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Sulfur-containing volatile organic compounds emitted during wildfire events, such as dimethyl sulfide, are known to form secondary aerosols containing inorganic sulfate (SO4 2-) and surfactant-like organic compounds; however, little is known about the fate of sulfur in other emitted reduced organosulfur species. This study aimed to determine the sulfurous product distribution resulting from the nighttime oxidation of thiophene as a model system. Ion chromatography (IC) and aerosol mass spectrometry (a mini aerosol mass spectrometer, mAMS) were used to constrain the proportions of sulfurous compounds produced under wildfire-relevant conditions ([NO2]/[O3] = 0.1). With constraints from IC, results indicated that the sulfurous particle mass consisted of 30.3 ± 6.6% SO4 2-, while mAMS fractionation attributed 24.5 ± 1.6% of total sulfate signal to SO4 2-, 15.4 ± 1.9% to organosulfates, and 60.1 ± 0.9% to sulfonates. Empirical formulas of organosulfur products were identified as C1-C8 organosulfates and sulfonates using complementary mass spectrometry techniques. This study highlights the nighttime oxidation of thiophene and its derivatives as a source of SO4 2- and particulate organosulfur compounds, which have important implications for the atmospheric sulfur budget and aerosol/droplet physical and chemical properties.

Light-absorbing secondary organic aerosols (SOAs), also known as secondary brown carbon (BrC), are major components of wildfire smoke that can have a significant impact on the climate system; however, how environmental factors such as relative humidity (RH) influence their formation is not fully understood, especially for heterocyclic precursors. We conducted chamber experiments to investigate secondary BrC formation from the nighttime oxidation of furan and pyrrole, two primary heterocyclic precursors in wildfires, in the presence of pre-existing particles at RH < 20% and ∼ 50%. Our findings revealed that increasing RH significantly affected the size distribution dynamics of both SOAs, with pyrrole SOA showing a stronger potential to generate ultrafine particles via intensive nucleation processes. Higher RH led to increased mass fractions of oxygenated compounds in both SOAs, suggesting enhanced gas-phase and/or multiphase oxidation under humid conditions. Moreover, higher RH reduced the mass absorption coefficients of both BrC, contrasting with those from homocyclic precursors, due to the formation of non-absorbing high-molecular-weight oxygenated compounds and the decreasing mass fractions of molecular chromophores. Overall, our findings demonstrate the unique RH dependence of secondary BrC formation from heterocyclic precursors, which may critically modulate the radiative effects of wildfire smoke on climate change.

The chemical and optical properties of secondary organic aerosols (SOA) have been widely studied through environmental chamber experiments, and some of the results have been parametrized in atmospheric models to help understand their radiative effects and climate influence. While most chamber studies investigate the aerosol formed from a single volatile organic compound (VOC), the potential interactions between reactive intermediates derived from VOC mixtures are not well understood. In this study, we investigated the SOA formed from pure and mixtures of anthropogenic (phenol and 1-methylnaphthalene) and/or biogenic (longifolene) VOCs using continuous-flow, high-NOx photooxidation chamber experiments to better mimic ambient conditions. SOA optical properties, including single scattering albedo (SSA), mass absorption coefficient (MAC), and refractive index (RI) at 375 nm, and chemical composition, including the formation of oxygenated organic compounds, organic-nitrogen compounds (including organonitrates and nitro-organics), and the molecular structure of the major chromophores, were explored. Additionally, the imaginary refractive index values of SOA in the multi-VOC system were predicted using a linear-combination assumption and compared with the measured values. When two VOCs were oxidized simultaneously, we found evidence for changes in SOA chemical composition compared to SOA formed from single-VOC systems, and this change led to nonlinear effects on SOA optical properties. The nonlinear effects were found to vary between different systems.

As part of the summer 2022 NYC-METS (New York City metropolitan Measurements of Emissions and TransformationS) campaign and the ASCENT (Atmospheric Science and Chemistry mEasurement NeTwork) observational network, speciated particulate matter was measured in real time in Manhattan and Queens, NY, with additional gas-phase measurements. Largely due to observed reductions in inorganic sulfate aerosol components over the 21st century, summertime aerosol composition in NYC has become predominantly organic (80-83%). Organic aerosol source apportionment via positive matrix factorization showed that this is dominated by secondary production as oxygenated organic aerosol (OOA) source factors comprised 73-76% of OA. Primary factors, including cooking-related organic aerosol (COA) and hydrocarbon-like organic aerosol (HOA) comprised minor fractions of OA, only 13-15% and 10-11%, respectively. The two sites presented considerable spatiotemporal variations in OA source factor concentrations despite similar average PM2.5 concentrations. The less- and more-oxidized OOA factors exhibited clear temperature dependences at both sites with increased concentrations and greater degrees of oxidation at higher temperatures, including during a heatwave. With strong temperature sensitivity and minimal changes in summertime concentrations since 2001, secondary OA poses a particular challenge for air quality policy in NYC that will very likely be exacerbated by continued climate change and extreme heat events.

The light absorption properties of brown carbon (BrC), which are linked to molecular chromophores, may play a significant role in the Earths energy budget. While nitroaromatic compounds have been identified as strong chromophores in wildfire-driven BrC, other types of chromophores remain to be investigated. Given the electron-withdrawing nature of carbonyls ubiquitous in the atmosphere, we characterized carbonyl chromophores in BrC samples from the nighttime oxidation of furan and pyrrole derivatives, which are important but understudied precursors of secondary organic aerosols primarily found in wildfire emissions. Various carbonyl chromophores were characterized and quantified in BrC samples, and their ultraviolet-visible spectra were simulated by using time-dependent density functional theory. Our findings suggest that chromophores with carbonyls bonded to nitrogen (i.e., imides and amides) derived from N-containing heterocyclic precursors substantially contribute to BrC light absorption. The quantified N-containing carbonyl chromophores contributed to over 40% of the total light absorption at wavelengths below 350 nm and above 430 nm in pyrrole BrC. The contributions of chromophores to total light absorption differed significantly by wavelength, highlighting their divergent importance in different wavelength ranges. Overall, our findings highlight the significance of carbonyl chromophores in secondary BrC and underscore the need for further investigation.

Wintertime episodes of high aerosol concentrations occur frequently in urban and agricultural basins and valleys worldwide. These episodes often arise following development of persistent cold-air pools (PCAPs) that limit mixing and modify chemistry. While field campaigns targeting either basin meteorology or wintertime pollution chemistry have been conducted, coupling between interconnected chemical and meteorological processes remains an insufficiently studied research area. Gaps in understanding the coupled chemical-meteorological interactions that drive high pollution events make identification of the most effective air-basin specific emission control strategies challenging. To address this, a September 2019 workshop occurred with the goal of planning a future research campaign to investigate air quality in Western U.S. basins. Approximately 120 people participated, representing 50 institutions and 5 countries. Workshop participants outlined the rationale and design for a comprehensive wintertime study that would couple atmospheric chemistry and boundary-layer and complex-terrain meteorology within western U.S. basins. Participants concluded the study should focus on two regions with contrasting aerosol chemistry: three populated valleys within Utah (Salt Lake, Utah, and Cache Valleys) and the San Joaquin Valley in California. This paper describes the scientific rationale for a campaign that will acquire chemical and meteorological datasets using airborne platforms with extensive range, coupled to surface-based measurements focusing on sampling within the near-surface boundary layer, and transport and mixing processes within this layer, with high vertical resolution at a number of representative sites. No prior wintertime basin-focused campaign has provided the breadth of observations necessary to characterize the meteorological-chemical linkages outlined here, nor to validate complex processes within coupled atmosphere-chemistry models.

Dimethyl selenide (DMSe) is one of the major volatile organoselenium compounds released from aquatic and terrestrial environments through microbial transformation and plant metabolism. The detailed processes of DMSe leading to secondary organic aerosol (SOA) formation and the pulmonary health effects induced by inhalation of DMSe-derived SOA remain largely unknown. In this study, we characterized the chemical composition and formation yields of SOA produced from the oxidation of DMSe with OH radicals and O3 in controlled chamber experiments. Further, we profiled the transcriptome-wide gene expression changes in human airway epithelial cells (BEAS-2B) after exposure to DMSe-derived SOA. Our analyses indicated a significantly higher SOA yield resulting from the OH-initiated oxidation of DMSe. The oxidative potential of DMSe-derived SOA, as measured by the dithiothreitol (DTT) assay, suggested the presence of oxidizing moieties in DMSe-derived SOA at levels higher than typical ambient aerosols. Utilizing RNA sequencing (RNA-Seq) techniques, gene expression profiling followed by pathway enrichment analysis revealed several major biological pathways perturbed by DMSe-derived SOA, including elevated genotoxicity, DNA damage, and p53-mediated stress responses, as well as downregulated cholesterol biosynthesis, glycolysis, and interleukin IL-4/IL-13 signaling. This study highlights the significance of DMSe-derived SOA as a stressor in human airway epithelial cells.

Abstract. The evolution of organic aerosols (OAs) and their precursors in the boundary layer (BL) of the Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.085±0.003 µg m−3 ppbv−1. At background mixing ratios of CO, up to  ∼  1.8 µg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was  ∼  40 % higher than in urban-influenced plumes. Positive matrix factorization (PMF) confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high-O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to

Abstract. NH3 retrievals from the NASA Tropospheric Emission Spectrometer (TES), as well as surface and aircraft observations of NH3(g) and submicron NH4(p), are used to evaluate modeled concentrations of NH3(g) and NH4(p) from the Community Multiscale Air Quality (CMAQ) model in the San Joaquin Valley (SJV) during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. We find that simulations of NH3 driven with the California Air Resources Board (CARB) emission inventory are qualitatively and spatially consistent with TES satellite observations, with a correlation coefficient (r2) of 0.64. However, the surface observations at Bakersfield indicate a diurnal cycle in the model bias, with CMAQ overestimating surface NH3 at night and underestimating it during the day. The surface, satellite, and aircraft observations all suggest that daytime NH3 emissions in the CARB inventory are underestimated by at least a factor of 2, while the nighttime overestimate of NH3(g) is likely due to a combination of overestimated NH3 emissions and underestimated deposition.Running CMAQ v5.0.2 with the bi-directional NH3 scheme reduces NH3 concentrations at night and increases them during the day. This reduces the model bias when compared to the surface and satellite observations, but the increased concentrations aloft significantly increase the bias relative to the aircraft observations. We attempt to further reduce model bias by using the surface observations at Bakersfield to derive an empirical diurnal cycle of NH3 emissions in the SJV, in which nighttime and midday emissions differ by about a factor of 4.5. Running CMAQv5.0.2 with a bi-directional NH3 scheme together with this emissions diurnal profile further reduces model bias relative to the surface observations. Comparison of these simulations with the vertical profile retrieved by TES shows little bias except for the lowest retrieved level, but the model bias relative to flight data aloft increases slightly. Our results indicate that both diurnally varying emissions and a bi-directional NH3 scheme should be applied when modeling NH3(g) and NH4(p) in this region. The remaining model errors suggest that the bi-directional NH3 scheme in CMAQ v5.0.2 needs further improvements to shift the peak NH3 land–atmosphere flux to earlier in the day. We recommend that future work include updates to the current CARB NH3 inventory to account for NH3 from fertilizer application, livestock, and other farming practices separately; adding revised information on crop management practices specific to the SJV region to the bi-directional NH3 scheme; and top-down studies focused on determining the diurnally varying biases in the canopy compensation point that determines the net land–atmosphere NH3 fluxes.

The Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) field experiment took place during late winter, 2011, at a site 33 km north of Denver, Colorado. The study included fixed-height measurements of aerosols, soluble trace gases, and volatile organic compounds near surface level, as well as vertically resolved measurements of nitrogen oxides, aerosol composition, soluble gas-phase acids, and halogen species from 3 to 270 m above ground level. There were 1928 individual profiles during the three-week campaign to characterize trace gas and aerosol distributions in the lower levels of the boundary layer. Nitrate and ammonium dominated the ionic composition of aerosols and originated primarily from local or regional sources. Sulfate and organic matter were also significant and were associated primarily with longer-range transport to the region. Aerosol chloride was associated primarily with supermicron size fractions and was always present in excess of gas-phase chlorine compounds. The nighttime radical reservoirs, nitryl chloride, ClNO2, and nitrous acid, HONO, were both consistently present in nighttime urban air. Nitryl chloride was especially pronounced in plumes from large point sources sampled aloft at night. Nitrous acid was typically most concentrated near the ground surface and was the dominant contributor (80%) to diurnally averaged primary OH radical production in near-surface air. Large observed mixing ratios of light alkanes, both in near-surface air and aloft, were attributable to local emissions from oil and gas activities.

Author(s): Colin D. O'Dowd (corresponding author) [1, 2]; Jose L. Jimenez [3]; Roya Bahreini [3]; Richard C. Flagan [3]; John H. Seinfeld [3]; Kaarle Hämeri [4]; Liisa Pirjola [2, 5]; [...]