Urban aerosol pollution is evolving rapidly with global change and poses significant risks to public health. Measurements and machine learning-enabled chemical analysis of aerosol from a suburb of New York City in 2023 reveal emerging sources and drivers in a modern megacity. Regional wildfire smoke averaged 25% of organic aerosol (OA) mass and drove variability via enhancements of biogenic OA formation within smoke plumes. This biogenic OA contributed 40% of aerosol mass. Urban heatwaves enhanced both biogenic and anthropogenic sources, with ~20% of OA mass exhibiting significant heatwave sensitivity. For the first time, volatile chemical product (VCP) compounds were directly observed, speciated, and characterized in urban aerosol. Contributions to total OA averaged 15%, double the contribution from traffic. Together, this work identifies wildfire smoke, biogenic emissions, heat, and emerging anthropogenic emissions as critical global change vulnerabilities for North American urban aerosol pollution that pose unique challenges for control strategies.

Isoprene is a reactive hydrocarbon emitted to the atmosphere in large quantities by terrestrial vegetation. Annual total isoprene emissions exceed 300 Tg a −1 , but emission rates vary widely among plant species and are sensitive to meteorological and environmental conditions including temperature, sunlight, and soil moisture. Due to its high reactivity, isoprene has a large impact on air quality and climate pollutants such as ozone and aerosols. It is also an important sink for the hydroxyl radical which impacts the lifetime of the important greenhouse gas methane along with many other trace gas species. Modeling the impacts of isoprene emissions on atmospheric chemistry and climate requires accurate isoprene emission estimates. These can be obtained using the empirical Model of Emissions of Gases and Aerosols from Nature (MEGAN), but the parameterization of this model is uncertain due in part to limited field observations. In this study, we use ground‐based measurements of isoprene concentrations and fluxes from 11 field sites to assess the variability of the isoprene emission temperature response across ecosystems. We then use these observations in a Metropolis‐Hastings Markov Chain Monte Carlo (MHMCMC) data assimilation framework to optimize the MEGAN temperature response function. We find that the performance of MEGAN can be significantly improved at several high‐latitude field sites by increasing the modeled sensitivity of isoprene emissions to past temperatures. At some sites, the optimized model was nearly four times more sensitive to temperature than the unoptimized model. This has implications for air quality modeling in a warming climate.

AbstractBecause of its global abundance and reactivity with hydroxyl radicals (OH•), tropospheric carbon monoxide indirectly impacts the lifetimes of other OH•‐reactive gases, in particular methane and reactive hydrocarbons. The origin and chemistry of atmospheric CO have been studied using stable isotopes. Both 13CO and C18O undergo isotopic fractionation during its main chemical loss reaction, CO + OH•. The kinetic isotope effect (KIE) for 13CO is mass dependent, with a value of ∼5‰; 12CO reacts faster than 13CO with OH. Whereas C18O + OH• exhibits an inversely mass dependent KIE ∼−10‰. We hypothesize these KIEs result in a relative depletion of 13C18O, a CO clumped isotope. To test this, we collected CO from air samples on Long Island, NY, and discovered a −3 to −8‰ difference in the clumped isotope ratio, Δ31, relative to a random distribution of 13C and 18O in CO. A clear negative trend between [CO] and Δ31 is driven by two factors: (a) the atmospheric addition of CO from either a primary or secondary source with a Δ31 of ∼0‰ and (b) the continuing reaction of CO with OH•, leaving the remaining CO pool relatively depleted in 13C18O. This is analogous to the mechanism that determines CO Δ17O values. This study is among the first to show clumped isotope fractionation resulting from atmospheric chemistry and not thermal equilibration, which may inform the identification of clumped isotope KIEs in other atmospheric trace gases. These first Δ31 observations motivate future experimental and observational studies targeted at characterizing the clumped isotopes of CO sources, background CO, and experimentally fractionated CO.

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C5H8H+), acetaldehyde (m/z 45, CH3CHO+), and benzene (m/z 79, C6H6H+). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra.

As cities strive for ambitious increases in tree canopy cover and reductions in anthropogenic volatile organic compound (AVOC) emissions, accurate assessments of the impacts of biogenic VOCs (BVOCs) on air quality become more important. In this study, we aim to quantify the impact of future urban greening on ozone production. BVOC emissions in dense urban areas are often coarsely represented in regional models. We set up a high-resolution (30 m) MEGAN (The Model of Emissions of Gases and Aerosols from Nature version 3.2) to estimate summertime biogenic isoprene emissions in the New York City metro area (NYC-MEGAN). Coupling an observation-constrained box model with NYC-MEGAN isoprene emissions successfully reproduced the observed isoprene concentrations in the city core. We then estimated future isoprene emissions from likely urban greening scenarios and evaluated the potential impact on future ozone production. NYC-MEGAN predicts up to twice as much isoprene emissions in NYC as the coarse-resolution (1.33 km) Biogenic Emission Inventory System version 3.61 (BEIS) on hot summer days. We find that BVOCs drive ozone production on hot summer days, even in the city core, despite large AVOC emissions. If high isoprene emitting species (e.g., oak trees) are planted, future isoprene emissions could increase by 1.4-2.2 times in the city core, which would result in 8-19 ppbv increases in peak ozone on ozone exceedance days with current NOx concentrations. We recommend planting non- or low-isoprene emitting trees in cities with high NOx concentrations to avoid an increase in the frequency and severity of future ozone exceedance events.

Active chlorine in the atmosphere is poorly constrained and so is its role in the oxidation of the potent greenhouse gas methane, causing uncertainty in global methane budgets. We propose a photocatalytic mechanism for chlorine atom production that occurs when Sahara dust mixes with sea spray aerosol. The mechanism is validated by implementation in a global atmospheric model and thereby explaining the episodic, seasonal, and location-dependent 13C depletion in CO in air samples from Barbados [J.E. Mak, G. Kra, T. Sandomenico, P. Bergamaschi, J. Geophys. Res. Atmos.108 (2003)], which remained unexplained for decades. The production of Cl can also explain the anomaly in the CO:ethane ratio found at Cape Verde [K. A. Read et al., J. Geophys. Res. Atmos.114 (2009)], in addition to explaining the observation of elevated HOCl [M. J. Lawler et al., Atmos. Chem. Phys.11, 7617-7628 (2011)]. Our model finds that 3.8 Tg(Cl) y-1 is produced over the North Atlantic, making it the dominant source of chlorine in the region; globally, chlorine production increases by 41%. The shift in the methane sink budget due to the increased role of Cl means that isotope-constrained top-down models fail to allocate 12 Tg y-1 (2% of total methane emissions) to 13C-depleted biological sources such as agriculture and wetlands. Since 2014, an increase in North African dust emissions has increased the 13C isotope of atmospheric CH4, thereby partially masking a much greater decline in this isotope, which has implications for the interpretation of the drivers behind the recent increase of methane in the atmosphere.

Air quality policies have made substantial gains by reducing pollutant emissions from the transportation sector. In March 2020, New York City's activities were severely curtailed in response to the COVID-19 pandemic, resulting in 60–90% reductions in human activity. We continuously measured major volatile organic compounds (VOCs) during January–April 2020 and 2021 in Manhattan. Concentrations of many VOCs decreased significantly during the shutdown with variations in daily patterns reflective of human activity perturbations, resulting in a temporary ∼28% reduction in chemical reactivity. However, the limited effect of these dramatic measures was outweighed by larger increases in VOC-related reactivity during the anomalously warm spring 2021. This emphasizes the diminishing returns from transportation-focused policies alone and the risk of increased temperature-dependent emissions undermining policy-related gains in a warming climate.

Volatile chemical products (VCPs) and other non-combustion-related sources have become important for urban air quality, and bottom-up calculations report emissions of a variety of functionalized compounds that remain understudied and uncertain in emissions estimates. Using a new instrumental configuration, we present online measurements of oxygenated organic compounds in a U.S. megacity over a 10-day wintertime sampling period, when biogenic sources and photochemistry were less active. Measurements were conducted at a rooftop observatory in upper Manhattan, New York City, USA using a Vocus chemical ionization time-of-flight mass spectrometer with ammonium (NH4 +) as the reagent ion operating at 1 Hz. The range of observations spanned volatile, intermediate-volatility, and semi-volatile organic compounds with targeted analyses of ~150 ions whose likely assignments included a range of functionalized compound classes such as glycols, glycol ethers, acetates, acids, alcohols, acrylates, esters, ethanolamines, and ketones that are found in various consumer, commercial, and industrial products. Their concentrations varied as a function of wind direction with enhancements over the highly-populated areas of the Bronx, Manhattan, and parts of New Jersey, and included abundant concentrations of acetates, acrylates, ethylene glycol, and other commonly-used oxygenated compounds. The results provide top-down constraints on wintertime emissions of these oxygenated/functionalized compounds with ratios to common anthropogenic marker compounds, and comparisons of their relative abundances to two regionally-resolved emissions inventories used in urban air quality models.

The co-occurrence of enhancement in aerosol concentration, temperatures, and ozone mixing ratio was observed between June 29 and July 4, 2018 (enhanced period, EP) on Long Island (LI) and the greater NYC metropolitan area during part of the 2018 Long Island Sound Tropospheric Ozone Study (LISTOS). Two aerosol formation pathways were identified during the EP, the first being the condensation of semi- and intermediate volatility oxidation products of anthropogenic volatile organic compounds (AVOCs) under stagnant synoptic flow conditions, high temperatures and afternoon sea-breeze circulation. While this first pathway was prevalent, the most abundant organic aerosol factor was less oxidized oxygenated organic aerosol or LO-OOA. The second formation pathway occurred during a period of more persistent (synoptic) on-shore flow transporting more aged aerosol which consisted of an internal mixture of more oxidized oxygenated organic aerosol (MO-OOA), methanesulfonic acid (MSA) and sulfate. It was estimated that 35% of the sulfate observed during the mature period (an average of about 1.2 mu g m(-3)) originated from oceanic dimethyl sulfide (DMS) emissions. These two formation pathways helped elucidate the sources of fine particle pollution, highlighted the interaction between human emissions and natural DMS emission, and will help our understanding of pollution affecting other urban areas adjacent to large bodies of water during hot and stagnant periods. (C) 2020 The Authors. Published by Elsevier Ltd.

We report OH reactivity observations by a chemical ionization mass spectrometer–comparative reactivity method (CIMS-CRM) instrument in a suburban forest of the Seoul metropolitan area (SMA) during the Korea–United States Air Quality Study (KORUS-AQ 2016) from mid-May to mid-June of 2016. A comprehensive observational suite was deployed to quantify reactive trace gases inside of the forest canopy including a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). An average OH reactivity of 30.7±5.1 s−1 was observed, while the OH reactivity calculated from CO, NO+NO2 (NOx), ozone (O3), sulfur dioxide (SO2), and 14 volatile organic compounds (VOCs) was 11.8±1.0 s−1. An analysis of 346 peaks from the PTR-ToF-MS accounted for an additional 6.0±2.2 s−1 of the total measured OH reactivity, leaving 42.0 % missing OH reactivity. A series of analyses indicate that the missing OH reactivity most likely comes from VOC oxidation products of both biogenic and anthropogenic origin.

We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.

AbstractThe Southeast Atmosphere Studies (SAS), which included the Southern Oxidant and Aerosol Study (SOAS); the Southeast Nexus (SENEX) study; and the Nitrogen, Oxidants, Mercury and Aerosols: Distributions, Sources and Sinks (NOMADSS) study, was deployed in the field from 1 June to 15 July 2013 in the central and eastern United States, and it overlapped with and was complemented by the Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. SAS investigated atmospheric chemistry and the associated air quality and climate-relevant particle properties. Coordinated measurements from six ground sites, four aircraft, tall towers, balloon-borne sondes, existing surface networks, and satellites provide in situ and remotely sensed data on trace-gas composition, aerosol physicochemical properties, and local and synoptic meteorology. Selected SAS findings indicate 1) dramatically reduced NOx concentrations have altered ozone production regimes; 2) indicators of “biogenic” secondary organic aerosol (SOA), once considered part of the natural background, were positively correlated with one or more indicators of anthropogenic pollution; and 3) liquid water dramatically impacted particle scattering while biogenic SOA did not. SAS findings suggest that atmosphere–biosphere interactions modulate ambient pollutant concentrations through complex mechanisms and feedbacks not yet adequately captured in atmospheric models. The SAS dataset, now publicly available, is a powerful constraint to develop predictive capability that enhances model representation of the response and subsequent impacts of changes in atmospheric composition to changes in emissions, chemistry, and meteorology.

The emission, dispersion, and photochemistry of isoprene (C5H8) and related chemical species in the convective boundary layer (CBL) during sunlit daytime were studied over a mixed forest in the southeastern United States by combining ground-based and aircraft observations. Fluxes of isoprene and monoterpenes were quantified at the top of the forest canopy using a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS). Snapshot (∼ 2 min sampling duration) vertical profiles of isoprene, methyl vinyl ketone (MVK) + methacrolein (MACR), and monoterpenes were collected from aircraft every hour in the CBL (100–1000 m). Both ground-based and airborne collected volatile organic compound (VOC) data are used to constrain the initial conditions of a mixed-layer chemistry model (MXLCH), which is applied to examine the chemical evolution of the O3–NOx–HOx–VOC system and how it is affected by boundary layer dynamics in the CBL. The chemical loss rate of isoprene (∼ 1 h) is similar to the turbulent mixing timescale (0.1–0.5 h), which indicates that isoprene concentrations are equally dependent on both photooxidation and boundary layer dynamics. Analysis of a model-derived concentration budget suggests that diurnal evolution of isoprene inside the CBL is mainly controlled by surface emissions and chemical loss; the diurnal evolution of O3 is dominated by entrainment. The NO to HO2 ratio (NO : HO2) is used as an indicator of anthropogenic impact on the CBL chemical composition and spans a wide range (1–163). The fate of hydroxyl-substituted isoprene peroxyl radical (HOC5H8OO·; ISOPOO) is strongly affected by NO : HO2, shifting from NO-dominant to NO–HO2-balanced conditions from early morning to noontime. This chemical regime change is reflected in the diurnal evolution of isoprene hydroxynitrates (ISOPN) and isoprene hydroxy hydroperoxides (ISOPOOH).