Search

In recent years, clean air policies have led to reductions in air pollution across China. Alongside this, emerging carbon neutrality (CN) policies that aim to address the impacts of climate change may also deliver air quality (AQ) co-benefits or climate penalties. Different CN policies will lead to different changes in volatile organic compound (VOC), NOx and particulate matter (PM) emissions, which will in turn impact the photochemical production of secondary pollutants such as ozone (O3). It is currently unclear how different combinations of AQ and CN policies may impact in situ O3 production across China in the future. A detailed chemical box model incorporating the Master Chemical Mechanism was developed to investigate the impact of combined AQ and CN policies on O3 formation in Beijing. The Multi-resolution Emission Inventory model for Climate and air pollution research (MEIC) and the Dynamic Projection model for Emissions in China (DPEC) were used to estimate future pollutant mixing ratios, relative to ambient observations of 35 VOCs, NOx, CO and aerosol surface area (ASA) during the APHH-Beijing 2017 summer campaign. The most ambitious policy scenario, “Ambitious Pollution 1.5D Goals”, led to the largest reduction in O3 production by 2060 but was not the most impactful scenario for reducing O3 production between 2030–2045. Larger reductions were observed under the “Ambitious Pollution Neutral Goals” policy, which focuses on achieving net zero by 2060. O3 production was found to be most sensitive to changes in the OLE2 group of VOCs (alkenes where kOH>7×104 ppm−1 min−1; a 5 % increase in OLE2 increased simulated O3 production by 1.12 %). However, reducing less reactive but higher concentration species in Beijing (such as short-chain alkanes) led to larger reductions in O3 production under all scenarios. O3 production was not sensitive to changes in ASA, with a 69 % decrease in ASA leading to a change of % in O3. However, doubling biogenic VOCs in the model further increased O3 production in 2060 under all future scenarios by up to 18 %, indicating that the influence of future climate-induced changes in biogenic emissions may have a significant impact on in situ O3 formation in Beijing. This study highlights that the emission trajectories of certain specific VOCs are highly influential in determining possible future O3 air quality effects that may arise from increasing ambient temperatures and decarbonisation in Beijing.

Lab-based experimental and computational methods were used to study the atmospheric degradation of two promising “green” solvents: pinacolone, (CH3)3CC(O)CH3, and methyl pivalate, (CH3)3CC(O)OCH3. Pulsed laser photolysis coupled to pulsed laser-induced fluorescence was used to determine absolute rate coefficients (in 10−12 cm3 molec.−1 s−1) of k1(297 K) = (1.2 ± 0.2) for OH + (CH3)3CC(O)CH3 (Reaction R1) and k2(297 K) = (1.3 ± 0.2) for OH + (CH3)3CC(O)OCH3 (Reaction R2), in good agreement with one previous experimental study. Rate coefficients for both reactions were found to increase at elevated temperature, with k1(T) adequately described by k1(297–485 K) = 2.1 × 10−12 exp(-200/T) cm3 molec.−1 s−1. k2(T) exhibited more complex behaviour, with a local minimum at around 300 K. In the course of this work, k3(295–450 K) was obtained for the well-characterised reaction OH + C2H5OH (ethanol; Reaction R3), in satisfactory agreement with the evaluated literature. UV–Vis spectroscopy experiments and computational calculations were used to explore cross-sections for (CH3)3CC(O)CH3 photolysis (Reaction R4), while (CH3)3CC(O)OCH3 showed no sign of absorption over the wavelengths of interest. Absorption cross-sections for (CH3)3CC(O)CH3, σ4(λ), in the actinic region were larger, and the maximum was red-shifted compared to estimates (methyl ethyl ketone (MEK) values) used in current state-of-science models. As a consequence, we note that photolysis (Reaction R4) is likely the dominant pathway for removal of (CH3)3CC(O)CH3 from the troposphere. Nonetheless, large uncertainties remain as quantum yields φ4(λ) remain unmeasured. Lifetime estimates based upon Reactions (R1) and (R4) span the range 2–9 d and are consequently associated with a poorly constrained estimated photochemical ozone creation potential (POCPE). In accord with previous studies, (CH3)3CC(O)OCH3 did not absorb in the actinic region, allowing for straightforward calculation of an atmospheric lifetime of ≈ 9 d and a small POCPE ≈ 11.

Isoprene and monoterpene emissions to the atmosphere are generally dominated by biogenic sources. The oxidation of these compounds can lead to the production of secondary organic aerosol; however the impact of this chemistry in polluted urban settings has been poorly studied. Isoprene and monoterpenes can form secondary organic aerosol (SOA) heterogeneously via anthropogenic–biogenic interactions, resulting in the formation of organosulfate (OS) and nitrooxy-organosulfate (NOS) species. Delhi, India, is one of the most polluted cities in the world, but little is known about the emissions of biogenic volatile organic compounds (VOCs) or the sources of SOA. As part of the DELHI-FLUX project, gas-phase mixing ratios of isoprene and speciated monoterpenes were measured during pre- and post-monsoon measurement campaigns in central Delhi. Nocturnal mixing ratios of the VOCs were substantially higher during the post-monsoon (isoprene: (0.65±0.43) ppbv; limonene: (0.59±0.11) ppbv; α-pinene: (0.13±0.12) ppbv) than the pre-monsoon (isoprene: (0.13±0.18) ppbv; limonene: 0.011±0.025 (ppbv); α-pinene: 0.033±0.009) period. At night, isoprene and monoterpene concentrations correlated strongly with CO during the post-monsoon period. Filter samples of particulate matter less than 2.5 µm in diameter (PM2.5) were collected and the OS and NOS content analysed using ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS2). Inorganic sulfate was shown to facilitate the formation of isoprene OS species across both campaigns. Sulfate contained within OS and NOS species was shown to contribute significantly to the sulfate signal measured via AMS. Strong nocturnal enhancements of NOS species were observed across both campaigns. The total concentration of OS and NOS species contributed an average of (2.0±0.9) % and (1.8±1.4) % to the total oxidized organic aerosol and up to a maximum of 4.2 % and 6.6 % across the pre- and post-monsoon periods, respectively. Overall, this study provides the first molecular-level measurements of SOA derived from isoprene and monoterpene in Delhi and demonstrates that both biogenic and anthropogenic sources of these compounds can be important in urban areas.

Isoprene nitrates are important chemical species in the atmosphere which contribute to the chemical cycles that form ozone and secondary organic aerosol (SOA) with implications for climate and air quality. Accurate chemical mechanisms are important for the prediction of the atmospheric chemistry of species such as isoprene nitrates in chemical models. In recent years, studies into the chemistry of isoprene nitrates have resulted in the development of a range of mechanisms available for use in the simulation of atmospheric isoprene oxidation. This work uses a 0-D chemical box model to assess the ability of three chemically detailed mechanisms to predict the observed diurnal profiles of four groups of isoprene-derived nitrates in the summertime in the Chinese megacity of Beijing. An analysis of modelled C5H9NO5 isomers, including isoprene hydroperoxy nitrate (IPN) species, highlights the significant contribution of non-IPN species to the C5H9NO5 measurement, including the potentially large contribution of nitrooxy hydroxyepoxide (INHE). The changing isomer distribution of isoprene hydroxy nitrates (IHNs) derived from OH-initiated and NO3-initiated chemistry is discussed, as is the importance of up-to-date alkoxy radical chemistry for the accurate prediction of isoprene carbonyl nitrate (ICN) formation. All mechanisms under-predicted C4H7NO5 as predominately formed from the major isoprene oxidation products, methyl vinyl ketone (MVK) and methacrolein (MACR). This work explores the current capability of existing chemical mechanisms to accurately represent isoprene nitrate chemistry in urban areas significantly impacted by anthropogenic and biogenic chemical interactions. It suggests considerations to be taken when investigating isoprene nitrates in ambient scenarios, investigates the potential impact of varying isomer distributions on iodide chemical ionisation mass spectrometry (I−-CIMS) calibrations, and makes some proposals for the future development of isoprene mechanisms.

Reaction with ozone is an important atmospheric removal process for alkenes. The ozonolysis reaction produces carbonyls and carbonyl oxides (Criegee intermediates, CI), which can rapidly decompose to yield a range of closed shell and radical products, including OH radicals. Consequently, it is essential to accurately represent the complex chemistry of Criegee intermediates in atmospheric models in order to fully understand the impact of alkene ozonolysis on atmospheric composition. A mechanism construction protocol is presented which is suitable for use in automatic mechanism generation. The protocol defines the critical parameters for describing the chemistry following the initial reaction, namely the primary carbonyl/CI yields from the primary ozonide fragmentation, the amount of stabilisation of the excited CI, the unimolecular decomposition pathways, rates and products of the CI, and the bimolecular rates and products of atmospherically important reactions of the stabilised CI (SCI). This analysis implicitly predicts the yield of OH from the alkene–ozone reaction. A comprehensive database of experimental OH, SCI and carbonyl yields has been collated using reported values in the literature and used to assess the reliability of the protocol. The protocol provides estimates of OH, SCI and carbonyl yields with root mean square errors of 0.13 and 0.12 and 0.14, respectively. Areas where new experimental and theoretical data would improve the protocol and its assessment are identified and discussed.

The Indian megacity of Delhi suffers from some of the poorest air quality in the world. While ambient NO2 and particulate matter (PM) concentrations have received considerable attention in the city, high ground-level ozone (O3) concentrations are an often overlooked component of pollution. O3 can lead to significant ecosystem damage and agricultural crop losses, and adversely affect human health. During October 2018, concentrations of speciated non-methane hydrocarbon volatile organic compounds (C2–C13), oxygenated volatile organic compounds (o-VOCs), NO, NO2, HONO, CO, SO2, O3, and photolysis rates, were continuously measured at an urban site in Old Delhi. These observations were used to constrain a detailed chemical box model utilising the Master Chemical Mechanism v3.3.1. VOCs and NOx (NO + NO2) were varied in the model to test their impact on local O3 production rates, P(O3), which revealed a VOC-limited chemical regime. When only NOx concentrations were reduced, a significant increase in P(O3) was observed; thus, VOC co-reduction approaches must also be considered in pollution abatement strategies. Of the VOCs examined in this work, mean morning P(O3) rates were most sensitive to monoaromatic compounds, followed by monoterpenes and alkenes, where halving their concentrations in the model led to a 15.6 %, 13.1 %, and 12.9 % reduction in P(O3), respectively. P(O3) was not sensitive to direct changes in aerosol surface area but was very sensitive to changes in photolysis rates, which may be influenced by future changes in PM concentrations. VOC and NOx concentrations were divided into emission source sectors, as described by the Emissions Database for Global Atmospheric Research (EDGAR) v5.0 Global Air Pollutant Emissions and EDGAR v4.3.2_VOC_spec inventories, allowing for the impact of individual emission sources on P(O3) to be investigated. Reducing road transport emissions only, a common strategy in air pollution abatement strategies worldwide, was found to increase P(O3), even when the source was removed in its entirety. Effective reduction in P(O3) was achieved by reducing road transport along with emissions from combustion for manufacturing and process emissions. Modelled P(O3) reduced by ∼ 20 ppb h−1 when these combined sources were halved. This study highlights the importance of reducing VOCs in parallel with NOx and PM in future pollution abatement strategies in Delhi.

The impact of emissions of volatile organic compounds (VOCs) to the atmosphere on the production of secondary pollutants, such as ozone and secondary organic aerosol (SOA), is mediated by the concentration of nitric oxide (NO). Polluted urban atmospheres are typically considered to be “high-NO” environments, while remote regions such as rainforests, with minimal anthropogenic influences, are considered to be “low NO”. However, our observations from central Beijing show that this simplistic separation of regimes is flawed. Despite being in one of the largest megacities in the world, we observe formation of gas- and aerosol-phase oxidation products usually associated with low-NO “rainforest-like” atmospheric oxidation pathways during the afternoon, caused by extreme suppression of NO concentrations at this time. Box model calculations suggest that during the morning high-NO chemistry predominates (95 %) but in the afternoon low-NO chemistry plays a greater role (30 %). Current emissions inventories are applied in the GEOS-Chem model which shows that such models, when run at the regional scale, fail to accurately predict such an extreme diurnal cycle in the NO concentration. With increasing global emphasis on reducing air pollution, it is crucial for the modelling tools used to develop urban air quality policy to be able to accurately represent such extreme diurnal variations in NO to accurately predict the formation of pollutants such as SOA and ozone.

Twenty-nine different fuel types used in residential dwellings in northern India were collected from across Delhi (76 samples in total). Emission factors of a wide range of non-methane volatile organic compounds (NMVOCs) (192 compounds in total) were measured during controlled burning experiments using dual-channel gas chromatography with flame ionisation detection (DC-GC-FID), two-dimensional gas chromatography (GC × GC-FID), proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) and solid-phase extraction two-dimensional gas chromatography with time-of-flight mass spectrometry (SPE-GC × GC–ToF-MS). On average, 94 % speciation of total measured NMVOC emissions was achieved across all fuel types. The largest contributors to emissions from most fuel types were small non-aromatic oxygenated species, phenolics and furanics. The emission factors (in g kg−1) for total gas-phase NMVOCs were fuelwood (18.7, 4.3–96.7), cow dung cake (62.0, 35.3–83.0), crop residue (37.9, 8.9–73.8), charcoal (5.4, 2.4–7.9), sawdust (72.4, 28.6–115.5), municipal solid waste (87.3, 56.6–119.1) and liquefied petroleum gas (5.7, 1.9–9.8). The emission factors measured in this study allow for better characterisation, evaluation and understanding of the air quality impacts of residential solid-fuel combustion in India.

Biomass burning emits significant quantities of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) in a complex mixture, probably containing many thousands of chemical species. These components are significantly more toxic and have poorly understood chemistry compared to volatile organic compounds routinely quantified in ambient air; however, analysis of I/SVOCs presents a difficult analytical challenge. The gases and particles emitted during the test combustion of a range of domestic solid fuels collected from across Delhi were sampled and analysed. Organic aerosol was collected onto Teflon (PTFE) filters, and residual low-volatility gases were adsorbed to the surface of solid-phase extraction (SPE) discs. A new method relying on accelerated solvent extraction (ASE) coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC–ToF-MS) was developed. This highly sensitive and powerful analytical technique enabled over 3000 peaks from I/SVOC species with unique mass spectra to be detected. A total of 15 %–100 % of gas-phase emissions and 7 %–100 % of particle-phase emissions were characterised. The method was analysed for suitability to make quantitative measurements of I/SVOCs using SPE discs. Analysis of SPE discs indicated phenolic and furanic compounds were important for gas-phase I/SVOC emissions and levoglucosan to the aerosol phase. Gas- and particle-phase emission factors for 21 polycyclic aromatic hydrocarbons (PAHs) were derived, including 16 compounds listed by the US EPA as priority pollutants. Gas-phase emissions were dominated by smaller PAHs. The new emission factors were measured (mg kg−1) for PAHs from combustion of cow dung cake (615), municipal solid waste (1022), crop residue (747), sawdust (1236), fuelwood (247), charcoal (151) and liquefied petroleum gas (56). The results of this study indicate that cow dung cake and municipal solid waste burning are likely to be significant PAH sources, and further study is required to quantify their impact alongside emissions from fuelwood burning.

Reaction with ozone (O3) is an important removal process for unsaturated volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of O3 with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models. Updated and extended structure–activity relationship (SAR) methods are presented for the reactions of O3 with mono- and poly-unsaturated organic compounds. The methods are optimized using a preferred set of data including reactions of O3 with 221 unsaturated compounds. For conjugated dialkene structures, site-specific rates are defined, and for isolated poly-alkenes rates are defined for each double bond to determine the branching ratios for primary ozonide formation. The information can therefore guide the representation of the O3 reactions in the next generation of explicit detailed chemical mechanisms.

The multivariate relative rate method was applied to a range of volatile organic compound (VOC) reactions with OH. This previously published method (Shaw et al., 2018) was improved to increase the sensitivity towards more slowly reacting VOCs, broadening the range of compounds which can be examined. A total of 35 room temperature relative rate coefficients were determined, eight of which have not previously been reported. Five of the new reaction rate coefficients were for large alkyl substituted mono-aromatic species recently identified in urban air masses, likely with large ozone production potentials. The new results (with kOH (296 K) values in units of 10−12 cm3 molec.−1 s−1) were n-butylbenzene, 11 (±4); n-pentylbenzene, 7 (±2); 1,2-diethylbenzene, 14 (±4); 1,3-diethylbenzene, 22 (±4); and 1,4-diethylbenzene, 16 (±4). Interestingly, whilst results for smaller VOCs agreed well with available structure–activity relationship (SAR) calculations, the larger alkyl benzenes were found to be less reactive than the SAR prediction, indicating that our understanding of the oxidation chemistry of these compounds is still limited. kOH (296 K) rate coefficients (in units of 10−12 cm3 molec.−1 s−1) for reactions of three large alkanes with OH were also determined for the first time: 2-methylheptane, 9.1 (±0.3); 2-methylnonane, 11.0 (±0.3); and ethylcyclohexane, 14.4 (±0.3), all in reasonable agreement with SAR predictions. Rate coefficients for the 27 previously studied OH + VOC reactions agreed well with available literature values, lending confidence to the application of this method for the rapid and efficient simultaneous study of gas-phase reaction kinetics.

Aromatic volatile organic compounds (VOCs) are key anthropogenic pollutants emitted to the atmosphere and are important for both ozone and secondary organic aerosol (SOA) formation in urban areas. Recent studies have indicated that aromatic hydrocarbons may follow previously unknown oxidation chemistry pathways, including autoxidation that can lead to the formation of highly oxidised products. In this study we evaluate the gas- and particle-phase ions measured by online mass spectrometry during the hydroxyl radical oxidation of substituted C9-aromatic isomers (1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, propylbenzene and isopropylbenzene) and a substituted polyaromatic hydrocarbon (1-methylnaphthalene) under low- and medium-NOx conditions. A time-of-flight chemical ionisation mass spectrometer (ToF-CIMS) with iodide–anion ionisation was used with a filter inlet for gases and aerosols (FIGAERO) for the detection of products in the particle phase, while a Vocus proton-transfer-reaction mass spectrometer (Vocus-PTR-MS) was used for the detection of products in the gas phase. The signal of product ions observed in the mass spectra were compared for the different precursors and experimental conditions. The majority of mass spectral product signal in both the gas and particle phases comes from ions which are common to all precursors, though signal distributions are distinct for different VOCs. Gas- and particle-phase composition are distinct from one another. Ions corresponding to products contained in the near-explicit gas phase Master Chemical Mechanism (MCM version 3.3.1) are utilised as a benchmark of current scientific understanding, and a comparison of these with observations shows that the MCM is missing a range of highly oxidised products from its mechanism. In the particle phase, the bulk of the product signal from all precursors comes from ring scission ions, a large proportion of which are more oxidised than previously reported and have undergone further oxidation to form highly oxygenated organic molecules (HOMs). Under the perturbation of OH oxidation with increased NOx, the contribution of HOM-ion signals to the particle-phase signal remains elevated for more substituted aromatic precursors. Up to 43 % of product signal comes from ring-retaining ions including HOMs; this is most important for the more substituted aromatics. Unique products are a minor component in these systems, and many of the dominant ions have ion formulae concurrent with other systems, highlighting the challenges in utilising marker ions for SOA.

Isoprene-derived secondary organic aerosol (iSOA) is a significant contributor to organic carbon (OC) in some forested regions, such as tropical rainforests and the Southeastern US. However, its contribution to organic aerosol in urban areas that have high levels of anthropogenic pollutants is poorly understood. In this study, we examined the formation of anthropogenically influenced iSOA during summer in Beijing, China. Local isoprene emissions and high levels of anthropogenic pollutants, in particular NOx and particulate SO42-, led to the formation of iSOA under both high- and low-NO oxidation conditions, with significant heterogeneous transformations of isoprene-derived oxidation products to particulate organosulfates (OSs) and nitrooxy-organosulfates (NOSs). Ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was combined with a rapid automated data processing technique to quantify 31 proposed iSOA tracers in offline PM2.5 filter extracts. The co-elution of the inorganic ions in the extracts caused matrix effects that impacted two authentic standards differently. The average concentration of iSOA OSs and NOSs was 82.5 ng m−3, which was around 3 times higher than the observed concentrations of their oxygenated precursors (2-methyltetrols and 2-methylglyceric acid). OS formation was dependant on both photochemistry and the sulfate available for reactive uptake, as shown by a strong correlation with the product of ozone (O3) and particulate sulfate (SO42-). A greater proportion of high-NO OS products were observed in Beijing compared with previous studies in less polluted environments. The iSOA-derived OSs and NOSs represented 0.62 % of the oxidized organic aerosol measured by aerosol mass spectrometry on average, but this increased to ∼3 % on certain days. These results indicate for the first time that iSOA formation in urban Beijing is strongly controlled by anthropogenic emissions and results in extensive conversion to OS products from heterogenous reactions.

AtChem is an open-source zero-dimensional box model for atmospheric chemistry. Any general set of chemical reactions can be used with AtChem, but the model was designed specifically for use with the Master Chemical Mechanism (MCM, http://mcm.york.ac.uk/, last access: 16 January 2020). AtChem was initially developed within the EUROCHAMP project as a web application (AtChem-online, https://atchem.leeds.ac.uk/webapp/, last access: 16 January 2020) for modelling environmental chamber experiments; it was recently upgraded and further developed into a stand-alone offline version (AtChem2), which allows the user to run complex and long simulations, such as those needed for modelling of intensive field campaigns, as well as to perform batch model runs for sensitivity studies. AtChem is installed, set up and configured using semi-automated scripts and simple text configuration files, making it easy to use even for inexperienced users. A key feature of AtChem is that it can easily be constrained to observational data which may have different timescales, thus retaining all the information contained in the observations. Implementation of a continuous integration workflow, coupled with a comprehensive suite of tests and version control software, makes the AtChem code base robust, reliable and traceable. The AtChem2 code and documentation are available at https://github.com/AtChem/ (last access: 16 January 2020) under the open-source MIT License.

Organic peroxy radicals (RO2), formed from the degradation of hydrocarbons and other volatile organic compounds (VOCs), play a key role in tropospheric oxidation mechanisms. Several competing reactions may be available for a given RO2 radical, the relative rates of which depend on both the structure of RO2 and the ambient conditions. Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3, OH and HO2; and for their self-reactions and cross-reactions with other RO2 radicals. This information is used to define generic rate coefficients and structure–activity relationship (SAR) methods that can be applied to the bimolecular reactions of a series of important classes of hydrocarbon and oxygenated RO2 radicals. Information for selected unimolecular isomerization reactions (i.e. H-atom shift and ring-closure reactions) is also summarized and discussed. The methods presented here are intended to guide the representation of RO2 radical chemistry in the next generation of explicit detailed chemical mechanisms.

The Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-Beijing) programme is an international collaborative project focusing on understanding the sources, processes and health effects of air pollution in the Beijing megacity. APHH-Beijing brings together leading China and UK research groups, state-of-the-art infrastructure and air quality models to work on four research themes: (1) sources and emissions of air pollutants; (2) atmospheric processes affecting urban air pollution; (3) air pollution exposure and health impacts; and (4) interventions and solutions. Themes 1 and 2 are closely integrated and support Theme 3, while Themes 1–3 provide scientific data for Theme 4 to develop cost-effective air pollution mitigation solutions. This paper provides an introduction to (i) the rationale of the APHH-Beijing programme and (ii) the measurement and modelling activities performed as part of it. In addition, this paper introduces the meteorology and air quality conditions during two joint intensive field campaigns – a core integration activity in APHH-Beijing. The coordinated campaigns provided observations of the atmospheric chemistry and physics at two sites: (i) the Institute of Atmospheric Physics in central Beijing and (ii) Pinggu in rural Beijing during 10 November–10 December 2016 (winter) and 21 May–22 June 2017 (summer). The campaigns were complemented by numerical modelling and automatic air quality and low-cost sensor observations in the Beijing megacity. In summary, the paper provides background information on the APHH-Beijing programme and sets the scene for more focused papers addressing specific aspects, processes and effects of air pollution in Beijing.

Reaction with the hydroxyl (OH) radical is the dominant removal process for volatile organic compounds (VOCs) in the atmosphere. Rate coefficients for reactions of OH with VOCs are therefore essential parameters for chemical mechanisms used in chemistry transport models, and are required more generally for impact assessments involving the estimation of atmospheric lifetimes or oxidation rates for VOCs. Updated and extended structure–activity relationship (SAR) methods are presented for the reactions of OH with aliphatic organic compounds, with the reactions of aromatic organic compounds considered in a companion paper. The methods are optimized using a preferred set of data including reactions of OH with 489 aliphatic hydrocarbons and oxygenated organic compounds. In each case, the rate coefficient is defined in terms of a summation of partial rate coefficients for H abstraction or OH addition at each relevant site in the given organic compound, so that the attack distribution is defined. The information can therefore guide the representation of the OH reactions in the next generation of explicit detailed chemical mechanisms. Rules governing the representation of the subsequent reactions of the product radicals under tropospheric conditions are also summarized, specifically their reactions with O2 and competing processes.

The gas-phase reaction of alkenes with ozone is known to produce stabilised Criegee intermediates (SCIs). These biradical/zwitterionic species have the potential to act as atmospheric oxidants for trace pollutants such as SO2, enhancing the formation of sulfate aerosol with impacts on air quality and health, radiative transfer and climate. However, the importance of this chemistry is uncertain as a consequence of limited understanding of the abundance and atmospheric fate of SCIs. In this work we apply experimental, theoretical and numerical modelling methods to quantify the atmospheric impacts, abundance and fate of the structurally diverse SCIs derived from the ozonolysis of monoterpenes, the second most abundant group of unsaturated hydrocarbons in the atmosphere. We have investigated the removal of SO2 by SCIs formed from the ozonolysis of three atmospherically important monoterpenes (α-pinene, β-pinene and limonene) in the presence of varying amounts of water vapour in large-scale simulation chamber experiments that are representative of boundary layer conditions. The SO2 removal displays a clear dependence on water vapour concentration, but this dependence is not linear across the range of [H2O] explored. At low [H2O] a strong dependence of SO2 removal on [H2O] is observed, while at higher [H2O] this dependence becomes much weaker. This is interpreted as being caused by the production of a variety of structurally (and hence chemically) different SCIs in each of the systems studied, which displayed different rates of reaction with water and of unimolecular rearrangement or decomposition. The determined rate constants, k(SCI+H2O), for those SCIs that react primarily with H2O range from 4 to 310 × 10−15 cm3 s−1. For those SCIs that predominantly react unimolecularly, determined rates range from 130 to 240 s−1. These values are in line with previous results for the (analogous) stereo-specific SCI system of syn-/anti-CH3CHOO. The experimental results are interpreted through theoretical studies of the SCI unimolecular reactions and bimolecular reactions with H2O, characterised for α-pinene and β-pinene at the M06-2X/aug-cc-pVTZ level of theory. The theoretically derived rates agree with the experimental results within the uncertainties. A global modelling study, applying the experimental results within the GEOS-Chem chemical transport model, suggests that > 97 % of the total monoterpene-derived global SCI burden is comprised of SCIs with a structure that determines that they react slowly with water and that their atmospheric fate is dominated by unimolecular reactions. Seasonally averaged boundary layer concentrations of monoterpene-derived SCIs reach up to 1.4 × 104 cm−3 in regions of elevated monoterpene emissions in the tropics. Reactions of monoterpene-derived SCIs with SO2 account for 2 removal over areas of tropical forests, with significant localised impacts on the formation of sulfate aerosol and hence the lifetime and distribution of SO2.

The molecular composition of the water-soluble fraction of secondary organic aerosol (SOA) generated from the ozonolysis of α-phellandrene is investigated for the first time using high-pressure liquid chromatography coupled to high-resolution quadrupole–Orbitrap tandem mass spectrometry. In total, 21 prominent products or isomeric product groups were identified using both positive and negative ionisation modes, with potential formation mechanisms discussed. The aerosol was found to be composed primarily of polyfunctional first- and second-generation species containing one or more carbonyl, acid, alcohol and hydroperoxide functionalities, with the products significantly more complex than those proposed from basic gas-phase chemistry in the companion paper (Mackenzie-Rae et al., 2017). Mass spectra show a large number of dimeric products are also formed. Both direct scavenging evidence using formic acid and indirect evidence from double bond equivalency factors suggest the dominant oligomerisation mechanism is the bimolecular reaction of stabilised Criegee intermediates (SCIs) with non-radical ozonolysis products. Saturation vapour concentration estimates suggest monomeric species cannot explain the rapid nucleation burst of fresh aerosol observed in chamber experiments; hence, dimeric species are believed to be responsible for new particle formation, with detected first- and second-generation products driving further particle growth in the system. Ultimately, identification of the major constituents and formation pathways of α-phellandrene SOA leads to a greater understanding of the atmospheric processes and implications of monoterpene emissions and SCIs, especially around eucalypt forests where α-phellandrene is primarily emitted.

Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (±0.3) × 10−11 cm3 molecule−1 s−1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

The chemistry of isoprene degradation in the Master Chemical Mechanism (MCM) has been systematically refined and updated to reflect recent advances in understanding, with these updates appearing in the latest version, MCM v3.3.1. The complete isoprene degradation mechanism in MCM v3.3.1 consists of 1926 reactions of 602 closed shell and free radical species, which treat the chemistry initiated by reaction with OH radicals, NO3 radicals and ozone (O3). A detailed overview of the updates is provided, within the context of reported kinetic and mechanistic information. The revisions mainly relate to the OH-initiated chemistry, which tends to dominate under atmospheric conditions, although these include updates to the chemistry of some products that are also generated from the O3- and NO3-initiated oxidation. The revisions have impacts in a number of key areas, including HOx recycling, NOx recycling and the formation of species reported to play a role in SOA (secondary organic aerosol)-formation mechanisms. The performance of the MCM v3.3.1 isoprene mechanism has been compared with those of earlier versions (MCM v3.1 and MCM v3.2) over a range of relevant conditions, using a box model of the tropical forested boundary layer. The results of these calculations are presented and discussed and are used to illustrate the impacts of the mechanistic updates in MCM v3.3.1.

Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London), which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20–30 % of the total hydrocarbon mixing ratio but comprise more than 50 % of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that 60 % of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50 % of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for, but very significant, under-reporting of diesel-related hydrocarbons; an underestimation of a factor ~4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide.

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol) and NO2 processing (affecting NOx levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + H2O) / k(SCI + SO2), of 3.1 (±0.5) × 10−5 for isoprene-derived SCIs. The relative rate constant for k(SCI decomposition) / k(SCI+SO2) is 3.0 (±3.2) × 1011 cm−3. Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprene-derived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isoprene–ozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS) / k(SCI + SO2), of 3.5 (±1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS.

Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.

The α-dicarbonyl compounds glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO) are produced in the atmosphere by the oxidation of hydrocarbons and emitted directly from pyrogenic sources. Measurements of ambient concentrations inform about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation. We present results from a comprehensive instrument comparison effort at two simulation chamber facilities in the US and Europe that included nine instruments, and seven different measurement techniques: broadband cavity enhanced absorption spectroscopy (BBCEAS), cavity-enhanced differential optical absorption spectroscopy (CE-DOAS), white-cell DOAS, Fourier transform infrared spectroscopy (FTIR, two separate instruments), laser-induced phosphorescence (LIP), solid-phase micro extraction (SPME), and proton transfer reaction mass spectrometry (PTR-ToF-MS, two separate instruments; for methyl glyoxal only because no significant response was observed for glyoxal). Experiments at the National Center for Atmospheric Research (NCAR) compare three independent sources of calibration as a function of temperature (293–330 K). Calibrations from absorption cross-section spectra at UV-visible and IR wavelengths are found to agree within 2% for glyoxal, and 4% for methyl glyoxal at all temperatures; further calibrations based on ion–molecule rate constant calculations agreed within 5% for methyl glyoxal at all temperatures. At the European Photoreactor (EUPHORE) all measurements are calibrated from the same UV-visible spectra (either directly or indirectly), thus minimizing potential systematic bias. We find excellent linearity under idealized conditions (pure glyoxal or methyl glyoxal, R2 > 0.96), and in complex gas mixtures characteristic of dry photochemical smog systems (o-xylene/NOx and isoprene/NOx, R2 > 0.95; R2 ∼ 0.65 for offline SPME measurements of methyl glyoxal). The correlations are more variable in humid ambient air mixtures (RH > 45%) for methyl glyoxal (0.58 < R2 < 0.68) than for glyoxal (0.79 < R2 < 0.99). The intercepts of correlations were insignificant for the most part (below the instruments' experimentally determined detection limits); slopes further varied by less than 5% for instruments that could also simultaneously measure NO2. For glyoxal and methyl glyoxal the slopes varied by less than 12 and 17% (both 3-σ) between direct absorption techniques (i.e., calibration from knowledge of the absorption cross section). We find a larger variability among in situ techniques that employ external calibration sources (75–90%, 3-σ), and/or techniques that employ offline analysis. Our intercomparison reveals existing differences in reports about precision and detection limits in the literature, and enables comparison on a common basis by observing a common air mass. Finally, we evaluate the influence of interfering species (e.g., NO2, O3 and H2O) of relevance in field and laboratory applications. Techniques now exist to conduct fast and accurate measurements of glyoxal at ambient concentrations, and methyl glyoxal under simulated conditions. However, techniques to measure methyl glyoxal at ambient concentrations remain a challenge, and would be desirable.

Wet deposition is the dominant mechanism for removing black carbon (BC) from the atmosphere and is key in determining its atmospheric lifetime, vertical gradient and global transport. Despite the importance of BC in the climate system, especially in terms of its ability to modulate the radiative energy budget, there are few quantitative case studies of wet removal in ambient environments. We present a case study of BC wet removal by examining aerosol size distributions and BC coating properties sampled in three Canadian boreal biomass burning plumes, one of which passed through a precipitating cloud. This depleted the majority of the plume's BC mass, and the largest and most coated BC-containing particles were found to be preferentially removed, suggesting that nucleation scavenging was likely the dominant mechanism. Calculated single-scattering albedo (SSA) showed little variation, as a large number of non-BC particles were also present in the precipitation-affected plume. The remaining BC cores were smaller than those observed in previous studies of BC in post-precipitation outflow over Asia, possibly due to the thick coating by hydrophilic compounds associated with the Canadian biomass burning particles. This study provides measurements of BC size, mixing state and removal efficiency to constrain model parameterisations of BC wet removal in biomass burning regions, which will help to reduce uncertainty in radiative forcing calculations.

We present measurements of a long-range smoke transport event recorded on 20–21 July 2011 over Halifax, Nova Scotia, Canada, during the Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS-B) campaign. Ground-based Fourier transform spectrometers and photometers detected air masses associated with large wildland fires burning in eastern Manitoba and western Ontario. We investigate a plume with high trace gas amounts but low amounts of particles that preceded and overlapped at the Halifax site with a second plume with high trace gas loadings and significant amounts of particulate material. We show that the first plume experienced a meteorological scavenging event, but the second plume had not been similarly scavenged. This points to the necessity to account carefully for the plume history when considering long-range transport since simultaneous or near-simultaneous times of arrival are not necessarily indicative of either similar trajectories or meteorological history. We investigate the origin of the scavenged plume, and the possibility of an aerosol wet deposition event occurring in the plume ~ 24 h prior to the measurements over Halifax. The region of lofting and scavenging is only monitored on an intermittent basis by the present observing network, and thus we must consider many different pieces of evidence in an effort to understand the early dynamics of the plume. Through this discussion we also demonstrate the value of having many simultaneous remote-sensing measurements in order to understand the physical and chemical behaviour of biomass burning plumes.

Reaction with the hydroxyl radical (OH) is the dominant removal mechanism for virtually all volatile organic compounds (VOCs) in the atmosphere; however, it can be difficult to reconcile measured OH reactivity with known sinks. Unresolved higher molecular weight VOCs contribute to OH sinks, of which monoaromatics are potentially an important sub-class. A method based on comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC-TOFMS) has been developed that extends the degree with which larger VOCs can be individually speciated from whole air samples (WAS). The technique showed excellent sensitivity, resolution and good agreement with an established gas chromatography–flame ionisation (GC-FID) method, for compounds amenable to analysis on both instruments. Measurements have been made of VOCs within the UK east coast marine boundary layer and free troposphere, using samples collected from five aircraft flights in winter 2011. Ten monoaromatic compounds with an array of different alkyl ring substituents have been quantified, in addition to the simple aromatics, benzene, toluene, ethyl benzene and Σm- and p-xylene. These additional compounds were then included in constrained box model simulations of atmospheric chemistry occurring at two UK rural and suburban field sites in order to assess the potential impact of these larger monoaromatics species on OH reactivity; they have been calculated to contribute an additional 2–6% to the overall modelled OH loss rate, providing a maximum additional OH sink of ~0.9 s−1.

The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound (VOC) that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high-performance liquid chromatography mass spectrometry (HPLC-ITMS), high-performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18 and 29% for an initial VOC mixing ratio of 212 and 460 ppbv (parts per billion by volume) respectively; using a VOC:NOx ratio of ~5:1. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high-resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro-functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O:C ratios, where functionalisation rather than fragmentation is mainly observed as a result of the stability of the ring. The SOA species observed can be characterised as semi-volatile to low-volatility oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

A microfluidic lab-on-a-chip derivatisation technique has been developed to measure part per billion (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method is compared with other techniques in a smog chamber experiment. The method uses o-(2, 3, 4, 5, 6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatisation reagent and a microfabricated planar glass micro-reactor comprising an inlet, gas and fluid splitting and combining channels, mixing junctions, and a heated capillary reaction microchannel. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the micro-reactor resulted in a fast and highly efficient derivatisation reaction, generating an effluent stream ready for direct introduction to a gas chromatograph-mass spectrometer (GC-MS). A linear response for GLY was observed over a calibration range 0.7 to 400 ppbV, and for MGLY of 1.2 to 300 ppbV, when derivatised under optimal reaction conditions. The analytical performance shows good accuracy (6.6% for GLY and 7.5% for MGLY), suitable precision (r2) of 0.84, Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS) (r2 = 0.75), solid phase micro extraction (SPME) (r2 = 0.89), and a photochemical chamber box modelling calculation (r2 = 0.79) for GLY measurements. For MGLY measurements, the microfluidic technique showed good agreement with BBCEAS (r2 = 0.87), SPME (r2 = 0.76), and the modeling simulation (r2 = 0.83), FTIR (r2 = 0.72) but displayed a discrepancy with Proton-Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) with r2 value of 0.39.

We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

We describe the design and execution of the BORTAS (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites) experiment, which has the overarching objective of understanding the chemical aging of air masses that contain the emission products from seasonal boreal wildfires and how these air masses subsequently impact downwind atmospheric composition. The central focus of the experiment was a two-week deployment of the UK BAe-146-301 Atmospheric Research Aircraft (ARA) over eastern Canada, based out of Halifax, Nova Scotia. Atmospheric ground-based and sonde measurements over Canada and the Azores associated with the planned July 2010 deployment of the ARA, which was postponed by 12 months due to UK-based flights related to the dispersal of material emitted by the Eyjafjallajökull volcano, went ahead and constituted phase A of the experiment. Phase B of BORTAS in July 2011 involved the same atmospheric measurements, but included the ARA, special satellite observations and a more comprehensive ground-based measurement suite. The high-frequency aircraft data provided a comprehensive chemical snapshot of pyrogenic plumes from wildfires, corresponding to photochemical (and physical) ages ranging from < 1 day to ~<45 sr 10 days, largely by virtue of widespread fires over Northwestern Ontario. Airborne measurements reported a large number of emitted gases including semi-volatile species, some of which have not been been previously reported in pyrogenic plumes, with the corresponding emission ratios agreeing with previous work for common gases. Analysis of the NOy data shows evidence of net ozone production in pyrogenic plumes, controlled by aerosol abundance, which increases as a function of photochemical age. The coordinated ground-based and sonde data provided detailed but spatially limited information that put the aircraft data into context of the longer burning season in the boundary layer. Ground-based measurements of particulate matter smaller than 2.5 μm (PM2.5) over Halifax show that forest fires can on an episodic basis represent a substantial contribution to total surface PM2.5.

Forests fires are a significant source of chemicals to the atmosphere including numerous non-methane organic compounds (NMOCs). We report airborne measurement of hydrocarbons, acetone and methanol from >500 whole air samples collected over Eastern Canada, including interceptions of several different boreal biomass burning plumes. From these and concurrent measurements of carbon monoxide (CO) we derive fire emission ratios for 29 different organic species relative to the emission of CO. These range from 8.9 ± 3.2 ppt ppb−1 CO for methanol to 0.007 ± 0.004 ppt ppb−1 CO for cyclopentane. The ratios are in good to excellent agreement with literature values. Using the GEOS-Chem global 3-D chemical transport model (CTM) we show the influence of biomass burning on the global distributions of benzene, toluene, ethene and propene (species which are controlled for air quality purposes and sometimes used as indicative tracers of anthropogenic activity). Using our observationally derived emission ratios and the GEOS-Chem CTM, we show that biomass burning can be the largest fractional contributor to observed benzene, toluene, ethene and propene levels in many global locations. The widespread biomass burning contribution to atmospheric benzene, a heavily regulated air pollutant, suggests that pragmatic approaches are needed when setting air quality targets as tailpipe and solvent emissions decline in developed countries. We subsequently determine the extent to which the 28 global-status World Meteorological Organisation – Global Atmosphere Watch stations worldwide are influenced by biomass burning sourced benzene, toluene, ethene and propene as compared to their exposure to anthropogenic emissions.

A degradation mechanism for β-caryophyllene has recently been released as part of version 3.2 of the Master Chemical Mechanism (MCM v3.2), describing the gas phase oxidation initiated by reaction with ozone, OH radicals and NO3 radicals. A detailed overview of the construction methodology is given, within the context of reported experimental and theoretical mechanistic appraisals. The performance of the mechanism has been evaluated in chamber simulations in which the gas phase chemistry was coupled to a representation of the gas-to-aerosol partitioning of 280 multi-functional oxidation products. This evaluation exercise considered data from a number of chamber studies of either the ozonolysis of β-caryophyllene, or the photo-oxidation of β-caryophyllene/NOx mixtures, in which detailed product distributions have been reported. This includes the results of a series of photo-oxidation experiments performed in the University of Manchester aerosol chamber, also reported here, in which a comprehensive characterization of the temporal evolution of the organic product distribution in the gas phase was carried out, using Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS), in conjunction with measurements of NOx, O3 and SOA mass loading. The CIR-TOF-MS measurements allowed approximately 45 time-resolved product ion signals to be detected, which were assigned on the basis of the simulated temporal profiles of the more abundant MCM v3.2 species, and their probable fragmentation patterns. The evaluation studies demonstrate that the MCM v3.2 mechanism provides an acceptable description of β-caryophyllene degradation under the chamber conditions considered, with the temporal evolution of the observables identified above generally being recreated within the uncertainty bounds of key parameters within the mechanism. The studies have highlighted a number of areas of uncertainty or discrepancy, where further investigation would be valuable to help interpret the results of chamber studies and improve detailed mechanistic understanding. These particularly include: (i) quantification of the yield and stability of the secondary ozonide (denoted BCSOZ in MCM v3.2), formed from β-caryophyllene ozonolysis, and elucidation of the details of its further oxidation, including whether the products retain the "ozonide" functionality; (ii) investigation of the impact of NOx on the β-caryophyllene ozonolysis mechanism, in particular its effect on the formation of β-caryophyllinic acid (denoted C137CO2H in MCM v3.2), and elucidation of its formation mechanism; (iii) routine independent identification of β-caryophyllinic acid, and its potentially significant isomer β-nocaryophyllonic acid (denoted C131CO2H in MCM v3.2); (iv) more precise quantification of the primary yield of OH (and other radicals) from β-caryophyllene ozonolysis; (v) quantification of the yields of the first-generation hydroxy nitrates (denoted BCANO3, BCBNO3 and BCCNO3 in MCM v3.2) from the OH-initiated chemistry in the presence of NOx; and (vi) further studies in general to improve the identification and quantification of products formed from both ozonolysis and photo-oxidation, including confirmation of the simulated formation of multifunctional species containing hydroperoxide groups, and their important contribution to SOA under NOx-free conditions.

Forests are the dominant source of volatile organic compounds into the atmosphere, with isoprene being the most significant species. The oxidation chemistry of these compounds is a significant driver of local, regional and global atmospheric composition. Observations made over Borneo during the OP3 project in 2008, together with an observationally constrained box model are used to assess our understanding of this oxidation chemistry. In line with previous work in tropical forests, we find that the standard model based on MCM chemistry significantly underestimates the observed OH concentrations. Geometric mean observed to modelled ratios of OH and HO2 in airmasses impacted with isoprene are 5.32−4.43+3.68 and 1.18−0.30+0.30 respectively, with 68 % of the observations being within the specified variation. We implement a variety of mechanistic changes into the model, including epoxide formation and unimolecular decomposition of isoprene peroxy radicals, and assess their impact on the model success. We conclude that none of the current suggestions can simultaneously remove the bias from both OH and HO2 simulations and believe that detailed laboratory studies are now needed to resolve this issue.

Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC), but the processes governing secondary organic aerosol (SOA) formation from isoprene oxidation are only beginning to become understood and selective quantification of the atmospheric particulate burden remains difficult. Organic aerosol above a tropical rainforest located in Danum Valley, Borneo, Malaysia, a high isoprene emission region, was studied during Summer 2008 using Aerosol Mass Spectrometry and offline detailed characterisation using comprehensive two dimensional gas chromatography. Observations indicate that a substantial fraction (up to 15% by mass) of atmospheric sub-micron organic aerosol was observed as methylfuran (MF) after thermal desorption. This observation was associated with the simultaneous measurements of established gas-phase isoprene oxidation products methylvinylketone (MVK) and methacrolein (MACR). Observations of MF were also made during experimental chamber oxidation of isoprene. Positive matrix factorisation of the AMS organic mass spectral time series produced a robust factor which accounts for an average of 23% (0.18 μg m−3), reaching as much as 53% (0.50 μg m−3) of the total oraganic loading, identified by (and highly correlated with) a strong MF signal. Assuming that this factor is generally representative of isoprene SOA, isoprene derived aerosol plays a significant role in the region. Comparisons with measurements from other studies suggest this type of isoprene SOA plays a role in other isoprene dominated environments, albeit with varying significance.

Secondary Organic Aerosol (SOA) affects atmospheric composition, air quality and radiative transfer, however major difficulties are encountered in the development of reliable models for SOA formation. Constraints on processes involved in SOA formation can be obtained by interpreting the speciation and evolution of organics in the gaseous and condensed phase simultaneously. In this study we investigate SOA formation from dark α-pinene ozonolysis with particular emphasis upon the mass distribution of gaseous and particulate organic species. A detailed model for SOA formation is compared with the results from experiments performed in the EUropean PHOtoREactor (EUPHORE) simulation chamber, including on-line gas-phase composition obtained from Chemical-Ionization-Reaction Time-Of-Flight Mass-Spectrometry measurements, and off-line analysis of SOA samples performed by Ion Trap Mass Spectrometry and Liquid Chromatography. The temporal profile of SOA mass concentration is relatively well reproduced by the model. Sensitivity analysis highlights the importance of the choice of vapour pressure estimation method, and the potential influence of condensed phase chemistry. Comparisons of the simulated gaseous- and condensed-phase mass distributions with those observed show a generally good agreement. The simulated speciation has been used to (i) propose a chemical structure for the principal gaseous semi-volatile organic compounds and condensed monomer organic species, (ii) provide evidence for the occurrence of recently suggested radical isomerisation channels not included in the basic model, and (iii) explore the possible contribution of a range of accretion reactions occurring in the condensed phase. We find that oligomer formation through esterification reactions gives the best agreement between the observed and simulated mass spectra.

The oxidation capacity of the highly polluted urban area of Santiago, Chile has been evaluated during a summer measurement campaign carried out from 8–20 March 2005. The hydroxyl (OH) radical budget was evaluated employing a simple quasi-photostationary-state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O3, NO, NO2, j(O1D), j(NO2), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used to estimate production rates and total free radical budgets, including OH, HO2 and RO2. Besides the above parameters, the MCM model has been constrained by the measured CO and volatile organic compounds (VOCs) including alkanes and aromatics. Both models simulate the same OH concentration during daytime indicating that the primary OH sources and sinks included in the simple PSS model predominate. Mixing ratios of the main OH radical precursors were found to be in the range 0.8–7 ppbv (HONO), 0.9–11 ppbv (HCHO) and 0–125 ppbv (O3). The alkenes average mixing ratio was ~58 ppbC accounting for ~12% of the total identified non-methane hydrocarbons (NMHCs). During the daytime (08:00 h–19:00 h), HONO photolysis was shown to be the most important primary OH radical source comprising alone ~55% of the total initial production rate, followed by alkene ozonolysis (~24%) and photolysis of HCHO (~16%) and O3 (~5%). The calculated average and maximum daytime OH production rates from HONO photolysis was 1.7 ppbv h−1 and 3.1 ppbv h−1, respectively. Based on the experimental results a strong photochemical daytime source of HONO is proposed. A detailed analysis of the sources of OH radical precursors has also been carried out.

A series of photooxidation experiments were conducted in an atmospheric simulation chamber in order to investigate the oxidation mechanism and secondary organic aerosol (SOA) formation potential of the model anthropogenic gas phase precursor, 1,3,5-trimethylbenzene. Alongside specific aerosol measurements, comprehensive gas phase measurements, primarily by Chemical Ionisation Reaction Time-of-Flight Mass Spectrometry (CIR-TOF-MS), were carried out to provide detailed insight into the composition and behaviour of the organic components of the gas phase matrix during SOA formation. An array of gas phase organic compounds was measured during the oxidation process, including several previously unmeasured primary bicyclic compounds possessing various functional groups. Analysis of results obtained during this study implies that these peroxide bicyclic species along with a series of ring opening products and organic acids contribute to SOA growth. The effect of varying the VOC/NOx ratio on SOA formation was explored, as was the effect of acid seeding. It was found that low NOx conditions favour more rapid aerosol formation and a higher aerosol yield, a result that implies a role for organic peroxides in the nucleation process and SOA growth.

Several zero-dimensional box-models with different levels of chemical complexity, based on the Master Chemical Mechanism (MCM), have been used to study the chemistry of OH and HO2 in a coastal environment in the Northern Hemisphere. The models were constrained to and compared with measurements made during the NAMBLEX campaign (Mace Head, Ireland) in summer 2002. The base models, which were constrained to measured CO, CH4 and NMHCs, were able to reproduce [OH] within 25%, but overestimated [HO2] by about a factor of 2. Agreement was improved when the models were constrained to oxygenated compounds (acetaldehyde, methanol and acetone), highlighting their importance for the radical budget. When the models were constrained to measured halogen monoxides (IO, BrO) and used a more detailed, measurements-based, treatment to describe the heterogeneous uptake, modelled [OH] increased by up to 15% and [HO2] decreased by up to 30%. The actual impact of halogen monoxides on the modelled concentrations of HOx was dependant on the uptake coefficients used for HOI, HOBr and HO2. Better agreement, within the combined uncertainties of the measurements and of the model, was achieved when using high uptake coefficients for HO2 and HOI (γHO2=1, γHOI=0.6). A rate of production and destruction analysis of the models allowed a detailed study of OH and HO2 chemistry under the conditions encountered during NAMBLEX, showing the importance of oxygenates and of XO (where X=I, Br) as co-reactants for OH and HO2 and of HOX photolysis as a source for OH.

Peroxy radicals (HO2+Σ RO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h−1 and 1.11±0.47 ppbv h−1, respectively). The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state.

Peroxy radical (HO2+ΣRO2) measurements, using the PEroxy Radical Chemical Amplification (PERCA) technique at the North Atlantic Marine Boundary Layer EXperiment (NAMBLEX) at Mace Head in summer 2002, are presented and put into the context of marine, boundary-layer chemistry. A suite of other chemical parameters (NO, NO2, NO3, CO, CH4, O3, VOCs, peroxides), photolysis frequencies and meteorological measurements, are used to present a detailed analysis of the role of peroxy radicals in tropospheric oxidation cycles and ozone formation. Under the range of conditions encountered the peroxy radical daily maxima varied from 10 to 40 pptv. The diurnal cycles showed an asymmetric shape typically shifted to the afternoon. Using a box model based on the master chemical mechanism the average model measurement agreement was 2.5 across the campaign. The addition of halogen oxides to the model increases the level of model/measurement agreement, apparently by respeciation of HOx. A good correlation exists between j(HCHO).[HCHO] and the peroxy radicals indicative of the importance of HCHO in the remote atmosphere as a HOx source, particularly in the afternoon. The peroxy radicals showed a strong dependence on [NO2] with a break point at 0.1 ppbv, where the radicals increased concomitantly with the reactive VOC loading, this is a lower value than seen at representative urban campaigns. The HO2/(HO2+ΣRO2) ratios are dependent on [NOx] ranging between 0.2 and 0.6, with the ratio increasing linearly with NOx. Significant night-time levels of peroxy radicals were measured up to 25 pptv. The contribution of ozone-alkenes and NO3-alkene chemistry to night-time peroxy radical production was shown to be on average 59 and 41%. The campaign mean net ozone production rate was 0.11±0.3 ppbv h-1. The ozone production rate was strongly dependent on [NO] having linear sensitivity (dln(P(O3))/dln(NO)=1.0). The results imply that the N(O3) (the in-situ net photochemical rate of ozone production/destruction) will be strongly sensitive in the marine boundary layer to small changes in [NO] which has ramifications for changing NOx loadings in the European continental boundary layer.

The North Atlantic Marine Boundary Layer Experiment (NAMBLEX), involving over 50 scientists from 12 institutions, took place at Mace Head, Ireland (53.32° N, 9.90° W), between 23 July and 4 September 2002. A wide range of state-of-the-art instrumentation enabled detailed measurements of the boundary layer structure and atmospheric composition in the gas and aerosol phase to be made, providing one of the most comprehensive in situ studies of the marine boundary layer to date. This overview paper describes the aims of the NAMBLEX project in the context of previous field campaigns in the Marine Boundary Layer (MBL), the overall layout of the site, a summary of the instrumentation deployed, the temporal coverage of the measurement data, and the numerical models used to interpret the field data. Measurements of some trace species were made for the first time during the campaign, which was characterised by predominantly clean air of marine origin, but more polluted air with higher levels of NOx originating from continental regions was also experienced. This paper provides a summary of the meteorological measurements and Planetary Boundary Layer (PBL) structure measurements, presents time series of some of the longer-lived trace species (O3, CO, H2, DMS, CH4, NMHC, NOx, NOy, PAN) and summarises measurements of other species that are described in more detail in other papers within this special issue, namely oxygenated VOCs, HCHO, peroxides, organo-halogenated species, a range of shorter lived halogen species (I2, OIO, IO, BrO), NO3 radicals, photolysis frequencies, the free radicals OH, HO2 and (HO2+Σ RO2), as well as a summary of the aerosol measurements. NAMBLEX was supported by measurements made in the vicinity of Mace Head using the NERC Dornier-228 aircraft. Using ECMWF wind-fields, calculations were made of the air-mass trajectories arriving at Mace Head during NAMBLEX, and were analysed together with both meteorological and trace-gas measurements. In this paper a chemical climatology for the duration of the campaign is presented to interpret the distribution of air-mass origins and emission sources, and to provide a convenient framework of air-mass classification that is used by other papers in this issue for the interpretation of observed variability in levels of trace gases and aerosols.

Renewal of ultrafine aerosols in the marine boundary layer may lead to repopulation of the marine distribution and ultimately determine the concentration of cloud condensation nuclei (CCN). Thus the formation of nanometre-scale particles can lead to enhanced scattering of incoming radiation and a net cooling of the atmosphere. The recent demonstration of the chamber formation of new particles from the photolytic production of condensable iodine-containing compounds from diiodomethane (CH2I2), (O'Dowd et al., 2002; Kolb, 2002; Jimenez et al., 2003a; Burkholder and Ravishankara, 2003), provides an additional mechanism to the gas-to-particle conversion of sulphuric acid formed in the photo-oxidation of dimethylsulphide for marine aerosol repopulation. CH2I2 is emitted from seaweeds (Carpenter et al., 1999, 2000) and has been suggested as an initiator of particle formation. We demonstrate here for the first time that ultrafine iodine-containing particles are produced by intertidal macroalgae exposed to ambient levels of ozone. The particle composition is very similar both to those formed in the chamber photo-oxidation of diiodomethane and in the oxidation of molecular iodine by ozone. The particles formed in all three systems are similarly aspherical. When small, those formed in the molecular iodine system swell only moderately when exposed to increased humidity environments, and swell progressively less with increasing size; this behaviour occurs whether they are formed in dry or humid environments, in contrast to those in the CH2I2 system. Direct coastal boundary layer observations of molecular iodine, ultrafine particle production and iodocarbons are reported. Using a newly measured molecular iodine photolysis rate, it is shown that, if atomic iodine is involved in the observed particle bursts, it is of the order of at least 1000 times more likely to result from molecular iodine photolysis than diiodomethane photolysis. A hypothesis for molecular iodine release from intertidal macroalgae is presented and the potential importance of macroalgal iodine particles in their contribution to CCN and global radiative forcing are discussed.