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The impact of heterogeneous uptake of HO2 on aerosol surfaces on radical concentrations and the O3 production regime in Beijing in summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO campaign in Beijing, in summer 2017, as a function of measured aerosol soluble copper concentration, [Cu2+]eff, aerosol liquid water content, [ALWC], and particulate matter concentration, [PM]. An average γHO2 across the entire campaign of 0.070±0.035 was calculated, with values ranging from 0.002 to 0.15, and found to be significantly lower than the value of γHO2=0.2, commonly used in modelling studies. Using the calculated γHO2 values for the summer AIRPRO campaign, OH, HO2 and RO2 radical concentrations were modelled using a box model incorporating the Master Chemical Mechanism (v3.3.1), with and without the addition of γHO2, and compared to the measured radical concentrations. The rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the summer Beijing campaign, with HO2 uptake contributing % to the total loss of HO2 on average. This result for Beijing summertime would suggest that under most conditions encountered, HO2 uptake onto aerosol surfaces is not important to consider when investigating increasing O3 production with decreasing [PM] across the North China Plain. At low [NO], however, i.e. ppb, which was often encountered in the afternoons, up to 29 % of modelled HO2 loss was due to HO2 uptake on aerosols when calculated γHO2 was included, even with the much lower γHO2 values compared to γHO2= 0.2, a result which agrees with the aerosol-inhibited O3 regime recently proposed by Ivatt et al. (2022). As such it can be concluded that in cleaner environments, away from polluted urban centres where HO2 loss chemistry is not dominated by NO but where aerosol surface area is high still, changes in PM concentration and hence aerosol surface area could still have a significant effect on both overall HO2 concentration and the O3 production regime. Using modelled radical concentrations, the absolute O3 sensitivity to NOx and volatile organic compounds (VOCs) showed that, on average across the summer AIRPRO campaign, the O3 production regime remained VOC-limited, with the exception of a few days in the afternoon when the NO mixing ratio dropped low enough for the O3 regime to shift towards being NOx-limited. The O3 sensitivity to VOCs, the dominant regime during the summer AIRPRO campaign, was observed to decrease and shift towards a NOx-sensitive regime both when NO mixing ratio decreased and with the addition of aerosol uptake. This suggests that if [NOx] continues to decrease in the future, ozone reduction policies focussing solely on NOx reductions may not be as efficient as expected if [PM] and, hence, HO2 uptake to aerosol surfaces continue to decrease. The addition of aerosol uptake into the model, for both the γHO2 calculated from measured data and when using a fixed value of γHO2=0.2, did not have a significant effect on the overall O3 production regime across the campaign. While not important for this campaign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.

The photostationary state (PSS) equilibrium between NO and NO2 is reached within minutes in the atmosphere and can be described by the PSS parameter, φ. Deviations from expected values of φ have previously been used to infer missing oxidants in diverse locations, from highly polluted regions to the extremely clean conditions observed in the remote marine boundary layer (MBL), and have been interpreted as missing understanding of fundamental photochemistry. Here, contrary to these previous observations, we observe good agreement between PSS-derived NO2 ([NO2]PSS ext.), calculated from measured NO, O3, and jNO2 and photochemical box model predictions of peroxy radicals (RO2 and HO2), and observed NO2 ([NO2]Obs.) in extremely clean air containing low levels of CO ( ppbV) and VOCs (volatile organic compounds). However, in clean air containing small amounts of aged pollution (CO > 100 ppbV), we observed higher levels of NO2 than inferred from the PSS, with [NO2]Obs. / [NO2]PSS ext. of 1.12–1.68 (25th–75th percentile), implying underestimation of RO2 radicals by 18.5–104 pptV. Potential NO2 measurement artefacts have to be carefully considered when comparing PSS-derived NO2 to observed NO2, but we show that the NO2 artefact required to explain the deviation would have to be ∼ 4 times greater than the maximum calculated from known interferences. If the additional RO2 radicals inferred from the PSS convert NO to NO2 with a reaction rate equivalent to that of methyl peroxy radicals (CH3O2), then the calculated net ozone production rate (NOPR, ppbV h−1) including these additional oxidants is similar to the average change in O3 observed, within estimated uncertainties, once halogen oxide chemistry is accounted for. This implies that such additional peroxy radicals cannot be excluded as a missing oxidant in clean marine air containing aged pollution and that modelled RO2 concentrations are significantly underestimated under these conditions.

This study explores our ability to simulate the atmospheric chemistry stemming from isoprene emissions in pristine and polluted regions of the Amazon basin. We confront two atmospheric chemistry models – a global, Eulerian chemistry-climate model (UM-UKCA) and a trajectory-based Lagrangian model (CiTTyCAT) – with recent airborne measurements of atmospheric composition above the Amazon made during the SAMBBA campaign of 2012. The simulations with the two models prove relatively insensitive to the chemical mechanism employed; we explore one based on the Mainz Isoprene Mechanism, and an updated one that includes changes to the chemistry of first generation isoprene nitrates (ISON) and the regeneration of hydroxyl radicals via the formation of hydroperoxy-aldehydes (HPALDS) from hydroperoxy radicals (ISO2). In the Lagrangian model, the impact of increasing the spatial resolution of trace gas emissions employed from 3.75° × 2.5° to 0.1° × 0.1° varies from one flight to another, and from one chemical species to another. What consistently proves highly influential on our simulations, however, is the model framework itself – how the treatment of transport, and consequently mixing, differs between the two models. The lack of explicit mixing in the Lagrangian model yields variability in atmospheric composition more reminiscent of that exhibited by the measurements. In contrast, the combination of explicit (and implicit) mixing in the Eulerian model removes much of this variability but yields better agreement with the measurements overall. We therefore explore a simple treatment of mixing in the Lagrangian model that, drawing on output from the Eulerian model, offers a compromise between the two models. We use this Lagrangian/Eulerian combination, in addition to the separate Eulerian and Lagrangian models, to simulate ozone at a site in the boundary layer downwind of Manaus, Brazil. The Lagrangian/Eulerian combination predicts a value for an AOT40-like accumulated exposure metric of around 1000 ppbv h, compared to just 20 ppbv h with the Eulerian model. The model framework therefore has considerable bearing on our understanding of the frequency at which, and the duration for which, the rainforest is exposed to damaging ground-level ozone concentrations.

Concern over mental health and well-being is acute, particularly following stressful pandemic times, marked by social disconnection and loneliness. At risk is one’s sense of social belonging, a fundamental human need critical to human survival. We echo Holt-Lunstad’s (2022) call for prioritizing social factors when addressing public health during and in recovery from the pandemic, arguing that workplace supervisors and leaders can play an important role. As a workplace context, the military is especially focused on social relationships as service member employees face extreme health and safety challenges, not unlike other high risk first responder occupations. This study evaluated the efficacy of an evidence-based supportive-leadership training intervention targeting active-duty U.S. Army platoon leaders. The goal of the training was to increase service members’ social connectedness through leaders providing social support for psychological health and resilience, thereby decreasing loneliness. One hundred-four platoon leaders completed the 90-minute training that consisted of both in-person and computer-based components. Intervention effects were tested using an intent-to-treat approach and revealed a significant effect, whereby loneliness for service members who were randomized to the intervention group (N=118) was significantly reduced compared to loneliness reports for service members in the control group (N=158). Service members with higher baseline loneliness were more strongly and positively impacted by the supervisor training, reporting higher levels of emotional support and stigma-reduction behaviors from their leaders at 3 months post-baseline. In sum, these results suggest how workplaces and their leaders play a critical role in a national strategy to address Americans’ well-being.

Challenging behavior exhibited by young children with neurodevelopmental disabilities is known to negatively affect their optimal development and families’ quality of life. Although some support exists for English-speaking parents of children with autism who live in high-resource countries, it is scarce for others. Such disparity may also be heightened during the coronavirus disease 2019 (COVID-19) pandemic with its various societal restrictions. To mitigate the treatment gap, we developed and adapted a series of online training modules on behavioral principles and examined its effectiveness with 88 South Korean parents using a randomized controlled trial. We found significant interaction effects on increasing parents’ knowledge of behavioral principles, increasing positive parenting practices, and decreasing parental stress. Qualitative social validity data also indicated that parents were highly satisfied with the goals, procedures, and outcomes and that the program positively affected their parenting styles.

Challenging behaviors exhibited by young children negatively affect development and may also prevent children from receiving appropriate education. These behaviors may also hinder positive family interactions and have a significant impact on parents and other family members. Although various parent training approaches exist to increase parents' capacity to address these challenging behaviors, many parents are reportedly not able to access training due to time and resource constraints. To address inequitable dissemination of information, we developed and piloted the use of the Challenging Behavior Online Modules with 10 parents of children with disabilities. In particular, we examined the feasibility of the Challenging Behavior Online Modules for increasing parents' knowledge and use of positive parenting practices with their young children. Parents reported satisfaction with the contents and delivery method of the intervention. Implications and directions for future research are also suggested.

Particulate nitrate ( pNO 3 − ) has long been considered a permanent sink for NO x (NO and NO 2 ), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of pNO 3 − can recycle HONO and NO x back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in “renoxification” photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of pNO 3 − , thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O 3 in both polluted and clean environments.

Flux measurements of nitrogen oxides (NOx) were made over London using airborne eddy covariance from a low-flying aircraft. Seven low-altitude flights were conducted over Greater London, performing multiple overpasses across the city during eight days in July 2014. NOx fluxes across the Greater London region (GLR) exhibited high heterogeneity and strong diurnal variability, with central areas responsible for the highest emission rates (20–30 mg m−2 h−1). Other high-emission areas included the M25 orbital motorway. The complexity of London's emission characteristics makes it challenging to pinpoint single emissions sources definitively using airborne measurements. Multiple sources, including road transport and residential, commercial and industrial combustion sources, are all likely to contribute to measured fluxes. Measured flux estimates were compared to scaled National Atmospheric Emissions Inventory (NAEI) estimates, accounting for monthly, daily and hourly variability. Significant differences were found between the flux-driven emissions and the NAEI estimates across Greater London, with measured values up to 2 times higher in Central London than those predicted by the inventory. To overcome the limitations of using the national inventory to contextualise measured fluxes, we used physics-guided flux data fusion to train environmental response functions (ERFs) between measured flux and environmental drivers (meteorological and surface). The aim was to generate time-of-day emission surfaces using calculated ERF relationships for the entire GLR; 98 % spatial coverage was achieved across the GLR at 400 m2 spatial resolution. All flight leg projections showed substantial heterogeneity across the domain, with high emissions emanating from Central London and major road infrastructure. The diurnal emission structure of the GLR was also investigated, through ERF, with the morning rush hour distinguished from lower emissions during the early afternoon. Overall, the integration of airborne fluxes with an ERF-driven strategy enabled the first independent generation of surface NOx emissions, at high resolution using an eddy-covariance approach, for an entire city region.

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.

Fluxes of nitrogen oxides (NOx=NO+NO2) and carbon dioxide (CO2) were measured using eddy covariance at the British Telecommunications (BT) Tower in central London during the coronavirus pandemic. Comparing fluxes to those measured in 2017 prior to the pandemic restrictions and the introduction of the Ultra-Low Emissions Zone (ULEZ) highlighted a 73 % reduction in NOx emissions between the two periods but only a 20 % reduction in CO2 emissions and a 32 % reduction in traffic load. Use of a footprint model and the London Atmospheric Emissions Inventory (LAEI) identified transport and heat and power generation to be the two dominant sources of NOx and CO2 but with significantly different relative contributions for each species. Application of external constraints on NOx and CO2 emissions allowed the reductions in the different sources to be untangled, identifying that transport NOx emissions had reduced by >73 % since 2017. This was attributed in part to the success of air quality policy in central London but crucially due to the substantial reduction in congestion that resulted from pandemic-reduced mobility. Spatial mapping of the fluxes suggests that central London was dominated by point source heat and power generation emissions during the period of reduced mobility. This will have important implications on future air quality policy for NO2 which, until now, has been primarily focused on the emissions from diesel exhausts.

Air pollution in urban environments has been shown to have a negative impact on air quality and human health, particularly in megacities. Over recent decades, Delhi, India, has suffered high atmospheric pollution, with significant particulate matter (PM) concentrations as a result of anthropogenic activities. Organic aerosols (OAs) are composed of thousands of different chemical species and are one of the main constituents of submicron particles. However, quantitative knowledge of OA composition, their sources and their processes in urban environments is still limited. This is important particularly in India, as Delhi is a massive, inhomogeneous conurbation, where we would expect the apportionment and concentrations to vary depending on where in Delhi the measurements/source apportionment is performed, indicating the need for multisite measurements. This study presents the first multisite analysis carried out in India over different seasons, with a focus on identifying OA sources. The measurements were taken during 2018 at two sites in Delhi, India. One site was located at the India Meteorological Department, New Delhi (ND). The other site was located at the Indira Gandhi Delhi Technical University for Women, Old Delhi (OD). Non-refractory submicron aerosol (NR-PM1) concentrations (ammonium, nitrate, sulfate, chloride and organic aerosols) of four aerosol mass spectrometers were analysed. Collocated measurements of volatile organic compounds, black carbon, NOx and CO were performed. Positive matrix factorisation (PMF) analysis was performed to separate the organic fraction, identifying a number of conventional factors: hydrocarbon-like OAs (HOAs) related to traffic emissions, biomass burning OAs (BBOAs), cooking OAs (COAs) and secondary OAs (SOAs). A composition-based estimate of PM1 is defined by combining black carbon (BC) and NR-PM1 (C-PM1= BC + NR-PM1). No significant difference was observed in C-PM1 concentrations between sites, OD (142 ± 117 µg m−3) compared to ND (123 ± 71 µg m3), from post-monsoon measurements. A wider variability was observed between seasons, where pre-monsoon and monsoon showed C-PM1 concentrations lower than 60 µg m−3. A seasonal variation in C-PM1 composition was observed; SO42- showed a high contribution over pre-monsoon and monsoon seasons, while NO3- and Cl− had a higher contribution in winter and post-monsoon. The main primary aerosol source was from traffic, which is consistent with the PMF analysis and Aethalometer model analysis. Thus, in order to reduce PM1 concentrations in Delhi through local emission controls, traffic emission control offers the greatest opportunity. PMF–aerosol mass spectrometer (AMS) mass spectra will help to improve future aerosol source apportionment studies. The information generated in this study increases our understanding of PM1 composition and OA sources in Delhi, India. Furthermore, the scientific findings provide significant information to strengthen legislation that aims to improve air quality in India.

Volatile organic compounds (VOCs) are important precursors to the formation of ozone (O3) and secondary organic aero-sols (SOA) and can also have direct human health impacts. Generally, given the range and number of VOC species, their emissions are poorly characterised. The VOC levels in Beijing during two campaigns (APHH) were investigated using a dispersion model (NAME), and a chemical box model (AtChem2) in order to understand how chemistry and transport affect the VOC concentrations in Beijing. Emissions of VOCs in Beijing and contributions from outside Beijing were modelled using the NAME dispersion model combined with the emission inventories and were used to initialize the AtChem2 box model. The modelled concentrations of VOCs from the NAME-AtChem2 combination were then compared to the output of a chemical transport model (GEOS-Chem). The results from the emission inventories and the NAME air mass pathways suggest that industrial sources to the south of Beijing and within Beijing both in summer and winter are very important in con-trolling the VOC levels in Beijing. A number of scenarios with different nitrogen oxides to ozone ratios (NOx / O3) and hydroxyl (OH) levels were simulated to determine the changes in VOC levels. In Beijing over 80 % of VOC are emitted locally during winter, while during summer about 35 % of VOC concentrations (greater for some individual species) are transported into Beijing from the surrounding regions. Most winter scenarios are in good agreement with daily GEOS-Chem simulations, with the best agreements seen for the modelled concentrations of ethanol, benzene and propane with correlation coefficients of 0.67, 0.63 and 0.64 respectively. Furthermore, the production of formaldehyde within 24 hours air travel from Beijing was investigated, and it was determined that 90 % of formaldehyde in the winter and 83 % in the summer in Beijing is secondary, produced from oxidation of non-methane volatile organic compounds (NMVOCs). The benzene / CO and toluene / CO ratios during the campaign is very similar to the ratio derived from literature for 2014 in Beijing, however more data are needed to enable investigation of more species over longer timeframes to determine whether this ratio can be applied to predicting VOCs in Beijing. The results suggest that VOC concentrations in Beijing are driven predominantly by sources within Beijing and by local atmospheric chemistry during the winter, and by a combination of transport and chemistry during the summer. Moreover, the relationship of the NOx / VOC and O3 during winter and summer shows the need for season-specific policy measures.

Atmospheric nitrogen oxides (NO + NO 2 = NO x ) have been measured at the Cape Verde Atmospheric Observatory (CVAO) in the tropical Atlantic (16 ∘ 51 ′ N, 24 ∘ 52 ′ W) since October 2006. These measurements represent a unique time series of NO x in the background remote troposphere. Nitrogen dioxide (NO 2 ) is measured via photolytic conversion to nitric oxide (NO) by ultraviolet light-emitting diode arrays followed by chemiluminescence detection. Since the measurements began, a blue light converter (BLC) has been used for NO 2 photolysis, with a maximum spectral output of 395 nm from 2006 to 2015 and of 385 nm from 2015 onwards. The original BLC used was constructed with a Teflon-like material and appeared to cause an overestimation of NO 2 when illuminated. To avoid such interferences, a new additional photolytic converter (PLC) with a quartz photolysis cell (maximum spectral output also 385 nm) was implemented in March 2017. Once corrections are made for the NO 2 artefact from the original BLC, the two NO 2 converters are shown to give comparable NO 2 mixing ratios (BLC = 0.99 × PLC + 0.7 ppt, linear least-squares regression), giving confidence in the quantitative measurement of NO x at very low levels. Data analysis methods for the NO x measurements made at CVAO have been developed and applied to the entire time series to produce an internally consistent and high-quality long-term data set. NO has a clear diurnal pattern with a maximum mixing ratio of 2–10 ppt during the day depending on the season and ∼ 0 ppt during the night. NO 2 shows a fairly flat diurnal signal, although a small increase in daytime NO x is evident in some months. Monthly average mixing ratios of NO 2 vary between 5 and 30 ppt depending on the season. Clear seasonal trends in NO and NO 2 levels can be observed with a maximum in autumn and winter and a minimum in spring and summer.

Chronic disease management requires achievement of critical individualised targets to mitigate again long-term morbidity and premature mortality associated with diabetes mellitus. The responsibility for this lies with both the patient and health care professionals. Care plans have been introduced in many healthcare settings to provide a patient-centred approach that is both evidence-based to deliver positive clinical outcomes and allow individualised care. The Alphabet strategy (AS) for diabetes is based around such a care plan and has been evidenced to deliver high clinical standards in both well-resourced and under-resourced settings. Additional patient educational resources include special care plans for those people with diabetes undertaking fasting during Ramadan, Preconception Care, Prevention and Remission of Diabetes. The Strategy and Care Plan has facilitated evidence-based, cost-efficient multifactorial intervention with an improvement in the National Diabetes Audit targets for blood pressure, cholesterol levels and glycated haemoglobin. Many of these attainments were of the standard seen in intensively treated cohorts of key randomized controlled trials in diabetes care such as the Steno-2 and United Kingdom Prospective Diabetes Study. This is despite working in a relatively under-resourced service within the United Kingdom National Health Service. The AS for diabetes care is a useful tool to consider for planning care, education of people with diabetes and healthcare professional. During the time of the coronavirus disease 2019 pandemic the risk factors for the increased mortality observed have to be addressed aggressively. The AS has the potential to help with this aspiration.

Measurements of OH, HO2, complex RO2 (alkene- and aromatic-related RO2) and total RO2 radicals taken during the integrated Study of AIR Pollution PROcesses in Beijing (AIRPRO) campaign in central Beijing in the summer of 2017, alongside observations of OH reactivity, are presented. The concentrations of radicals were elevated, with OH reaching up to 2.8×107moleculecm-3, HO2 peaking at 1×109moleculecm-3 and the total RO2 concentration reaching 5.5×109moleculecm-3. OH reactivity (k(OH)) peaked at 89 s−1 during the night, with a minimum during the afternoon of ≈22s-1 on average. An experimental budget analysis, in which the rates of production and destruction of the radicals are compared, highlighted that although the sources and sinks of OH were balanced under high NO concentrations, the OH sinks exceeded the known sources (by 15 ppbv h−1) under the very low NO conditions (

Tropospheric ozone (O3) negatively impacts human health and is also a greenhouse gas. It is formed photochemically by reactions of nitrogen oxides (NOx) and volatile organic compounds (VOCs), of which wildfires are an important source. This study presents data from research flights sampling wildfires in West and Central African savannah regions, both close to the fires and after the emissions had been transported several days over the tropical North Atlantic Ocean. Emission factors (EFs) in g kg−1 for NOx (as NO), six VOCs and formaldehyde were calculated from enhancement to mole fractions in data taken close to the fires. For NOx, the emission factor was calculated as 2.05 ± 0.43 g kg−1 for Senegal and 1.20 ± 0.28 g kg−1 for Uganda, both higher than the average value of 1.13 ± 0.6 g kg−1 for previous studies of African savannah regions. For most VOCs (except acetylene), EFs in Uganda were lower by factors of 20–50% compared to Senegal, with almost all the values below those in the literature. O3 enhancement in the fire plumes was investigated by examining the ΔO3/ΔCO enhancement ratio, with values ranging from 0.07–0.14 close to the fires up to 0.25 for measurements taken over the Atlantic Ocean up to 200 hours downwind. In addition, measurements of O3 and its precursors were compared to the output of a global chemistry transport model (GEOS-CF) for the flights over the Atlantic Ocean. Normalised mean bias (NMB) comparison between the measured and modelled data was good outside of the fire plumes, with CO showing a model under-prediction of 4.6% and O3 a slight over-prediction of 0.7% (both within the standard deviation of the data). For NOx the agreement was poorer, with an under-prediction of 9.9% across all flights. Inside the fire plumes the agreement between modelled and measured values is worse, with the model being biased significantly lower for all three species. In total across all flights, there was an under-prediction of 29.4%, 16.5% and 37.5% for CO, O3 and NOx respectively. Finally, the measured ΔO3/ΔCO enhancement ratios were compared to those in the model for the equivalent flight data, with the model showing a lower value of 0.17 ± 0.03 compared to an observed value of 0.29 ± 0.05. The results detailed here show that the O3 burden to the North Atlantic Ocean from African wildfires may be underestimated and that further study is required to better study the O3 precursor emissions and chemistry.

Organic aerosols, a major constituent of fine particulate mass in megacities, can be directly emitted or formed from secondary processing of biogenic and anthropogenic volatile organic compound emissions. The complexity of volatile organic compound emission sources, speciation and oxidation pathways leads to uncertainties in the key sources and chemistry leading to formation of organic aerosol in urban areas. Historically, online measurements of organic aerosol composition have been unable to resolve specific markers of volatile organic compound oxidation, while offline analysis of markers focus on a small proportion of organic aerosol and lack the time resolution to carry out detailed statistical analysis required to study the dynamic changes in aerosol sources and chemistry. Here we use data collected as part of the joint UK-China Air Pollution and Human Health (APHH-Beijing) collaboration during a field campaign in urban Beijing in the summer of 2017 alongside laboratory measurements of secondary organic aerosol from oxidation of key aromatic precursors (1,3,5-Trimethyl benzene, 1,2,4-Trimethyl benzene, propyl benzene, isopropyl benzene and 1-methyl naphthalene) to study the anthropogenic and biogenic contributions to organic aerosol. For the first time in Beijing, this study applies positive matrix factorisation to online measurements of organic aerosol composition from a time-of-flight iodide chemical ionisation mass spectrometer fitted with a filter inlet for gases and aerosols (FIGAERO-ToF-I-CIMS). This approach identifies the real-Time variations in sources and oxidation processes influencing aerosol composition at a near-molecular level. We identify eight factors with distinct temporal variability, highlighting episodic differences in OA composition attributed to regional influences and in situ formation. These have average carbon numbers ranging from C5-C9 and can be associated with oxidation of anthropogenic aromatic hydrocarbons alongside biogenic emissions of isoprene, α-pinene and sesquiterpenes. This journal is

We report changes in surface nitrogen dioxide ( NO2 ) across the UK during the COVID-19 pandemic when large and rapid emission reductions accompanied a nationwide lockdown (23 March–31 May 2020, inclusively), and compare them with values from an equivalent period over the previous 5 years. Data are from the Automatic Urban and Rural Network (AURN), which forms the basis of checking nationwide compliance with ambient air quality directives. We calculate that NO2 reduced by 42 %±9.8 % on average across all 126 urban AURN sites, with a slightly larger ( 48 %±9.5 % ) reduction at sites close to the roadside (urban traffic). We also find that ozone ( O3 ) increased by 11 % on average across the urban background network during the lockdown period. Total oxidant levels ( O x = NO 2 + O 3 ) increased only slightly on average ( 3.2 %±0.2 % ), suggesting the majority of this change can be attributed to photochemical repartitioning due to the reduction in NOx . Generally, we find larger, positive Ox changes in southern UK cities, which we attribute to increased UV radiation and temperature in 2020 compared to previous years. The net effect of the NO2 and O3 changes is a sharp decrease in exceedances of the NO2 air quality objective limit for the UK, with only one exceedance in London in 2020 up until the end of May. Concurrent increases in O3 exceedances in London emphasize the potential for O3 to become an air pollutant of concern as NOx emissions are reduced in the next 10–20 years.

During March–June 2017 emissions of nitrogen oxides were measured via eddy covariance at the British Telecom Tower in central London, UK. Through the use of a footprint model the expected emissions were simulated from the spatially resolved National Atmospheric Emissions Inventory for 2017 and compared with the measured emissions. These simulated emissions were shown to underestimate measured emissions during the daytime by a factor of 1.48, but they agreed well overnight. Furthermore, underestimations were spatially mapped, and the areas around the measurement site responsible for differences in measured and simulated emissions were inferred. It was observed that areas of higher traffic, such as major roads near national rail stations, showed the greatest underestimation by the simulated emissions. These discrepancies are partially attributed to a combination of the inventory not fully capturing traffic conditions in central London and both the spatial and temporal resolution of the inventory not fully describing the high heterogeneity of the urban centre. Understanding of this underestimation may be further improved with longer measurement time series to better understand temporal variation and improved temporal scaling factors to better simulate sub-annual emissions.

Nitrogen oxides (NOx=NO+NO2) are critical intermediates in atmospheric chemistry and air pollution. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3 and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also atmospheric pollutants, and NO2 is commonly included in air quality objectives and regulations. NOx levels also affect the production of the nitrate component of secondary aerosol particles and other pollutants, such as the lachrymator peroxyacetyl nitrate (PAN). The accurate measurement of NO and NO2 is therefore crucial for air quality monitoring and understanding atmospheric composition. The most commonly used approach for the measurement of NO is the chemiluminescent detection of electronically excited NO2 (NO2∗) formed from the NO + O3 reaction within the NOx analyser. Alkenes, ubiquitous in the atmosphere from biogenic and anthropogenic sources, also react with ozone to produce chemiluminescence and thus may contribute to the measured NOx signal. Their ozonolysis reaction may also be sufficiently rapid that their abundance in conventional instrument background cycles, which also utilises the reaction with ozone, differs from that in the measurement cycle such that the background subtraction is incomplete, and an interference effect results. This interference has been noted previously, and indeed, the effect has been used to measure both alkenes and ozone in the atmosphere. Here we report the results of a systematic investigation of the response of a selection of commercial NOx monitors to a series of alkenes. These NOx monitors range from systems used for routine air quality monitoring to atmospheric research instrumentation. The species-investigated range was from short-chain alkenes, such as ethene, to the biogenic monoterpenes. Experiments were performed in the European PHOtoREactor (EUPHORE) to ensure common calibration and samples for the monitors and to unequivocally confirm the alkene levels present (via Fourier transform infrared spectroscopy – FTIR). The instrument interference responses ranged from negligible levels up to 11 %, depending upon the alkene present and conditions used (e.g. the presence of co-reactants and differing humidity). Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high VOC, low NOx environments such as forests or indoor environments where alkene abundance from personal care and cleaning products may be significant.

High rates of alcohol use have been documented within military personnel and spouses. However, scant research has investigated alcohol consumption behaviors in matched couples or nonclinical vetera...

Arctic wetlands and surrounding ecosystems are both a significant source of methane (CH4) and a sink of carbon dioxide (CO2) during summer months. However, precise quantification of this regional CH4source and CO2sink remains poorly characterized. A research flight using the UK Facility for Airborne Atmospheric Measurement was conducted in July 2019 over an area (approx. 78 000 km2) of mixed peatland and forest in northern Sweden and Finland. Area-averaged fluxes of CH4and carbon dioxide were calculated using an aircraft mass balance approach. Net CH4fluxes normalized to wetland area ranged between 5.93 ± 1.87 mg m−2 h−1and 4.44 ± 0.64 mg m−2 h−1(largest to smallest) over the region with a meridional gradient across three discrete areas enclosed by the flight survey. From largest to smallest, net CO2sinks ranged between −513 ± 74 mg m−2 h−1and −284 ± 89 mg m−2 h−1and result from net uptake of CO2by vegetation and soils in the biosphere. A clear gradient of decreasing bulk and area-averaged CH4flux was identified from north to south across the study region, correlated with decreasing peat bog land area from north to south identified from CORINE land cover classifications. While N2O mole fraction was measured, no discernible gradient was measured over the flight track, but a minimum flux threshold using this mass balance method was calculated. Bulk (total area) CH4fluxes determined via mass balance were compared with area-weighted upscaled chamber fluxes from the same study area and were found to agree well within measurement uncertainty. The mass balance CH4fluxes were found to be significantly higher than the CH4fluxes reported by many land-surface process models compiled as part of the Global Carbon Project. There was high variability in both flux distribution and magnitude between the individual models. This further supports previous studies that suggest that land-surface models are currently ill-equipped to accurately capture carbon fluxes inthe region.This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 2)'.

The oil and gas (O&G) sector is a significant source of methane (CH4) emissions. Quantifying these emissions remains challenging, with many studies highlighting discrepancies between measurements and inventory-based estimates. In this study, we present CH4 emission fluxes from 21 offshore O&G facilities collected in 10 O&G fields over two regions of the Norwegian continental shelf in 2019. Emissions of CH4 derived from measurements during 13 aircraft surveys were found to range from 2.6 to 1200 t yr−1 (with a mean of 211 t yr−1 across all 21 facilities). Comparing this with aggregated operator-reported facility emissions for 2019, we found excellent agreement (within 1σ uncertainty), with mean aircraft-measured fluxes only 16 % lower than those reported by operators. We also compared aircraft-derived fluxes with facility fluxes extracted from a global gridded fossil fuel CH4 emission inventory compiled for 2016. We found that the measured emissions were 42 % larger than the inventory for the area covered by this study, for the 21 facilities surveyed (in aggregate). We interpret this large discrepancy not to reflect a systematic error in the operator-reported emissions, which agree with measurements, but rather the representativity of the global inventory due to the methodology used to construct it and the fact that the inventory was compiled for 2016 (and thus not representative of emissions in 2019). This highlights the need for timely and up-to-date inventories for use in research and policy. The variable nature of CH4 emissions from individual facilities requires knowledge of facility operational status during measurements for data to be useful in prioritising targeted emission mitigation solutions. Future surveys of individual facilities would benefit from knowledge of facility operational status over time. Field-specific aggregated emissions (and uncertainty statistics), as presented here for the Norwegian Sea, can be meaningfully estimated from intensive aircraft surveys. However, field-specific estimates cannot be reliably extrapolated to other production fields without their own tailored surveys, which would need to capture a range of facility designs, oil and gas production volumes, and facility ages. For year-on-year comparison to annually updated inventories and regulatory emission reporting, analogous annual surveys would be needed for meaningful top-down validation. In summary, this study demonstrates the importance and accuracy of detailed, facility-level emission accounting and reporting by operators and the use of airborne measurement approaches to validate bottom-up accounting.

In this work, the kinematics and basic laws of microcontinuum field theories, including micromorphic theory and micropolar theory, are introduced. Then, constitutive equations for micromorphic thermo-visco-elastic solids, heat conducting fluids, and thermal plasticity are rigorously derived. The concept of material force, which may also be named as Eshelby mechanics, is briefly introduced. The balance law of pseudo-momentum, including the detailed expression of the material forces, for the mathematical theory of micromorphic plasticity is rigorously derived. Finally, a set of finite element equations for the coupling of finite displacement, micromotion, and temperature fields is rigorously formulated.

Particle nucleation is one of the main sources of atmospheric particulate matter by number, with new particles having great relevance for human health and climate. Highly oxidized multifunctional organic molecules (HOMs) have been recently identified as key constituents in the growth and, sometimes, in initial formation of new particles. While there have been many studies of HOMs in atmospheric chambers, flow tubes, and clean environments, analyses of data from polluted environments are scarce. Here, measurements of HOMs and particle size distributions down to small molecular clusters are presented alongside volatile organic compounds (VOCs) and trace-gas data from a campaign in June 2017, in Beijing. Many gas-phase HOMs have been characterized and their temporal trends and behaviours analysed in the context of new particle formation. The HOMs identified have a degree of oxidation comparable to that seen in other, cleaner, environments, likely due to an interplay between the higher temperatures facilitating rapid hydrogen abstractions and the higher concentrations of NOx and other RO2⚫ terminators ending the autoxidation sequence more rapidly. Our data indicate that alkylbenzenes, monoterpenes, and isoprene are important precursor VOCs for HOMs in Beijing. Many of the C5 and C10 compounds derived from isoprene and monoterpenes have a slightly greater degree of average oxidation state of carbon compared to those from other precursors. Most HOMs except for large dimers have daytime peak concentrations, indicating the importance of OH⚫ chemistry in the formation of HOMs, as O3 tends to be lower on days with higher HOM concentrations; similarly, VOC concentrations are lower on the days with higher HOM concentrations. The daytime peaks of HOMs coincide with the growth of freshly formed new particles, and their initial formation coincides with the peak in sulfuric acid vapours, suggesting that the nucleation process is sulfuric-acid-dependent, with HOMs contributing to subsequent particle growth.

In situ field measurements of glyoxal at the surface in the tropical marine boundary layer have been made with a temporal resolution of a few minutes during two 4-week campaigns in June–July and August–September 2014 at the Cape Verde Atmospheric Observatory (CVAO; 16∘52′ N, 24∘52′ W). Using laser-induced phosphorescence spectroscopy with an instrumental detection limit of ∼1 pptv (1 h averaging), volume mixing ratios up to ∼10 pptv were observed, with 24 h averaged mixing ratios of 4.9 and 6.3 pptv observed during the first and second campaigns, respectively. Some diel behaviour was observed, but this was not marked. A box model using the detailed Master Chemical Mechanism (version 3.2) and constrained with detailed observations of a suite of species co-measured at the observatory was used to calculate glyoxal mixing ratios. There is a general model underestimation of the glyoxal observations during both campaigns, with mean midday (11:00–13:00) observed-to-modelled ratios for glyoxal of 3.2 and 4.2 for the two campaigns, respectively, and higher ratios at night. A rate of production analysis shows the dominant sources of glyoxal in this environment to be the reactions of OH with glycolaldehyde and acetylene, with a significant contribution from the reaction of OH with the peroxide HC(O)CH2OOH, which itself derives from OH oxidation of acetaldehyde. Increased mixing ratios of acetaldehyde, which is unconstrained and potentially underestimated in the base model, can significantly improve the agreement between the observed and modelled glyoxal during the day. Mean midday observed-to-modelled glyoxal ratios decreased to 1.3 and 1.8 for campaigns 1 and 2, respectively, on constraint to a fixed acetaldehyde mixing ratio of 200 pptv, which is consistent with recent airborne measurements near CVAO. However, a significant model under-prediction remains at night. The model showed limited sensitivity to changes in deposition rates of model intermediates and the uptake of glyoxal onto aerosol compared with sensitivity to uncertainties in chemical precursors. The midday (11:00–13:00) mean modelled glyoxal mixing ratio decreased by factors of 0.87 and 0.90 on doubling the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively, and increased by factors of 1.10 and 1.06 on halving the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively. Although measured levels of monoterpenes at the site (total of ∼1 pptv) do not significantly influence the model calculated levels of glyoxal, transport of air from a source region with high monoterpene emissions to the site has the potential to give elevated mixing ratios of glyoxal from monoterpene oxidation products, but the values are highly sensitive to the deposition rates of these oxidised intermediates. A source of glyoxal derived from production in the ocean surface organic microlayer cannot be ruled out on the basis of this work and may be significant at night.

Strict seasonal emission controls are a popular measure in China for addressing severe air pollution, in particular fine particulate matter (PM2.5). Here we evaluate the efficacy of these measures, with a particular focus on the strict emission controls imposed on pollution sources in 28 cities in and around the Beijing-Tianjin-Hebei region (BTH) in autumn-winter 2017/2018. For this we use the GEOS-Chem chemical transport model and air pollutant measurements from the national and Beijing local monitoring networks, after evaluating the network data with independent measurements and correcting large biases in the bottom-up emissions inventory. The network measurements are temporally consistent (r > 0.9 for PM2.5 and r > 0.7 for gases) with the independent measurements, though with systematic differences of 5–17 % for nitrogen dioxide (NO2) and 16–28 % for carbon monoxide (CO). The average decrease in monitoring network PM2.5 in BTH in autumn-winter 2017/2018 relative to the previous year is 27 %, declining from 103 to 75 µg m−3. The regional decline in PM2.5 in the model is 20 %, exceeding the regional target of 15 %. According to the model, pollution control measures led to decline in PM2.5 precursor emissions of 0.27 Tg NOx (as NO), 0.66 Tg sulfur dioxide (SO2), 70 Gg organic carbon (OC), and 50 Gg black carbon (BC). We find though that these alone only lead to an 8 % decline in PM2.5 and that interannual variability in meteorology accounts for more than half (57 %) the decline. This demonstrates that year-on-year comparisons are misleading for assessing the efficacy of air pollution measures and should be taken into consideration when extending such measures beyond BTH.

Nitrous acid, HONO, is a key net photolytic precursor to OH radicals in the atmospheric boundary later. As OH is the dominant atmospheric oxidant, driving the removal of many primary pollutants and the formation of secondary species, a quantitative understanding of HONO sources is important to predict atmospheric oxidising capacity. While a number of HONO formation mechanisms have been identified, recent work has ascribed significant importance to the dark, ocean-surface mediated conversion of NO2 to HONO in the coastal marine boundary layer. In order to evaluate the role of this mechanism, here we analyse measurements of HONO and related species obtained at two contrasting coastal locations – Cape Verde (Atlantic Ocean), representative of the clean remote tropical marine boundary layer, and Weybourne (United Kingdom), representative of semi-polluted Northern European coastal waters. As expected, higher average concentrations of HONO (70 ppt) were observed in marine air for the more anthropogenically influenced Weybourne location compared to Cape Verde (HONO 2 ratio at night pointed to a low importance for the dark ocean-surface mediated conversion of NO2 into HONO, whereas the midday maximum in the HONO/NO2 ratios indicated significant contributions from photo-enhanced HONO formation mechanisms (or other sources). We obtained an upper limit to the rate coefficient of dark ocean-surface HONO-to-NO2 conversion of CHONO = 0.0011 ppb hr−1 from the Cape Verde observations; this is a factor of 5 lower than the slowest rate reported previously. These results point to significant geographical variation in the predominant HONO formation mechanisms in marine environments and indicate that caution is required when extrapolating the importance of such mechanisms from individual study locations to assess regional and/or global impacts on oxidising capacity. As a significant fraction of atmospheric processing occurs in the marine boundary layer, particularly in the tropics, better constraint of the possible ocean surface source of HONO is important for a quantitative understanding of chemical processing of primary trace gases in the global atmospheric boundary layer and associated impacts upon air pollution and climate.

Atmospheric NH3 plays a vital role not only in the environmental ecosystem but also in atmosphere chemistry. To further understand the effects of NH3 on the formation of haze pollution in Beijing, ambient NH3 and related species were measured and simulated at high resolutions during the wintertime Air Pollution and Human Health‐Beijing (APHH‐Beijing) campaign in 2016. We found that the total NHx (gaseous NH3+particle NH4+) was mostly in excess of the SO42−‐NO3−‐NH4+‐water equilibrium system during our campaign. This NHx excess made medium aerosol acidity, with the median pH value being 3.6 and 4.5 for polluted and nonpolluted conditions, respectively, and enhanced the formation of particle phase nitrate. Our analysis suggests that NH4NO3 is the most important factor driving the increasing of aerosol water content with NO3− controlling the prior pollution stage and NH4+ the most polluted stage. Increased formation of NH4NO3 under excess NHx, especially during the nighttime, may trigger the decreasing of aerosol deliquescence relative humidity even down to less than 50% and hence lead to hygroscopic growth even under RH conditions lower than 50% and the wet aerosol particles become better medium for rapid heterogeneous reactions. A further increase of RH promotes the positive feedback “aerosol water content‐heterogeneous reactions” and ultimately leads to the formation of severe haze. Modeling results by Nested Air Quality Prediction Monitor System (NAQPMS) show the control of 20% NH3 emission may affect 5–11% of particulate matter PM2.5 formation under current emissions conditions in the North China Plain.

We describe the development and envisioned use case applications of a comprehensive insider threat ontology—“Sociotechnical and Organizational Factors for Insider Threat” (SOFIT)—that comprises more than 300 indicators of technical, behavioral, and organizational factors. Requirements, design, and engineering development for the Web Ontology Language (OWL) implementation of the SOFIT knowledge base are reviewed; additional relationships among constructs are defined that extend the representation beyond a simple taxonomic hierarchy and that enable inferences for qualitative and quantitative threat assessment. We show how queries may be constructed to support these inferences and threat assessments. Several major application concepts are reviewed to show how the ontology may be used by the insider threat research and operational communities. To this end, the SOFIT knowledge base may be shared with stakeholders to advance research and practice for proactive insider threat mitigation.

Isoprene is the most important biogenic volatile organic compound in the atmosphere. Its calculated impact on ozone (O3) is critically dependent on the model isoprene oxidation chemical scheme, in particular the way the isoprene-derived nitrates (IN) are treated. By combining gas chromatography with mass spectrometry, we have developed a system capable of separating, and unambiguously measuring, individual IN isomers. In this paper we report measurements from its first field deployment, which took place in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-Beijing) programme, along with box model simulations using the Master Chemical Mechanism (MCM) (v.3.3.1) to assess the key processes affecting the production and loss of the IN. Seven individual isoprene nitrates were identified and quantified during the summer campaign: two β-isoprene hydroxy nitrates (IHN); four δ isoprene carbonyl nitrates (ICN); and propanone nitrate. Whilst we had previously demonstrated that the system can measure the four δ-IHN, we found no evidence of them in Beijing. The two β-IHN mixing ratios are well correlated with an R2 value of 0.85. The mean for their ratio ((1-OH, 2-ONO2)-IHN : (4-OH, 3-ONO2)-IHN) is 3.4 and exhibits no clear diel cycle (the numbers in the names indicate the carbon (C) atom in the isoprene chain to which the radical is added). Examining this in a box model demonstrates its sensitivity to nitric oxide (NO), with lower NO mixing ratios favouring (1-OH, 2-ONO2)-IHN over (4-OH, 3-ONO2)-IHN. This is largely a reflection of the modelled ratios of their respective precursor peroxy radicals which, at NO mixing ratios of less than 1 part per billion (ppb), increase substantially with decreasing NO. Interestingly, this ratio in the peroxy radicals still exceeds the kinetic ratio (i.e. their initial ratio based on the yields of the adducts from OH addition to isoprene and the rates of reaction of the adducts with oxygen (O2)) even at NO mixing ratios as high as 100 ppb. The relationship of the observed β-IHN ratio with NO is much weaker than modelled, partly due to far fewer data points, but it agrees with the model simulation in so far as there tend to be larger ratios at sub 1 ppb amounts of NO. Of the δ-ICN, the two trans (E) isomers are observed to have the highest mixing ratios and the mean isomer ratio (E-(4-ONO2, 1-CO)-ICN to E-(1-ONO2, 4-CO)-ICN)) is 1.4, which is considerably lower than the expected ratio of 6 for addition of NO3 in the C1 and C4 carbon positions in the isoprene chain. The MCM produces far more δ-ICN than observed, particularly at night and it also simulates an increase in the daytime δ-ICN that greatly exceeds that seen in the observations. Interestingly, the modelled source of δ-ICN is predominantly during the daytime, due to the presence in Beijing of appreciable daytime amounts of NO3 along with isoprene. The modelled ratios of δ-ICN to propanone nitrate are very different to the observed. This study demonstrates the value of speciated IN measurements to test our understanding of the isoprene degradation chemistry. Our interpretation is limited by the uncertainties in our measurements and relatively small data set, but highlights areas of the isoprene chemistry that warrant further study, in particular the NO3 initiated isoprene degradation chemistry.

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, agricultural crop losses, and adversely affect human health. During October 2018, concentrations of speciated non-methane hydrocarbons 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 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.

Domestic solid fuel combustion is a major source of organic compounds to the atmosphere in gas and aerosol phases; however, large uncertainties exist in the current understanding of the gas-to-particle partitioning and the drivers of the reactivity of these emissions. This study developed comprehensive, model-ready organic emission profiles for domestic solid fuel combustion sources collected from Delhi, India. It also examined the organic species responsible for secondary organic aerosol (SOA) production potential and hydroxyl radical (OH) reactivity of these emissions. The profiles spanned the entire volatility range, including non-methane volatile organic compounds (NMVOCs, effective saturation concentration, C* = 3 × 106 to 1011 μg m−3), intermediate-volatility organic compounds (IVOCs, C* = 300 to 3 × 106 μg m−3), semi-volatile organic compounds (SVOCs, C* = 0.3–300 μg m−3) as well as low- and extremely low-volatility organic compounds (L/ELVOCs, where LVOC C* ≤ 0.3 μg m−3). The profiles predicted that IVOCs would contribute significantly to SOA production and that the combustion of fuel wood and charcoal released some of the smallest proportions of SVOCs. A model was developed to examine SOA production from burning emissions which estimated that phenolics would contribute 10–70% of the SOA. Furanics were the most important reactive species, contributing 9–48% of the OH reactivity and 9–58% of the SOA. Different combustion sources were also compared, with emissions from fuel wood, crop residue, cow dung cake and municipal solid waste (MSW) burning shown to be 30, 90, 120 and 230 times more reactive with the OH radical than emissions from liquefied petroleum gas (LPG) fuel. This study also estimated 3–4 times more SOA from cow dung cake combustion and 6–7 more from MSW combustion than fuel wood under comparable combustion conditions. The results of this study suggest that emissions from the combustion of domestic solid fuel sources in Delhi have the potential to significantly degrade local and regional air quality. As a result, more effective mitigation strategies are required to limit the impacts of solid fuel combustion on human health in countries like India.

The formation of isoprene nitrates (IsN) can lead to significant secondary organic aerosol (SOA) production and they can act as reservoirs of atmospheric nitrogen oxides. In this work, we estimate the rate of production of IsN from the reactions of isoprene with OH and NO3 radicals during the summertime in Beijing. While OH dominates the loss of isoprene during the day, NO3 plays an increasingly important role in the production of IsN from the early afternoon onwards. Unusually low NO concentrations during the afternoon resulted in NO3 mixing ratios of ca. 2 pptv at approximately 15:00, which we estimate to account for around a third of the total IsN production in the gas phase. Heterogeneous uptake of IsN produces nitrooxyorganosulfates (NOS). Two mono-nitrated NOS were correlated with particulate sulfate concentrations and appear to be formed from sequential NO3 and OH oxidation. Di- and tri-nitrated isoprene-related NOS, formed from multiple NO3 oxidation steps, peaked during the night. This work highlights that NO3 chemistry can play a key role in driving biogenic-anthropogenic interactive chemistry in Beijing with respect to the formation of IsN during both the day and night.

The dramatic and sudden reduction in anthropogenic activity due to lockdown measures in the UK in response to the COVID-19 outbreak has resulted in a concerted effort to estimate local and regional changes in air quality, though changes in underlying emissions remain uncertain. Here we combine satellite observations of tropospheric NO2 from TROPOspheric Monitoring Instrument and the Goddard Earth Observing System (GEOS)-Chem 3D chemical transport model to estimate that NO x emissions declined nationwide by ∼20% during the lockdown (23 March to 31 May 2020). Regionally, these range from 22% to 23% in the western portion of the country to 29% in the southeast and Manchester, and >40% in London. We apply a uniform 20% lockdown period emission reduction to GEOS-Chem anthropogenic emissions over the UK to determine that decline in lockdown emissions led to a national decline in PM2.5 of 1.1 μg m−3, ranging from 0.6 μg m−3 in Scotland to 2 μg m−3 in the southwest. The decline in emissions in cities (>40%) is greater than the national average and causes an increase in ozone of ∼2 ppbv in London and Manchester. The change in ozone and PM2.5 concentrations due to emission reductions alone is about half the total change from 2019 to 2020. This emphasizes the need to account for emissions and other factors, in particular meteorology, in future air pollution abatement strategies and regulatory action.