Dimethyl sulfide (DMS; CH3SCH3) from marine phytoplankton is a notable source of atmospheric sulfur1. Its oxidation products include sulfuric acid (SA; H2SO4) and methanesulfonic acid (MSA; CH3SO3H), which has a higher yield than SA below 10 °C (ref. 2). Although SA is known to drive the formation of new particles3, which may subsequently grow and act as cloud condensation nuclei (CCN), the role of MSA remains unclear4. Here, in experiments performed under atmospheric conditions at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we show that MSA nucleates together with ammonia (NH3) below -10 °C, at rates comparable with SA-NH3. Moreover, MSA and SA nucleate synergistically below -10 °C, forming multi-acid molecular clusters with NH3. Even at ultralow NH3 levels, MSA drives particle growth at or near the kinetic limit below 9 °C and above 40% relative humidity (RH). Because MSA and SA generally coexist at similar concentrations in cool marine regions, our findings indicate that nucleation rates may be accelerated up to tenfold and growth rates up to twofold compared with SA-NH3 alone. Our global model simulations indicate that MSA can enhance CCN concentrations, especially in polar regions. We propose that MSA might be an important driver of biogenic particles in cool, pristine marine regions of both the present-day and pre-industrial atmospheres and yet is unaccounted for in global climate models5.

For accurate prediction and modelling of air quality and climate, it is necessary to understand the emissions of volatile organic compounds (VOCs) from the potpourri of sources that they are emitted from: traffic, industry, households, plants, agriculture, etc. In the past, efforts to understand the magnitude and composition of VOC emissions have often relied on indirect methods – either using bottom-up emission models, or inferring emissions top-down from concentration measurements via chemical transport models. Both approaches rely on a number of assumptions regarding chemical reactions and transport - and thus are subject to large uncertainties.Airborne flux observations provide direct emission and deposition information at landscape scale with a resolution of a few km. We performed airborne eddy covariance measurements of a large range of VOCs on board a Twin Otter aircraft in Los Angeles and the agricultural San Joaquin Valley in California using PTR-ToF-MS. Combining these observations with a footprint model, we matched them with gridded inventories in space and time. The comparison with the inventories showed a good representation of typical traffic VOCs, but a significant underestimation of oxygenated VOCs (likely from volatile chemical products and cooking) and terpenoids by the inventories.Using airborne flux footprints in combination with landcover information of the San Joaquin Valley, we disaggregated the observed VOC emissions by multivariate linear regression and attributed them to their sources. This way, we obtained typical VOC emission rates and composition for dairy farms, citrus crops, citrus processing facilities, oak forests, oil and gas wells, and urban areas.

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 similar to 68% higher during midday (statistically significant at 95% confidence), although this difference reduces to similar to 35% when comparing observations at ambient temperatures of 25-30 degrees C only. Future trends in temperature are important in predicting ozone production.

Despite declines in transportation emissions, urban North America and Europe still face unhealthy air pollution levels. This has challenged conventional understanding of the sources of their volatile organic compound (VOC) precursors. Using airborne flux measurements to map emissions of a wide range of VOCs, we demonstrate that biogenic terpenoid emissions contribute ~60% of emitted VOC OH reactivity, ozone, and secondary organic aerosol formation potential in summertime Los Angeles and that this contribution strongly increases with temperature. This implies that control of nitrogen oxides is key to reducing ozone formation in Los Angeles. We also show some anthropogenic VOC emissions increase with temperature, which is an effect not represented in current inventories. Air pollution mitigation efforts must consider that climate warming will strongly change emission amounts and composition.

This study describes a modeling framework, model evaluation, and source apportionment to understand the causes of Los Angeles (LA) air pollution. A few major updates are applied to the Community Multiscale Air Quality (CMAQ) model with a high spatial resolution (1 km × 1 km). The updates include dynamic traffic emissions based on real-time, on-road information and recent emission factors and secondary organic aerosol (SOA) schemes to represent volatile chemical products (VCPs). Meteorology is well predicted compared to ground-based observations, and the emission rates from multiple sources (i.e., on-road, volatile chemical products, area, point, biogenic, and sea spray) are quantified. Evaluation of the CMAQ model shows that ozone is well predicted despite inaccuracies in nitrogen oxide (NOx) predictions. Particle matter (PM) is underpredicted compared to concurrent measurements made with an aerosol mass spectrometer (AMS) in Pasadena. Inorganic aerosol is well predicted, while SOA is underpredicted. Modeled SOA consists of mostly organic nitrates and products from oxidation of alkane-like intermediate volatility organic compounds (IVOCs) and has missing components that behave like less-oxidized oxygenated organic aerosol (LO-OOA). Source apportionment demonstrates that the urban areas of the LA Basin and vicinity are NOx-saturated (VOC-sensitive), with the largest sensitivity of O3 to changes in VOCs in the urban core. Differing oxidative capacities in different regions impact the nonlinear chemistry leading to PM and SOA formation, which is quantified in this study.

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.

With respect to air quality, the San Antonio metropolitan area, with a population of 1.45 million and the second largest city in Texas, has been designated as non-attainment by the United States Environmental Protection Agency in recent years. Despite the operation of multiple stationary air quality monitoring sites by the Texas Commission on Environmental Quality, the in -situ measurements of submicron aerosol and its precursors in the region is limited. To better understand the formation of secondary organic aerosol (SOA) in the San Antonio urban core, we conducted observations of a range of trace gases, volatile organic compounds, submicron aerosol, and meteorological parameters in May 2017. Data from a High-Resolution Time -of -Flight Aerosol Mass Spectrometer (HR-ToF-AMS) show that organic aerosol (OA) was the dominant component of non-refractory submicron particulate matter (average +/- 1a, 55 +/- 32 %, 5.86 +/- 3.40 mu g m-3), followed by sulfate (33 +/- 23 %, 3.52 +/- 2.47 mu g m-3). Aerosol liquid water contents predicted by ISORROPIA-II greatly increase from Continental to Oceanic airmass history scenarios, while inorganic aerosol pH remains very acidic. Positive matrix factorization (PMF) analysis of the OA mass spectra indicates that two classes of oxygenated OA (less and more-oxidized OOA, LO and MO) together constituted the bulk of OA mass during the study period (MO-OOA: 44 +/- 39 %, 2.35 +/- 2.07 mu g m- 3; LO-OOA: 42 +/- 34 %, 2.22 +/- 1.77 mu g m-3), while the fraction of hydrocarbon-like OA was limited (13 +/- 21 %, 0.71 +/- 1.11 mu g m- 3). Using in -situ meteorological data and location-specific empirical coefficients, a zero-dimensional model that utilized PMF factors as proxies to calculate the net rate of formation of types of SOA has been developed; similar calculations were used to estimate the formation rate of particulate organonitrates (pON). The results from the model reveal the importance of pON formation in LO-OOA formation overnight and the influence of temperature and photochemistry during the day. The relationships between local atmospheric factors and the net rate of formation of MO-OOA are not statistically significant. These results emphasize how HR-ToF-AMS-PMF factors could be incorporated into chemistry modeling to evaluate quantitatively the rates of formation of SOA and reveal diurnal differences in SOA formation pathways in a major urban area in southern United States.

Oxygenated organic molecules (OOMs) play an important role in the formation of atmospheric aerosols. Due to various analytical challenges with respect to measuring organic vapors, uncertainties remain regarding the formation and fate of OOMs. The chemical ionization Orbitrap (CI-Orbitrap) mass spectrometer has recently been shown to be a powerful technique that is able to accurately identify gaseous organic compounds due to its greater mass resolution. Here, we present the ammonium-ion-based CI-Orbitrap (NH4+-Orbitrap) as a technique capable of measuring a wide range of gaseous OOMs. The performance of the NH4+-Orbitrap is compared with that of state-of-the-art mass spectrometers, including a nitrate-ion-based chemical ionization atmospheric pressure interface coupled to a time-of-flight mass spectrometer (NO3--LTOF), a new generation of proton transfer reaction-TOF mass spectrometer (PTR3-TOF), and an iodide-based CI-TOF mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (I−-CIMS). The instruments were deployed simultaneously in the Cosmic Leaving OUtdoors Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN) during the CLOUD14 campaign in 2019. Products generated from α-pinene ozonolysis under various experimental conditions were simultaneously measured by the mass spectrometers. The NH4+-Orbitrap was able to identify the widest range of OOMs (i.e., O ≥ 2), from less-oxidized species to highly oxygenated organic molecules (HOMs). Excellent agreement was found between the NH4+-Orbitrap and the NO3--LTOF with respect to characterizing HOMs and with the PTR3-TOF for the less-oxidized monomeric species. OOM concentrations measured by NH4+-Orbitrap were estimated using calibration factors derived from the OOMs with high time-series correlations during the side-by-side measurements. As with the other mass spectrometry techniques used during this campaign, the detection sensitivity of the NH4+-Orbitrap to OOMs is greatly affected by relative humidity, which may be related to changes in ionization efficiency and/or multiphase chemistry. Overall, this study shows that NH4+-ion-based chemistry associated with the high mass resolution of the Orbitrap mass analyzer can measure almost all inclusive compounds. As a result, it is now possible to cover the entire range of compounds, which can lead to a better understanding of the oxidation processes.

State inventories indicate that dairy operations account for nearly half of California's methane budget. Recent analyses suggest, however, that these emissions may be underestimated, complicating efforts to develop emission reduction strategies. Here, we report estimates of dairy methane emissions in the southern San Joaquin Valley (SJV) of California in June 2021 using airborne flux measurements. We find average dairy methane fluxes of 512 ± 178 mg m-2 h-1 from a region of 300+ dairies near Visalia, CA using a combination of eddy covariance and mass balance-based techniques, corresponding to 118 ± 41 kg dairy-1 h-1. These values estimated during our June campaign are 39 ± 48% larger than annual average estimates from the recently developed VISTA-CA inventory. We observed notable increases in emissions with temperature. Our estimates align well with inventory predictions when parametrizations for the temperature dependence of emissions are applied. Our measurements further demonstrate that the VISTA-CA emission inventory is considerably more accurate than the EPA GHG-I inventory in this region. Source apportionment analyses confirm that dairy operations produce the majority of methane emissions in the southern SJV (∼65%). Fugitive oil and gas (O&G) sources account for the remaining ∼35%. Our results support the accuracy of the process-based models used to develop dairy emission inventories and highlight the need for additional investigation of the meteorological dependence of these emissions.

Nitrogen oxides (NOx≡NO+NO2) are involved in most atmospheric photochemistry, including the formation of tropospheric ozone (O3). While various methods exist to accurately measure NOx concentrations, it is still a challenge to quantify the source and flux of NOx emissions. We present airborne measurements of NOx and winds used to infer the emission of NOx across Los Angeles. The measurements were obtained during the research aircraft campaign RECAP-CA (Re-Evaluating the Chemistry of Air Pollutants in CAlifornia) in June 2021. Geographic allocations of the fluxes are compared to the NOx emission inventory from the California Air Resources Board (CARB). We find that the NOx fluxes have a pronounced weekend effect and are highest in the eastern part of the San Bernardino Valley. The comparison of the RECAP-CA and the modeled CARB NOx fluxes suggests that the modeled emissions are higher than expected near the coast and in Downtown Los Angeles and lower than expected further inland in the eastern part of the San Bernardino Valley.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, in marine and polar regions, NH3 is generally low, and H2SO4 is frequently found together with iodine oxoacids [HIOx, i.e., iodic acid (HIO3) and iodous acid (HIO2)]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H2SO4 and HIOx during atmospheric particle nucleation. We found that HIOx greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds with H2SO4 in charged clusters so they drive particle nucleation synergistically. Second, HIO2 substitutes for NH3, forming strongly bound H2SO4-HIO2 acid-base pairs in molecular clusters. Global observations imply that HIOx is enhancing H2SO4(-NH3) nucleation rates 10- to 10,000-fold in marine and polar regions.

Abstract. Nitrogen oxides (NOx) are principle components of air pollution and serve as important ozone precursors. As the San Joaquin Valley (SJV) experiences some of the worst air quality in the United States, reducing NOx emissions is a pressing need, yet quantifying current emissions is complicated due to a mixture of mobile and agriculture sources. We performed airborne eddy covariance flux measurements during the Re-Evaluating the Chemistry of Air Pollutants in California (RECAP-CA) field campaign in June 2021. Combining footprint calculations and land cover statistics, we disaggregate the observed fluxes into component fluxes characterized by three different land cover types. On average, we find emissions of 0.95 mg N m−2 h−1 over highways, 0.43 mg N m−2 h−1 over urban areas, and 0.30 mg N m−2 h−1 over croplands. The calculated NOx emissions using flux observations are utilized to evaluate anthropogenic emissions inventories and soil NOx emissions schemes. We show that two anthropogenic inventories for mobile sources, EMFAC (EMission FACtors) and FIVE (Fuel-based Inventory for Vehicle Emissions), yield strong agreement with emissions derived from measured fluxes over urban regions. Three soil NOx schemes, including the MEGAN v3 (Model of Emissions of Gases and Aerosols from Nature), BEIS v3.14 (Biogenic Emission Inventory System), and BDISNP (Berkeley–Dalhousie–Iowa Soil NO Parameterization), show substantial underestimates over the study domain. Compared to the cultivated soil NOx emissions derived from measured fluxes, MEGAN and BEIS are lower by more than 1 order of magnitude, and BDISNP is lower by a factor of 2.2. Despite the low bias, observed soil NOx emissions and BDISNP present a similar spatial pattern and temperature dependence. We conclude that soil NOx is a key feature of the NOx emissions in the SJV and that a biogeochemical-process-based model of these emissions is needed to simulate emissions for modeling air quality in the region.

Los Angeles is a major hotspot for ozone and particulate matter air pollution in the United States. Ozone and PM2.5 in this region have not improved substantially for the past decade, despite a reduction in vehicular emissions of their precursors, NOx and volatile organic compounds (VOCs). This reduction in "traditional" sources has made the current emission mixture of air pollutant precursors more uncertain. To map and quantify emissions of a wide range of VOCs in this urban area, we performed airborne eddy covariance measurements with wavelet analysis. VOC fluxes measured include tracers for source categories, such as traffic, vegetation, and volatile chemical products (VCPs). Mass fluxes were dominated by oxygenated VOCs, with ethanol contributing ∼29% of the total. In terms of OH reactivity and aerosol formation potential, terpenoids contributed more than half. Observed fluxes were compared with two commonly used emission inventories: the California Air Resources Board inventory and the combination of the Biogenic Emission Inventory System with the Fuel-based Inventory of Vehicle Emissions combined with Volatile Chemical Products (FIVE-VCP). The comparison shows mismatches regarding the amount, spatial distribution, and weekend effects of observed VOC emissions with the inventories. The agreement was best for typical transportation related VOCs, while discrepancies were larger for biogenic and VCP-related VOCs.

Aerosol particles have an important role in Earth's radiation balance and climate, both directly and indirectly through aerosol-cloud interactions. Most aerosol particles in the atmosphere are weakly charged, affecting both their collision rates with ions and neutral molecules, as well as the rates by which they are scavenged by other aerosol particles and cloud droplets. The rate coefficients between ions and aerosol particles are important since they determine the growth rates and lifetimes of ions and charged aerosol particles, and so they may influence cloud microphysics, dynamics, and aerosol processing. However, despite their importance, very few experimental measurements exist of charged aerosol collision rates under atmospheric conditions, where galactic cosmic rays in the lower troposphere give rise to ion pair concentrations of around 1000 cm(-3). Here we present measurements in the CERN CLOUD chamber of the rate coefficients between ions and small (< 10 nm) aerosol particles containing up to 9 elementary charges, e. We find the rate coefficient of a singly charged ion with an oppositely charged particle increases from 2.0 (0.4-4.4) x 10(-6) cm(3) s(-1) to 30.6 (24.9-45.1) x 10(-6) cm(3) s(-1) for particles with charges of 1 to 9 e, respectively, where the parentheses indicate the +/- 1 sigma uncertainty interval. Our measurements are compatible with theoretical predictions and show excellent agreement with the model of Gatti and Kortshagen (2008).

The San Joaquin Valley is an agricultural region in California that suffers from poor air quality. Since traffic emissions are decreasing, other sources of volatile organic compounds (VOCs) are gaining importance in the formation of secondary air pollutants. Using airborne eddy covariance, we conducted direct, spatially resolved flux observations of a wide range of VOCs in the San Joaquin Valley during June 2021 at 23–36 ∘C. Through land-cover-informed footprint disaggregation, we were able to attribute emissions to sources and identify tracers for distinct source types. VOC mass fluxes were dominated by alcohols, mainly from dairy farms, while oak isoprene and citrus monoterpenes were important sources of reactivity. Comparisons with two commonly used inventories showed that isoprene emissions in the croplands were overestimated, while dairy and highway VOC emissions were generally underestimated in the inventories, and important citrus and biofuel VOC point sources were missing from the inventories. This study thus presents unprecedented insights into the VOC sources in an intensive agricultural region and provides much needed information for the improvement of inventories, air quality predictions, and regulations.

New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN)1-4. However, the precursor vapours that drive the process are not well understood. With experiments performed under upper tropospheric conditions in the CERN CLOUD chamber, we show that nitric acid, sulfuric acid and ammonia form particles synergistically, at rates that are orders of magnitude faster than those from any two of the three components. The importance of this mechanism depends on the availability of ammonia, which was previously thought to be efficiently scavenged by cloud droplets during convection. However, surprisingly high concentrations of ammonia and ammonium nitrate have recently been observed in the upper troposphere over the Asian monsoon region5,6. Once particles have formed, co-condensation of ammonia and abundant nitric acid alone is sufficient to drive rapid growth to CCN sizes with only trace sulfate. Moreover, our measurements show that these CCN are also highly efficient ice nucleating particles-comparable to desert dust. Our model simulations confirm that ammonia is efficiently convected aloft during the Asian monsoon, driving rapid, multi-acid HNO3-H2SO4-NH3 nucleation in the upper troposphere and producing ice nucleating particles that spread across the mid-latitude Northern Hemisphere.

New particle formation in the upper free troposphere is a major global source of cloud condensation nuclei (CCN) 1 – 4 . However, the precursor vapours that drive the process are not well understood. With experiments performed under upper tropospheric conditions in the CERN CLOUD chamber, we show that nitric acid, sulfuric acid and ammonia form particles synergistically, at rates that are orders of magnitude faster than those from any two of the three components. The importance of this mechanism depends on the availability of ammonia, which was previously thought to be efficiently scavenged by cloud droplets during convection. However, surprisingly high concentrations of ammonia and ammonium nitrate have recently been observed in the upper troposphere over the Asian monsoon region 5 , 6 . Once particles have formed, co-condensation of ammonia and abundant nitric acid alone is sufficient to drive rapid growth to CCN sizes with only trace sulfate. Moreover, our measurements show that these CCN are also highly efficient ice nucleating particles—comparable to desert dust. Our model simulations confirm that ammonia is efficiently convected aloft during the Asian monsoon, driving rapid, multi-acid HNO 3 –H 2 SO 4 –NH 3 nucleation in the upper troposphere and producing ice nucleating particles that spread across the mid-latitude Northern Hemisphere.

The population of Texas has increased rapidly in the past decade. The San Antonio Field Study (SAFS) was designed to investigate ozone (O3) production and precursors in this rapidly changing, sprawling metropolitan area. There are still many questions regarding the sources and chemistry of volatile organic compounds (VOCs) in urban areas like San Antonio which are affected by a complex mixture of industry, traffic, biogenic sources and transported pollutants. The goal of the SAFS campaign in May 2017 was to measure inorganic trace gases, VOCs, methane (CH4), and ethane (C2H6). The SAFS field design included two sites to better assess air quality across the metro area: an urban site (Traveler's World; TW) and a downwind/suburban site (University of Texas at San Antonio; UTSA). The results indicated that acetone (2.52 ± 1.17 and 2.39 ± 1.27 ppbv), acetaldehyde (1.45 ± 1.02 and 0.93 ± 0.45 ppbv) and isoprene (0.64 ± 0.49 and 1.21 ± 0.85 ppbv; TW and UTSA, respectively) were the VOCs with the highest concentrations. Additionally, positive matrix factorization showed three dominant factors of VOC emissions: biogenic, aged urban mixed source, and acetone. Methyl vinyl ketone and methacrolein (MVK + MACR) exhibited contributions from both secondary photooxidation of isoprene and direct emissions from traffic. The C2H6:CH4 demonstrated potential influence of oil and gas activities in San Antonio. Moreover, the high O3 days during the campaign were in the NOx-limited O3 formation regime and were preceded by evening peaks in select VOCs, NOx and CO. Overall, quantification of the concentration and trends of VOCs and trace gases in a major city in Texas offers vital information for general air quality management and supports strategies for reducing O3 pollution. The SAFS campaign VOC results will also add to the growing body of literature on urban sources and concentrations of VOCs in major urban areas.

San Antonio, the second-most populous city in Texas and the seventh-most populous city in the United States (US), has been designated a marginal non-attainment area by the US Environmental Protection Agency with respect to the 2015 ozone (O3) National Ambient Air Quality Standard. While stationary air quality monitoring sites are operated in the region by the Texas Commission on Environmental Quality (TCEQ), there are limited in situ field measurements for O3 and its precursors in the urban core. To better understand O3 dynamics in San Antonio, a suite of meteorological and gas instruments was deployed during May 2017. We incorporate field measurements from two campaign sites and one TCEQ stationary monitoring site into a zero-dimensional O3 model to characterize the local formation and destruction rates of O3, hydroxyl radical (OH) reactivity of volatile organic compounds (VOCs), O3 production efficiency, and O3 formation regime in the urban core and directly downwind of San Antonio. Upwind/downwind differences indicate the importance of photochemical processing of VOCs with carbon-carbon double bonds. San Antonio was mostly in a nitrogen oxide (NOX)-sensitive regime throughout the daytime during the campaign period, with O3 formation peaking at noon in the city center and early afternoon at the downwind region. Formaldehyde (HCHO), isoprene, and alkenes dominated VOC reactivity, with alkenes and isoprene from San Antonio's core (upwind) likely contributing to the downwind formation of HCHO and enhancing its OH reactivity. However, their direct impact on downwind O3 production was not observed. Model results suggest further strengthening NOX emission controls to decrease O3 formation in San Antonio.

Particle size measurement in the low nanometer regime is of great importance to the study of cloud condensation nuclei formation and to better understand aerosol–cloud interactions. Here we present the design, modeling, and experimental characterization of the nano-scanning electrical mobility spectrometer (nSEMS), a recently developed instrument that probes particle physical properties in the 1.5–25 nm range. The nSEMS consists of a novel differential mobility analyzer and a two-stage condensation particle counter (CPC). The mobility analyzer, a radial opposed-migration ion and aerosol classifier (ROMIAC), can classify nanometer-sized particles with minimal degradation of its resolution and diffusional losses. The ROMIAC operates on a dual high-voltage supply with fast polarity-switching capability to minimize sensitivity to variations in the chemical nature of the ions used to charge the aerosol. Particles transmitted through the mobility analyzer are measured using a two-stage CPC. They are first activated in a fast-mixing diethylene glycol (DEG) stage before being counted by a second detection stage, an ADI MAGIC™ water-based CPC. The transfer function of the integrated instrument is derived from both finite-element modeling and experimental characterization. The nSEMS performance has been evaluated during measurement of transient nucleation and growth events in the CLOUD atmospheric chamber at CERN. We show that the nSEMS can provide high-time- and size-resolution measurement of nanoparticles and can capture the critical aerosol dynamics of newly formed atmospheric particles. Using a soft x-ray bipolar ion source in a compact housing designed to optimize both nanoparticle charging and transmission efficiency as a charge conditioner, the nSEMS has enabled measurement of the contributions of both neutral and ion-mediated nucleation to new particle formation.