ORCID Profile
0000-0002-3166-9415
Current Organisation
University of Reading
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Publisher: Copernicus GmbH
Date: 14-12-2022
Publisher: American Meteorological Society
Date: 05-2015
DOI: 10.1175/BAMS-D-12-00245.1
Abstract: Air quality and heat are strong health drivers, and their accurate assessment and forecast are important in densely populated urban areas. However, the sources and processes leading to high concentrations of main pollutants, such as ozone, nitrogen dioxide, and fine and coarse particulate matter, in complex urban areas are not fully understood, limiting our ability to forecast air quality accurately. This paper introduces the Clean Air for London (ClearfLo www.clearflo.ac.uk) project’s interdisciplinary approach to investigate the processes leading to poor air quality and elevated temperatures. Within ClearfLo, a large multi-institutional project funded by the U.K. Natural Environment Research Council (NERC), integrated measurements of meteorology and gaseous, and particulate composition/loading within the atmosphere of London, United Kingdom, were undertaken to understand the processes underlying poor air quality. Long-term measurement infrastructure installed at multiple levels (street and elevated), and at urban background, curbside, and rural locations were complemented with high-resolution numerical atmospheric simulations. Combining these (measurement–modeling) enhances understanding of seasonal variations in meteorology and composition together with the controlling processes. Two intensive observation periods (winter 2012 and the Summer Olympics of 2012) focus upon the vertical structure and evolution of the urban boundary layer chemical controls on nitrogen dioxide and ozone production—in particular, the role of volatile organic compounds and processes controlling the evolution, size, distribution, and composition of particulate matter. The paper shows that mixing heights are deeper over London than in the rural surroundings and that the seasonality of the urban boundary layer evolution controls when concentrations peak. The composition also reflects the seasonality of sources such as domestic burning and biogenic emissions.
Publisher: Copernicus GmbH
Date: 27-01-2020
DOI: 10.5194/ACP-2019-964
Abstract: Abstract. 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, in idual 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 in idual isoprene nitrates were identified and quantified during the summer c aign: 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.
Publisher: Copernicus GmbH
Date: 12-02-2021
Abstract: Abstract. 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) c aign 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 ( .5 ppbv) 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 ( ppbv) 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 concentrations. The model also under-predicted the observed k(OH) consistently by ≈10s-1 across all NOx levels, highlighting that the good agreement for OH was fortuitous due to a cancellation of missing OH source and sink terms in its budget. Including heterogeneous loss of HO2 to aerosol surfaces did reduce the modelled HO2 concentrations in line with the observations but only at NO mixing ratios .3 ppbv. The inclusion of Cl atoms, formed from the photolysis of nitryl chloride, enhanced the modelled RO2 concentration on several mornings when the Cl atom concentration was calculated to exceed 1×104atomscm-3 and could reconcile the modelled and measured RO2 concentrations at these times. However, on other mornings, when the Cl atom concentration was lower, large under-predictions in total RO2 remained. Furthermore, the inclusion of Cl atom chemistry did not enhance the modelled RO2 beyond the first few hours after sunrise and so was unable to resolve the modelled under-prediction in RO2 observed at other times of the day. Model scenarios, in which missing VOC reactivity was included as an additional reaction that converted OH to RO2, highlighted that the modelled OH, HO2 and RO2 concentrations were sensitive to the choice of RO2 product. The level of modelled to measured agreement for HO2 and RO2 (both complex and simple) could be improved if the missing OH reactivity formed a larger RO2 species that was able to undergo reaction with NO, followed by isomerisation reactions reforming other RO2 species, before eventually generating HO2. In this work an α-pinene-derived RO2 species was used as an ex le. In this simulation, consistent with the experimental budget analysis, the model underestimated the observed OH, indicating a missing OH source. The model uncertainty, with regards to the types of RO2 species present and the radicals they form upon reaction with NO (HO2 directly or another RO2 species), leads to over an order of magnitude less O3 production calculated from the predicted peroxy radicals than calculated from the observed peroxy radicals at the highest NO concentrations. This demonstrates the rate at which the larger RO2 species propagate to HO2, to another RO2 or indeed to OH needs to be understood to accurately simulate the rate of ozone production in environments such as Beijing, where large multifunctional VOCs are likely present.
Publisher: Wiley
Date: 25-10-2023
DOI: 10.1002/QJ.4589
Publisher: Copernicus GmbH
Date: 28-03-2022
DOI: 10.5194/EGUSPHERE-EGU22-7046
Abstract: & & The development of urban areas impacts the local climate and hydrology. Cities have been modelled with an array of models with different complexities. These models are called urban land surface models (ULSM) and focus on radiation, and turbulent sensible and latent heat fluxes. Grimmond et al. (2010) evaluated these models finding that the latent heat flux is the most challenging to simulate. This flux is part of both the energy balance and water balance, as the latent heat flux is the energy equivalent of the mass evapotranspiration. Thus, the hydrological circumstances may be crucial to correctly model the turbulent heat fluxes. However, the representation of the water balance in these models has not been the focus of a multi-model evaluation. As a part of the follow-up project to the work by Grimmond et al. and Urban-PLUMBER we evaluated the representation of the water balance in ULSMs with varying complexity and representation of the water balance. It is difficult to evaluate the water balance fluxes against observations, as not all terms are observed. For ex le, changes in water storage require knowledge of the state of all the in idual stores (e.g. soil moisture, detention ponds). Analysis of 14 models shows a large spread in the magnitude of the in idual water balance fluxes. The rate of reduction of the latent heat flux/evapotranspiration during periods without rainfall varies widely between models, consistent with literature (e.g. Jongen et al., 2022). Initial analysis suggests that models that simulate the water balance and conserve mass are more likely to accurately simulate turbulent heat fluxes. It is thus crucial that both the water and energy balance are accounted for in future urban model improvements.& &
Publisher: Copernicus GmbH
Date: 03-06-2022
DOI: 10.5194/ESSD-2022-65
Abstract: Abstract. Twenty urban neighbourhood-scale eddy covariance flux tower datasets have been harmonized and quality controlled, producing a 50 site-year collection with broad ersity in climate and urban surface characteristics. Observations are gap-filled and prepended with 10 years of reanalysis-derived local data to enable use as spin up and forcing for land surface model evaluation. For both gap filling and spin-up, ERA5 reanalysis meteorological data are bias corrected using tower observations, accounting for diurnal, seasonal and local urban effects not modelled in ERA5. The bias correction methods developed perform well compared to methods used in other datasets (e.g. WFDE5 or FLUXNET2015 linear regression). Site description metadata includes local land cover fractions (buildings, roads, trees, grass etc.), building height and morphology, aerodynamic roughness estimates, population density and satellite imagery. Together, this collection can help extend our understanding of urban environmental processes through observational synthesis studies or in the evaluation of land surface environmental models in a wide range of urban settings.
Publisher: Copernicus GmbH
Date: 04-03-2021
DOI: 10.5194/EGUSPHERE-EGU21-15230
Abstract: & & We present initial results of the Urban-PLUMBER international model evaluation project. This project assesses the performance of land surface models used in meteorological simulations of urban areas. Phase 1 included 24 models of varying complexity, from simple slab models through to multi-layer urban canopy models.& & & & model output variables are requested, including primary surface energy fluxes, anthropogenic heat and moisture fluxes, soil variables, albedo, canopy and building air temperatures. This rich dataset is used to both compare model outputs with observations and to understand factors contributing to model performance.& & & & The project involved a number of other innovations including:& & & ul& & li& An online portal (modelevaluation.org) is used to distribute site data and accept submissions.& /li& & li& Upon submission to the portal participants are provided with variable near-instant compliance checks and analyses allowing participants to make corrections if required.& /li& & li& A ten-year ERA5-derived spin up which overcomes the typically short period of urban flux tower observations and allows the entire observed period to be used in analyses.& /li& & li& Testing models alongside simple empirical benchmarks (e.g. out-of-s le linear regression of turbulent fluxes on shortwave radiation) to assess if input information is used effectively.& /li& & /ul& & & We also discuss the initial stages of Phase 2 which involves testing models at many urban sites. From the known global urban flux tower observations, following assessment, 25 are selected to capture a range of urban characteristics and climates. Surface characteristics are gathered, observations quality controlled and prepended with ten years of bias corrected ERA5 meteorological data for spinup. This new standardised urban flux tower dataset will become a valuable tool in future urban modelling projects.& &
Publisher: Copernicus GmbH
Date: 23-03-2020
DOI: 10.5194/EGUSPHERE-EGU2020-20987
Abstract: & & We welcome participants in the new project to evaluate land surface models (LSMs) in urban areas at multiple sites. Urban-PLUMBER will evaluate both specialised urban parameterisations and general LSMs typically used in weather/climate simulations. Assessment will be offline (uncoupled with an atmosphere model), with driving meteorology and general site characteristics provided at the neighbourhood scale.& & & & The project builds upon the PLUMBER project (PALS Land sUrface Model Benchmarking Evaluation pRoject) by assessing models using simple benchmarks as well as error metrics. The PLUMBER experience indicates benchmarking can reveal where LSMs are not utilising available information effectively, helping focus future model development.& & & & The project& #8217 s two phases are: 1) initial evaluation at one suburban site and 2) evaluation across multiple sites with varying degrees urbanised and vegetation ervious fractions. The project will establish where on the urbanised/vegetated continuum models are more skilful, and assess the progress made in modelling urban areas over the last decade since the last major offline urban model comparison project (PILPS-Urban).& & & & We expect the project to benefit both participating modelling groups and improve understanding of modelling urban areas as a whole. Contact us to get involved.& &
Publisher: Copernicus GmbH
Date: 27-01-2020
Publisher: Copernicus GmbH
Date: 04-03-2021
DOI: 10.5194/EGUSPHERE-EGU21-15389
Abstract: & & The WMO World Weather Research Programme (WWRP) & #8220 romotes international and interdisciplinary research for more accurate and reliable forecasts from minutes to seasons, expanding the frontiers of weather science to enhance society& #8217 s resilience to high-impact weather and the value of weather information for users. In the 2016-2023 WWRP implementation plan, activities focus on 4 challenges: High-Impact Weather, Water, Urbanization, Evolving technologies. Furthermore, the WMO Global Atmosphere Watch Urban Research Meteorology and Environment (GURME) focus on the development of models and associated research activities to enhance the capabilities in providing urban-environmental forecasting and air quality services, illustrating the linkages between meteorology and air quality (public.wmo.int/en rogrammes).& & & & This talk presents an international Research Demonstration Project (RDP), that will focus on international research on scientific urban issues addressed by both WWRP and GURME. The strategic objective of this RDP is to focus on the Olympic Games of Paris in 2024 in order to advance research on the theme of the & #8220 future Meteorological Forecasting systems at 100m (or finer) resolution for urban areas& #8221 . Such systems would prefigure the numerical weather prediction at the horizon 2030. The focus will be on themes related to extreme weather events in summer which both are influenced by and impacts urbanization: thunderstorms and strong Urban Heat Islands, and their consequences.& & & & There are 5 scientific questions that will be addressed during this Paris RDP:& & & ul& & li& Nowcasting & Numerical Weather Prediction in cities at order 100m resolution& /li& & li& High resolution thunderstorm nowcasting (probabilistic and deterministic) in the urban environment,& Urban heat islands, cool areas and air quality& /li& & li& Nowcasting and forecast in coastal cities (for the Marseilles site)& /li& & li& How to improve and better use observational networks in urban areas, including (big) non-conventional data& /li& & li& Conception and Communication of tailored weather, climate, environmental information at infra-urban resolution.& /li& & /ul& & & Several High-Impact weather case studies were selected. Storm cases (starting with one the 10th July 2017) will allow to evaluate the role of the urban area on their enhancement. Extreme Heat wave aggravated by a strong Urban Heat Island are also studied (July 2019). Open urban data describing the agglomerations at very high resolution are provided. New innovative methods to produce maps of urban form characteristics (e.g. from street images) and meteorological data (from personal meteorological stations) will be explored.& & & & This talk will describe these scientific questions, as well as the common methodology approach that is being discussed within the partners. A focus will be the international experimental c aign that will take place in 2022 over the Paris agglomeration, with an Intensive Observation Period in the summer 2022. Interactions between urban surface and the atmospheric boundary layer, the interactions between air quality and aerosols between city and biogenic plumes, and the local effect of urban trees on micro-climate and chemistry are some of the axes of the c aign. It will provide additional meteorological and air quality observations, to both help to improve the nowcasting and NWP systems at urban scale, and aim to define the required additional instrumentation that should be deployed during the Olympics games themselves.& &
Publisher: Copernicus GmbH
Date: 22-11-2022
DOI: 10.5194/ESSD-14-5157-2022
Abstract: Abstract. A total of 20 urban neighbourhood-scale eddy covariance flux tower datasets are made openly available after being harmonized to create a 50 site–year collection with broad ersity in climate and urban surface characteristics. Variables needed as inputs for land surface models (incoming radiation, temperature, humidity, air pressure, wind and precipitation) are quality controlled, gap-filled and prepended with 10 years of reanalysis-derived local data, enabling an extended spin up to equilibrate models with local climate conditions. For both gap filling and spin up, ERA5 reanalysis meteorological data are bias corrected using tower-based observations, accounting for diurnal, seasonal and local urban effects not modelled in ERA5. The bias correction methods developed perform well compared to methods used in other datasets (e.g. WFDE5 or FLUXNET2015). Other variables (turbulent and upwelling radiation fluxes) are harmonized and quality controlled without gap filling. Site description metadata include local land cover fractions (buildings, roads, trees, grass etc.), building height and morphology, aerodynamic roughness estimates, population density and satellite imagery. This open collection can help extend our understanding of urban environmental processes through observational synthesis studies or in the evaluation of land surface environmental models in a wide range of urban settings. These data can be accessed from 0.5281/zenodo.7104984 (Lipson et al., 2022).
Publisher: Routledge
Date: 08-01-2016
Publisher: Copernicus GmbH
Date: 05-06-2019
Abstract: Abstract. The Atmospheric Pollution and Human Health in a Chinese Megacity (APHH-Beijing) programme is an international collaborative project focusing on understanding the sources, processes and health effects of air pollution in the Beijing megacity. APHH-Beijing brings together leading China and UK research groups, state-of-the-art infrastructure and air quality models to work on four research themes: (1) sources and emissions of air pollutants (2) atmospheric processes affecting urban air pollution (3) air pollution exposure and health impacts and (4) interventions and solutions. Themes 1 and 2 are closely integrated and support Theme 3, while Themes 1–3 provide scientific data for Theme 4 to develop cost-effective air pollution mitigation solutions. This paper provides an introduction to (i) the rationale of the APHH-Beijing programme and (ii) the measurement and modelling activities performed as part of it. In addition, this paper introduces the meteorology and air quality conditions during two joint intensive field c aigns – a core integration activity in APHH-Beijing. The coordinated c aigns provided observations of the atmospheric chemistry and physics at two sites: (i) the Institute of Atmospheric Physics in central Beijing and (ii) Pinggu in rural Beijing during 10 November–10 December 2016 (winter) and 21 May–22 June 2017 (summer). The c aigns were complemented by numerical modelling and automatic air quality and low-cost sensor observations in the Beijing megacity. In summary, the paper provides background information on the APHH-Beijing programme and sets the scene for more focused papers addressing specific aspects, processes and effects of air pollution in Beijing.
Publisher: Copernicus GmbH
Date: 22-05-2023
Abstract: Abstract. 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 c aign 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 c aign 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 c aign, 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 c aign, with HO2 uptake contributing .3 % 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. .1 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 c aign, 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 c aign, 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 c aign. While not important for this c aign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.
Publisher: Copernicus GmbH
Date: 15-10-2018
DOI: 10.5194/ACP-2018-922
Abstract: Abstract. APHH-Beijing (Atmospheric Pollution and Human Health in a Chinese Megacity) is an international collaborative project to examine the emissions, processes and health effects of air pollution in Beijing. The four research themes of APHH-China are: (1) sources and emissions of urban atmospheric pollution (2) processes affecting urban atmospheric pollution (3) exposure science and impacts on health and (4) interventions and solutions to reduce health impacts. Themes 1 and 2 are closely integrated and support Theme 3, while Themes 1–3 provide scientific data for Theme 4 on the development of cost-effective solutions. A key activity within APHH-Beijing was the two month-long intensive field c aigns at two sites: (i) central Beijing, and (ii) rural Pinggu. The coordinated c aigns provided observations of the atmospheric chemistry and physics in and around Beijing during November–December 2016 and May–June 2017. The c aigns were complemented by numerical air quality modelling and air quality and meteorology data at the 12 national monitoring stations in Beijing. This introduction paper provides an overview of (i) APHH-Beijing programme, (ii) the measurement and modelling activities performed as part of it in Beijing, and (iii) the air quality and meteorological conditions during the two field c aigns. The winter c aign was characterized by high PM2.5 pollution events whereas the summer experienced high ozone pollution events. Air quality was poor during the winter c aign, but less severe than in the same period in 2015 when there were a number of major pollution episodes. PM2.5 levels were relatively low during the summer period, matching the cleanest periods over the previous five years. Synoptic scale meteorological analysis suggests that the greater stagnation and weak southerly circulation in November/December 2016 may have contributed to the poor air quality.
Publisher: Copernicus GmbH
Date: 27-04-2021
Abstract: Abstract. 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 organic nitrates (IN) are treated. By combining gas chromatography with mass spectrometry, we have developed a system capable of separating and unambiguously measuring in idual IN isomers. In this paper we use measurements from its first field deployment, which took place in Beijing as part of the Atmospheric Pollution and Human Health in a Chinese Megacity programme, to test understanding of the isoprene chemistry as simulated in the Master Chemical Mechanism (MCM) (v.3.3.1). Seven in idual isoprene nitrates were identified and quantified during the c aign: two β-hydroxy nitrates (IHN), four δ-carbonyl nitrates (ICN), and propanone nitrate. Our measurements show that in the summertime conditions experienced in Beijing the ratio of (1-OH, 2-ONO2)-IHN to (4-OH, 3-ONO2)-IHN (the numbers indicate the carbon atom in the isoprene chain to which the radical is added) increases at NO mixing ratios below 2 ppb. This provides observational field evidence of the redistribution of the peroxy radicals derived from OH oxidation of isoprene away from the kinetic ratio towards a new thermodynamic equilibrium consistent with box model calculations. The observed amounts of δ-ICN demonstrate the importance of daytime addition of NO3 to isoprene in Beijing but suggest that the predominant source of the δ-ICN in the model (reaction of NO with δ-nitrooxy peroxy radicals) may be too large. Our speciated measurements of the four δ-ICN exhibit a mean C1 : C4 isomer ratio of 1.4 and a mean trans : cis isomer ratio of 7 and provide insight into the isomeric distribution of the δ-nitrooxy peroxy radicals. Together our measurements and model results indicate that propanone nitrate was formed from the OH oxidation of δ-ICN both during the day and night, as well as from NO3 addition to propene at night. This study demonstrates the value of speciated IN measurements in testing understanding of the isoprene degradation chemistry and shows how more extensive measurements would provide greater constraints. It highlights areas of the isoprene chemistry that warrant further study, in particular the impact of NO on the formation of the IHN and the NO3-initiated isoprene degradation chemistry, as well as the need for further laboratory studies on the formation and the losses of IN, in particular via photolysis of δ-ICN and hydrolysis.
Publisher: Springer Science and Business Media LLC
Date: 10-09-2019
DOI: 10.1007/S10546-019-00472-1
Abstract: Tower-based measurements from within and above the urban canopy in two cities are used to evaluate several existing approaches that parametrize the vertical profiles of wind speed and temperature within the urban roughness sublayer (RSL). It is shown that current use of Monin–Obukhov similarity theory (MOST) in numerical weather prediction models can be improved upon by using RSL corrections when modelling the vertical profiles of wind speed and friction velocity in the urban RSL using MOST. Using anisotropic building morphological information improves the agreement between observed and parametrized profiles of wind speed and momentum fluxes for selected methods. The largest improvement is found when using dynamically-varying aerodynamic roughness length and displacement height. Adding a RSL correction to MOST, however, does not improve the parametrization of the vertical profiles of temperature and heat fluxes. This is expected since sources and sinks of heat are assumed uniformly distributed through a simple flux boundary condition in all RSL formulations, yet are highly patchy and anisotropic in a real urban context. Our results can be used to inform the choice of surface-layer representations for air quality, dispersion, and numerical weather prediction applications in the urban environment.
Publisher: Copernicus GmbH
Date: 03-09-2020
DOI: 10.5194/ACP-2020-785
Abstract: Abstract. Measurements of OH, HO2, RO2-complex (alkene and aromatic-related RO2) and total RO2 radicals taken during the AIRPRO c aign 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 peaked at 1 × 109 molecule cm−3 and the total RO2 concentration reached 5.5 × 109 molecule cm−3. OH reactivity (k(OH)) peaked at 89 s−1 during the night, with a minimum during the afternoons of ~ 22 s−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 hr−1) under the very low NO conditions (
Publisher: Wiley
Date: 07-10-2010
DOI: 10.1002/JOC.2227
Publisher: Copernicus GmbH
Date: 14-12-2022
DOI: 10.5194/ACP-2022-800
Abstract: Abstract. The impact of heterogeneous uptake of HO2 onto aerosol surfaces on radical concentrations and the O3 production regime in Beijing summertime was investigated. The uptake coefficient of HO2 onto aerosol surfaces, γHO2, was calculated for the AIRPRO c aign in Beijing, 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 c aign 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 c aign, 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. Rate of destruction analysis showed the dominant HO2 loss pathway to be HO2 + NO for all NO concentrations across the Summer Beijing c aign with HO2 uptake contributing 0.3 % 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. 0.1 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 results 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 VOC showed that, on average across the summer AIRPRO c aign, 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 NOx-limited. The O3 sensitivity to VOC, the dominant regime during the summer AIRPRO c aign, 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, continues 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 c aign. While not important for this c aign, aerosol uptake could be important for areas of lower NO concentration that are already in a NOx-sensitive regime.
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
No related grants have been discovered for Sue Grimmond.