO2 formation from photoexcitation of but-3-ene-1,2-diyl dinitrate at 290 nm is significantly lower than those for the alkyl (mono) nitrates: a best estimate of ΦNO2 ≤ 0.25 is obtained from the experimental measurements.

The chemistry of carbonyl oxides, known as Criegee intermediates, is central to many aspects of tropospheric chemistry. For decades it has been known that these reactive species, whose electronic structure contains zwitterionic and biradical character, are formed in the ozonolysis of alkenes. However it is only recently that direct measurements of their reaction kinetics have become possible. In this perspective we describe the most recent progress in understanding the reactivity of these historically elusive molecules, explore the atmospheric chemistry implications of new experimental discoveries, and propose important new areas for investigation.

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

Although carbonyl oxides, "Criegee intermediates," have long been implicated in tropospheric oxidation, there have been few direct measurements of their kinetics, and only for the simplest compound in the class, CH2OO. Here, we report production and reaction kinetics of the next larger Criegee intermediate, CH3CHOO. Moreover, we independently probed the two distinct CH3CHOO conformers, syn- and anti-, both of which react readily with SO2 and with NO2. We demonstrate that anti-CH3CHOO is substantially more reactive toward water and SO2 than is syn-CH3CHOO. Reaction with water may dominate tropospheric removal of Criegee intermediates and determine their atmospheric concentration. An upper limit is obtained for the reaction of syn-CH3CHOO with water, and the rate constant for reaction of anti-CH3CHOO with water is measured as 1.0 × 10(-14) ± 0.4 × 10(-14) centimeter(3) second(-1).

Carbonyl oxides ("Criegee intermediates"), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al, Sci, Total Environ., 2006, 360, 5, Gäb et al., Nature, 1985, 316, 535, ref. 1-3). Recently it was shown that small Criegee intermediates, C.I.'s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204, ref. 4) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of 502 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipilä et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U. S. A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429, ref. 5-7). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007, ref. 8). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved experimentally obtained estimates of the rate coefficients of Criegee intermediate reactions. Using both regional and global scale modelling, we show that this enhancement is likely to be highly variable spatially with local hot-spots in e.g. urban outflows. This conclusion is however contingent on a number of remaining uncertainties in Criegee intermediate chemistry.

CH(2)OO, the simplest Criegee intermediate, and ozone are isoelectronic. They both play very important roles in atmospheric chemistry. Whilst extensive experimental studies have been made on ozone, there were no direct gas-phase studies on CH(2)OO until very recently when its photoionization spectrum was recorded and kinetics studies were made of some reactions of CH(2)OO with a number of molecules of atmospheric importance, using photoionization mass spectrometry to monitor CH(2)OO. In order to encourage more direct studies on CH(2)OO and other Criegee intermediates, the electronic and photoelectron spectra of CH(2)OO have been simulated using high level electronic structure calculations and Franck-Condon factor calculations, and the results are presented here. Adiabatic and vertical excitation energies of CH(2)OO were calculated with TDDFT, EOM-CCSD, and CASSCF methods. Also, DFT, QCISD and CASSCF calculations were performed on neutral and low-lying ionic states, with single energy calculations being carried out at higher levels to obtain more reliable ionization energies. The results show that the most intense band in the electronic spectrum of CH(2) OO corresponds to the B(1)A' ← X(1)A' absorption. It is a broad band in the region 250-450 nm showing extensive structure in vibrational modes involving O-O stretching and C-O-O bending. Evidence is presented to show that the electronic absorption spectrum of CH(2)OO has probably been recorded in earlier work, albeit at low resolution. We suggest that CH(2)OO was prepared in this earlier work from the reaction of CH(2)I with O(2) and that the assignment of the observed spectrum solely to CH(2)IOO is incorrect. The low ionization energy region of the photoelectron spectrum of CH(2)OO consists of two overlapping vibrationally structured bands corresponding to one-electron ionizations from the highest two occupied molecular orbitals of the neutral molecule. In each case, the adiabatic component is the most intense and the adiabatic ionization energies of these bands are expected to be very close, at 9.971 and 9.974 eV at the highest level of theory used., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Criegee biradicals, i.e., carbonyl oxides, are critical intermediates in ozonolysis and have been implicated in autoignition chemistry and other hydrocarbon oxidation systems, but until recently the direct measurement of their gas-phase kinetics has not been feasible. Indirect determinations of Criegee intermediate kinetics often rely on the introduction of a scavenger molecule into an ozonolysis system and analysis of the effects of the scavenger on yields of products associated with Criegee intermediate reactions. Carbonyl species, in particular hexafluoroacetone (CF(3)COCF(3)), have often been used as scavengers. In this work, the reactions of the simplest Criegee intermediate, CH(2)OO (formaldehyde oxide), with three carbonyl species have been measured by laser photolysis/tunable synchrotron photoionization mass spectrometry. Diiodomethane photolysis produces CH(2)I radicals, which react with O(2) to yield CH(2)OO + I. The formaldehyde oxide is reacted with a large excess of a carbonyl reactant and both the disappearance of CH(2)OO and the formation of reaction products are monitored. The rate coefficient for CH(2)OO + hexafluoroacetone is k(1) = (3.0 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1), supporting the use of hexafluoroacetone as a Criegee-intermediate scavenger. The reactions with acetaldehyde, k(2) = (9.5 ± 0.7) × 10(-13) cm(3) molecule(-1) s(-1), and with acetone, k(3) = (2.3 ± 0.3) × 10(-13) cm(3) molecule(-1) s(-1), are substantially slower. Secondary ozonides and products of ozonide isomerization are observed from the reactions of CH(2)OO with acetone and hexafluoroacetone. Their photoionization spectra are interpreted with the aid of quantum-chemical and Franck-Condon-factor calculations. No secondary ozonide was observable in the reaction of CH(2)OO with acetaldehyde, but acetic acid was identified as a product under the conditions used (4 Torr and 293 K).

The rates of ozonolysis of four sesquiterpenes, β-caryophyllene, α-humulene, isolongifolene and α-cedrene, are determined in the gas phase at an elevated temperature of 366 ± 3 K and a pressure of ~780 Torr using the EXTreme RAnge chamber (EXTRA). The experimentally obtained rate coefficients agree with extrapolated room temperature rate coefficients for isolongifolene and α-cedrene but not for β-caryophyllene and α-humulene, which were found to be three orders of magnitude slower than this in the literature. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution., (This journal is © the Owner Societies 2012)

A temperature and pressure kinetic study for the CH(3)O(2) + ClO reaction has been performed using the turbulent flow technique with a chemical ionisation mass spectrometry detection system. An Arrhenius expression was obtained for the overall rate coefficient of CH(3)O(2) + ClO reaction: k(10)(T) = (1.96(−0.24)(+0.28)) × 10(-11) exp[(-626 ± 35)/T] cm(3) molecule(-1) s(-1) where the uncertainty associated with the rate coefficient is given at the one standard deviation level. Over a range of pressure (100-200 Torr) and temperature (298-223 K) no pressure dependence is observed. The smaller rate coefficients measured at lower temperatures compared with both previous low temperature studies are believed to arise through the reduction of secondary chemistry and greater sensitivity in terms of reactant detection (hence much lower initial concentrations were employed). These new data reduce the effectiveness of ozone loss cycles involving reaction of CH(3)O(2) + ClO in the polar stratosphere by around a factor of 1.5 and restrict the importance of the reaction to the tropical and extra-tropical clean marine environments in the troposphere.