OH and HO₂ radicals chemistry at a suburban site during the EXPLORE-YRD campaign in 2018

The first OH and HO2 radical observation in Yangtze River Delta, one of the four major urban agglomerations in China, was carried out at a suburban site Taizhou in summer 2018 from May to June, aiming to elucidate the atmospheric oxidation capacity in this region. The maximum diurnal averaged OH and HO2 concentrations were 1.0 × 107 cm−3 and 1.1 × 109 cm−3, respectively, which were the second highest HOx (sum of OH and HO2) radical concentrations observed in China. HONO photolysis was the dominant radical primary source, accounting for 42 % of the total radical initiation rate. Other contributions were from carbonyl photolysis (including HCHO, 24 %), O3 photolysis (17 %), alkenes ozonolysis (14 %), and NO3 oxidation (3 %). A chemical box model based on RACM2-LIM1 mechanism could generally reproduce the observed HOx radicals, but systematic discrepancy remained in the afternoon for OH radical, when NO mixing ratio was less than 0.3 ppb. Additional recycling mechanism equivalent to 100 ppt NO was capable to fill the gap. The sum of monoterpenes was on average up to 0.4 ppb during daytime, which was allocated all to α-pinene in the base model. Sensitivity test without monoterpene input showed the modelled OH and HO2 concentrations would increase by 7 % and 4 %, respectively, but modelled RO2 concentration would significantly decrease by 23 %, indicating that monoterpene was an important precursor of RO2 radicals in this study. Consequently, the daily integrated net ozone production would reduce by 6.3 ppb if without monoterpene input, proving the significant role of monoterpene on the photochemical O3 production in this study. Besides, the generally good agreement between observed and modelled HOx concentrations suggested no significant HO2 heterogeneous uptake process during this campaign. Incorporation of HO2 heterogeneous uptake process would worsen the agreement between HOx radical observation and simulation, and the discrepancy would be beyond the measurement-model combined uncertainties using an effective uptake coefficient of 0.2. Finally, the ozone production efficiency (OPE) was only 1.7 in this study, a few folds lower than other studies in (sub)urban environments. The low OPE indicated slow radical propagation rate and short chain length. As a consequence, ozone formation was suppressed by the low NO concentration in this study.

A prominent maximum in surface ozone concentration during winter months at Pune (India)

ABSTRACT. Concentration of ozone near the ground has been recorded at Pune (India) since 1972 with the help of a continuous surface ozone recorder using electro-chemical sensor. The analysis of the records of winter season indicates a sharp rise in ozone amount in the forenoon around 1000 to 1200 LST. Prior to 1985 this forenoon: higher value in surface ozone concentration was followed by another maximum in the afternoon hours coinciding with the maximum temperature epoch of the day. After 1985 the surface ozone data indicates that the forenoon peak value has become invariably higher than the afternoon value. Due to increasing concentration of anthropogenic gases in the atmosphere there is a possibility of photochemical production of ozone in the troposphere which may give rise to higher surface ozone values, when the meteorological conditions are favourable for the accumulation of such gases which are involved in ozone production.

Tropospheric ozone production and chemical regime analysis during the COVID-19 lockdown over Europe

The COVID-19 (Coronavirus disease 2019) European lockdowns have lead to a significant reduction in the emissions of primary pollutants such as NO (nitric oxide) and NO2 (nitrogen dioxide). As most photochemical processes are related to nitrogen oxide (NOx ≡ NO + NO2) chemistry, this event has presented an exceptional opportunity to investigate its effects on air quality and secondary pollutants, such as tropospheric ozone (O3). In this study, we present the effects of the COVID-19 lockdown on atmospheric trace gas concentrations, net ozone production rates (NOPR) and the dominant chemical regime throughout the troposphere based on three different research aircraft campaigns across Europe. These are the UTOPIHAN campaigns in 2003 and 2004, the HOOVER campaigns in 2006 and 2007 and the BLUESKY campaign in 2020, the latter performed during the COVID-19 lockdown. We present in situ observations and simulation results from the ECHAM5/MESSy Atmospheric Chemistry model which allows for scenario calculations with business as usual emissions during the BLUESKY campaign, referred to as "no-lockdown scenario". We show that the COVID-19 lockdown reduced NO and NO2 mixing ratios in the upper troposphere by around 55 % compared to the no-lockdown scenario due to reduced air traffic. O3 production and loss terms reflected this reduction with a deceleration in O3 cycling due to reduced mixing ratios of NOx while NOPRs were largely unaffected. We also study the role of methyl peroxyradicals forming HCHO (αCH3O2) to show that the COVID-19 lockdown shifted the chemistry in the upper troposphere/tropopause region to a NOx limited regime during BLUESKY. In comparison, we find a VOC limited regime to be dominant during UTOPIHAN.

Large contribution of biomass burning emissions to ozone throughout the global remote troposphere

Ozone is the third most important anthropogenic greenhouse gas after carbon dioxide and methane but has a larger uncertainty in its radiative forcing, in part because of uncertainty in the source characteristics of ozone precursors, nitrogen oxides, and volatile organic carbon that directly affect ozone formation chemistry. Tropospheric ozone also negatively affects human and ecosystem health. Biomass burning (BB) and urban emissions are significant but uncertain sources of ozone precursors. Here, we report global-scale, in situ airborne measurements of ozone and precursor source tracers from the NASA Atmospheric Tomography mission. Measurements from the remote troposphere showed that tropospheric ozone is regularly enhanced above background in polluted air masses in all regions of the globe. Ozone enhancements in air with high BB and urban emission tracers (2.1 to 23.8 ppbv [parts per billion by volume]) were generally similar to those in BB-influenced air (2.2 to 21.0 ppbv) but larger than those in urban-influenced air (−7.7 to 6.9 ppbv). Ozone attributed to BB was 2 to 10 times higher than that from urban sources in the Southern Hemisphere and the tropical Atlantic and roughly equal to that from urban sources in the Northern Hemisphere and the tropical Pacific. Three independent global chemical transport models systematically underpredict the observed influence of BB on tropospheric ozone. Potential reasons include uncertainties in modeled BB injection heights and emission inventories, export efficiency of BB emissions to the free troposphere, and chemical mechanisms of ozone production in smoke. Accurately accounting for intermittent but large and widespread BB emissions is required to understand the global tropospheric ozone burden.

Measurement report: Photochemical production and loss rates of formaldehyde and ozone across Europe

Various atmospheric sources and sinks regulate the abundance of tropospheric formaldehyde (HCHO), which is an important trace gas impacting the HOx (≡ HO2 + OH) budget and the concentration of ozone (O3). In this study, we present the formation and destruction terms of ambient HCHO and O3 calculated from in situ observations of various atmospheric trace gases measured at three different sites across Europe during summertime. These include a coastal site in Cyprus, in the scope of the Cyprus Photochemistry Experiment (CYPHEX) in 2014, a mountain site in southern Germany, as part of the Hohenpeißenberg Photochemistry Experiment (HOPE) in 2012, and a forested site in Finland, where measurements were performed during the Hyytiälä United Measurements of Photochemistry and Particles (HUMPPA) campaign in 2010. We show that, at all three sites, formaldehyde production from the OH oxidation of methane (CH4), acetaldehyde (CH3CHO), isoprene (C5H8) and methanol (CH3OH) can almost completely balance the observed loss via photolysis, OH oxidation and dry deposition. Ozone chemistry is clearly controlled by nitrogen oxides (NOx ≡ NO + NO2) that include O3 production from NO2 photolysis and O3 loss via the reaction with NO. Finally, we use the HCHO budget calculations to determine whether net ozone production is limited by the availability of VOCs (volatile organic compounds; VOC-limited regime) or NOx (NOx-limited regime). At the mountain site in Germany, O3 production is VOC limited, whereas it is NOx limited at the coastal site in Cyprus. The forested site in Finland is in the transition regime.

Unraveling pathways of elevated ozone induced by the 2020 lockdown in Europe by an observationally constrained regional model using TROPOMI

Questions about how emissions are changing during the COVID-19 lockdown periods cannot be answered by observations of atmospheric trace gas concentrations alone, in part due to simultaneous changes in atmospheric transport, emissions, dynamics, photochemistry, and chemical feedback. A chemical transport model simulation benefiting from a multi-species inversion framework using well-characterized observations should differentiate those influences enabling to closely examine changes in emissions. Accordingly, we jointly constrain NOx and VOC emissions using well-characterized TROPOspheric Monitoring Instrument (TROPOMI) HCHO and NO2 columns during the months of March, April, and May 2020 (lockdown) and 2019 (baseline). We observe a noticeable decline in the magnitude of NOx emissions in March 2020 (14 %–31 %) in several major cities including Paris, London, Madrid, and Milan, expanding further to Rome, Brussels, Frankfurt, Warsaw, Belgrade, Kyiv, and Moscow (34 %–51 %) in April. However, NOx emissions remain at somewhat similar values or even higher in some portions of the UK, Poland, and Moscow in March 2020 compared to the baseline, possibly due to the timeline of restrictions. Comparisons against surface monitoring stations indicate that the constrained model underrepresents the reduction in surface NO2. This underrepresentation correlates with the TROPOMI frequency impacted by cloudiness. During the month of April, when ample TROPOMI samples are present, the surface NO2 reductions occurring in polluted areas are described fairly well by the model (model: −21 ± 17 %, observation: −29 ± 21 %). The observational constraint on VOC emissions is found to be generally weak except for lower latitudes. Results support an increase in surface ozone during the lockdown. In April, the constrained model features a reasonable agreement with maximum daily 8 h average (MDA8) ozone changes observed at the surface (r=0.43), specifically over central Europe where ozone enhancements prevail (model: +3.73 ± 3.94 %, +1.79 ppbv, observation: +7.35 ± 11.27 %, +3.76 ppbv). The model suggests that physical processes (dry deposition, advection, and diffusion) decrease MDA8 surface ozone in the same month on average by −4.83 ppbv, while ozone production rates dampened by largely negative JNO2[NO2]-kNO+O3[NO][O3] become less negative, leading ozone to increase by +5.89 ppbv. Experiments involving fixed anthropogenic emissions suggest that meteorology contributes to 42 % enhancement in MDA8 surface ozone over the same region with the remaining part (58 %) coming from changes in anthropogenic emissions. Results illustrate the capability of satellite data of major ozone precursors to help atmospheric models capture ozone changes induced by abrupt emission anomalies.

Electrochemical Ozone Generation Using Compacted High Pressure High Temperature Synthesized Boron Doped Diamond Microparticle Electrodes

Electrochemical ozone production (EOP) from water is an attractive, green technology for disinfection. Boron doped diamond (BDD) electrodes, grown by chemical vapor deposition (CVD), have been widely adopted for EOP due to their wide anodic window in water and excellent chemical and electrochemical stability. High pressure high temperature (HPHT) synthesis, an alternative growth technique used predominantly for the high-volume synthesis of nitrogen doped diamond microparticles, has been seldom employed for the production of conductive BDD electrodes. In this letter, we demonstrate, for the first time, the use of BDD electrodes fabricated from HPHT conductive BDD microparticles for EOP. The BDD microparticles are first compacted to produce freestanding solid electrodes and then laser micromachined to produce a perforated electrode. The compacted HPHT BDD microparticle electrodes are shown to exhibit high EOP, producing 2.23 ± 0.07 mg L-1 of ozone per ampere of current, at consistent levels for a continuous 20 hr period with no drop off in performance. The HPHT electrodes also achieve a reasonable current efficiency of 23%, at a current density of 770 mA cm-2.