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Isoprene has the highest emission into Earth’s atmosphere of any nonmethane hydrocarbon. Atmospheric processing of alkenes, including isoprene, via ozonolysis leads to the formation of zwitterionic reactive intermediates, known as Criegee intermediates (CIs). Direct studies have revealed that reactions involving simple CIs can significantly impact the tropospheric oxidizing capacity, enhance particulate formation, and degrade local air quality. Methyl vinyl ketone oxide (MVK-oxide) is a four-carbon, asymmetric, resonance-stabilized CI, produced with 21 to 23% yield fromisoprene ozonolysis, yet its reactivity has not been directly studied. We present direct kinetic measurements of MVK-oxide reactions with key atmospheric species using absorption spectroscopy. Direct UV-Vis absorption spectra from two independent flow cell experiments overlap with the molecular beam UV-Vis-depletion spectra reported recently [M. F. Vansco, B. Marchetti, M. I. Lester, J. Chem. Phys. 149, 44309 (2018)] but suggest different conformer distributions under jetcooled and thermal conditions. Comparison of the experimental lifetime herein with theory indicates only the syn-conformers are observed; anti-conformers are calculated to be removed much more rapidly via unimolecular decay. We observe experimentally and predict theoretically fast reaction of syn-MVK-oxide with SO₂ and formic acid, similar to smaller alkyl-substituted CIs, and by contrast, slow removal in the presence of water. We determine products through complementary multiplexed photoionization mass spectrometry, observing SO₃ and identifying organic hydroperoxide formation from reaction with SO₂ and formic acid, respectively. The tropospheric implications of these reactions are evaluated using a global chemistry and transport model.

Methacrolein oxide (MACR-oxide) is a four-carbon, resonance-stabilized Criegee intermediate produced from isoprene ozonolysis, yet its reactivity is not well understood. This study identifies the functionalized hydroperoxide species, 1-hydroperoxy-2-methylallyl formate (HPMAF), generated from the reaction of MACR-oxide with formic acid using multiplexed photoionization mass spectrometry (MPIMS, 298 K = 25 °C, 10 torr = 13.3 hPa). Electronic structure calculations indicate the reaction proceeds via an energetically favorable 1,4-addition mechanism. The formation of HPMAF is observed by the rapid appearance of a fragment ion at m/z 99, consistent with the proposed mechanism and characteristic loss of HO2 upon photoionization of functional hydroperoxides. The identification of HPMAF is confirmed by comparison of the appearance energy of the fragment ion with theoretical predictions of its photoionization threshold. The results are compared to analogous studies on the reaction of formic acid with methyl vinyl ketone oxide (MVK-oxide), the other four-carbon Criegee intermediate in isoprene ozonolysis.

Volatile chemical products (VCPs) and other non-traditional anthropogenic sources, such as cooking, contribute substantially to the volatile organic compound (VOC) budget in urban areas, but their impact on ozone formation is less certain. This study employs Lagrangian box modeling and sensitivity analyses to evaluate ozone response to sector-specific VOC and nitrogen oxide (NOx) emissions in two Los Angeles (LA) Basin cities during the summer of 2021. The model simulated the photochemical processing and transport of temporally and spatially gridded emissions from the FIVE-VCP-NEI17NRT inventory and accurately simulates the variability and magnitude of O3, NOx, and speciated VOCs in Pasadena, CA. VOC sensitivity analyses show that anthropogenic VOCs (AVOC) enhance the mean daily maximum 8 h average ozone in Pasadena by 13 ppb, whereas biogenic VOCs (BVOCs) contribute 9.4 ppb. Of the ozone influenced by AVOCs, VCPs represent the largest fraction at 45 %, while cooking and fossil fuel VOCs are comparable at 26 % and 29 %, respectively. NOx sensitivity analyses along trajectory paths indicate that the photochemical regime of ozone varies spatially and temporally. The modeled ozone response is primarily NOx-saturated across the dense urban core and during peak ozone production in Pasadena. Lowering the inventory emissions of NOx by 25 % moves Pasadena to NOx-limited chemistry during afternoon hours and shrinks the spatial extent of NOx saturation towards downtown LA. Further sensitivity analyses show that using VOCs represented by a separate state inventory requires steeper NOx reductions to transition to NOx sensitivity, further suggesting that accurately representing VOC reactivity in inventories is critical to determining the effectiveness of future NOx reduction policies.

The NOAA Chemical Sciences Laboratory (CSL) conducted the Southwest Urban NO.sub.x and VOCs Experiment (SUNVEx) to study emissions and the role of boundary layer (BL) dynamics and sea-breeze (SB) transitions in the evolution of coastal air quality. The study presented utilizes remote sensing and in situ observations in Pasadena, California. Separate analyses are conducted on the synoptic conditions during ozone (O.sub.3) exceedance (70 ppb) and non-exceedance (<70 ppb) days, as well as the fine-structure variability of in situ chemistry measurements during BL growth and SB transitions.

The NOAA Chemical Sciences Laboratory (CSL) conducted the Southwest Urban NOx and VOCs Experiment (SUNVEx) to study emissions and the role of boundary layer (BL) dynamics and sea-breeze (SB) transitions in the evolution of coastal air quality. The study presented utilizes remote sensing and in situ observations in Pasadena, California. Separate analyses are conducted on the synoptic conditions during ozone (O3) exceedance (>70 ppb) and non-exceedance (<70 ppb) days, as well as the fine-structure variability of in situ chemistry measurements during BL growth and SB transitions. Diurnal analyses spanning August 2021 revealed a markedly different wind direction during evenings preceding O3 exceedance (northerly) versus non-exceedance (easterly) days. Increased O3 occurred simultaneously with warmer and drier conditions, a reduction in winds, and an increase in volatile organic compounds (VOCs) and fine particulate matter (PM2.5). While the average BL height was lower and surface pressure was higher, the day-to-day variability of these quantities led to an overall weak statistical relationship. Investigations focused on the fine-structure variability of in situ chemistry measurements superimposed on background trends were conducted using a novel multivariate spectral coherence mapping (MSCM) technique that combined the spectral structure of two or more independent measurements through a wavelet analysis as reported by maximum-normalized scaleograms. A case study was chosen to illustrate the MSCM technique, where the dominant peaks in scaleograms were identified and compared to BL height during the growth phase. The temporal widths of peaks (τmax) derived from VOC and nitrogen oxide (NOx) scaleograms, as well as scaleograms combining VOCs, NOx, and variations in BL height, indicated a broadening with respect to time as the BL increased in depth. A separate section focused on comparisons between τmax and BL height during August 2021 revealed uncorrelated or weakly correlated scatter, except in the case of VOCs when really large τmax and relatively deep BL heights were ignored. Instances of large τmax and relatively deep BL heights occurred near sunrise and as onshore flow entered Pasadena, respectively. Wind transitions likely influenced both the dynamical evolution of the BL and tracer advection and thus offer additional challenges when separating factors contributing to the fine structure. Other insights gained from this work include observations of descending wind jets from the San Gabriel Mountains that were not resolved by the High-Resolution Rapid Refresh (HRRR) model and the derivation of intrinsic properties of oscillations observed in NOx and O3 during the interaction between an SB and enhanced winds above the BL that flowed in opposition to the SB.

The NOAA Chemical Sciences Laboratory (CSL) conducted the Southwest Urban NOx and VOCs Experiment (SUNVEx) to study emissions and the role of boundary layer (BL) dynamics and sea-breeze (SB) transitions in the evolution of coastal air quality. The study presented utilizes remote sensing and in situ observations in Pasadena, California. Separate analyses are conducted on the synoptic conditions during ozone (O3) exceedance (>70 ppb) and non-exceedance (<70 ppb) days, as well as the fine-structure variability of in situ chemistry measurements during BL growth and SB transitions.Diurnal analyses spanning August 2021 revealed a markedly different wind direction during evenings preceding O3 exceedance (northerly) versus non-exceedance (easterly) days. Increased O3 occurred simultaneously with warmer and drier conditions, a reduction in winds, and an increase in volatile organic compounds (VOCs) and fine particulate matter (PM2.5). While the average BL height was lower and surface pressure was higher, the day-to-day variability of these quantities led to an overall weak statistical relationship. Investigations focused on the fine-structure variability of in situ chemistry measurements superimposed on background trends were conducted using a novel multivariate spectral coherence mapping (MSCM) technique that combined the spectral structure of two or more independent measurements through a wavelet analysis as reported by maximum-normalized scaleograms. A case study was chosen to illustrate the MSCM technique, where the dominant peaks in scaleograms were identified and compared to BL height during the growth phase. The temporal widths of peaks (τmax) derived from VOC and nitrogen oxide (NOx) scaleograms, as well as scaleograms combining VOCs, NOx, and variations in BL height, indicated a broadening with respect to time as the BL increased in depth. A separate section focused on comparisons between τmax and BL height during August 2021 revealed uncorrelated or weakly correlated scatter, except in the case of VOCs when really large τmax and relatively deep BL heights were ignored. Instances of large τmax and relatively deep BL heights occurred near sunrise and as onshore flow entered Pasadena, respectively. Wind transitions likely influenced both the dynamical evolution of the BL and tracer advection and thus offer additional challenges when separating factors contributing to the fine structure. Other insights gained from this work include observations of descending wind jets from the San Gabriel Mountains that were not resolved by the High-Resolution Rapid Refresh (HRRR) model and the derivation of intrinsic properties of oscillations observed in NOx and O3 during the interaction between an SB and enhanced winds above the BL that flowed in opposition to the SB.

During summer 2023 Canada experienced its most intense wildfire season on record. Smoke plumes from these fires advected across the United States (U.S.) Upper Midwest, producing regional scale surface enhancements of PM2.5 and ozone, as recorded by the U.S. surface monitoring network. These events are notable because they occurred early in the fire season (May 15‐June 30), and they produced the highest regional‐scale surface ozone levels ever recorded across the northern tier of the U.S. during early (May–June) or late (July‐August) summer. Specifically, the Upper Midwest 50th ozone percentile was greater than in any other year since 1995, when the ozone monitoring network had sufficient coverage to assess regional‐scale ozone levels; the 90th percentile was the highest since 2002. Satellite and aircraft measurements demonstrate the availability of ozone precursors and ozone production within the smoke plumes. Plain Language Summary Ozone is a trace gas in the atmosphere that acts as an important greenhouse gas, and high concentrations near Earth's surface are a form of air pollution, detrimental to human health and vegetation productivity. Ozone is formed by sunlight reacting with precursor gases, such as those emitted by fossil fuel combustion. Wildfires are also an important source of ozone precursor gases. During summer 2023 Canada experienced its most intense wildfire season on record. Smoke from these fires impacted the U.S. Upper Midwest during May–June 2023, leading to regional scale surface enhancements of fine particulate matter and ozone. These unusual early season fires produced the highest regional‐scale surface ozone levels ever recorded across the northern U.S. Mid‐latitude wildfires have increased as the planet warms, and their frequency is expected to increase further with continued climate change. This analysis suggests that extreme ozone pollution episodes associated with wildfires could also increase in the future. Key Points During summer 2023 Canada experienced its most intense wildfire season on record Smoke from these fires impacted the United States (U.S.) Upper Midwest during May–June, leading to regional scale surface enhancements of PM2.5 and ozone These unusual early season fires produced the highest regional‐scale surface ozone levels ever recorded across the northern United States

Ozone profile measurements at high temporal and vertical resolution are needed to better understand physical and chemical processes driving tropospheric ozone variability and to validate the tropospheric ozone measurements from spaceborne missions such as TEMPO (Tropospheric Emissions: Monitoring Pollution). As part of the Tropospheric Ozone Lidar Network (TOLNet) efforts allocated to provide such measurements and leveraging on the experience of more than 20 years of ozone lidar measurements at Table Mountain Facility, the JPL lidar group developed the SMOL (Small Mobile Ozone Lidar), an affordable differential absorption lidar (DIAL) system covering all altitudes from 200 to 10 km above ground level (a.g.l.). The transmitter is based on a quadrupled Nd:YAG laser, which is further converted into a 289/299 nm wavelength pair using Raman shifting cells, and the receiver consists of three ozone DIAL pairs, including one that is 266/289 nm and two that are 289/299 nm. Two units were deployed in the Los Angeles basin area during the Synergistic TEMPO Air Quality Science (STAQS) and Atmospheric Emissions and Reactions Observed from Megacities to Marine Areas (AEROMMA) campaigns in summer 2023. The comparison with airborne in situ and lidar measurements shows very good agreement, with systematic differences below 10 % throughout most of the measurement range. An additional comparison with nearby surface ozone measuring instruments indicates unbiased measurements by the SMOL lidars down to 200 m a.g.l. Further comparison with the Goddard Earth Observing System Composition Forecast (GEOS-CF) model suggests that such lidars are a critical tool to perform model validation and can potentially be used for assimilation to air quality forecasts.

The declining trend in vehicle emissions has underscored the growing significance of volatile organic compound (VOC) emissions from volatile chemical products (VCPs). However, accurately representing VOC chemistry in simplified chemical mechanisms remains challenging due to its chemical complexity including speciation and reactivity. Previous studies have predominantly focused on VOCs from fossil fuel sources, leading to an underrepresentation of VOC chemistry from VCP sources. We developed an integrated chemical mechanism, RACM2B-VCP, that is compatible with WRF-Chem and is aimed at enhancing the representation of VOC chemistry, particularly from VCP sources, within the present urban environment. Evaluation against the Air Quality System (AQS) network data demonstrates that our model configured with RACM2B-VCP reproduces both the magnitude and spatial variability of O3 and PM2.5 in Los Angeles. Furthermore, evaluation against comprehensive measurements of O3 and PM2.5 precursors from the Reevaluating the Chemistry of Air Pollutants in California (RECAP-CA) airborne campaign and the Southwest Urban NOx and VOC Experiment (SUNVEx) ground site and mobile laboratory campaign confirm the model's accuracy in representing NOx and many VOCs and highlight remaining biases. Although there exists an underprediction in the total VOC reactivity of observed VOC species, our model with RACM2B-VCP exhibits good agreement for VOC markers emitted from different sectors, including biogenic, fossil fuel, and VCP sources. Through sensitivity analyses, we probe the contributions of VCP and fossil fuel emissions to total VOC reactivity and O3. Our results reveal that 52 % of the VOC reactivity and 35 % of the local enhancement of MDA8 O3 arise from anthropogenic VOC emissions in Los Angeles. Significantly, over 50 % of this anthropogenic fraction of either VOC reactivity or O3 is attributed to VCP emissions. The RACM2B-VCP mechanism created, described, and evaluated in this work is ideally suited for accurately representing ozone for the right reasons in the present urban environment where mobile, biogenic, and VCP VOCs are all important contributors to ozone formation.

Volatile chemical products (VCPs) and other non-traditional anthropogenic sources, such as cooking, contribute substantially to the volatile organic compound (VOC) budget in urban areas, but their impact on ozone formation is less certain. This study employs Lagrangian box modeling and sensitivity analyses to evaluate ozone response to sector-specific VOC and nitrogen oxide (NO.sub.x) emissions in two Los Angeles (LA) Basin cities during the summer of 2021. The model simulated the photochemical processing and transport of temporally and spatially gridded emissions from the FIVE-VCP-NEI17NRT inventory and accurately simulates the variability and magnitude of O.sub.3, NO.sub.x, and speciated VOCs in Pasadena, CA. VOC sensitivity analyses show that anthropogenic VOCs (AVOC) enhance the mean daily maximum 8 h average ozone in Pasadena by 13 ppb, whereas biogenic VOCs (BVOCs) contribute 9.4 ppb. Of the ozone influenced by AVOCs, VCPs represent the largest fraction at 45 %, while cooking and fossil fuel VOCs are comparable at 26 % and 29 %, respectively. NO.sub.x sensitivity analyses along trajectory paths indicate that the photochemical regime of ozone varies spatially and temporally. The modeled ozone response is primarily NO.sub.x -saturated across the dense urban core and during peak ozone production in Pasadena. Lowering the inventory emissions of NO.sub.x by 25 % moves Pasadena to NO.sub.x -limited chemistry during afternoon hours and shrinks the spatial extent of NO.sub.x saturation towards downtown LA. Further sensitivity analyses show that using VOCs represented by a separate state inventory requires steeper NO.sub.x reductions to transition to NO.sub.x sensitivity, further suggesting that accurately representing VOC reactivity in inventories is critical to determining the effectiveness of future NO.sub.x reduction policies.