Ozone Production Efficiency Research Articles

Tropospheric nitric acid columns from the IASI satellite instrument interpreted with a chemical transport model: Implications for parameterizations of nitric oxide production by lightning

AbstractThis paper interprets tropical tropospheric nitric acid columns from the Infrared Atmospheric Sounding Interferometer (IASI) satellite instrument with a global chemical transport model (GEOS‐Chem). GEOS‐Chem and IASI columns generally agree over the tropical ocean to within 10%. However, the GEOS‐Chem simulation underestimates IASI nitric acid over Southeast Asia by a factor of 2. The regional nitric acid bias is confirmed by comparing the GEOS‐Chem simulation with additional satellite (High Resolution Dynamics Limb Sounder, Atmospheric Chemistry Experiment Fourier Transform Spectrometer) and aircraft (Pacific Exploratory Mission (PEM)‐Tropics A and PEM‐West B) observations of the middle and upper troposphere. This bias appears to be driven by the lightning NOx parameterization, both in terms of the magnitude of the NOx source and the ozone production efficiency of concentrated lightning NOx plumes. We tested a subgrid lightning plume parameterization and found that an ozone production efficiency of 15 mol/mol in lightning plumes over Southeast Asia in conjunction with an additional 0.5 Tg N would reduce the regional nitric acid bias from 92% to 6% without perturbing the rest of the tropics. Other sensitivity studies such as modified NOx yield per flash, increased altitude of lightning NOx emissions, decreased convective mass flux, or increased scavenging of nitric acid required unrealistic changes to reduce the bias.

Temporal variations of O3 and NOx in the urban background atmosphere of the coastal city Jeddah, Saudi Arabia

Ozone is a pollutant of major concern because of its well recognized effects upon human health and crop yields. This study analyses in depth a new dataset for ozone from Jeddah, a coastal city in Saudi Arabia within the Middle Eastern region, for which very few ozone data are currently available, collected between March 2012 and February 2013. The measurements presented include NO, NO2 and ozone as well as relevant meteorological variables. The data show a marked seasonal variation in ozone with highest concentrations in the summer months and lowest average concentrations in the winter. Concentrations also show a substantial difference between weekdays and weekends, with higher NO and NO2 on weekdays, but lower concentrations of ozone. Plots of total oxidant versus NOx concentration indicate background concentrations of ozone (at zero NOx) ranging from 38.2 ppb in January to 59 ppb in May consistent with the northern hemisphere spring maximum in ozone concentrations. The slope of total oxidant/NOx varies from 0.13 in March to 0.68 in August. The two summer months of July and August are anomalous with slopes of around double that of other months, suggesting a higher efficiency of ozone production at lower primary pollutant concentrations arising from much reduced daytime traffic. A substantial weekend/weekday difference in ozone which is higher at weekends appears to be attributable to lower daytime traffic activity and hence reduced emissions of NOx to a “NOx-saturated” atmosphere.

Slower ozone production in Houston, Texas following emission reductions: evidence from Texas Air Quality Studies in 2000 and 2006

Abstract. Airborne measurements from two Texas Air Quality Study (TexAQS) field campaigns have been used to investigate changes of ozone production in Houston, Texas, from 2000 to 2006, a period of major emission reduction measures for petrochemical and other sources. Simultaneous declines in nitrogen oxides (NOx = NO + NO2) and highly reactive volatile organic compounds (HRVOCs) were observed between the two periods. We simulate HOx (OH and HO2) and organic radicals with a box model, the Dynamically Simple Model of Atmospheric Chemical Complexity, constrained by available airborne observations. Parameters such as total radical production, total OH reactivity of VOCs and ozone production rate (OPR) are computed to characterize the change of ozone production between 2000 and 2006 in the Houston area. The reduction in HRVOCs led to a decline in total radical production by 20–50%. Ozone production rates in the Houston area declined by 40–50% from 2000 to 2006, to which the reduction in NOx and HRVOCs made large contributions. Despite the significant decline in OPR, ozone production efficiency held steady, and VOC-sensitive conditions dominated during times of most rapid ozone formation, while the slow ozone formation continued to be NOx-limited. Our results highlight the importance of a balanced approach of ongoing HRVOC controls with NOx controls to further reduce O3 levels in the Houston area.

Ozone weekend effects in the Beijing–Tianjin–Hebei metropolitan area, China

Abstract. The ozone weekend effect (OWE) was first investigated in the metropolitan area of Beijing–Tianjin–Hebei (BTH), China, using in situ measurements from the Atmospheric Environment Monitoring Network from July 2009 to August 2011. The results indicate that there is an obvious weekly periodical variation in the surface ozone concentration. There is a lower ozone concentration from Wednesday to Friday (weekday) and a higher concentration from Saturday to Monday (weekend) at all the locations of the study. NOx also displays a weekly cycle, with the maximum level occurring on weekdays and the minimum level on weekends, especially later on Sunday night and early Monday morning. This pattern may be responsible for the higher concentration of ozone on weekends. Additionally, the vertical variations in O3 and NOx from the 8 m, 47 m, 120 m and 280 m observation platforms on the 325 m Beijing meteorological tower displayed obvious weekly cycles that corresponded to the surface results. A smaller decrease in volatile organic compounds (VOCs; using CO as a proxy) and much lower NOx concentrations on the weekend may lead to higher VOC / NOx ratio, which can enhance the ozone production efficiency in VOC-limited regime areas. Additionally, a clear weekly cycle in the fine aerosol concentration was observed, with maximum values occurring on weekdays and minimum values occurring on weekends. Higher concentrations of aerosol on weekdays can reduce the UV radiation flux by scattering or absorbing, which leads to a decrease in the ozone production efficiency. A significant weekly cycle in UV radiation, consistent with the aerosol concentration, was discovered at the Beijing meteorological tower site (BJT), validating the assumption. A comprehensive understanding of the ozone weekend effect in the BTH area can provide deep insights into controlling photochemical pollution.

Ozone in the southeastern United States: An observation-based model using measurements from the SEARCH network

A generalized additive model (GAM) is used to examine the influence of meteorological factors, nitrogen oxides (NOx = NO + NO2), and non-methane hydrocarbons (NMOC) on daily peak 8-h ozone (O3) concentrations. Application to 2002–2011 monitoring data from the Southeastern Aerosol Research and Characterization (SEARCH) program showed sensitivity of peak 8-h O3 to morning concentrations of nitric oxide (NO) and nitrogen dioxide (NO2) and to afternoon concentrations of NO2 reaction products (NOz). Peak O3 decreased with increasing NO and increased with increasing NO2 concentrations, consistent with reactions involving O3, NO, and NO2. Ozone production efficiency (OPE), estimated from the modeled relation between peak 8-h O3 and afternoon NOz, was ∼40–100 percent higher at rural compared to urban sites. OPE was nonlinear at all sites, decreasing with increasing NOz concentration. The mean ratio of NOz/NOy showed a two-fold increase from urban to rural sites, associated with chemical aging in stagnant air masses from one day (urban sites) to two or more days (non-urban sites). Peak 8-h O3 concentrations in Atlanta were sensitive to concentrations of both non-biogenic NMOC and NOz. Non-urban Yorkville, Georgia, peak 8-h O3 concentrations were sensitive to NOz but not to non-biogenic NMOC concentrations. The results are consistent with expected NMOC and NOx sensitivity in urban and non-urban locales.

Ozone generation in a kHz-pulsed He-O2 capillary dielectric barrier discharge operated in ambient air

The generation of reactive oxygen species using nonequilibrium atmospheric pressure plasma jet devices has been a subject of recent interest due to their ability to generate localized concentrations from a compact source. To date, such studies with plasma jet devices have primarily utilized radio-frequency excitation. In this work, we characterize ozone generation in a kHz-pulsed capillary dielectric barrier discharge configuration comprised of an active discharge plasma jet operating in ambient air that is externally grounded. The plasma jet flow gas was composed of helium with an admixture of up to 5% oxygen. A unipolar voltage pulse train with a 20 ns pulse risetime was used to drive the discharge at repetition rates between 2–25 kHz. Using UVLED absorption spectroscopy centered at 255 nm near the Hartley-band absorption peak, ozone was detected over 1 cm from the capillary axis. We observed roughly linear scaling of ozone production with increasing pulse repetition rate up to a “turnover frequency,” beyond which ozone production steadily dropped and discharge current and 777 nm O(5P→5S°) emission sharply increased. The turnover in ozone production occurred at higher pulse frequencies with increasing flow rate and decreasing applied voltage with a common energy density of 55 mJ/cm3 supplied to the discharge. The limiting energy density and peak ozone production both increased with increasing O2 admixture. The power dissipated in the discharge was obtained from circuit current and voltage measurements using a modified parallel plate dielectric barrier discharge circuit model and the volume-averaged ozone concentration was derived from a 2D ozone absorption measurement. From these measurements, the volume-averaged efficiency of ozone production was calculated to be 23 g/kWh at conditions for peak ozone production of 41 mg/h at 11 kV applied voltage, 3% O2, 2 l/min flow rate, and 13 kHz pulse repetition rate, with 1.79 W dissipated in the discharge.

High ozone concentrations on hot days: The role of electric power demand and NOx emissions

AbstractHigh ambient temperatures intensify photochemical production of tropospheric ozone, leading to concerns that global warming may exacerbate smog episodes. This widely observed phenomenon has been termed the climate penalty factor (CPF). A variety of meteorological and photochemical processes have been suggested to explain why surface ozone increases on hot days. Here, we quantify an anthropogenic factor previously overlooked: the rise of ozone precursor emissions on hot summer days due to high electricity demand. Between 1997 and 2011, power plant emissions of NOx in the eastern U.S. increased by ~2.5–4.0%/°C, raising surface NOx concentrations by 0.10–0.25 ppb/°C. Given an ozone production efficiency (OPE) of ~8 mol/mol based on the 2011 NASA DISCOVER‐AQ campaign, at least one third of the CPF observed in the eastern U.S. can be attributed to the temperature dependence of NOx emissions. This finding suggests that controlling emissions associated with electricity generation on hot summer days can mitigate the CPF.

A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

Abstract. We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.

Ozone and organic nitrates over the eastern United States: Sensitivity to isoprene chemistry

AbstractWe implement a new isoprene oxidation mechanism in a global 3‐D chemical transport model (GEOS‐Chem). Model results are evaluated with observations for ozone, isoprene oxidation products, and related species from the International Consortium for Atmospheric Research on Transport and Transformation aircraft campaign over the eastern United States in summer 2004. The model achieves an unbiased simulation of ozone in the boundary layer and the free troposphere, reflecting canceling effects from recent model updates for isoprene chemistry, bromine chemistry, and HO2 loss to aerosols. Simulation of the ozone‐CO correlation is improved relative to previous versions of the model, and this is attributed to a lower and reversible yield of isoprene nitrates, increasing the ozone production efficiency per unit of nitrogen oxides (NOx ≡ NO + NO2). The model successfully reproduces the observed concentrations of organic nitrates (∑ANs) and their correlations with HCHO and ozone. ∑ANs in the model is principally composed of secondary isoprene nitrates, including a major contribution from nighttime isoprene oxidation. The correlations of ∑ANs with HCHO and ozone then provide sensitive tests of isoprene chemistry and argue in particular against a fast isomerization channel for isoprene peroxy radicals. ∑ANs can provide an important reservoir for exporting NOx from the U.S. boundary layer. We find that the dependence of surface ozone on isoprene emission is positive throughout the U.S., even if NOx emissions are reduced by a factor of 4. Previous models showed negative dependences that we attribute to erroneous titration of OH by isoprene.

Nitrogen dioxide measurement by cavity attenuated phase shift spectroscopy (CAPS) and implications in ozone production efficiency and nitrate formation in Beijing, China

AbstractNitrogen dioxide (NO2) is a key species in studying photochemical smog and formation mechanisms of nitrate in fine particles. However, the conventional commercially available chemiluminescence (CL)‐based method often has uncertainties in measuring NO2 because of interferences with other reactive nitrogen species. In this study, an Aerodyne Cavity Attenuated Phase Shift Spectroscopy (CAPS) NO2 monitor that essentially has no interferences with nitrogen containing species was deployed in Beijing for the first time during August 2012. The CAPS NO2 monitor is highly sensitive with a detection limit (3σ) of 46.6 ppt for 1 min integration. The NO2 measured by CAPS shows overall agreement with that from CL, yet large differences up to 20% were also observed in the afternoon. Further, the discrepancies of NO2 measurements between CAPS and CL appear to be NOz dependent with larger differences at higher NOz concentrations (e.g., > 14 ppb). As a result, the ozone production efficiency of NOx (OPEx) derived from the correlations of Ox‐NOz with the CL NO2 can be overestimated by 19–37% in Beijing. The daily OPEx calculated with the CAPS NO2 ranges from 1.0 to 6.8 ppb/ppb with an average (±1σ) of 2.6 (±1.3) for the entire study. The relatively low OPEx and the relationship between OPEx and NOx suggest that ozone production chemistry is VOC sensitive during summer in Beijing. Two case studies further show that high concentrations of NOx can significantly enhance the formation of nitrate in fine particles in the presence of high O3 and favorable meteorological conditions.

Ozone photochemistry in boreal biomass burning plumes

Abstract. We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

Trends in ozone, its precursors, and related secondary oxidation products in Los Angeles, California: A synthesis of measurements from 1960 to 2010

AbstractDecreases in ozone (O3) observed in California's South Coast Air Basin (SoCAB) over the past five decades have resulted from decreases in local emissions of its precursors, nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). Ozone precursors have been characterized in the SoCAB with measurements dating back to 1960. Here we compile an extensive historical data set using measurements in the SoCAB between 1960 and 2010. Faster rates of decrease have occurred in abundances of VOCs (−7.3 ± 0.7% yr−1) than in NOx (−2.6 ± 0.3% yr−1), which have resulted in a decrease in VOC/NOx ratio (−4.8 ± 0.9% yr−1) over time. Trends in the NOx oxidation products peroxyacetyl nitrate (PAN) and nitric acid (HNO3), measured in the SoCAB since 1973, show changes in ozone production chemistry resulting from changes in precursor emissions. Decreases in abundances of PAN (−9.3 ± 1.1% yr−1) and HNO3 (−3.0 ± 0.8% yr−1) reflect trends in VOC and NOx precursors. Enhancement ratios of O3 to (PAN + HNO3) show no detectable trend in ozone production efficiency, while a positive trend in the oxidized fraction of total reactive nitrogen (+2.2 ± 0.5% yr−1) suggests that atmospheric oxidation rates of NOx have increased over time as a result of the emissions changes. Changes in NOx oxidation pathways have increasingly favored production of HNO3, a radical termination product associated with quenching the ozone formation cycle.

Impacts of urban land-surface forcing on ozone air quality in the Seoul metropolitan area

Abstract. Modified local meteorology owing to heterogeneities in the urban–rural surface can affect urban air quality. In this study, the impacts of urban land-surface forcing on ozone air quality during a high ozone (O3) episode in the Seoul metropolitan area, South Korea, are investigated using a high-resolution chemical transport model (CMAQ). Under fair weather conditions, the temperature excess (urban heat island) significantly modifies boundary layer characteristics/structures and local circulations. The modified boundary layer and local circulations result in an increase in O3 levels in the urban area of 16 ppb in the nighttime and 13 ppb in the daytime. Enhanced turbulence in the deep urban boundary layer dilutes pollutants such as NOx, and this contributes to the elevated O3 levels through the reduced O3 destruction by NO in the NOx-rich environment. The advection of O3 precursors over the mountains near Seoul by the prevailing valley-breeze circulation in the mid- to late morning results in the build-up of O3 over the mountains in conjunction with biogenic volatile organic compound (BVOC) emissions there. As the prevailing local circulation in the afternoon changes to urban-breeze circulation, the O3-rich air masses over the mountains are advected over the urban area. The urban-breeze circulation exerts significant influences on not only the advection of O3 but also the chemical production of O3 under the circumstances in which both anthropogenic and biogenic (natural) emissions play important roles in O3 formation. As the air masses that are characterized by low NOx and high BVOC levels and long OH chain length are advected over the urban area from the surroundings, the ozone production efficiency increases in the urban area. The relatively strong vertical mixing in the urban boundary layer embedded in the sea-breeze inflow layer reduces NOx levels, thus contributing to the elevated O3 levels in the urban area.

Chemical characteristics of air masses from different urban and industrial centers in the Huabei region of China

North China, or Huabei in Chinese, is one of the most severely polluted regions in China. There are many large, complex and strong emission sources in Beijing, Tianjin and Tangshan (together called Jing-Jin-Tang in Chinese) and other urban and industrial centers in Huabei, and the chemical characteristics of air masses coming from these pollution centers are expected to be quite different. As part of the project “Influence of Pollution on Aerosols and Cloud Microphysics in North China (IPAC-NC)”, surface ozone and related trace gases were measured at the Xin'an rural station (39.73°N, 117.51°E), located in the central part of larger Jing-Jin-Tang area, during 2 April-16 May 2006. Here we investigate the chemical characteristics and impact of air masses from these different pollution hotspots on the regional distributions of ozone and nitrogen oxides in Huabei, based on measurement data as well as a regional chemical transport model. Simulated reactive nitrogen compounds are attributed to the different emission sources in the Huabei region using the tracer-tagging method implemented in the model. We find that the chemical characteristics of pollution plumes from different urban and industrial centers are rather different. The OPEx, defined as ozone production efficiency of nitrogen oxides (NOx), for general pollution plumes from Beijing, Tianjin, Tangshan and Shijiazhuang are estimated to be 3.35, 2.75, 1.43 and 2.33 mol mol−1, respectively. During the IPAC-NC field campaign period, the Xin'an site was influenced alternatively by air masses from Beijing and Tianjin megacities and the Tangshan industrial area. The estimated OPEx in Beijing, Tianjin and Tangshan air masses arriving at Xin'an are comparable to those in their general pollution plumes. This indicates that air masses from different urban and industrial centers in Huabei also maintain their different chemical characteristics while being transported to the rural areas.

Effect of Generating Heat on Ozone Generation in Dielectric Cylinder-Cylinder DBD Ozone Generator

A cylinder-cylinder dielectric-barrier discharge (DBD) ozone generator has been developed. The ozone concentration was measured at an oxygen pressure of 1.02 atm and an oxygen flow rate of 12 L/min. The heat generated in the ozone tube during the operation of the ozone generator was investigated using a thermal camera. The infrared (IR) images and corresponding temperatures of the ozone tube surfaces at different operating times were observed. The IR images showed the generating of the inhomogeneous heat-up along the ozone tube surface which results in the decrease of the ozone production efficiency.

Effects of biogenic nitrate chemistry on the NO<sub>x</sub> lifetime in remote continental regions

Abstract. We present an analysis of the NOx budget in conditions of low NOx (NOx = NO + NO2) and high biogenic volatile organic compound (BVOC) concentrations that are characteristic of most continental boundary layers. Using a steady-state model, we show that below 500 pptv of NOx, the NOx lifetime is extremely sensitive to organic nitrate (RONO2) formation rates. We find that even for RONO2 formation values that are an order of magnitude smaller than is typical for continental conditions significant reductions in NOx lifetime, and consequently ozone production efficiency, are caused by nitrate forming reactions. Comparison of the steady-state box model to a 3-D chemical transport model (CTM) confirms that the concepts illustrated by the simpler model are a useful approximation of predictions provided by the full CTM. This implies that the regional and global budgets of NOx, OH, and ozone will be sensitive to assumptions regarding organic nitrate chemistry. Changes in the budgets of these species affect the representation of processes important to air quality and climate. Consequently, CTMs must include an accurate representation of organic nitrate chemistry in order to provide accurate assessments of past, present, and future air quality and climate. These findings suggest the need for further experimental constraints on the formation and fate of biogenic RONO2.

Effect of pulse power characteristics and gas flow rate on ozone production in a cylindrical dielectric barrier discharge ozonizer

The effect of pulse voltage, polarity, duty cycle, and oxygen flow rate on ozone production is studied in a coaxial cylindrical-type dielectric barrier discharge ozonizer at atmospheric pressure. For a constant oxygen flow rate, the ozone concentration increases with increasing input voltage and is nearly proportional to the ozone production efficiency. The bipolar waveform of the applied voltage results in higher ozone concentration and production efficiency than the unipolar one (positive or negative) regardless of duty cycle. A higher duty cycle increases the ozone concentration slightly for the unipolar voltage, while it affects little the ozone production efficiency for either voltage polarity. For constant pulse polarity and duty cycle, the ozone concentration decreases with increasing oxygen flow rate, however, the maximum ozone production efficiency for each flow rate shows only a minor difference for the change in flow rate. The results confirm that the ozone production efficiency depends more on the pulse power characteristics and less on the oxygen flow rate.

Ozone Production Using a Power Modulated Surface Dielectric Barrier Discharge in Dry Synthetic Air

The measurements of electrical and optical characteristics of the discharge and concentrations of produced ozone and nitrogen oxides were performed to evaluate the efficiency of ozone production in an AC surface dielectric barrier discharge in dry synthetic air at atmospheric pressure. The discharge was driven in an amplitude-modulated regime with driving AC frequencies of 1, 5 and 10 kHz, variable discharge duty cycle of 0.02–0.8 and synthetic air flow rate of 2–10 slm. The experimental results show that ozone and nitrogen oxides concentrations increased with increasing AC high-voltage amplitude, increasing discharge duty cycle and with increasing residence time. The highest calculated ozone production yield reached ~90 g/kWh with a corresponding energy cost of about 20 eV/molecule. The production yield was found to be independent of the driving AC frequency and specific energy density in the 10−4–10−2 Wh/l range.

Effect of voltage waveform on dielectric barrier discharge ozone production efficiency

Dielectric barrier discharges (DBDs) are commonly used for gas effluent cleanup and ozone generation. For these applications, the energy efficiency of the discharge is a major concern. This paper reports on investigations carried out on the voltage shape applied to DBD reactor electrodes, aiming to evaluate a possible energy efficiency improvement for ozone production. Two DBD reactor geometries were used: pin-to-pin and cylinder-to-cylinder, both driven either by a bi-directional power supply (voltage rise rate 1 kV/ μ s) or by a pulsed power supply (voltage rise rate 1 kV/ns). Ozone formed in dry air was measured at the reactor outlet. Special attention was paid to discharge input power evaluation using different methods including instantaneous current-voltage product and transferred charge-applied voltage figures. The charge transferred by the discharges was also correlated to the ozone production. It is shown that, in the case of the DBD reactors under investigation, the applied voltage shape has no influence on the ozone production efficiency. For the considered voltage rise rate, the charge deposit on the dielectric inserted inside the discharge gap is the important factor (as opposed to the voltage shape) governing the efficiency of the discharge – it does this by tailoring the duration of the current peak into the tens of nanosecond range.

Airborne and ground‐based observations of a weekend effect in ozone, precursors, and oxidation products in the California South Coast Air Basin

Airborne and ground‐based measurements during the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May/June 2010 show a weekend effect in ozone in the South Coast Air Basin (SoCAB) consistent with previous observations. The well‐known and much‐studied weekend ozone effect has been attributed to weekend reductions in nitrogen oxide (NOx = NO + NO2) emissions, which affect ozone levels via two processes: (1) reduced ozone loss by titration and (2) enhanced photochemical production of ozone due to an increased ratio of non‐methane volatile organic compounds (VOCs) to NOx. In accord with previous assessments, the 2010 airborne and ground‐based data show an average decrease in NOx of 46 ± 11% and 34 ± 4%, respectively, and an average increase in VOC/NOxratio of 48 ± 8% and 43 ± 22%, respectively, on weekends. This work extends current understanding of the weekend ozone effect in the SoCAB by identifying its major causes and quantifying their relative importance from the available CalNex data. Increased weekend production of a VOC‐NOxoxidation product, peroxyacetyl nitrate, compared to a radical termination product, nitric acid, indicates a significant contribution from increased photochemical production on weekends. Weekday‐to‐weekend differences in the products of NOx oxidation show 45 ± 13% and 42 ± 12% more extensive photochemical processing and, when compared with odd oxygen (Ox = O3 + NO2), 51 ± 14% and 22 ± 17% greater ozone production efficiency on weekends in the airborne and ground‐based data, respectively, indicating that both contribute to higher weekend ozone levels in the SoCAB.