An official website of the United States government
Abstract High ozone concentrations have become the major summertime air quality problem in China. Extensive in situ observations are deployed for developing strategies to effectively control the emissions of ozone precursors, that is, nitrogen oxides (NOX = NO + NO2) and volatile organic compounds (VOCs). The modeling analysis of in situ observations often makes uses of the dependence of ozone peak concentration on NOXand VOC emissions, because ozone observations are among the most widely available air quality measurements. To extract more information from regulatory ozone observations, we extend the ozone‐precursor relationship to ozone peak time in this study. We find that the sensitivities of ozone peak time and concentration are complementary for regions with large anthropogenic emissions such as China. The ozone peak time is sensitive to both VOC and NOXemissions, and the sensitivity is nearly linear in the transition regime of ozone production compared to the changing ozone peak concentration sensitivity in this regime, making the diagnostics of ozone peak time particularly valuable. The extended ozone‐precursor relationships can be readily applied to understand the effects on ozone by emission changes of NOXand VOC and to assess potential biases of NOXand VOC emission inventories. These observation constraints based on regulatory ozone observations can complement the other measurement and modeling analysis methods nicely. Furthermore, we suggest that the ozone peak time sensitivity we discussed here to be used as a model evaluation measure before the empirical kinetic modeling approach (EKMA) diagram is applied to understand the effectiveness of emission control on ozone concentrations.
more »
« less
Photochemistry of Volatile Organic Compounds in the Yellow River Delta, China: Formation of O 3 and Peroxyacyl Nitrates
Abstract An extensive set of primary and secondary pollutants was measured at a ground site in a remote location in the Yellow River Delta, China during the Ozone Photochemistry and Export from China Experiment (OPECE) from March to April 2018. The measurements include volatile organic compounds (VOCs), peroxyacyl nitrates (PANs), ozone (O3), particulate species, nitrogen oxides (NOx), and SO2. Observed VOC mixing ratios were comparable to those measured in heavily polluted cities in the U.S. and China. The VOC source signatures suggest a strong influence from Oil and Natural Gas (O&NG) emissions with potentially large contributions from Liquified Petroleum Gas (LPG) sources as well. Consistently elevated concentrations of O3, PAN, and its rarely measured homologs peroxybenzoylic nitric anhydride (PBzN) and peroxyacrylic nitric anhydride (APAN) at the OPECE site indicate complex photochemistry in a heterogeneous VOC environment. Diagnostic 0‐D box model simulations are used to investigate the budgets of ROx(OH + HO2 + RO2), and the rate and efficiency of O3production. Model sensitivity calculations indicate that O3production at OPECE site is VOC limited in spring. This suggests that reduction in VOCs should be a priority for reducing O3, where production and fugitive emissions from O&NG provide an attractive target. While initial reductions in NOxmight increase O3production, reduction of NOxalong with VOCs will be a necessary step to achieve long‐term ozone reduction.
more »
« less
- Award ID(s):
- 1743401
- PAR ID:
- 10446470
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Geophysical Research: Atmospheres
- Volume:
- 126
- Issue:
- 23
- ISSN:
- 2169-897X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Ambient ozone (O3) concentrations in Southeast Michigan (SEMI) can exceed the U.S. National Ambient Air Quality Standard. Despite past efforts to measure O3precursors and elucidate reaction mechanisms, changing emission patterns and atmospheric composition in SEMI warrant new measurements and updated mechanisms to understand the causes of observed O3exceedances. In this study, we examine the chemical drivers of O3exceedances in SEMI, based on the Phase I MOOSE (Michigan‐Ontario Ozone Source Experiment) field study performed during May to June 2021. A zero‐dimensional (0‐D) box model is constrained with measurement data of meteorology and trace gas concentrations. Box model sensitivity simulations suggest that the formaldehyde to nitrogen dioxide ratio (HCHO/NO2) for the transition between the volatile organic compounds (VOCs)‐ and nitrogen oxides (NOx)‐limited O3production regimes is 3.0 ± 0.3 in SEMI. The midday (12:00–16:00) averaged HCHO/NO2ratio during the MOOSE Phase I study is 1.62 ± 1.03, suggesting that O3production in SEMI is limited by VOC emissions. This finding implies that imposing stricter regulations on VOC emissions should be prioritized for the SEMI O3nonattainment area. This study, through its use of ground‐based HCHO/NO2ratios and box modeling to assess O3‐VOC‐NOxsensitivities, has significant implications for air quality policy and the design of effective O3pollution control strategies, especially in O3nonattainment areas.more » « less
-
The ozone air quality standard is regularly surpassed in the Los Angeles air basin, and efforts to mitigate ozone production have targeted emissions of precursor volatile organic compounds (VOCs), especially from mobile sources. In order to assess how VOC concentrations, emissions, and chemistry have changed over the past decade, VOCs were measured in this study using a Vocus‐2R proton‐transfer reaction time‐of‐flight mass spectrometer in Pasadena, California, downwind of Los Angeles, in summer 2022. Relative to 2010, ambient concentrations of aromatic hydrocarbons have declined at a similar rate as carbon monoxide, suggesting reduced overall emissions from mobile sources. However, the ambient concentrations of oxygenated VOCs have remained similar or increased, suggesting a greater relative importance of oxidation products and other emission sources, such as volatile chemical products whose emissions are largely unregulated. Relative to 2010, the range of measured VOCs was expanded, including higher aromatics and additional volatile chemical products, allowing a better understanding of a wider range of emission sources. Emission ratios relative to carbon monoxide were estimated and compared with 2010 emission ratios. Average measured ozone concentrations were generally comparable between 2022 and 2010; however, at the same temperature, daytime ozone concentrations were lower in 2022 than 2010. Faster photochemistry was observed in 2022, with average hydroxyl radical exposure being ∼68% higher during midday (statistically significant at 95% confidence), although this difference reduces to ∼35% when comparing observations at ambient temperatures of 25–30°C only. Future trends in temperature are important in predicting ozone production.more » « less
-
Abstract We present measurements of volatile organic compounds (VOCs) and other trace gases taken in Salt Lake City, Utah in August and September 2022. As part of the Salt Lake regional Smoke, Ozone and Aerosol Study (SAMOZA), 35 VOCs were measured with two methods: a proton‐transfer‐reaction time‐of‐flight mass spectrometer (PTR‐ToF‐MS) and 2,4‐dinitrophenylhydrazine (DNPH) cartridges analyzed by high‐performance liquid chromatography (HPLC). Over two months, the total measured VOCs averaged 32 ± 24 ppb (mean ± standard deviation) with the hourly maximum at 141 ppb, and the total calculated OH reactivity averaged 3.7 ± 3.0 s−1(maximum at 20.7 s−1). Among them, methanol and ethanol were the most abundant VOCs, making up 42% of the ambient mixing ratio. Isoprene and monoterpenes contributed 25% of the OH reactivity from VOCs, while formaldehyde and acetaldehyde made up another 30%. The positive matrix factorization analysis showed 5 major sources of VOCs, with 32% of abundance being attributed to secondary production/biogenic sources, 44% from the combination of traffic and personal care products, 15% from industrial solvent use, and the rest from biomass burning (10%). Moderate smoke‐impacted days elevated various hazardous air pollutants (HAPs) on average by 45%–217% compared to smoke‐free days. The ratio of OH reactivity from NOxto that from VOCs showed that ozone production was mostly VOC‐limited throughout the campaign, consistent with our modeling study. VOCs and NOxboth showed increased OH reactivity due to smoke influence. NOxfeatured increased reactivity on weekdays compared to weekends, an effect not shown for VOC reactivity during SAMOZA.more » « less
-
Building insulation materials can affect indoor air by (i) releasing primary volatile organic compounds (VOCs) from building enclosure cavities to the interior space, (ii) mitigating exposure to outdoor pollutants through reactive deposition (of oxidants, e.g. , ozone) or filtration (of particles) in infiltration air, and (iii) generating secondary VOCs and other gas-phase byproducts resulting from oxidant reactions. This study reports primary VOC emission fluxes, ozone (O 3 ) reaction probabilities ( γ ), and O 3 reaction byproduct yields for eight common, commercially available insulation materials. Fluxes of primary VOCs from the materials, measured in a continuous flow reactor using proton transfer reaction-time of flight-mass spectrometry, ranged from 3 (polystyrene with thermal backing) to 61 (cellulose) μmol m −2 h −1 (with total VOC mass emission rates estimated to be between ∼0.3 and ∼3.3 mg m −2 h −1 ). Major primary VOC fluxes from cellulose were tentatively identified as compounds likely associated with cellulose chemical and thermal decomposition products. Ozone-material γ ranged from ∼1 × 10 −6 to ∼30 × 10 −6 . Polystyrene with thermal backing and polyisocyanurate had the lowest γ , while cellulose and fiberglass had the highest. In the presence of O 3 , total observed volatile byproduct yields ranged from 0.25 (polystyrene) to 0.85 (recycled denim) moles of VOCs produced per mole of O 3 consumed, or equivalent to secondary fluxes that range from 0.71 (polystyrene) to 10 (recycled denim) μmol m −2 h −1 . Major emitted products in the presence of O 3 were generally different from primary emissions and were characterized by yields of aldehydes and acetone. This work provides new data that can be used to evaluate and eventually model the impact of “hidden” materials ( i.e. , those present inside wall cavities) on indoor air quality. The data may also guide building enclosure material selection, especially for buildings in areas of high outdoor O 3 .more » « less
