Aged Biomass Burning Research Articles

Molecular Insights into Gas-Particle Partitioning and Viscosity of Atmospheric Brown Carbon.

Biomass burning organic aerosol (BBOA), containing brown carbon chromophores, plays a critical role in atmospheric chemistry and climate forcing. However, the effects of evaporation on BBOA volatility and viscosity under different environmental conditions remain poorly understood. This study focuses on the molecular characterization of laboratory-generated BBOA proxies from wood pyrolysis emissions. The initial mixture, "pyrolysis oil (PO1)", was progressively evaporated to produce more concentrated mixtures (PO1.33, PO2, and PO3) with volume reduction factors of 1.33, 2, and 3, respectively. Chemical speciation and volatility were investigated using temperature-programmed desorption combined with direct analysis in real-time ionization and high-resolution mass spectrometry (TPD-DART-HRMS). This novel approach quantified saturation vapor pressures and enthalpies of individual species, enabling the construction of volatility basis set distributions and the quantification of gas-particle partitioning. Viscosity estimates, validated by poke-flow experiments, showed a significant increase with evaporation, slowing particle-phase diffusion and extending equilibration times. These findings suggest that highly viscous tar ball particles in aged biomass burning emissions form as semivolatile components evaporate. The study highlights the importance of evaporation processes in shaping BBOA properties, underscoring the need to incorporate these factors into atmospheric models for better predictions of BBOA aging and its environmental impact.

Measurement report: Characteristics of nitrogen-containing organics in PM2.5 in Ürümqi, northwestern China – differential impacts of combustion of fresh and aged biomass materials

Abstract. Nitrogen-containing organic compounds (NOCs) are abundant and important aerosol components deeply involved in the global nitrogen cycle. However, the sources and formation processes of NOCs remain largely unknown, particularly in the city (Ürümqi, China) farthest from the ocean worldwide. Here, NOCs in PM2.5 collected in Ürümqi over a 1-year period were characterized by ultra-high-resolution mass spectrometry. The abundance of CHON compounds (mainly oxygen-poor unsaturated aliphatic-like species) in the positive ion mode was higher in the warm period than in the cold period, which was largely attributed to the contribution of fresh biomass material combustion (e.g., forest fires) associated with amidation of unsaturated fatty acids in the warm period, rather than the oxidation processes. However, CHON compounds (mainly nitro-aromatic species) in the negative ion mode increased significantly in the cold period, which was tightly related to aged biomass combustion (e.g., dry straws) in wintertime Ürümqi. For CHN compounds, alkyl nitriles and aromatic species showed higher abundance in the warm and cold periods, respectively. Alkyl nitriles can be derived from fresh biomass material combustion associated with the dehydration of amides (the main CHON compounds in the warm period). In contrast, aromatic species were tightly related to aged biomass burning. These findings further suggested different impacts of the combustion of fresh and aged biomass materials on NOC compositions in different seasons. The overall results shed light on the mechanisms by which fresh and aged biomass materials release different NOCs during combustion.

Reactive oxygen species generation from winter water-soluble organic aerosols in Delhi's PM2.5

In this study, we evaluate the relative redox activity of various water-soluble organic aerosol (WSOA) sources in Delhi's winter PM2.5, focusing on their capacity to generate reactive oxygen species (ROS). Using offline-aerosol mass spectrometry (AMS) and positive matrix factorization (PMF), we identified two oxidized factors—more oxidized oxygenated organic aerosol (MO-OOA) and less oxidized oxygenated organic aerosol (LO-OOA)—and three primary factors, namely nitrogen-enriched hydrocarbon-like organic aerosol (NHOA), biomass-burning organic aerosol (BBOA), and solid-fuel combustion organic aerosol (SFC-OA). The ROS-generating capability of PM2.5 was assessed using a real-time oxidative potential (OP) measurement system based on the dithiothreitol (DTT) assay. We employed multivariate linear regression technique (MLR) to explore the association between the DTT activity of water-soluble PM2.5 and these identified factors. We found BBOA, SFCOA, and MO-OOA significantly contributed to volume-normalized OP, with intrinsic water-soluble activities of 39 ± 11, 106 ± 31 and 160 ± 43 pmol/min/μg, respectively. MO-OOA, primarily from non-fossil precursors, serves as a proxy for aged biomass burning, which intensifies during winter and significantly influences the DTT activity. Additionally, OP is significantly influenced by WSOA derived from local incomplete solid fuel combustion sources, including coal and wood burning for household cooking and heating, burning of leaves, biodegradable waste, and garbage along the roadside. Interestingly, water-soluble metals (Mn, Cu, and Fe) showed no discernible contribution to the OP. These findings highlight the need for targeted mitigation strategies addressing local combustion processes and unregulated biomass burning to effectively reduce PM health exposure in Delhi.

Long‐Emission‐Wavelength Humic‐Like Component (L‐HULIS) as a Secondary Source Tracer of Brown Carbon in the Atmosphere

AbstractThe optical properties of secondary brown carbon (BrC) aerosols are poorly understood, hampering quantitative assessments of their impact. We propose a new method for estimating secondary source of BrC using excitation‐emission matrix (EEM) fluorescence spectroscopy, combined with parallel factor analysis (PARAFAC) and partial least squares regression (PLSR). Experiments were conducted on a collection of PM2.5 samples from urban areas in five Chinese cities during winter and summer. The humic‐like component with long‐emission wavelengths (L‐HULIS) was identified as a secondary source tracer of BrC. This was confirmed by correlating PARAFAC components with secondary organic aerosol tracers and molecular oxidation indices obtained from Fourier transform ion cyclotron resonance mass spectrometry analysis. Using L‐HULIS as a secondary tracer of BrC, it was determined that the contribution of secondary sources to water‐soluble BrC (WS‐BrC) in source emission samples is significantly smaller than in PM2.5 from five Chinese cities, supporting our method. In the five cities, secondary source derived via L‐HULIS contributes a dominant potion (80% ± 3.5%) of WS‐BrC at 365 nm during the summer, which is approximately twice as high as during the winter (45% ± 4.9%). Radiocarbon isotope (14C) analysis provides additional constraints to the sources of L‐HULIS‐derived secondary WS‐BrC in urban PM2.5, suggesting that aged biomass burning is the dominant contributor to secondary WS‐BrC in winter, and biogenic emission is dominant during summer. This study is the first report on identification of secondary sources of BrC using the fluorescence technique. It demonstrates the potential of this method in characterizing non‐fossil source secondary BrC in the atmosphere.

Airborne Observations Constrain Heterogeneous Nitrogen and Halogen Chemistry on Tropospheric and Stratospheric Biomass Burning Aerosol

AbstractHeterogeneous chemical cycles of pyrogenic nitrogen and halides influence tropospheric ozone and affect the stratosphere during extreme Pyrocumulonimbus (PyroCB) events. We report field‐derived N2O5 uptake coefficients, γ(N2O5), and ClNO2 yields, φ(ClNO2), from two aircraft campaigns observing fresh smoke in the lower and mid troposphere and processed/aged smoke in the upper troposphere and lower stratosphere (UTLS). Derived φ(ClNO2) varied across the full 0–1 range but was typically <0.5 and smallest in a PyroCB (<0.05). Derived γ(N2O5) was low in agricultural smoke (0.2–3.6 × 10−3), extremely low in mid‐tropospheric wildfire smoke (0.1 × 10−3), but larger in PyroCB processed smoke (0.7–5.0 × 10−3). Aged biomass burning aerosol in the UTLS had a higher γ(N2O5) of 17 × 10−3 that increased with sulfate and liquid water, but that was 1–2 orders of magnitude lower than values for aqueous sulfuric aerosol used in stratospheric models.

Real-time chemical characterization of primary and aged biomass burning aerosols derived from sub-Saharan African biomass fuels in smoldering fires.

The influence of biomass burning (BB)-derived organic aerosol (OA) emissions on solar radiation via absorption and scattering is related to their physicochemical properties and can change upon atmospheric aging. We systematically examined the compositionally-resolved mass concentration and production of primary and secondary organic aerosol (POA and SOA, respectively) in the NC A&T University smog chamber facility. Mass spectral profiles of OA measured by the Aerosol Chemical Speciation Monitor (ACSM) revealed the influence of dark- and photo-aging, fuel type, and relative humidity. Unit mass resolution (UMR) mapping, the ratio of the fraction of the OA mass spectrum signal at m/z 55 and 57 (f 55/f 57) vs. the same fraction at m/z 60 (f 60) was used to identify source-specific emission profiles. Furthermore, Positive Matrix Factorization (PMF) analysis was conducted using OA mass spectra, identifying four distinct factors: low-volatility oxygenated OA (LV-OOA), primary biomass-burning OA (BBOA), BB secondary OA (BBSOA), and semi-volatile oxygenated OA (SV-OOA). Data supports a robust four-factor solution, providing insights into the chemical transformations under different experimental conditions, including dark- and photo-aged, humidified, and dark oxidation with NO3 radicals. This work presents the first such laboratory study of African-derived BBOA particles, addressing a gap in global atmospheric chemistry research.

Molecular-level transformations of biomass burning-derived water-soluble organic carbon during dark aqueous OH oxidation: Insights from absorption, fluorescence, high-performance size exclusion chromatography and high-resolution mass spectrometry analysis

Biomass burning (BB) releases large amounts of water-soluble organic carbon (WSOC), which would undergo heterogenous oxidation processes that induce transformations in both molecular structures and compositions within BB WSOC. This study designed an aqueous oxidation initiated by OH radicals in the absence of light for WSOC extracted from smoke particles generated by burning of corn straw and fir wood. The BB WSOC was comprehensively characterized using a combination of UV–visible spectra, excitation-emission matrix fluorescence in conjunction with parallel factor analysis (EEM-PARAFAC), high-performance size exclusion chromatography (HPSEC), and high-resolution mass spectrometry (HRMS) analyses. Over the course of oxidation, both chromophores and fluorophores exhibited gradual decreases. Moreover, EEM-PARAFAC revealed a preferential degradation of larger-sized protein-like/phenol-like organic matters, accompanied by the accumulation and/or formation of humic-like substances in aged BB WSOC. HPSEC analysis showed notable changes in molecular weight (MW) distributions for both types of BB WSOC during oxidation. Specifically, high MW species (>1 kDa) displayed a tendency to form along with oxidation, possibly attributed to the formation of assemblies via intermolecular weak forces. After oxidation, evidence of CHO compound degradation and enrichment/formation of CHON compounds was observed for both types of BB WSOC. Remarkably, the resistant, degraded and produced molecules for BB WSOC were dominated by CHO (38–73 %) and lignin-like molecules (41–47 %), suggesting diverse responses to oxidation within these two groups. Furthermore, polyphenols experienced selective degradation, while CHON, aliphatic and poly-aromatic molecules tended to form during the oxidation process for both types of BB WSOC. In summary, this study provides a comprehensive understanding of the molecular-level transformations undergone by BB WSOC during dark aqueous OH oxidation. The findings significantly contribute to our insights into atmospheric evolution of BB WSOC, thereby playing a crucial role in accurately assessing their effects within climate models and informing policy decisions.

Evaluation of aerosol- and gas-phase tracers for identification of transported biomass burning emissions in an industrially influenced location in Texas, USA

Abstract. As criteria pollutants from anthropogenic emissions have declined in the US in the last 2 decades, biomass burning (BB) emissions are becoming more important for urban air quality. Tracking the transported BB emissions and their impacts is challenging, especially in areas that are also burdened by anthropogenic sources like the Texas Gulf Coast. During the Corpus Christi and San Antonio (CCSA) field campaign in spring 2021, two long-range-transport BB events (BB1 and BB2) were identified. The observed patterns of an absorption Ångström exponent (AAE), a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) BB tracer (f60), equivalent black carbon (eBC), acetonitrile and carbon monoxide (CO) during BB1 and BB2 indicated differences in the mixing of transported BB plumes with local anthropogenic sources. The combined information from HYSPLIT backward-trajectory (BT) and satellite observations revealed that BB1 had mixed influence of transported smoke plumes from fires in central Mexico, the Yucatán Peninsula and the central US, whereas BB2 was influenced by fires in the central US. The estimated transport times of smoke from the Mexican fires and the central US fires to our study site were not too different (48–54 and 24–36 h, respectively), and both events appeared to have undergone similar levels of atmospheric processing, as evident in the elemental ratios of bulk organic aerosol (OA). We observed an aging trend for f44 vs. f60 and f44 vs. f43 as a function of time during BB2 but not during BB1. Positive matrix factorization (PMF) analysis of OA showed that BB1 had a mixture of organics from aged BB emissions with an anthropogenic marine signal, while the oxidized organic compounds from aged BB emissions dominated the aerosols during BB2. The size distribution of aerosol composition revealed distinct characteristics between BB1 and BB2, where BB1 was found to be externally mixed, exhibiting a combination of BB and anthropogenic marine aerosols. On the other hand, BB2 exhibited internal mixing dominated by aged BB aerosol. Our analysis from mobile and stationary measurements highlights that both CO and acetonitrile are likely impacted by local sources even during the BB events and specifically that acetonitrile cannot be used as a unique BB tracer for dilute BB plumes in an industrially influenced location. A suitable volatile organic compound (VOC) tracer would need to be emitted in high concentrations during BB, resistant to degradation during transport, unique to BB and able to be measured in the field. This study effectively demonstrates that AAE and aerosol BB tracers served as precise and effective tracers in these complex emission scenarios. Network deployment of multiwavelength photometers holds promise for enhancing our understanding of BB impacts on air quality and supporting informed decision-making for effective mitigation strategies in locations with mixed sources and influence of dilute BB plumes. To demonstrate the relevance of such an aerosol optical network, we provide evidence of the potential regional impacts of these transported BB events on urban O3 levels using measurements from the surface air quality monitoring network in Texas.

Source apportionment of volatile organic compounds during paddy-residue burning season in north-west India reveals large pool of photochemically formed air toxics

Paddy-residue burning is associated with poor air quality in north-west India during October–November every year. However, till date a quantitative study of its contribution to ambient volatile organic compounds (VOCs) using highly time-resolved measurements within the region has been lacking. Several VOCs like benzene are carcinogenic and also fuel formation of secondary pollutants such as secondary organic aerosol (SOA) and ozone. Here, we undertake quantitative source-apportionment using a PMF source-receptor model on a high-quality in-situ measured dataset of 54 VOCs in Punjab, India, and validate the model results using source profiles. The contribution of the seven most dominant sources to the total VOC mass concentrations were: daytime photochemistry and biogenic VOCs (BVOCs) (26%), followed by solid-fuel usage and waste-disposal (18%), traffic (two-wheeler 14% and four-wheeler 10%), photochemically aged biomass burning (17%), industries and solvent usage (9%), and fresh paddy residue burning (6%). Ozone production potential was dominated by solid fuel usage and waste disposal (25%), followed by traffic (two-wheeler 11% and four-wheeler 12%), BVOCs and photooxidation products (21%), photochemically aged biomass burning (16%), industries & solvent usage (9%) and fresh paddy residue burning (6%). SOA production was dominated by traffic (two-wheeler 26% and four-wheeler 28%) followed by solid fuel usage and waste disposal (22%), photochemically aged biomass burning emissions (15%) with minor contribution from industries & solvents (6%), fresh paddy residue burning (2%) and photochemistry and biogenic VOCs (1%). Comparisons with global emission inventories REASv3.2.1 and EDGARv4.3.2, showed both overestimate the industry and solvent source. Further, EDGARv4.3.2 underestimated the traffic source whereas paddy residue burning emissions are absent in REASv3.2.1. Although the overall mass contribution of paddy-residue burning emissions isn't high, our results show that health-relevant compounds emitted directly and formed photochemically from biomass burning sources active at this time are majorly responsible for the unhealthy air.

Investigation of four-year chemical composition and organic aerosol sources of submicron particles at the ATOLL site in northern France

This study presents the first long-term online measurements of submicron (PM1) particles at the ATOLL (ATmospheric Observations in liLLe) platform, in northern France. The ongoing measurements using an Aerosol Chemical Speciation Monitor (ACSM) started at the end of 2016 and the analysis presented here spans through December 2020. At this site, the mean PM1 concentration is 10.6 μg m−3, dominated by organic aerosols (OA, 42.3%) and followed by nitrate (28.9%), ammonium (12.3%), sulfate (8.6%), and black carbon (BC, 8.0%). Large seasonal variations of PM1 concentrations are observed, with high concentrations during cold seasons, associated with pollution episodes (e.g. over 100 μg m−3 in January 2017). To study OA origins over this multiannual dataset we performed source apportionment analysis using rolling positive matrix factorization (PMF), yielding two primary OA factors, a traffic-related hydrocarbon-like OA (HOA) and biomass-burning OA (BBOA), and two oxygenated OA (OOA) factors. HOA showed a homogeneous contribution to OA throughout the seasons (11.8%), while BBOA varied from 8.1% (summer) to 18.5% (winter), the latter associated with residential wood combustion. The OOA factors were distinguished between their less and more oxidized fractions (LO-OOA and MO-OOA, on average contributing 32% and 42%, respectively). During winter, LO-OOA is identified as aged biomass burning, so at least half of OA is associated with wood combustion during this season. Furthermore, ammonium nitrate is also a predominant aerosol component during cold-weather pollution episodes – associated with fertilizer usage and traffic emissions. This study provides a comprehensive analysis of submicron aerosol sources at the recently established ATOLL site in northern France from multiannual observations, depicting a complex interaction between anthropogenic and natural sources, leading to different mechanisms of air quality degradation in the region across different seasons.

Case study of biomass-burning aerosol events over Sofia, Bulgaria, based on AERONET sun photometer data

In the present work, the peculiarities were analyzed of aerosol events over Sofia, Bulgaria, characterized by a daily-mean aerosol optical depth (AOD) exceeding 0.3 and Ångström exponent (AE) above unity. Such aerosol situations arise most frequently in summer and early autumn, and sometimes in late autumn and winter. The analysis was based on AERONET sun photometer data and showed that the corresponding aerosol ensembles consisted mainly of fine-fraction biomass-burning (BB) smoke particles due to summer wildfires or domestic heating in winter, with a high sphericity factor (SF) that reached unity and a low linear particle depolarization ratio (LDR) of the order of thousandths. In the cases of aged BB smoke particles, the values of AE decrease without essential changes in SF and LDR. The presence or the periodic appearance of desert dust and/or marine aerosols during the day will also lead to a lower AE, accompanied however by a decreasing SF and an increasing LDR.

Airborne glyoxal measurements in the marine and continental atmosphere: comparison with TROPOMI observations and EMAC simulations

Abstract. We report on airborne limb and nadir measurements of vertical profiles and total vertical column densities (VCDs) of glyoxal (C2H2O2) in the troposphere, which were performed aboard the German research aircraft HALO (High Altitude and LOng Range) in different regions and seasons around the globe between 2014 and 2019. The airborne nadir and integrated limb profiles agree excellently among each other. Our airborne observations are further compared to collocated glyoxal measurements of the TROPOspheric Monitoring Instrument (TROPOMI), with good agreement between both data sets for glyoxal observations in (1) pristine terrestrial, (2) pristine marine, (3) mixed polluted, and (4) biomass-burning-affected air masses with high glyoxal concentrations. Exceptions to the overall good agreement are observations of (1) faint and aged biomass burning plumes over the oceans and (2) of low-lying biomass burning or anthropogenic plumes in the terrestrial or marine boundary layer, both of which contain elevated glyoxal that is mostly not captured by TROPOMI. These differences in airborne and satellite-detected glyoxal are most likely caused by the overall small contribution of plumes of a limited extent to the total glyoxal absorption in the atmosphere and the difficulty in remotely detecting weak absorbers located close to low reflective surfaces (e.g. the ocean in the visible wavelength range) or within dense aerosol layers. Observations of glyoxal in aged biomass burning plumes (e.g. observed over the tropical Atlantic off the coast of West Africa in summer 2018, off the coast of Brazil by the end of the dry season 2019, and the East China Sea in spring 2018) could be traced back to related wildfires, such as a plume crossing over the Drake Passage that originated from the Australian bushfires in late 2019. Our observations of glyoxal in such aged biomass burning plumes confirm recent findings of enhanced glyoxal and presumably secondary organic aerosol (SOA) formation in aged wildfire plumes from yet-to-be-identified, longer-lived organic precursor molecules (e.g. aromatics, acetylene, or aliphatic compounds) co-emitted in the fires. Furthermore, elevated glyoxal (median 44 ppt – parts per trillion), as compared to other marine regions (median 10–19 ppt), is observed in the boundary layer over the tropical oceans, which is well in agreement with previous reports. The airborne data sets are further compared to glyoxal simulations performed with the global atmosphere chemistry model EMAC (ECHAM/MESSy Atmospheric Chemistry). When using an EMAC set up that resembles recent EMAC studies focusing on complex chemistry, reasonable agreement is found for pristine air masses (e.g. the unperturbed free and upper troposphere), but a notable glyoxal overestimation of the model exists for regions with high emissions of glyoxal and glyoxal-producing volatile organic compounds (VOCs) from the biosphere (e.g. the Amazon). In all other investigated regions, the model underpredicts glyoxal to varying degrees, in particular when probing mixed emissions from anthropogenic activities (e.g. over continental Europe, the Mediterranean, and East China Sea) and potentially from the sea (e.g. the tropical oceans). Also, the model tends to largely underpredict glyoxal in city plumes and aged biomass burning plumes. The potential causes for these differences are likely to be multifaceted, but they all point to missing glyoxal sources from the degradation of the mixture of potentially longer-chained organic compounds emitted from anthropogenic activities, biomass burning, and from the organic microlayer of the sea surface.

Dynamic Wood Smoke Aerosol Toxicity during Oxidative Atmospheric Aging.

Wildfires are a major source of biomass burning aerosol to the atmosphere, with their incidence and intensity expected to increase in a warmer future climate. However, the toxicity evolution of biomass burning organic aerosol (BBOA) during atmospheric aging remains poorly understood. In this study, we report a unique set of chemical and toxicological metrics of BBOA from pine wood smoldering during multiphase aging by gas-phase hydroxyl radicals (OH). Both the fresh and OH-aged BBOA show activity relevant to adverse health outcomes. The results from two acellular assays (DTT and DCFH) show significant oxidative potential (OP) and reactive oxygen species (ROS) formation in OH-aged BBOA. Also, radical concentrations in the aerosol assessed by electron paramagnetic resonance (EPR) spectroscopy increased by 50% following heterogeneous aging. This enhancement was accompanied by a transition from predominantly carbon-centered radicals (85%) in the fresh aerosol to predominantly oxygen-centered radicals (76%) following aging. Both the fresh and aged biomass burning aerosols trigger prominent antioxidant defense during the in vitro exposure, indicating the induction of oxidative stress by BBOA in the atmosphere. By connecting chemical composition and toxicity using an integrated approach, we show that short-term aging initiated by OH radicals can produce biomass burning particles with a higher particle-bound ROS generation capacity, which are therefore a more relevant exposure hazard for residents in large population centers close to wildfire regions than previously studied fresh biomass burning emissions.

Surface Oxidation of Phenolic Aldehydes: Fragmentation, Functionalization, and Coupling Reactions.

Substantial amounts of phenolic aldehydes, represented by the structures of syringaldehyde, vanillin, and 4-hydroxybenzaldehyde, are emitted to the atmosphere during biomass burning. The oxidative transformation of phenolic aldehydes during atmospheric transport has the potential to modify the physicochemical properties of particulates, which play a vital role in Earth's climate and human health. Herein, thin solid films made of syringaldehyde, vanillin, and 4-hydroxybenzaldehyde are oxidized in contact with O3(g) under a relative humidity of 74% representative of average global conditions. New physical insights into the surface reactions are achieved by analyzing isopropanol-extracted films before and during oxidation by multiple techniques. Changes in electronic transitions at 220, 310, and 350-400 nm registered by UV-vis spectroscopy show that the oxidized films have enhanced mass absorption coefficients at λ > 300 nm. Electrospray ionization (ESI) mass spectrometry (MS) and ion chromatography with conductivity and MS detection of extracted oxidized films confirm aromatic ring cleavage of syringaldehyde and vanillin by O3(g) with the production of carboxylic acids. Carboxylic acids were observed as anions ([M - H]-) at m/z 45 (formic acid), 73 (glyoxylic acid), 75 (glycolic acid), 89 (oxalic acid), 115 (maleic acid), 117 (mesoxalic acid), 119 (tartronic acid), and 129 (maleic acid monomethyl ester), while other polyfunctional products were registered by ultrahigh-pressure liquid chromatography with UV-vis and MS detection. In situ production of hydroxyl radicals is confirmed by demethoxylation products and ipso attack at the C1 ring position holding the -C(H)═O group. The order of reactivity increased with the number of methoxy substituents that donate electron density to the aromatic ring. Combined oxidation mechanisms for the three compounds are proposed based on all of the experimental observations and explain the contribution of aged biomass burning material to secondary organic aerosol formation.

Biomass burning and marine aerosol processing over the southeast Atlantic Ocean: a TEM single-particle analysis

Abstract. This study characterizes single-particle aerosol composition from filters collected during the ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) and CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017 (CLARIFY-2017) campaigns. In particular the study describes aged biomass burning aerosol (BBA), its interaction with the marine boundary layer and the influence of biomass burning (BB) air on marine aerosol. The study finds evidence of BBA influenced by marine boundary layer processing as well as sea salt influenced by BB air. Secondary chloride aerosols were observed in clean marine air as well as in BB-influenced air in the free troposphere. Higher-volatility organic aerosol appears to be associated with increased age of biomass burning plumes, and photolysis or oxidation may be a mechanism for the apparent increased volatility. Aqueous processing and interaction with the marine boundary layer air may be a mechanism for the presence of sodium on many aged potassium salts. By number, biomass burning potassium salts and modified sea salts are the most observed particles on filter samples. The most commonly observed BC coatings are inorganic salts. These results suggest that atmospheric processes such as photolysis, oxidation and cloud processing are key drivers in the elemental composition and morphology of aged BBA. Fresh BBA inorganic salt content, as it has an important role in the particles' ability to uptake water, may be a key driver in how aqueous processing and atmospheric aging proceed.

Measurement report: Distinct size dependence and diurnal variation in organic aerosol hygroscopicity, volatility, and cloud condensation nuclei activity at a rural site in the Pearl River Delta (PRD) region, China

Abstract. Organic aerosol (OA) has a significant contribution to cloud formation and hence climate change. However, high uncertainties still exist in its impact on global climate, owing to the varying physical properties affected by the complex formation and aging processes. In this study, the hygroscopicity, volatility, cloud condensation nuclei (CCN) activity, and chemical composition of particles were measured using a series of online instruments at a rural site in the Pearl River Delta (PRD) region of China in fall 2019. During the campaign, the average hygroscopicity of OA (κOA) increased from 0.058 at 30 nm to 0.09 at 200 nm, suggesting a higher oxidation state of OA at larger particle sizes, supported by a higher fraction of extremely low volatility OA (ELVOA) for larger size particles. Significantly different diurnal patterns of κOA were observed between Aitken mode particles and accumulation mode particles. For Aitken mode particles (30–100 nm), the κOA values showed daily minima (0.02–0.07) during daytime, while the accumulation mode exhibited a daytime peak (∼ 0.09). Coincidently, a daytime peak was observed for both aged biomass burning organic aerosol (aBBOA) and less oxygenated organic aerosol (LOOA) based on source apportionment, which was attributed to the aging processes and gas–particle partitioning through photochemical reactions. In addition, the fraction of semi-volatile OA (SVOA) was higher at all measured sizes during daytime than during nighttime. These results indicate that the formation of secondary OA (SOA) through gas–particle partitioning can generally occur at all diameters, while the aging processes of pre-existing particles are more dominated in the accumulation mode. Furthermore, we found that applying a fixed κOA value (0.1) could lead to an overestimation of the CCN number concentration (NCCN) up to 12 %–19 % at 0.1 %–0.7 % supersaturation (SS), which was more obvious at higher SS during daytime. Better prediction of NCCN could be achieved by using size-resolved diurnal κOA, which indicates that the size dependence and diurnal variations in κOA can strongly affect the NCCN at different SS values. Our results highlight the need for accurately evaluating the atmospheric evolution of OA at different size ranges and their impact on the physicochemical properties and hence climate effects.

Highly time-resolved chemical speciation and source apportionment of organic aerosol components in Delhi, India, using extractive electrospray ionization mass spectrometry

Abstract. In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution, especially during winter. Comprehensive knowledge of the composition and sources of the organic aerosol (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary OA (POA) and showed that secondary OA (SOA) played a major role but were unable to resolve specific SOA sources. We address the latter through the first field deployment of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer (AMS). Measurements were conducted during the winter of 2018/19, and positive matrix factorization (PMF) was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning OA (BBOA-1 and BBOA-2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LO-OOA). On average, 40 % of the total OA mass was apportioned to the secondary factors. The SOA contribution to total OA mass varied greatly between the daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %, 21:00–04:00 LT). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin: aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA-dominated factors were related to the total AMS SOA (i.e. MO-OOA + LO-OOA) by multiple linear regression (MLR). Aromatic SOA was the major SOA component during the daytime, with a 55.2 % contribution to total SOA mass (42.4 % contribution to total OA). Its contribution to total SOA, however, decreased to 25.4 % (7.9 % of total OA) during the nighttime. This factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA accounted for 18.4 % of total SOA mass (14.2 % of total OA) during the daytime and 36.1 % of total SOA mass (11.2 % of total OA) during the nighttime. Aged biomass burning and mixed urban SOA accounted for 15.2 % and 11.0 % of total SOA mass (11.7 % and 8.5 % of total OA mass), respectively, during the daytime and 15.4 % and 22.9 % of total SOA mass (4.8 % and 7.1 % of total OA mass), respectively, during the nighttime. A simple dilution–partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed daytime concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production, likely from the oxidation of locally emitted volatile organic compounds (VOCs). In contrast, biogenic SOA was related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study show that in Delhi, the nighttime high concentrations are caused by POA emissions led by traffic and biomass burning and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction. Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the daytime suggests an increased OA toxicity and health-related consequences for the general public.

Persistent Influence of Wildfire Emissions in the Western United States and Characteristics of Aged Biomass Burning Organic Aerosols under Clean Air Conditions.

Wildfire-influenced air masses under regional background conditions were characterized at the Mt. Bachelor Observatory (∼2800 m a.s.l.) in summer 2019 to provide a better understanding of the aging of biomass burning organic aerosols (BBOAs) and their impacts on the remote troposphere in the western United States. Submicron aerosol (PM1) concentrations were low (average ± 1σ = 2.2 ± 1.9 μg sm-3), but oxidized BBOAs (average O/C = 0.84) were constantly detected throughout the study. The BBOA correlated well with black carbon, furfural, and acetonitrile and comprised above 50% of PM1 during plume events when the peak PM1 concentration reached 18.0 μg sm-3. Wildfire plumes with estimated transport times varying from ∼10 h to >10 days were identified. The plumes showed ΔOA/ΔCO values ranging from 0.038 to 0.122 ppb ppb-1 with a significant negative relation to plume age, indicating BBOA loss relative to CO during long-range transport. Additionally, increases of average O/C and aerosol sizes were seen in more aged plumes. The mass-based size mode was approximately 700 nm (Dva) in the most oxidized plume that likely originated in Siberia, suggesting aqueous-phase processing during transport. This work highlights the widespread impacts that wildfire emissions have on aerosol concentration and properties, and thus climate, in the western United States.

Nighttime chemistry of biomass burning emissions in urban areas: A dual mobile chamber study

Abstract. Residential biomass burning for heating purposes is an important source of air pollutants during winter. Here we test the hypothesis that significant secondary organic aerosol production can take place even during winter nights through oxidation of the emitted organic vapors by the nitrate (NO3) radical produced during the reaction of ozone and nitrogen oxides. We use a mobile dual smog chamber system which allows the study of chemical aging of ambient air against a control reference. Ambient urban air sampled during a wintertime campaign during nighttime periods with high concentrations of biomass burning emissions was used as the starting point for the aging experiments. Biomass burning organic aerosol (OA) was, on average, 70 % of the total OA at the beginning of our experiments. Ozone was added in the perturbed chamber to simulate mixing with background air (and subsequent NO3 radical production and aging), while the second chamber was used as a reference. Following the injection of ozone, rapid OA formation was observed in all experiments, leading to increases in the OA concentration by 20 %–70 %. The oxygen-to-carbon ratio of the OA increased on average by 50 %, and the mass spectra of the produced OA was quite similar to the oxidized OA mass spectra reported during winter in urban areas. Furthermore, good correlation was found for the OA mass spectra between the ambient-derived emissions in this study and the nocturnal aged laboratory-derived biomass burning emissions from previous work. Concentrations of NO3 radicals as high as 25 ppt (parts per trillion) were measured in the perturbed chamber, with an accompanying production of 0.1–3.2 µg m−3 of organic nitrate in the aerosol phase. Organic nitrate represented approximately 10 % of the mass of the secondary OA formed. These results strongly indicate that the OA in biomass burning plumes can chemically evolve rapidly even during wintertime periods with low photochemical activity.

Optical and Microphysical Properties of Aged Biomass Burning Aerosols and Mixtures, Based on 9-Year Multiwavelength Raman Lidar Observations in Athens, Greece

Mean optical and microphysical aerosol properties of long-range transported biomass burning (BB) particles and mixtures are presented from a 9-year (2011–2019) data set of multiwavelength Raman lidar data, obtained by the EOLE lidar over the city of Athens (37.58° N, 23.47° E), Greece. We studied 34 aerosol layers characterized as: (1) smoke; (2) smoke + continental polluted, and (3) smoke + mixed dust. We found, mainly, small-sized aerosols with mean backscatter-related (355 nm/532 nm, 532 nm/1064 nm) values and Ångström exponent (AE) values in the range 1.4–1.7. The lidar ratio (LR) value at 355 nm was found to be 57 ± 10 sr, 51 ± 5 sr, and 38 ± 9 sr for the aerosol categories (1), (2), and (3), respectively; while at 532 nm, we observed LR values of 73 ± 11 sr, 59 ± 10 sr, and 62 ± 12 for the same categories. Regarding the retrieved microphysical properties, the effective radius (reff) ranged from 0.24 ± 0.11 to 0.24 ± 0.14 μm for all aerosol categories, while the volume density (vd) ranged from 8.6 ± 3.2 to 20.7 ± 14.1 μm−3cm−3 with the higher values linked to aerosol categories (1) and (2); the real part of the refractive index (mR) ranged between 1.49 and 1.53, while for the imaginary part (mI), we found values within 0.0108 i and 0.0126 i. Finally, the single scattering albedo (SSA) of the propped particles varied from 0.915 to 0.936 at all three wavelengths (355–532–1064 nm). The novelty of this study is the provision of typical values of BB aerosol properties from the UV to the near IR, which can be used in forecasting the aerosol climatic effects in the European region.