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The NOAA Chemical Sciences Laboratory (CSL) conducted the Southwest Urban NO 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 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. Diurnal analyses spanning August 2021 revealed a markedly different wind direction during evenings preceding O 3 exceedance (northerly) versus non-exceedance (easterly) days. Increased O 3 occurred simultaneously with warmer and drier conditions, a reduction in winds, and an increase in volatile organic compounds (VOCs) and fine particulate matter (PM 2.5). 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 (NO x) scaleograms, as well as scaleograms combining VOCs, NO x , 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 NO x and O 3 during the interaction between an SB and enhanced winds above the BL that flowed in opposition to the SB. [ABSTRACT FROM AUTHOR]

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 PM 2.5 in Los Angeles. Furthermore, evaluation against comprehensive measurements of O3 and PM 2.5 precursors from the Reevaluating the Chemistry of Air Pollutants in California (RECAP-CA) airborne campaign and the Southwest Urban NO x and VOC Experiment (SUNVEx) ground site and mobile laboratory campaign confirm the model's accuracy in representing NO x 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. [ABSTRACT FROM AUTHOR]

Cooking is a source of volatile organic compounds (VOCs), which degrade air quality. Cooking VOCs have been investigated in laboratory and indoor studies, but the contribution of cooking to the spatial and temporal variability in urban VOCs is uncertain. In this study, a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) is used to identify and quantify cooking emission in Las Vegas, NV, with supplemental data from Los Angeles, CA, and Boulder, CO. Mobile laboratory data show that long-chain aldehydes, such as octanal and nonanal, are significantly enhanced in restaurant plumes and regionally enhanced in areas of Las Vegas with high restaurant densities. Correlation analyses show that long-chain fatty acids are also associated with cooking emissions and that the relative VOC enhancements observed in regions with dense restaurant activity are very similar to the distribution of VOCs observed in laboratory cooking studies. Positive matrix factorization (PMF) is used to quantify cooking emissions from ground site measurements and to compare the magnitude of cooking with other important urban sources, such as volatile chemical products and fossil fuel emissions. PMF shows that cooking may account for as much as 20 % of the total anthropogenic VOC emissions observed by PTR-ToF-MS. In contrast, emissions estimated from county-level inventories report that cooking accounts for less than 1 % of urban VOCs. Current emissions inventories do not fully account for the emission rates of long-chain aldehydes reported here; thus, further work is likely needed to improve model representations of important aldehyde sources, such as commercial and residential cooking. [ABSTRACT FROM AUTHOR]

Abstract. Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional–global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Niño event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs; grams of a compound per kilogram biomass burned) for up to  ∼  90 gases, including CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3, HCN, NOx, OCS, HCl, etc. The modified combustion efficiency (MCE) of the smoke sources ranged from 0.693 to 0.835 with an average of 0.772 ± 0.053 (n  =  35), indicating essentially pure smoldering combustion, and the emissions were not initially strongly lofted. The major trace gas emissions by mass (EF as g kg−1) were carbon dioxide (1564 ± 77), carbon monoxide (291 ± 49), methane (9.51 ± 4.74), hydrogen cyanide (5.75 ± 1.60), acetic acid (3.89 ± 1.65), ammonia (2.86 ± 1.00), methanol (2.14 ± 1.22), ethane (1.52 ± 0.66), dihydrogen (1.22 ± 1.01), propylene (1.07 ± 0.53), propane (0.989 ± 0.644), ethylene (0.961 ± 0.528), benzene (0.954 ± 0.394), formaldehyde (0.867 ± 0.479), hydroxyacetone (0.860 ± 0.433), furan (0.772 ± 0.035), acetaldehyde (0.697 ± 0.460), and acetone (0.691 ± 0.356). These field data support significant revision of the EFs for CO2 (−8 %), CH4 (−55 %), NH3 (−86 %), CO (+39 %), and other gases compared with widely used recommendations for tropical peat fires based on a lab study of a single sample published in 2003. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) are important air toxics and aerosol precursors and were emitted in total at 1.5 ± 0.6 g kg−1. Formaldehyde is probably the air toxic gas most likely to cause local exposures that exceed recommended levels. The field results from Kalimantan were in reasonable agreement with recent lab measurements of smoldering Kalimantan peat for “overlap species,” lending importance to the lab finding that burning peat produces large emissions of acetamide, acrolein, methylglyoxal, etc., which were not measurable in the field with the deployed equipment and implying value in continued similar efforts. The aerosol optical data measured include EFs for the scattering and absorption coefficients (EF Bscat and EF Babs, m2 kg−1 fuel burned) and the single scattering albedo (SSA) at 870 and 405 nm, as well as the absorption Ångström exponents (AAE). By coupling the absorption and co-located trace gas and filter data we estimated black carbon (BC) EFs (g kg−1) and the mass absorption coefficient (MAC, m2 g−1) for the bulk organic carbon (OC) due to brown carbon (BrC). Consistent with the minimal flaming, the emissions of BC were negligible (0.0055 ± 0.0016 g kg−1). Aerosol absorption at 405 nm was  ∼  52 times larger than at 870 nm and BrC contributed  ∼  96 % of the absorption at 405 nm. Average AAE was 4.97 ± 0.65 (range, 4.29–6.23). The average SSA at 405 nm (0.974 ± 0.016) was marginally lower than the average SSA at 870 nm (0.998 ± 0.001). These data facilitate modeling climate-relevant aerosol optical properties across much of the UV/visible spectrum and the high AAE and lower SSA at 405 nm demonstrate the dominance of absorption by the organic aerosol. Comparing the Babs at 405 nm to the simultaneously measured OC mass on filters suggests a low MAC ( ∼  0.1) for the bulk OC, as expected for the low BC/OC ratio in the aerosol. The importance of pyrolysis (at lower MCE), as opposed to glowing (at higher MCE), in producing BrC is seen in the increase of AAE with lower MCE (r2 =  0.65).

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) campaign took place in and around the Kathmandu Valley and in the Indo-Gangetic Plain (IGP) of southern Nepal during April 2015. The source characterization phase targeted numerous important but undersampled (and often inefficient) combustion sources that are widespread in the developing world such as cooking with a variety of stoves and solid fuels, brick kilns, open burning of municipal solid waste (a.k.a. trash or garbage burning), crop residue burning, generators, irrigation pumps, and motorcycles. NAMaSTE produced the first, or rare, measurements of aerosol optical properties, aerosol mass, and detailed trace gas chemistry for the emissions from many of the sources. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared (FTIR) spectroscopy, whole-air sampling (WAS), and photoacoustic extinctiometers (PAX; 405 and 870nm) based on field work with a moveable lab sampling authentic sources. The primary aerosol optical properties reported include emission factors (EFs) for scattering and absorption coefficients (EF Bscat, EF Babs, inm2kg-1 fuel burned), single scattering albedos (SSAs), and absorption Ångström exponents (AAEs). From these data we estimate black and brown carbon (BC, BrC) emission factors (gkg-1 fuel burned). The trace gas measurements provide EFs (gkg-1) for CO2, CO, CH4, selected non-methane hydrocarbons up to C10, a large suite of oxygenated organic compounds, NH3, HCN, NOx, SO2, HCl, HF, etc. (up to ∼ 80 gases in all). The emissions varied significantly by source, and light absorption by both BrC and BC was important for many sources. The AAE for dung-fuel cooking fires (4.63±0.68) was significantly higher than for wood-fuel cooking fires (3.01±0.10). Dung-fuel cooking fires also emitted high levels of NH3 (3.00±1.33gkg-1), organic acids (7.66±6.90gkg-1), and HCN (2.01±1.25gkg-1), where the latter could contribute to satellite observations of high levels of HCN in the lower stratosphere above the Asian monsoon. HCN was also emitted in significant quantities by several non-biomass burning sources. BTEX compounds (benzene, toluene, ethylbenzene, xylenes) were major emissions from both dung- (∼4.5gkg-1) and wood-fuel (∼1.5gkg-1) cooking fires, and a simple method to estimate indoor exposure to the many measured important air toxics is described. Biogas emerged as the cleanest cooking technology of approximately a dozen stove-fuel combinations measured. Crop residue burning produced relatively high emissions of oxygenated organic compounds (∼12gkg-1) and SO2 (2.54±1.09gkg-1). Two brick kilns co-firing different amounts of biomass with coal as the primary fuel produced contrasting results. A zigzag kiln burning mostly coal at high efficiency produced larger amounts of BC, HF, HCl, and NOx, with the halogenated emissions likely coming from the clay. The clamp kiln (with relatively more biomass fuel) produced much greater quantities of most individual organic gases, about twice as much BrC, and significantly more known and likely organic aerosol precursors. Both kilns were significant SO2 sources with their emission factors averaging 12.8±0.2gkg-1. Mixed-garbage burning produced significantly more BC (3.3±3.88gkg-1) and BTEX (∼4.5gkg-1) emissions than in previous measurements. For all fossil fuel sources, diesel burned more efficiently than gasoline but produced larger NOx and aerosol emission factors. Among the least efficient sources sampled were gasoline-fueled motorcycles during start-up and idling for which the CO EF was on the order of ∼700gkg-1 - or about 10 times that of a typical biomass fire. Minor motorcycle servicing led to minimal if any reduction in gaseous pollutants but reduced particulate emissions, as detailed in a companion paper (Jayarathne et al., 2016). A small gasoline-powered generator and an "insect repellent fire" were also among the sources with the highest emission factors for pollutants. These measurements begin to address the critical data gap for these important, undersampled sources, but due to their diversity and abundance, more work is needed.

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, C 5 H 8 H +), acetaldehyde (m/z 45, CH 3 CHO +), and benzene (m/z 79, C 6 H 6 H +). 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 O 2+ 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. [ABSTRACT FROM AUTHOR]

Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NO y) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO 2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of - 296 ± 51 g kg -1 , consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO 2 , NO y , and black carbon than with CO. More than half of the NO y in fresh plumes is NO 2 with an R2 of 0.95 and a ratio of NO 2 to NO y of 0.55 ± 0.05 ppbv ppbv -1 , highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NO y to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol. [ABSTRACT FROM AUTHOR]

The declining trend in vehicle emissions has underscored the growing significance of Volatile Organic Compound (VOC) emissions from Volatile Chemical Products (VCP). 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 to enhance 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 as well as 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. [ABSTRACT FROM AUTHOR]

The declining trend in vehicle emissions has underscored the growing significance of Volatile Organic Compound (VOC) emissions from Volatile Chemical Products (VCP). 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 to enhance 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 as well as 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. [ABSTRACT FROM AUTHOR]

Cooking is a source volatile organic compounds (VOCs) that degrades air quality. Cooking VOCs have been investigated in laboratory and indoor studies, but the contribution of cooking to the spatial and temporal variability of urban VOCs is uncertain. In this study, a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) is used to identify and quantify cooking emission in Las Vegas, NV with supplemental data from Los Angeles, CA and Boulder, CO. Mobile laboratory data show that long-chain aldehydes, such as octanal and nonanal, are significantly enhanced in restaurant plumes and regionally enhanced in areas of Las Vegas with high restaurant density. Correlation analyses show that long-chain fatty acids are also associated with cooking emissions and the relative VOC enhancements observed in regions with dense restaurant activity are very similar to the distribution of VOCs observed in laboratory cooking studies. Positive matrix factorization (PMF) is used to quantify cooking emissions from ground site measurements and compare the magnitude of cooking to other important urban sources, such as volatile chemical products and fossil fuel emissions. PMF shows that cooking may account for as much as 20 % of the total anthropogenic VOC emissions observed by PTR-ToF-MS. In contrast, emissions estimated from county-level inventories report that cooking accounts for less than 1 % of urban VOCs. Current emissions inventories do not fully account for the emission rates of long-chain aldehydes reported here and further work is likely needed to improve model representations of important aldehyde sources, such as commercial and residential cooking. [ABSTRACT FROM AUTHOR]

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 impacts 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 are 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 the fragmentation and secondary 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. [ABSTRACT FROM AUTHOR]

In this study, we describe the characterization and field deployment of a Chemical Ionization Mass Spectrometry (CIMS) using a recently developed focusing ion-molecule reactor (FIMR) and ammonium-water cluster (NH4+·H2O) as the reagent ion (denoted as NH4+ CIMS). We show that NH4+·H2O is a highly versatile reagent ion for measurements of a wide range of oxygenated organic compounds. The major product ion is the cluster with NH4+ produced via ligand-switching reactions. Other product ions (e.g., protonated ion, cluster ion with NH4+·H2O, with H3O+, and with H3O+·H2O) are also produced, but with minor fractions for most of the oxygenated compounds studied here. The instrument sensitivities (counts per second per ppbv, cps ppbv-1) and product distributions are strongly dependent on the instrument operating conditions, including the ratio of ammonia (NH3) and H2O flows and the drift voltages, which should be carefully selected to ensure NH4+·H2O as the predominant reagent ion and to optimize sensitivities. For monofunctional analytes, the NH4+·H2O chemistry exhibits high sensitivity (i.e., > 1000 cps ppbv-1) towards ketones, moderate sensitivity (i.e., between 100 and 1000 cps ppbv-1) towards aldehdyes, alcohols, organic acids, and monoterpenes, low sensitivity (i.e., between 10 and 100 cps ppbv-1) towards isoprene and C1 and C2 organics, and negligible sensitivity (i.e., < 10 cps ppbv-1) towards reduced aromatics. The instrumental sensitivities of analytes depend on the binding energy of the analyte-NH4+ cluster, which can be estimated using voltage scanning. This offers the possibility to constrain the sensitivity of analytes for which no calibration standards exist. This instrument was deployed in the RECAP campaign (Re-Evaluating the Chemistry of Air Pollutants in California) in Pasadena, California during summer 2021. Measurement comparisons against co-located mass spectrometers show that the NH4+ CIMS is capable of detecting compounds from a wide range of chemical classes. The NH4+ CIMS is valuable for quantification of oxygenated VOCs and is complementary to existing chemical ionization schemes. [ABSTRACT FROM AUTHOR]

The emissions of volatile organic compounds (VOCs) from volatile chemical products (VCPs) - specifically personal care products, cleaning agents, coatings, adhesives, and pesticides - are emerging as the largest source of petroleum-derived organic carbon in US cities. Previous work has shown that the ambient concentration of markers for most VCP categories correlate strongly with population density except for VOCs predominantly originating from solvent- and water-borne coatings (e.g., parachlorobenzotrifluoride (PCBTF) and Texanol®, respectively). Instead, these enhancements were dominated by distinct emission events likely driven by industrial usage patterns, such as construction activity. In this work, the headspace of a variety of coating products was analyzed using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) and a gas chromatography (GC) pre-separation front-end to identify composition differences for various coating types (e.g., paints, primers, sealers and stains). Evaporation experiments of several products showed high initial VOC emission rates and for the length of these experiments, the majority of the VOC mass was emitted during the first few hours following application. The percentage of mass emitted as measured VOCs (< 1 to 83 %) mirrored the VOC content reported by the manufacturer (< 5 to 550 g L-1). Ambient and laboratory measurements, usage trends, and ingredients compiled from architectural coatings surveys show both PCBTF and Texanol account for ~10 % of the total VOC ingredient sales and therefore can be useful tracers for solvent- and water-borne coatings. [ABSTRACT FROM AUTHOR]

Total reactive nitrogen (Nr, defined as all nitrogen-containing compounds except for N2 and N2O) was measured by catalytic conversion to NO and detection by NO-O3 chemiluminescence together with individual Nr species during a series of laboratory fires of fuels characteristic of Western U.S. wildfires, conducted as part of the FIREX FireLab 2016 study. Data from 75 stack fires were analyzed to examine the systematics of nitrogen emissions. The Nr/total-carbon ratios measured in the emissions were compared with fuel and ash N/C ratios and mass to estimate that a mean (± std. dev.) of 0.68 (± 0.14) of fuel nitrogen was emitted as N2 and N2O. The remaining fraction of Nr was emitted as individual compounds: nitric oxide (NO), nitrogen dioxide (NO2), nitrous acid (HONO), isocyanic acid (HNCO), hydrogen cyanide (HCN), ammonia (NH3), and 44 nitrogen-containing volatile organic compounds (NVOCs). The relative difference between the total reactive nitrogen measurement, Nr, and the sum of measured individual Nr compounds had a mean (± std. dev) of 0.152 (± 0.098). Much of this unaccounted Nr is expected to be particle-bound species, not included in this analysis. A number of key species, e.g. HNCO, HCN and HONO, were confirmed not to correlate only with flaming or only with smoldering combustion when using modified combustion efficiency (MCE = CO2/(CO + CO2)) as a rough indicator. However, the systematic variations of the abundance of these species relative to other nitrogen-containing species were successfully modeled using positive matrix factorization (PMF). Three distinct factors were found for the emissions from combined coniferous fuels, aligning with our understanding of combustion chemistry in different temperature ranges: a combustion factor (Comb-N) (800–1200 °C) with emissions of the inorganic compounds NO, NO2 and HONO, and a minor contribution from organic nitro compounds (R-NO2); a high-temperature pyrolysis factor (HT-N) (500–800 °C) with emissions of HNCO, HCN and nitriles; and a low-temperature pyrolysis factor (LT-N) (< 500 °C) with mostly ammonia, and NVOCs, with the temperature ranges being based on known combustion and pyrolysis chemistry considerations. The mix of emissions in the PMF factors from the chaparral fuels had a slightly different composition: the Comb-N factor was also mostly NO, with small amounts of HNCO, HONO and NH3, the HT-N factor was dominated by NO2 and had HONO, HCN, and HNCO, and the LT-N factor was mostly NH3 with a slight amount of NO contributing. In both cases, the Comb-N factor correlated best with CO2 emission, while the HT-N factors from coniferous fuels correlated closely with the high temperature VOC factors recently reported by Sekimoto et al., (2018) and the LT-N had some correspondence to the LT-VOC factors. As a consequence, CO2 is recommended as a marker for combustion Nr emissions, HCN is recommended as a marker for HT-N emissions and the family NH3/particle ammonium is recommended as a marker for LT-N emissions. [ABSTRACT FROM AUTHOR]