Browsing by Author "Shallcross, Dudley E."
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Item Abundance of no3 derived organo-nitrates and their importance in the atmosphere(MPDI, 2021) Foulds, Amy; Khan, M. Anwar H.; Shallcross, Dudley E.The chemistry of the nitrate radical and its contribution to organo-nitrate formation in the troposphere has been investigated using a mesoscale 3-D chemistry and transport model, WRFChem-CRI. The model-measurement comparisons of NO2 , ozone and night-time N2O5 mixing ratios show good agreement supporting the model’s ability to represent nitrate (NO3 ) chemistry reasonably. Thirty-nine organo-nitrates in the model are formed exclusively either from the reaction of RO2 with NO or by the reaction of NO3 with alkenes. Temporal analysis highlighted a significant contribution of NO3 -derived organo-nitrates, even during daylight hours. Night-time NO3 -derived organo-nitrates were found to be 3-fold higher than that in the daytime. The reactivity of daytime NO3 could be more competitive than previously thought, with losses due to reaction with VOCs (and subsequent organo-nitrate formation) likely to be just as important as photolysis. This has highlighted the significance of NO3 in daytime organo-nitrate formation, with potential implications for air quality, climate and human health. Estimated atmospheric lifetimes of organo-nitrates showed that the organo-nitrates act as NOx reservoirs, with particularly short-lived species impacting on air quality as contributors to downwind ozone formation.Item Aerosol mass and size‑resolved metal content in urban Bangkok, Thailand(Springer, 2022) Matthews, James C.; Navasumrit, Panida; Shallcross, Dudley E.Inhalable particulate matter (PM) is a health concern, and people living in large cities such as Bangkok are exposed to high concentrations. This exposure has been linked to respiratory and cardiac diseases and cancers of the lung and brain. Throughout 2018, PM was measured in northern Bangkok near a toll road (13.87°N, 100.58°E) covering all three seasons (cool, hot and rainy). PM10 was measured in 24- and 72-h samples. On selected dates aerodynamic size and mass distribution were measured as 3-day samples from a fxed 5th foor inlet. Particle number concentration was measured from the 5th foor inlet and in roadside survey measurements. There was a large fraction of particle number concentration in the sub-micron range, which showed the greatest variability compared with larger fractions. Metals associated with combustion sources were most found on the smaller size fraction of particles, which may have implications for associated adverse health outcomes because of the likely location of aerosol deposition in the distal airways of the lung. PM10 samples varied between 30 and 100 μg m−3, with highest concentrations in the cool season.Item Chlorine oxidation of VOCs at a semi-rural site in Beijing: significant chlorine liberation from ClNO2 and subsequent gas- and particle-phase Cl–VOC production(European Geosciences Union (EGU), 2018) Le Breton, Michael; Hallquist, Åsa M.; Pathak, Ravi Kant; Shallcross, Dudley E.Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day’s photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl–VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3 105 molecules cm3 from ClNO2 alone, peaking at 09:30 LT and up to 8.4 105 molecules cm3 when including the supporting inorganic halogen measurements. Cl–VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.Item Investigating the variation of benzene and 1,3 butadiene in the UK during 2000–2020(MDPI, 2022) Holland, Rayne; Khan, M. Anwar H.; Shallcross, Dudley E.The concentrations of benzene and 1,3-butadiene in urban, suburban, and rural sites of the U.K. were investigated across 20 years (2000–2020) to assess the impacts of pollution control strategies. Given the known toxicity of these pollutants, it is necessary to investigate national long-term trends across a range of site types. We conclude that whilst legislative intervention has been successful in reducing benzene and 1,3-butadiene pollution from vehicular sources, previously overlooked sources must now be considered as they begin to dominate in contribution to ambient pollution. Benzene concentrations in urban areaswere found to be ~5-fold greater than those in rural areas,whilst 1,3-butadiene concentrations were up to ~10-fold greater.Item A two-decade anthropogenic and biogenic isoprene emissions study in a London urban background and a London urban traffic site(MDPI, 2018) Khan, M. Anwar H.; Schlich, Billie-Louise; Jenkin, Michael E.; Shallcross, Beth M.A.; Moseley, Katherine; Walker, Catherine; Morris, William C.; Derwent, Richard G.; Percival, Carl J.; Shallcross, Dudley E.A relationship between isoprene and 1,3-butadiene mixing ratios was established to separate the anthropogenic and biogenic fractions of the measured isoprene in London air in both urban background (Eltham) and urban traffic (Marylebone Road) areas over two decades (1997–2017). The average daytime biogenic isoprene mixing ratios over this period reached 0.09 ± 0.04 ppb (Marylebone Road) and 0.11 ± 0.06 ppb (Eltham) between the period of 6:00 to 20:00 local standard time, contributing 40 and 75% of the total daytime isoprene mixing ratios. The average summertime biogenic isoprene mixing ratios for 1997–2017 are found to be 0.13 ± 0.02 and 0.15 ± 0.04 ppb which contribute 50 and 90% of the total summertime isoprene mixing ratios for Marylebone Road and Eltham, respectively. Significant anthropogenic isoprene mixing ratios are found during night-time (0.11 ± 0.04 ppb) and winter months (0.14 ± 0.01 ppb) at Marylebone Road. During high-temperature and high-pollution events (high ozone) there is a suggestion that ozone itself may be directly responsible for some of the isoprene emission. By observing the positive correlation between biogenic isoprene levels with temperature, photosynthetically active radiation and ozone mixing ratios during heatwave periods, the Cobb-Douglas production function was used to obtain a better understanding of the abiotic factors that stimulate isoprene emission from plants. Other reasons for a correlation between ozone and isoprene are discussed. The long-term effects of urban stressors on vegetation were also observed, with biogenic isoprene mixing ratios on Marylebone Road dropping over a 20-year period regardless of the sustained biomass levels.Item A Two-Decade Anthropogenic and Biogenic Isoprene Emissions Study in a London Urban Background and a London Urban Traffic Site(MDPI, 2018-10-03) Shallcross, Dudley E.A relationship between isoprene and 1,3-butadiene mixing ratios was established to separate the anthropogenic and biogenic fractions of the measured isoprene in London air in both urban background (Eltham) and urban traffic (Marylebone Road) areas over two decades (1997–2017). The average daytime biogenic isoprene mixing ratios over this period reached 0.09 ± 0.04 ppb (Marylebone Road) and 0.11 ± 0.06 ppb (Eltham) between the period of 6:00 to 20:00 local standard time, contributing 40 and 75% of the total daytime isoprene mixing ratios. The average summertime biogenic isoprene mixing ratios for 1997–2017 are found to be 0.13 ± 0.02 and 0.15 ± 0.04 ppb which contribute 50 and 90% of the total summertime isoprene mixing ratios for Marylebone Road and Eltham, respectively. Significant anthropogenic isoprene mixing ratios are found during night-time (0.11 ± 0.04 ppb) and winter months (0.14 ± 0.01 ppb) at Marylebone Road. During high-temperature and high-pollution events (high ozone) there is a suggestion that ozone itself may be directly responsible for some of the isoprene emission. By observing the positive correlation between biogenic isoprene levels with temperature, photosynthetically active radiation and ozone mixing ratios during heatwave periods, the Cobb-Douglas production function was used to obtain a better understanding of the abiotic factors that stimulate isoprene emission from plants. Other reasons for a correlation between ozone and isoprene are discussed. The long-term effects of urban stressors on vegetation were also observed, with biogenic isoprene mixing ratios on Marylebone Road dropping over a 20-year period regardless of the sustained biomass levels.