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Abstract. Cooking is an important but understudied source of urban anthropogenic fine particulate matter (PM2.5). Using a mobile laboratory, we measured PM size and composition in urban restaurant plumes. Size distribution measurements indicate that restaurants are a source of urban ultrafine particles (UFPs, particles <100 nm mobility diameter), with a mode diameter <50 nm across sampled restaurants and particle number concentrations (PNCs, a proxy for UFPs) that were substantially elevated relative to the urban background. In our observations, PM mass emitted from restaurants was almost entirely organic aerosol (OA). Aerosol mass spectra show that while emissions from most restaurants were similar, there were key mass spectral differences. All restaurants emit OA at m/z 41, 43, and 55, though the composition (e.g., the ratio of oxygenated to reduced ions at specific m/z) varied across locations. All restaurant emissions included reduced-nitrogen species detected as CxHyN+ fragments, making up ∼15 % of OA mass measured in plumes, with reduced molecular functionalities (e.g., amines, imides) that were often accompanied by oxygen-containing functional groups. The largest reduced-nitrogen emissions were observed from a commercial bread bakery (i.e., 30 %–50 % of OA mass), highlighting the marked differences between restaurants and their importance for emissions of both urban UFPs and reduced nitrogen. 

Abstract. We present a novel photolytic source of gas-phase NO3 suitable for use in atmospheric chemistry studies that has several advantages over traditional sources that utilize NO2 + O3 reactions and/or thermal dissociation of dinitrogen pentoxide (N2O5). The method generates NO3 via irradiation of aerated aqueous solutions of ceric ammonium nitrate (CAN, (NH4)2Ce(NO3)6) and nitric acid (HNO3) or sodium nitrate (NaNO3). We present experimental and model characterization of the NO3 formation potential of irradiated CAN / HNO3 and CAN / NaNO3 mixtures containing [CAN] = 10−3 to 1.0 M, [HNO3] = 1.0 to 6.0 M, [NaNO3] = 1.0 to 4.8 M, photon fluxes (I) ranging from 6.9 × 1014 to 1.0 × 1016 photons cm−2 s−1, and irradiation wavelengths ranging from 254 to 421 nm. NO3 mixing ratios ranging from parts per billion to parts per million by volume were achieved using this method. At the CAN solubility limit, maximum [NO3] was achieved using [HNO3] ≈ 3.0 to 6.0 M and UVA radiation (λmax⁡ = 369 nm) in CAN / HNO3 mixtures or [NaNO3] ≥ 1.0 M and UVC radiation (λmax⁡ = 254 nm) in CAN / NaNO3 mixtures. Other reactive nitrogen (NO2, N2O4, N2O5, N2O6, HNO2, HNO3, HNO4) and reactive oxygen (HO2, H2O2) species obtained from the irradiation of ceric nitrate mixtures were measured using a NOx analyzer and an iodide-adduct high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). To assess the applicability of the method for studies of NO3-initiated oxidative aging processes, we generated and measured the chemical composition of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) from the β-pinene + NO3 reaction using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the HR-ToF-CIMS. 

Low-cost sensors enable finer-scale spatiotemporal measurements within the existing methane (CH 4 ) monitoring infrastructure and could help cities mitigate CH 4 emissions to meet their climate goals. While initial studies of low-cost CH 4 sensors have shown potential for effective CH 4 measurement at ambient concentrations, sensor deployment remains limited due to questions about interferences and calibration across environments and seasons. This study evaluates sensor performance across seasons with specific attention paid to the sensor's understudied carbon monoxide (CO) interferences and environmental dependencies through long-term ambient co-location in an urban environment. The sensor was first evaluated in a laboratory using chamber calibration and co-location experiments, and then in the field through two 8 week co-locations with a reference CH 4 instrument. In the laboratory, the sensor was sensitive to CH 4 concentrations below ambient background concentrations. Different sensor units responded similarly to changing CH 4 , CO, temperature, and humidity conditions but required individual calibrations to account for differences in sensor response factors. When deployed in-field, co-located with a reference instrument near Baltimore, MD, the sensor captured diurnal trends in hourly CH 4 concentration after corrections for temperature, absolute humidity, CO concentration, and hour of day. Variable performance was observed across seasons with the sensor performing well ( R 2 = 0.65; percent bias 3.12%; RMSE 0.10 ppm) in the winter validation period and less accurately ( R 2 = 0.12; percent bias 3.01%; RMSE 0.08 ppm) in the summer validation period where there was less dynamic range in CH 4 concentrations. The results highlight the utility of sensor deployment in more variable ambient CH 4 conditions and demonstrate the importance of accounting for temperature and humidity dependencies as well as co-located CO concentrations with low-cost CH 4 measurements. We show this can be addressed via Multiple Linear Regression (MLR) models accounting for key covariates to enable urban measurements in areas with CH 4 enhancement. Together with individualized calibration prior to deployment, the sensor shows promise for use in low-cost sensor networks and represents a valuable supplement to existing monitoring strategies to identify CH 4 hotspots. 

Abstract. Low-cost sensors are often co-located with reference instruments to assess their performance and establish calibration equations, but limiteddiscussion has focused on whether the duration of this calibration period can be optimized. We placed a multipollutant monitor that containedsensors that measured particulate matter smaller than 2.5 µm (PM2.5), carbon monoxide (CO), nitrogendioxide (NO2), ozone (O3), and nitric oxide (NO) at a reference field site for 1 year. We developed calibration equationsusing randomly selected co-location subsets spanning 1 to 180 consecutive days out of the 1-year period and compared the potential root-mean-square error (RMSE) and Pearson correlation coefficient (r) values. The co-located calibration period required to obtain consistent results varied bysensor type, and several factors increased the co-location duration required for accurate calibration, including the response of a sensor toenvironmental factors, such as temperature or relative humidity (RH), or cross-sensitivities to other pollutants. Using measurements fromBaltimore, MD, where a broad range of environmental conditions may be observed over a given year, we found diminishing improvements in the medianRMSE for calibration periods longer than about 6 weeks for all the sensors. The best performing calibration periods were the ones that contained arange of environmental conditions similar to those encountered during the evaluation period (i.e., all other days of the year not used in thecalibration). With optimal, varying conditions it was possible to obtain an accurate calibration in as little as 1 week for all sensors, suggestingthat co-location can be minimized if the period is strategically selected and monitored so that the calibration period is representative of thedesired measurement setting. 

Liquid asphalt is a petroleum-derived substance commonly used in construction activities. Recent work has identified lower volatility, reactive organic carbon from asphalt as an overlooked source of secondary organic aerosol (SOA) precursor emissions. Here, we leverage potential emission estimates and usage data to construct a bottom-up inventory of asphalt-related emissions in the United States. In 2018, we estimate that hot-mix, warm-mix, emulsified, cutback, and roofing asphalt generated ∼380 Gg (317 Gg–447 Gg) of organic compound emissions. The impacts of these emissions on anthropogenic SOA and ozone throughout the contiguous United States are estimated using photochemical modeling. In several major cities, asphalt-related emissions can increase modeled summertime SOA, on average, by 0.1–0.2 μg m−3 (2–4% of SOA) and may reach up to 0.5 μg m−3 at noontime on select days. The influence of asphalt-related emissions on modeled ozone are generally small (∼0.1 ppb). We estimate that asphalt paving-related emissions are half of what they were nearly 50 years ago, largely due to the concerted efforts to reduce emissions from cutback asphalts. If on-road mobile emissions continue their multidecadal decline, contributions of urban SOA from evaporative and non-road mobile sources will continue to grow in relative importance. 

Anthropogenic organic carbon emissions reporting has been largely limited to subsets of chemically speciated volatile organic compounds. However, new aircraft-based measurements revealed total gas-phase organic carbon emissions that exceed oil sands industry–reported values by 1900% to over 6300%, the bulk of which was due to unaccounted-for intermediate-volatility and semivolatile organic compounds. Measured facility-wide emissions represented approximately 1% of extracted petroleum, resulting in total organic carbon emissions equivalent to that from all other sources across Canada combined. These real-world observations demonstrate total organic carbon measurements as a means of detecting unknown or underreported carbon emissions regardless of chemical features. Because reporting gaps may include hazardous, reactive, or secondary air pollutants, fully constraining the impact of anthropogenic emissions necessitates routine, comprehensive total organic carbon monitoring as an inherent check on mass closure. 

Abstract. Nitrogen-containing organic compounds, which may be directly emitted into the atmosphere or which may form via reactions with prevalent reactive nitrogen species (e.g., NH3, NOx, NO3), have important but uncertaineffects on climate and human health. Using gas and liquid chromatographywith soft ionization and high-resolution mass spectrometry, we performed amolecular-level speciation of functionalized organic compounds at a coastal site on the Long Island Sound in summer (during the 2018 Long Island Sound Tropospheric Ozone Study – LISTOS – campaign) and winter. This region often experiences poor air quality due to theemissions of reactive anthropogenic, biogenic, and marine-derived compoundsand their chemical transformation products. We observed a range offunctionalized compounds containing oxygen, nitrogen, and/or sulfur atomsresulting from these direct emissions and chemical transformations,including photochemical and aqueous-phase processing that was more pronounced in summer and winter, respectively. In both summer and winter, nitrogen-containing organic aerosols dominated the observed distribution offunctionalized particle-phase species ionized by our analytical techniques,with 85 % and 68 % of total measured ion abundance containing a nitrogenatom, respectively. Nitrogen-containing particles included reduced nitrogen functional groups (e.g., amines, imines, azoles) and common NOz contributors (e.g., organonitrates). Reduced nitrogen functional groups observed in the particle phase were frequently paired with oxygen-containing groups elsewhere on the molecule, and their prevalence often rivaled that of oxidized nitrogen groups detected by our methods. Supplemental gas-phasemeasurements, collected on adsorptive samplers and analyzed with a novelliquid chromatography-based method, suggest that gas-phase reduced nitrogen compounds are possible contributing precursors to the observed nitrogen-containing particles. Altogether, this work highlights theprevalence of reduced nitrogen-containing compounds in the less-studied northeastern US and potentially in other regions with similar anthropogenic, biogenic, and marine source signatures. 

Volatile chemical products (VCPs) and other non-combustion-related sourceshave become important for urban air quality, and bottom-up calculationsreport emissions of a variety of functionalized compounds that remainunderstudied and uncertain in emissions estimates. Using a new instrumentalconfiguration, we present online measurements of oxygenated organiccompounds in a US megacity over a 10 d wintertime sampling period, whenbiogenic sources and photochemistry were less active. Measurements wereconducted at a rooftop observatory in upper Manhattan, New York City, USAusing a Vocus chemical ionization time-of-flight mass spectrometer, withammonium (NH4+) as the reagent ion operating at 1 Hz. The range ofobservations spanned volatile, intermediate-volatility, and semi-volatileorganic compounds, with targeted analyses of ∼150 ions, whoselikely assignments included a range of functionalized compound classes suchas 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 winddirection, with enhancements over the highly populated areas of the Bronx,Manhattan, and parts of New Jersey, and included abundant concentrations ofacetates, acrylates, ethylene glycol, and other commonly used oxygenatedcompounds. The results provide top-down constraints on wintertime emissionsof these oxygenated and functionalized compounds, with ratios to commonanthropogenic marker compounds and comparisons of their relative abundancesto two regionally resolved emissions inventories used in urban air qualitymodels.