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Delhi, India, suffers from periods of very poor air quality, but little is known about the chemical production of secondary pollutants in this highly polluted environment. During the postmonsoon period in 2018, extremely high nighttime concentrations of NOx (NO and NO2) and volatile organic compounds (VOCs) were observed, with median NOx mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NOx measurements revealed very low nighttime concentrations of oxidants, NO3, O3, and OH, driven by high nighttime NO concentrations. This results in an atypical NO3 diel profile, not previously reported in other highly polluted urban environments, significantly perturbing nighttime radical oxidation chemistry. Low concentrations of oxidants and high nocturnal primary emissions coupled with a shallow boundary layer led to enhanced early morning photo-oxidation chemistry. This results in a temporal shift in peak O3 concentrations when compared to the premonsoon period (12:00 and 15:00 local time, respectively). This shift will likely have important implications on local air quality, and effective urban air quality management should consider the impacts of nighttime emission sources during the postmonsoon period.

Delhi, India, suffers from periods of very poor air quality, but little is known about the chemical production of secondary pollutants in this highly polluted environment. During the post-monsoon period in 2018, extremely high night-time concentrations of NOx (NO and NO2) and volatile organic compounds (VOCs) were observed, with median NOx mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NOx measurements revealed very low night-time concentrations of oxidants, NO3, O3, and OH, driven by high night-time NO concentrations. This results in an atypical NO3 diel profile, not previously reported in other highly polluted urban environments, significantly perturbing night-time radical oxidation chemistry. Low concentrations of oxidants and high nocturnal primary emissions coupled with a shallow boundary layer led to enhanced early morning photo-oxidation chemistry. This results in a temporal shift in peak O3 concentrations when compared to the pre-monsoon period (12:00 and 15:00 local time, respectively). This shift will likely have important implications on local air quality, and effective urban air quality management should consider the impacts of night-time emission sources during the post-monsoon period.

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 × 107 molecule cm-3, HO2 peaking at 1 × 109 molecule cm-3 and the total RO2 concentration reaching 5:5×109 molecule cm-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 ppbvh-1) under the very low NO conditions (< 0:5ppbv) experienced in the afternoons, demonstrating a missing OH source consistent with previous studies under high volatile organic compound (VOC) emissions and low NO loadings. Under the highest NO mixing ratios (104 ppbv), the HO2 production rate exceeded the rate of destruction by 50ppbvh-1, whilst the rate of destruction of total RO2 exceeded the production by the same rate, indicating that the net propagation rate of RO2 to HO2 may be substantially slower than assumed. If just 10 % of the RO2 radicals propagate to HO2 upon reaction with NO, the HO2 and RO2 budgets could be closed at high NO, but at low NO this lower RO2 to HO2 propagation rate revealed a missing RO2 sink that was similar in magnitude to the missing OH source. A detailed box model that incorporated the latest Master Chemical Mechanism (MCM3.3.1) reproduced the observed OH concentrations well but over-predicted the observed HO2 under low concentrations of NO (< 1ppbv) and under-predicted RO2 (both the complex RO2 fraction and other RO2 types which we classify as simple RO2) most significantly at the highest NO concent

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 × 107 molecule cm-3, HO2 peaking at 1 × 109 molecule cm-3 and the total RO2 concentration reaching 5:5×109 molecule cm-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 ppbvh-1) under the very low NO conditions (< 0:5ppbv) experienced in the afternoons, demonstrating a missing OH source consistent with previous studies under high volatile organic compound (VOC) emissions and low NO loadings. Under the highest NO mixing ratios (104 ppbv), the HO2 production rate exceeded the rate of destruction by 50ppbvh-1, whilst the rate of destruction of total RO2 exceeded the production by the same rate, indicating that the net propagation rate of RO2 to HO2 may be substantially slower than assumed. If just 10 % of the RO2 radicals propagate to HO2 upon reaction with NO, the HO2 and RO2 budgets could be closed at high NO, but at low NO this lower RO2 to HO2 propagation rate revealed a missing RO2 sink that was similar in magnitude to the missing OH source. A detailed box model that incorporated the latest Master Chemical Mechanism (MCM3.3.1) reproduced the observed OH concentrations well but over-predicted the observed HO2 under low concentrations of NO (< 1ppbv) and under-predicted RO2 (both the complex RO2 fraction and other RO2 types which we classify as simple RO2) most significantly at the highest NO concent

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 inc

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 t

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 × 107 molecule cm-3, HO2 peaking at 1 × 109 molecule cm-3 and the total RO2 concentration reaching 5:5×109 molecule cm-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 ppbvh-1) under the very low NO conditions (< 0:5ppbv) experienced in the afternoons, demonstrating a missing OH source consistent with previous studies under high volatile organic compound (VOC) emissions and low NO loadings. Under the highest NO mixing ratios (104 ppbv), the HO2 production rate exceeded the rate of destruction by 50ppbvh-1, whilst the rate of destruction of total RO2 exceeded the production by the same rate, indicating that the net propagation rate of RO2 to HO2 may be substantially slower than assumed. If just 10 % of the RO2 radicals propagate to HO2 upon reaction with NO, the HO2 and RO2 budgets could be closed at high NO, but at low NO this lower RO2 to HO2 propagation rate revealed a missing RO2 sink that was similar in magnitude to the missing OH source. A detailed box model that incorporated the latest Master Chemical Mechanism (MCM3.3.1) reproduced the observed OH concentrations well but over-predicted the observed HO2 under low concentrations of NO (< 1ppbv) and under-predicted RO2 (both the complex RO2 fraction and other RO2 types which we classify as simple RO2) most significantly at the highest NO concent

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 × 107 molecule cm-3, HO2 peaking at 1 × 109 molecule cm-3 and the total RO2 concentration reaching 5:5×109 molecule cm-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 ppbvh-1) under the very low NO conditions (< 0:5ppbv) experienced in the afternoons, demonstrating a missing OH source consistent with previous studies under high volatile organic compound (VOC) emissions and low NO loadings. Under the highest NO mixing ratios (104 ppbv), the HO2 production rate exceeded the rate of destruction by 50ppbvh-1, whilst the rate of destruction of total RO2 exceeded the production by the same rate, indicating that the net propagation rate of RO2 to HO2 may be substantially slower than assumed. If just 10 % of the RO2 radicals propagate to HO2 upon reaction with NO, the HO2 and RO2 budgets could be closed at high NO, but at low NO this lower RO2 to HO2 propagation rate revealed a missing RO2 sink that was similar in magnitude to the missing OH source. A detailed box model that incorporated the latest Master Chemical Mechanism (MCM3.3.1) reproduced the observed OH concentrations well but over-predicted the observed HO2 under low concentrations of NO (< 1ppbv) and under-predicted RO2 (both the complex RO2 fraction and other RO2 types which we classify as simple RO2) most significantly at the highest NO concent

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 inc

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 t

Wintertime in situ measurements of OH, HO2 and RO2 radicals and OH reactivity were made in central Beijing during November and December 2016. Exceptionally elevated NO was observed on occasions, up to ∼250 ppbv. The daily maximum mixing ratios for radical species varied significantly day-to-day over the ranges 1–8×106 cm−3 (OH), 0.2–1.5×108 cm−3 (HO2) and 0.3–2.5×108 cm−3 (RO2). Averaged over the full observation period, the mean daytime peak in radicals was 2.7×106, 0.39×108 and 0.88×108 cm−3 for OH, HO2 and total RO2, respectively. The main daytime source of new radicals via initiation processes (primary production) was the photolysis of HONO (∼83 %), and the dominant termination pathways were the reactions of OH with NO and NO2, particularly under polluted haze conditions. The Master Chemical Mechanism (MCM) v3.3.1 operating within a box model was used to simulate the concentrations of OH, HO2 and RO2. The model underpredicted OH, HO2 and RO2, especially when NO mixing ratios were high (above 6 ppbv). The observation-to-model ratio of OH, HO2 and RO2 increased from ∼1 (for all radicals) at 3 ppbv of NO to a factor of ∼3, ∼20 and ∼91 for OH, HO2 and RO2, respectively, at ∼200 ppbv of NO. The significant underprediction of radical concentrations by the MCM suggests a deficiency in the representation of gas-phase chemistry at high NOx. The OH concentrations were surprisingly similar (within 20 % during the day) in and outside of haze events, despite j(O1D) decreasing by 50 % during haze periods. These observations provide strong evidence that gas-phase oxidation by OH can continue to generate secondary pollutants even under high-pollution episodes, despite the reduction in photolysis rates within haze.

Wintertime in situ measurements of OH, HO2 and RO2 radicals and OH reactivity were made in central Beijing during November and December 2016. Exceptionally elevated NO was observed on occasions, up to ∼250 ppbv. The daily maximum mixing ratios for radical species varied significantly day-to-day over the ranges 1–8×106 cm−3 (OH), 0.2–1.5×108 cm−3 (HO2) and 0.3–2.5×108 cm−3 (RO2). Averaged over the full observation period, the mean daytime peak in radicals was 2.7×106, 0.39×108 and 0.88×108 cm−3 for OH, HO2 and total RO2, respectively. The main daytime source of new radicals via initiation processes (primary production) was the photolysis of HONO (∼83 %), and the dominant termination pathways were the reactions of OH with NO and NO2, particularly under polluted haze conditions. The Master Chemical Mechanism (MCM) v3.3.1 operating within a box model was used to simulate the concentrations of OH, HO2 and RO2. The model underpredicted OH, HO2 and RO2, especially when NO mixing ratios were high (above 6 ppbv). The observation-to-model ratio of OH, HO2 and RO2 increased from ∼1 (for all radicals) at 3 ppbv of NO to a factor of ∼3, ∼20 and ∼91 for OH, HO2 and RO2, respectively, at ∼200 ppbv of NO. The significant underprediction of radical concentrations by the MCM suggests a deficiency in the representation of gas-phase chemistry at high NOx. The OH concentrations were surprisingly similar (within 20 % during the day) in and outside of haze events, despite j(O1D) decreasing by 50 % during haze periods. These observations provide strong evidence that gas-phase oxidation by OH can continue to generate secondary pollutants even under high-pollution episodes, despite the reduction in photolysis rates within haze.

Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an intercomparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available a long-path absorption photometer (LOPAP) and a custom-built instrument) and two broadband cavity-enhanced absorption spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a selected ion flow tube mass spectrometer (SIFT-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends and variability in HONO (r2 > 0.97), yet they displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher overall than the BBCEAS systems by between 12 % and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location and/or inlet position, but this observation may have been more associative than casual.

Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an intercomparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available a long-path absorption photometer (LOPAP) and a custom-built instrument) and two broadband cavity-enhanced absorption spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a selected ion flow tube mass spectrometer (SIFT-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends and variability in HONO (r2 > 0.97), yet they displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher overall than the BBCEAS systems by between 12 % and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location and/or inlet position, but this observation may have been more associative than casual.

In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1–4 mbar, 30–120∘, respectively), as well as a reduced field strength E∕N in the range of 100–160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at E∕N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.

Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an intercomparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available a long-path absorption photometer (LOPAP) and a custom-built instrument) and two broadband cavity-enhanced absorption spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a selected ion flow tube mass spectrometer (SIFT-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends and variability in HONO (r2 > 0.97), yet they displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher overall than the BBCEAS systems by between 12 % and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location and/or inlet position, but this observation may have been more associative than casual.

Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an intercomparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available a long-path absorption photometer (LOPAP) and a custom-built instrument) and two broadband cavity-enhanced absorption spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a selected ion flow tube mass spectrometer (SIFT-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends and variability in HONO (r2 > 0.97), yet they displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher overall than the BBCEAS systems by between 12 % and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location and/or inlet position, but this observation may have been more associative than casual.

In September 2017, we conducted a proton-transfer-reaction mass-spectrometry (PTR-MS) intercomparison campaign at the CESAR observatory, a rural site in the central Netherlands near the village of Cabauw. Nine research groups deployed a total of 11 instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on timescales of seconds, and within a few minutes an automated sequence can be run allowing one to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass-dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1–4 mbar, 30–120∘, respectively), as well as a reduced field strength E∕N in the range of 100–160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at E∕N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. Deprotonation through reactive collisions of protonated organics with water molecules needs to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction and/or if protonated organics undergo many collisions with water molecules.

This work presents a comparative assessment of the impact of local traffic on ambient particle number concentrations (PNC) at schools in Brisbane, Australia and Barcelona, Spain. The cities are of similar climate but differ in various urban characteristics...

There is limited quantitative information on the air pollution sources and pollution concentrations in school microenvironments. This paper presents an overall synthesis of the work conducted under the scope of “Ultrafine Particles from Traffic Emissions and Children’s Health (UPTECH)” project and determines driving factors for air pollution in naturally ventilated classrooms in Brisbane Metropolitan Area in Australia.

An urban microenvironment where children spend a large portion of their day is school, and thus this is an important site for monitoring exposure to airborne particles. To determine the sources and driving factors of children’s exposure at school a comprehensive study was undertaken analysing the concentrations of organic carbon (OC) and elemental carbon (EC) at 25 schools in Brisbane, Australia. The EC tracer method was applied to quantify the concentrations of primary and secondary OC. Average OC/EC ratios ranged from 1.88 to 19.36 at the schools, indicating that both primary and secondary sources were present. The contributions of the sources above background levels were distinguished using multivariate techniques and clusters of schools were identified with differing exposure to primary and secondary sources. Levels of vehicle emissions at the schools were primarily dependent on total traffic counts on surrounding roads and secondly on the wind direction relative to the surrounding roads. At one group of schools, vehicle emissions were the principal source, characterised by elevated concentrations of primary OC and EC. High concentrations of secondary OC were observed at another group of schools, which were correlated with solar radiation levels indicting influence from photochemical secondary organic aerosols (SOA) formation. While local meteorology affected the measured concentrations, overall the range of concentrations measured at these schools can be considered as representative of children’s exposure to vehicle emissions and SOA.

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemistry of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-TOF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition and PNSD, respectively. Five NPF events, with growth rates in the range 3.3-4.6 nm, were detected at two sites. The NPF events happened on relatively warmer days with lower humidity and higher solar radiation. Temporal percent fractions of nitrate, sulphate, ammonium and organics were modelled using the Generalised Additive Model (GAM), with a basis of penalised spline. Percent fractions of organics increased after the NPF events, while the mass fraction of ammonium and sulphate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs f43 trends were compared between nucleation and non-nucleation days. f44 vs f43 followed a different pattern on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle emission generated particles, while both f44 and f43 decreased for NPF generated particles. It was found for the first time that vehicle generated and newly formed particles cluster in different locations on f44 vs f43 plot and this finding can be used as a tool for source apportionment of measured particles.

This thesis reports a comprehensive study on the physical and chemical properties of airborne particles in Brisbane, especially around schools. The sources and potential toxicity of the particles were identified, enabling an assessment of the contributing factors to children's exposure at school. The results from this thesis give a quantitative estimate of the range of airborne particles that children are exposed to at urban schools with different traffic conditions.

For fuel management and/or ecological reasons prescribed burnings are conducted each year across Australia. Smoke from prescribed burnings could be the major source of air pollution in urban environment during the period of intensive prescribed burning. To investigate the impact of prescribed burning on air quality and the characteristics of prescribed burning particles, field measurements were conducted during the end period of a prescribed burning event in September 2011, Brisbane, Australia.

Many Brisbane houses were affected by water inundation as a result of the flooding event which occurred in January 2011. The combination of waterlogged materials and large amounts of silt and organic debris in affected homes gave rise to a situation where exposures to airborne particles and dust could potentially be elevated. However, swift action to remove wet materials can help to reduce moisture and humidity in flooded houses, in an effort to improve indoor air quality in and around flooded areas. In order to gain an understanding of the effect of flooding on the concentration of inorganic elements in indoor dust, field measurements were carried out during 21 March and 3 May, 2011.

Vehicle emissions are a significant source of fine particles (Dp < 2.5 µm) in an urban environment. These fine particles have been shown to have detrimental health effects, with children thought to be more susceptible. Vehicle emissions are mainly carbonaceous in nature, and carbonaceous aerosols can be defined as either elemental carbon (EC) or organic carbon (OC). EC is a soot-like material emitted from primary sources while OC fraction is a complex mixture of hundreds of organic compounds from either primary or secondary sources (Cao et al., 2006). Therefore the ratio of OC/EC can aid in the identification of source. The purpose of this paper is to use the concentration of OC and EC in fine particles to determine the levels of vehicle emissions in schools. It is expected that this will improve the understanding of the potential exposure of children in a school environment to vehicle emissions.

The focus of this paper is on the measured particle number concentrations (PNC) as well as elemental and organic carbon in 17 primary schools. This study is part of the “Ultrafine Particles from Traffic Emissions and Children’s Health (UPTECH)”, which aims to determine the relationship between exposure to traffic related ultrafine (UF) particles and children’s health (http://www.ilaqh.qut.edu.au/Misc/UPTECH%20Home.htm). To achieve this, air quality and health data are being collected at 25 schools within Brisbane Metropolitan Area in Australia over two years. This paper presents the general aspects of UF particles data and preliminary results from the first 17 schools (S01 to S17), tested from Oct 2010 to Dec 2011.

Vehicle emissions have been linked to detrimental health effects with children thought to be more susceptible (See e.g., Ryan et al 2005). In an urban environment a major source of organic aerosols (OA) are vehicle emissions. The ambient concentration of OA is dynamic in nature and the use of an aerosol mass spectrometer can achieve the necessary temporal resolution to capture the daily variation of OA (Jimenez et al 2009). Currently there is a limited understanding of effects of long term exposure to traffic emissions on children’s health. In the present study, we used an aerosol mass spectrometer to monitor OA and determine children’s potential exposure at school to traffic emissions.In this paper, we present the preliminary results of this investigation. The study is a part of a larger project aimed at gaining a holistic picture of the exposure of children to traffic related pollutants, known as UPTECH (www.ilaqh.qut.edu.au/Misc/ UPTECH%20Home.htm).