Search

The NOAA Chemical Sciences Laboratory (CSL) conducted the Southwest Urban NOx 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 (O3) exceedance (>70 ppb) and non-exceedance ( 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 O3 exceedance (northerly) versus non-exceedance (easterly) days. Increased O3 occurred simultaneously with warmer and drier conditions, a reduction in winds, and an increase in volatile organic compounds (VOCs) and fine particulate matter (PM2.5). 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 (NOx) scaleograms, as well as scaleograms combining VOCs, NOx, 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 NOx and O3 during the interaction between an SB and enhanced winds above the BL that flowed in opposition to the SB.

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.

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.

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 (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), 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 NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv−1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy 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.

Chemical mechanisms describe how emissions of gases and particles evolve in the atmosphere and are used within chemical transport models to evaluate past, current, and future air quality. Thus, a chemical mechanism must provide robust and accurate predictions of air pollutants if it is to be considered for use by regulatory bodies. In this work, we provide an initial evaluation of the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMMv1.0) by assessing CRACMMv1.0 predictions of surface ozone (O3) across the northeastern US during the summer of 2018 within the Community Multiscale Air Quality (CMAQ) modeling system. CRACMMv1.0 O3 predictions of hourly and maximum daily 8 h average (MDA8) ozone were lower than those estimated by the Regional Atmospheric Chemistry Mechanism with aerosol module 6 (RACM2_ae6), which better matched surface network observations in the northeastern US (RACM2_ae6 mean bias of +4.2 ppb for all hours and +4.3 ppb for MDA8; CRACMMv1.0 mean bias of +2.1 ppb for all hours and +2.7 ppb for MDA8). Box model calculations combined with results from CMAQ emission reduction simulations indicated a high sensitivity of O3 to compounds with biogenic sources. In addition, these calculations indicated the differences between CRACMMv1.0 and RACM2_ae6 O3 predictions were largely explained by updates to the inorganic rate constants (reflecting the latest assessment values) and by updates to the representation of monoterpene chemistry. Updates to other reactive organic carbon systems between RACM2_ae6 and CRACMMv1.0 also affected ozone predictions and their sensitivity to emissions. Specifically, CRACMMv1.0 benzene, toluene, and xylene chemistry led to efficient NOx cycling such that CRACMMv1.0 predicted controlling aromatics reduces ozone without rural O3 disbenefits. In contrast, semivolatile and intermediate-volatility alkanes introduced in CRACMMv1.0 acted to suppress O3 formation across the regional background through the sequestration of nitrogen oxides (NOx) in organic nitrates. Overall, these analyses showed that the CRACMMv1.0 mechanism within the CMAQ model was able to reasonably simulate ozone concentrations in the northeastern US during the summer of 2018 with similar magnitude and diurnal variation as the current operational Carbon Bond (CB6r3_ae7) mechanism and good model performance compared to recent modeling studies in the literature.

Chemical mechanisms describe the atmospheric transformations of organic and inorganic species and connect air emissions to secondary species such as ozone, fine particles, and hazardous air pollutants (HAPs) like formaldehyde. Recent advances in our understanding of several chemical systems and shifts in the drivers of atmospheric chemistry warrant updates to mechanisms used in chemical transport models such as the Community Multiscale Air Quality (CMAQ) modeling system. This work builds on the Regional Atmospheric Chemistry Mechanism version 2 (RACM2) and develops the Community Regional Atmospheric Chemistry Multiphase Mechanism (CRACMM) version 1.0, which demonstrates a fully coupled representation of chemistry leading to ozone and secondary organic aerosol (SOA) with consideration of HAPs. CRACMMv1.0 includes 178 gas-phase species, 51 particulate species, and 508 reactions spanning gas-phase and heterogeneous pathways. To support estimation of health risks associated with HAPs, nine species in CRACMM cover 50 % of the total cancer and 60 % of the total non-cancer emission-weighted toxicity estimated for primary HAPs from anthropogenic and biomass burning sources in the US, with the coverage of toxicity higher (> 80 %) when secondary formaldehyde and acrolein are considered. In addition, new mechanism species were added based on the importance of their emissions for the ozone, organic aerosol, or atmospheric burden of total reactive organic carbon (ROC): sesquiterpenes, furans, propylene glycol, alkane-like low- to intermediate-volatility organic compounds (9 species), low- to intermediate-volatility oxygenated species (16 species), intermediate-volatility aromatic hydrocarbons (2 species), and slowly reacting organic carbon. Intermediate- and lower-volatility organic compounds were estimated to increase the coverage of anthropogenic and biomass burning ROC emissions by 40 % compared to current operational mechanisms. Autoxidation, a gas-phase reaction particularly effective in producing SOA, was added for C10 and larger alkanes, aromatic hydrocarbons, sesquiterpenes, and monoterpene systems including second-generation aldehydes. Integrating the radical and SOA chemistry put additional constraints on both systems and enabled the implementation of previously unconsidered SOA pathways from phenolic and furanone compounds, which were predicted to account for ∼ 30 % of total aromatic hydrocarbon SOA under typical atmospheric conditions. CRACMM organic aerosol species were found to span the atmospherically relevant range of species carbon number, number of oxygens per carbon, and oxidation state with a slight high bias in the number of hydrogens per carbon. In total, 11 new emitted species were implemented as precursors to SOA compared to current CMAQv5.3.3 representations, resulting in a bottom-up prediction of SOA, which is required for accurate source attribution and the design of control strategies. CRACMMv1.0 is available in CMAQv5.4.

Peat fires in Southeast Asia are a major source of trace gases and particles to the regional-global atmosphere that influence atmospheric chemistry, climate, and air quality. During the November 2015 record-high Ocean Niño Index (ONI, 2.6) our mobile smoke sampling team made the first, or rare, field measurements of numerous trace gases, aerosol optical properties, and aerosol chemistry and mass emissions for fires burning only peat in the Indonesian province of Central Kalimantan (on the island of Borneo). The measurements used Fourier transform infrared spectroscopy (FTIR), whole air sampling (WAS), photoacoustic extinctiometers (PAX, 401 and 870 nm), and detailed off-line analyses of particulate matter (PM) collected on filters. In September–November 2019 we measured peat fire trace gas emissions again, using WAS only, under El Niño–Southern Oscillation (ENSO)-neutral conditions (ONI, 0.3) in more remote areas of Central Kalimantan and also the Indonesian provinces of Riau, Jambi, and South Sumatra, all on the island of Sumatra. The 2019 measurements significantly expanded the geographic range and climate conditions sampled. This paper presents the 2019 results and synthesizes them with the previous fieldwork to converge on more robust regional average emission factors (EFs; grams of compound per kilogram of biomass burned) for authentic peat fires. In addition, samples of peat imported from Indonesia were burned in US laboratories, and the EFs and optical properties were characterized in more detail than in the field by a larger suite of instrumentation. We use the improved knowledge of regional emissions based on the expanded field measurements to select the most representative lab data and compute a synthesized, more “chemically complete” set of EFs and aerosol optical properties for tropical peat fires. The modified combustion efficiency (MCE) values for the peat smoke sampled in 2019 were within the range of MCEs sampled in 2015, but with a lower average in 2019 (0.718±0.021, range 0.687–0.736) than 2015 (0.772±0.035, range 0.693–0.835). Averaging the new and older data together suggests an updated MCE for tropical peat fires of ∼0.76. Despite the difference in MCE, the study-average methane emission factors (EF CH4) were remarkably similar across the 2 years probing different regions: 9.42±2.51 g kg−1 in 2019 and 9.51±4.74 g kg−1 in 2015. When parsing the 2019 samples by province, the EFs for non-methane organic gases (NMOGs) were about 3 times higher in South Sumatra and Central Kalimantan than in Jambi and Riau, but the overall 2019 study average was only ∼15 % higher than the 2015 study average. South Sumatra peat fires emitted higher amounts of carbonyl and dimethyl sulfide, suggesting a volcanic or marine influence or effects of agricultural chemicals. The lab and fieldwork taken together provide EFs for 230 trace gases including CO2 (1544 g kg−1), CO (315 g kg−1), and CH4 (9.8 g kg−1). These are significant adjustments to IPCC-recommended EFs, −9 %, +50 %, and −53 %, respectively. We also report EFs for numerous NMOGs, 46 N-containing compounds, and 14 sulfur- or halogen-containing species. The use of high-resolution mass spectrometry in the lab allowed measurement of 82 % more NMOG mass than in the field. Gravimetrically measured EF PM2.5 in the field in 2015 (17.3±5.8 g kg−1) was ∼20 % lower than the average from lab studies (22.4±10.4 g kg−1), perhaps due to higher field temperatures. Taken together the lab and field data show that the single-scattering albedo (SSA) was largely independent of wavelength and MCE in the visible (∼0.998), but lower at low MCE at 401 and 405 nm with a value of 0.958 at the study-average MCE. The absorption Ångström exponent (AAE) at the average MCE was 5.7. By far the largest PM component was weakly absorbing insoluble organic carbon.

Reactive nitrogen (Nr, defined as all nitrogen-containing compounds except for N2 and N2O) is one of the most important classes of compounds emitted from wildfire, as Nr impacts both atmospheric oxidation processes and particle formation chemistry. In addition, several Nr compounds can contribute to health impacts from wildfires. Understanding the impacts of wildfire on the atmosphere requires a thorough description of Nr emissions. Total reactive nitrogen 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 US wildfires, conducted as part of the FIREX Fire Lab 2016 study. Data from 75 stack fires were analyzed to examine the systematics of nitrogen emissions. The measured Nr ∕ total-carbon ratios averaged 0.37 % for fuels characteristic of western North America, and these gas-phase emissions were compared with fuel and residue N∕C ratios and mass to estimate that a mean (±SD) of 0.68 (±0.14) of fuel nitrogen was emitted as N2 and N2O. The Nr detected as speciated individual compounds included the following: 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 sum of these measured individual Nr compounds averaged 84.8 (±9.8) % relative to the total Nr, and much of the 15.2 % “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 with only flaming or with only smoldering combustion when using modified combustion efficiency, MCE=CO2/(CO+CO2), as a rough indicator. However, the systematic variations in 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: 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) ( ∘C) with mostly ammonia and NVOCs. The temperature ranges specified are based on known combustion and pyrolysis chemistry considerations. The mix of emissions in the PMF factors from chaparral fuels (manzanita and chamise) 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.

Combustion of biomass, garbage, and fossil fuels in South Asia has led to poor air quality in the region and has uncertain climate forcing impacts. Online measurements of submicron aerosol (PM1) emissions were conducted as part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) to investigate and report emission factors (EFs) and vacuum aerodynamic diameter (dva) size distributions from prevalent but poorly characterized combustion sources. The online aerosol instrumentation included a mini aerosol mass spectrometer (mAMS) and a dual-spot eight-channel aethalometer (AE33). The mAMS measured non-refractory PM1 mass, composition, and size. The AE33-measured black carbon (BC) mass and estimated light absorption at 370 nm due to organic aerosol or brown carbon. Complementary gas-phase measurements of carbon dioxide (CO2), carbon monoxide (CO), and methane (CH4) were collected using a Picarro Inc. cavity ring-down spectrometer (CRDS) to calculate fuel-based EFs using the carbon mass balance approach. The investigated emission sources include open garbage burning, diesel-powered irrigation pumps, idling motorcycles, traditional cookstoves fueled with dung and wood, agricultural residue fires, and coal-fired brick-making kilns, all of which were tested in the field. Open-garbage-burning emissions, which included mixed refuse and segregated plastics, were found to have some of the largest PM1 EFs (3.77–19.8 g kg−1) and the highest variability of the investigated emission sources. Non-refractory organic aerosol (OA) size distributions measured by the mAMS from garbage-burning emissions were observed to have lognormal mode dva values ranging from 145 to 380 nm. Particle-phase hydrogen chloride (HCl) was observed from open garbage burning and was attributed to the burning of chlorinated plastics. Emissions from two diesel-powered irrigation pumps with different operational ages were tested during NAMaSTE. Organic aerosol and BC were the primary components of the emissions and the OA size distributions were centered at ∼ 80 nm dva. The older pump was observed to have significantly larger EFOA than the newer pump (5.18 g kg−1 compared to 0.45 g kg−1) and similar EFBC. Emissions from two distinct types of coal-fired brick-making kilns were investigated. The less advanced, intermittently fired clamp kiln was observed to have relatively large EFs of inorganic aerosol, including sulfate (0.48 g kg−1) and ammonium (0.17 g kg−1), compared to the other investigated emission sources. The clamp kiln was also observed to have the largest absorption Ångström exponent (AAE  =  4) and organic carbon (OC) to BC ratio (OC  :  BC  =  52). The continuously fired zigzag kiln was observed to have the largest fraction of sulfate emissions with an EFSO4 of 0.96 g kg−1. Non-refractory aerosol size distributions for the brick kilns were centered at ∼ 400 nm dva. The biomass burning samples were all observed to have significant fractions of OA and non-refractory chloride; based on the size distribution results, the chloride was mostly externally mixed from the OA. The dung-fueled traditional cookstoves were observed to emit ammonium, suggesting that the chloride emissions were partially neutralized. In addition to reporting EFs and size distributions, aerosol optical properties and mass ratios of OC to BC were investigated to make comparisons with other NAMaSTE results (i.e., online photoacoustic extinctiometer (PAX) and off-line filter based) and the existing literature. This work provides critical field measurements of aerosol emissions from important yet under-characterized combustion sources common to South Asia and the developing world.

The Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) characterized widespread and under-sampled combustion sources common to South Asia, including brick kilns, garbage burning, diesel and gasoline generators, diesel groundwater pumps, idling motorcycles, traditional and modern cooking stoves and fires, crop residue burning, and heating fire. Fuel-based emission factors (EFs; with units of pollutant mass emitted per kilogram of fuel combusted) were determined for fine particulate matter (PM2.5), organic carbon (OC), elemental carbon (EC), inorganic ions, trace metals, and organic species. For the forced-draft zigzag brick kiln, EFPM2.5 ranged from 12 to 19 g kg−1 with major contributions from OC (7 %), sulfate expected to be in the form of sulfuric acid (31.9 %), and other chemicals not measured (e.g., particle-bound water). For the clamp kiln, EFPM2.5 ranged from 8 to 13 g kg−1, with major contributions from OC (63.2 %), sulfate (23.4 %), and ammonium (16 %). Our brick kiln EFPM2.5 values may exceed those previously reported, partly because we sampled emissions at ambient temperature after emission from the stack or kiln allowing some particle-phase OC and sulfate to form from gaseous precursors. The combustion of mixed household garbage under dry conditions had an EFPM2.5 of 7.4 ± 1.2 g kg−1, whereas damp conditions generated the highest EFPM2.5 of all combustion sources in this study, reaching up to 125 ± 23 g kg−1. Garbage burning emissions contained triphenylbenzene and relatively high concentrations of heavy metals (Cu, Pb, Sb), making these useful markers of this source. A variety of cooking stoves and fires fueled with dung, hardwood, twigs, and/or other biofuels were studied. The use of dung for cooking and heating produced higher EFPM2.5 than other biofuel sources and consistently emitted more PM2.5 and OC than burning hardwood and/or twigs; this trend was consistent across traditional mud stoves, chimney stoves, and three-stone cooking fires. The comparisons of different cooking stoves and cooking fires revealed the highest PM emissions from three-stone cooking fires (7.6–73 g kg−1), followed by traditional mud stoves (5.3–19.7 g kg−1), mud stoves with a chimney for exhaust (3.0–6.8 g kg−1), rocket stoves (1.5–7.2 g kg−1), induced-draft stoves (1.2–5.7 g kg−1), and the bhuse chulo stove (3.2 g kg−1), while biogas had no detectable PM emissions. Idling motorcycle emissions were evaluated before and after routine servicing at a local shop, which decreased EFPM2.5 from 8.8 ± 1.3 to 0.71 ± 0.45 g kg−1 when averaged across five motorcycles. Organic species analysis indicated that this reduction in PM2.5 was largely due to a decrease in emission of motor oil, probably from the crankcase. The EF and chemical emissions profiles developed in this study may be used for source apportionment and to update regional emission inventories.

Fine particulate matter (PM2.5) was collected in situ from peat smoke during the 2015 El Niño peat fire episode in Central Kalimantan, Indonesia. Twenty-one PM samples were collected from 18 peat fire plumes that were primarily smoldering with modified combustion efficiency (MCE) values of 0.725–0.833. PM emissions were determined and chemically characterized for elemental carbon (EC), organic carbon (OC), water-soluble OC, water-soluble ions, metals, and organic species. Fuel-based PM2.5 mass emission factors (EFs) ranged from 6.0 to 29.6 g kg−1 with an average of 17.3 ± 6.0 g kg−1. EC was detected only in 15 plumes and comprised ∼ 1 % of PM mass. Together, OC (72 %), EC (1 %), water-soluble ions (1 %), and metal oxides (0.1 %) comprised 74 ± 11 % of gravimetrically measured PM mass. Assuming that the remaining mass is due to elements that form organic matter (OM; i.e., elements O, H, N) an OM-to-OC conversion factor of 1.26 was estimated by linear regression. Overall, chemical speciation revealed the following characteristics of peat-burning emissions: high OC mass fractions (72 %), primarily water-insoluble OC (84 ± 11 %C), low EC mass fractions (1 %), vanillic to syringic acid ratios of 1.9, and relatively high n-alkane contributions to OC (6.2 %C) with a carbon preference index of 1.2–1.6. Comparison to laboratory studies of peat combustion revealed similarities in the relative composition of PM but greater differences in the absolute EF values. The EFs developed herein, combined with estimates of the mass of peat burned, are used to estimate that 3.2–11 Tg of PM2.5 was emitted to atmosphere during the 2015 El Niño peatland fire event in Indonesia. Combined with gas-phase measurements of CO2, CO, CH4, and volatile organic carbon from Stockwell et al. (2016), it is determined that OC and EC accounted for 2.1 and 0.04 % of total carbon emissions, respectively. These in situ EFs can be used to improve the accuracy of the representation of Indonesian peat burning in emission inventories and receptor-based models.

A wide range of globally significant biomass fuels were burned during the fourth Fire Lab at Missoula Experiment (FLAME-4). A multi-channel photoacoustic absorption spectrometer (PAS) measured dry absorption at 405, 532, and 660 nm and thermally denuded (250 °C) absorption at 405 and 660 nm. Absorption coefficients were broken into contributions from black carbon (BC), brown carbon (BrC), and lensing following three different methodologies, with one extreme being a method that assumes the thermal denuder effectively removes organics and the other extreme being a method based on the assumption that black carbon (BC) has an Ångström exponent of unity. The methodologies employed provide ranges of potential importance of BrC to absorption but, on average, there was a difference of a factor of 2 in the ratio of the fraction of absorption attributable to BrC estimated by the two methods. BrC absorption at shorter visible wavelengths is of equal or greater importance to that of BC, with maximum contributions of up to 92 % of total aerosol absorption at 405 nm and up to 58 % of total absorption at 532 nm. Lensing is estimated to contribute a maximum of 30 % of total absorption, but typically contributes much less than this. Absorption enhancements and the estimated fraction of absorption from BrC show good correlation with the elemental-carbon-to-organic-carbon ratio (EC ∕ OC) of emitted aerosols and weaker correlation with the modified combustion efficiency (MCE). Previous studies have shown that BrC grows darker (larger imaginary refractive index) as the ratio of black to organic aerosol (OA) mass increases. This study is consistent with those findings but also demonstrates that the fraction of total absorption attributable to BrC shows the opposite trend: increasing as the organic fraction of aerosol emissions increases and the EC ∕ OC ratio decreases.

Multiple trace-gas instruments were deployed during the fourth Fire Lab at Missoula Experiment (FLAME-4), including the first application of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) and comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC-TOFMS) for laboratory biomass burning (BB) measurements. Open-path Fourier transform infrared spectroscopy (OP-FTIR) was also deployed, as well as whole-air sampling (WAS) with one-dimensional gas chromatography–mass spectrometry (GC-MS) analysis. This combination of instruments provided an unprecedented level of detection and chemical speciation. The chemical composition and emission factors (EFs) determined by these four analytical techniques were compared for four representative fuels. The results demonstrate that the instruments are highly complementary, with each covering some unique and important ranges of compositional space, thus demonstrating the need for multi-instrument approaches to adequately characterize BB smoke emissions. Emission factors for overlapping compounds generally compared within experimental uncertainty, despite some outliers, including monoterpenes. Data from all measurements were synthesized into a single EF database that includes over 500 non-methane organic gases (NMOGs) to provide a comprehensive picture of speciated, gaseous BB emissions. The identified compounds were assessed as a function of volatility; 6–11 % of the total NMOG EF was associated with intermediate-volatility organic compounds (IVOCs). These atmospherically relevant compounds historically have been unresolved in BB smoke measurements and thus are largely missing from emission inventories. Additionally, the identified compounds were screened for published secondary organic aerosol (SOA) yields. Of the total reactive carbon (defined as EF scaled by the OH rate constant and carbon number of each compound) in the BB emissions, 55–77 % was associated with compounds for which SOA yields are unknown or understudied. The best candidates for future smog chamber experiments were identified based on the relative abundance and ubiquity of the understudied compounds, and they included furfural, 2-methyl furan, 2-furan methanol, and 1,3-cyclopentadiene. Laboratory study of these compounds will facilitate future modeling efforts.

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 current understanding of secondary organic aerosol (SOA) formation within biomass burning (BB) plumes is limited by the incomplete identification and quantification of the non-methane organic compounds (NMOCs) emitted from such fires. Gaseous organic compounds were collected on sorbent cartridges during laboratory burns as part of the fourth Fire Lab at Missoula Experiment (FLAME-4) and analyzed by two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC–ToFMS). The sensitivity and resolving power of GC × GC–ToFMS allowed the acquisition of the most extensive data set of BB NMOCs to date, with measurements for 708 positively or tentatively identified compounds. Estimated emission factors (EFs) are presented for these compounds for burns of six different vegetative fuels, including conifer branches, grasses, agricultural residue, and peat. The number of compounds meeting the peak selection criteria ranged from 129 to 474 among individual burns, and included extensive isomer groups. For example, 38 monoterpene isomers were observed in the emissions from coniferous fuels; the isomeric ratios were found to be consistent with those reported in relevant essential oils, suggesting that the composition of such oils may be very useful when predicting fuel-dependent terpene emissions. Further, 11 sesquiterpenes were detected and tentatively identified, providing the first reported speciation of sesquiterpenes in gas-phase BB emissions. The calculated EFs for all measured compounds are compared and discussed in the context of potential SOA formation.

We deployed a high-resolution proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) to measure biomass-burning emissions from peat, crop residue, cooking fires, and many other fire types during the fourth Fire Lab at Missoula Experiment (FLAME-4) laboratory campaign. A combination of gas standard calibrations and composition sensitive, mass-dependent calibration curves was applied to quantify gas-phase non-methane organic compounds (NMOCs) observed in the complex mixture of fire emissions. We used several approaches to assign the best identities to most major "exact masses", including many high molecular mass species. Using these methods, approximately 80–96% of the total NMOC mass detected by the PTR-TOF-MS and Fourier transform infrared (FTIR) spectroscopy was positively or tentatively identified for major fuel types. We report data for many rarely measured or previously unmeasured emissions in several compound classes including aromatic hydrocarbons, phenolic compounds, and furans; many of these are suspected secondary organic aerosol precursors. A large set of new emission factors (EFs) for a range of globally significant biomass fuels is presented. Measurements show that oxygenated NMOCs accounted for the largest fraction of emissions of all compound classes. In a brief study of various traditional and advanced cooking methods, the EFs for these emissions groups were greatest for open three-stone cooking in comparison to their more advanced counterparts. Several little-studied nitrogen-containing organic compounds were detected from many fuel types, that together accounted for 0.1–8.7% of the fuel nitrogen, and some may play a role in new particle formation.

An extensive program of experiments focused on biomass burning emissions began with a laboratory phase in which vegetative fuels commonly consumed in prescribed fires were collected in the southeastern and southwestern US and burned in a series of 71 fires at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured by an open-path Fourier transform infrared (OP-FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. Many of the 182 species quantified by the GC-MS have rarely, if ever, been measured in smoke before. An additional 153 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. In a second, "field" phase of this program, airborne and ground-based measurements were made of the emissions from prescribed fires that were mostly located in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. The field measurements of emission factors (EF) are useful both for modeling and to examine the representativeness of our lab fire EF. The lab EF/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for "smoldering compounds" emitted from the semiarid shrubland fuels should likely be increased by a factor of ~2.7 to better represent field fires. Based on the lab/field comparison, we present emission factors for 357 pyrogenic species (including unidentified species) for 4 broad fuel types: pine understory, semiarid shrublands, coniferous canopy, and organic soil. To our knowledge this is the most comprehensive measurement of biomass burning emissions to date and it should enable improved representation of smoke composition in atmospheric models. The results support a recent estimate of global NMOC emissions from biomass burning that is much higher than widely used estimates and they provide important insights into the nature of smoke. 31–72% of the mass of gas-phase NMOC species was attributed to species that we could not identify. These unidentified species are not represented in most models, but some provision should be made for the fact that they will react in the atmosphere. In addition, the total mass of gas-phase NMOC divided by the mass of co-emitted PM2.5 averaged about three (range ~2.0–8.7). About 35–64% of the NMOC were likely semivolatile or of intermediate volatility. Thus, the gas-phase NMOC represent a large reservoir of potential precursors for secondary formation of ozone and organic aerosol. For the single lab fire in organic soil about 28% of the emitted carbon was present as gas-phase NMOC and ~72% of the mass of these NMOC was unidentified, highlighting the need to learn more about the emissions from smoldering organic soils. The mass ratio of total NMOC to "NOx as NO" ranged from 11 to 267, indicating that NOx-limited O3 production would be common in evolving biomass burning plumes. The fuel consumption per unit area was 7.0 ± 2.3 Mg ha−1 and 7.7 ± 3.7 Mg ha−1 for pine-understory and semiarid shrubland prescribed fires, respectively.

Regional and global chemical transport models underpredict NOx (NO + NO2) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NOx bias has been shown in model evaluations using aircraft data (Singh et al., 2007) and total column NO2 (molecules cm−2) from satellite observations (Napelenok et al., 2008). The causes of NOx underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observation-based studies, in the upper troposphere, identify chemical rate coefficients as a potential source of error (Olson et al., 2006; Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology, and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NOx:HNO3, a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NOx removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NOx by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties.