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.

New Analytical Paradigm to Determine Concentration of Brown Carbon and Its Sample-by-Sample Mass Absorption Efficiency.

Brown carbon (BrC) has a substantial direct radiative effect, but current estimates of its impact on radiative balance are highly uncertain due to a lack of measurements of its light-absorbing properties, such as mass absorption efficiency (MAE). Here, we present a new analytical paradigm based on a Bayesian inference (BI) model that takes multiwavelength aethalometer measurements and total carbon data to resolve the concentrations of black carbon and BrC, and MAEs of BrC on a sample-by-sample basis. Hourly MAEs, unattainable in previous studies, can now be calculated, enabling the first-time observation of the darkening-bleaching dynamics of BrC in response to photochemical transformation. We demonstrate the application of this BI model to analyze measurements collected over one year (2021-2022) in Hong Kong. Diel variations in MAE370 nm of BrC reveal a darkening-to-bleaching transition occurring between 8 and 10 O'clock when the solar irradiance ranges from 30 to 400 W m-2. Furthermore, we consistently observe an increase in MAE370 nm of BrC with nitrogen oxide concentrations, suggesting the enhanced formation of nitrogenous organics. This BI model-based data analysis would bring forth a breakthrough in amassing observation data of BrC and its MAEs in diverse ambient environments and with high time resolution.

Aromatic Nitration Enhances Absorption of Biomass Burning Brown Carbon in an Oxidizing Urban Environment.

Brown carbon (BrC) from biomass burning constitutes a significant portion of light-absorbing components in the atmosphere. Although the aging of BrC surrogates from biomass burning has been studied in many laboratory settings, BrC aging behavior in real-world urban environments is not well understood. In this study, through a combination of online dynamic monitoring and offline molecular characterization, the ambient optical aging of BrC was linked to its dynamic changes in molecular composition. Enhanced light absorption by BrC was consistently observed during the periods dominated by oxygenated biomass burning organic aerosol (BBOA), in contrast to periods dominated by primary emissions or secondary formation in aqueous-phase. This enhancement was linked to the formation of nitrogen-containing compounds during the ambient aging of BBOA. Detailed molecular characterization, alongside analysis of environmental parameters, revealed that an increased atmospheric oxidizing capacity, marked by elevated levels of ozone and nighttime NO3 radicals, facilitated the formation of nitrated aromatic BrC chromophores. These chromophores were primarily responsible for the enhanced light absorption during the ambient aging of BBOA. This study elucidates the nitration processes that enhance BrC light absorption for ambient BBOA, and highlights the crucial role of meteorological conditions. Furthermore, our findings shed light on the chemical and optical aging processes of biomass burning BrC in ambient air, offering insights into its environmental behavior and effects.

Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH.

Dark aqueous-phase reactions involving the nitrosation and nitration of aromatic organic compounds play a significant role in the production of light-absorbing organic carbon in the atmosphere. This process constitutes a crucial aspect of tropospheric chemistry and has attracted growing research interest, particularly in understanding the mechanisms governing nighttime reactions between phenols and nitrogen oxides. In this study, we present new findings concerning the rapid dark reactions between phenols containing electron-donating groups and inorganic nitrite in acidic aqueous solutions with pH levels <3.5. This reaction generates a substantial amount of nitroso- and nitro-substituted phenolic compounds, known for their light-absorbing properties and toxicity. In experiments utilizing various substituted phenols, we demonstrate that their reaction rates with nitrite depend on the electron cloud density of the benzene ring, indicative of an electrophilic substitution reaction mechanism. Control experiments and theoretical calculations indicate that the nitrosonium ion (NO+) is the reactive nitrogen species responsible for undergoing electrophilic reactions with phenolate anions, leading to the formation of nitroso-substituted phenolic compounds. These compounds then undergo partial oxidation to form nitro-substituted phenols through reactions with nitrous acid (HONO) or other oxidants like oxygen. Our findings unveil a novel mechanism for swift atmospheric nitrosation and nitration reactions that occur within acidic cloud droplets or aerosol water, providing valuable insights into the rapid nocturnal formation of nitrogen-containing organic compounds with significant implications for climate dynamics and human health.

Black carbon and particulate matter concentrations amid central Chile's extreme wildfires.

The increase in the frequency and severity of global wildfires has been largely influenced by climate change and land use changes. From February 2 to 6, 2024, central Chile experienced its most devastating wildland-urban interface wildfire in history, severely impacting the Valparaíso region. This catastrophic event, which led to extensive forest destruction, the loss of thousands of homes, and over a hundred human fatalities, directly impacted the area surrounding the campus of Federico Santa María Technical University. In that period, an air quality monitoring campaign was set up on the campus to measure black carbon (BC) and particulate matter (PM) during the wildfire season. The monitoring station was located directly within the smoke plume, allowing for the collection of unprecedented air quality data. Extremely high concentrations of BC at 880 nm were reported during the wildfires, with a daily mean (±σ) of 14.83 ± 19.52 µg m-3. Peak concentrations measured at 880 nm and 375 nm reached 812.89 µg m-3 and 1561.24 µg m-3, respectively. The maximum daily mean BC concentrations at these wavelengths were 55 and 99 times higher, respectively, compared to the pre-event period. The mean Ångström absorbing coefficient during the event was 1.66, indicating biomass burning as the primary BC source, while the maximum BC/PM2.5 ratio (at 375 nm) reached 57 %. From February 2 to 5, 2024, PM concentrations exceeded the Chilean air quality standard by 82 % and 198 % for coarse and fine particles, respectively. These levels are 4.7 and 6.0 times higher than the World Health Organization's recommendations. These elevated concentrations persisted for up to three days after the fire was extinguished. This study provides unique evidence of the rapid deterioration of regional air quality during a wildfire event using in situ measurements, serving as a stark reminder of the far-reaching consequences of a warming climate.

Compositions and sources of fluorescent water-soluble and water-insoluble organic aerosols.

Brown carbon (BrC), the light-absorbing component of organic aerosols, plays a significant role in climate change and atmospheric photochemistry. However, the water-insoluble fractions of BrC have not been extensively studied, limiting the assessment of the overall climate effects of BrC. In this study, water-soluble and -insoluble organic carbon (i.e., WSOC and WIOC) in wintertime aerosols in Hefei were subsequently fractionated, and their fluorescence properties were comparatively investigated with the excitation-emission matrix method. WIOC contributing 57.1 % was the major component of organic carbon. WSOC with the largest contribution from humic-like regions exhibited a redshift compared to WIOC. Three humic-like substances (HULIS) with different oxidation degrees and one protein-like substances (PRLIS) were identified as the major fluorescent components by the parallel factor analysis. WSOC had more highly oxygenated HULIS, whereas low-oxygenated HULIS dominated WIOC. Nighttime WIOC contained more less-oxygenated species. The positive matrix factorization analysis suggested that biomass burning (43 %) was the largest source of both fluorescent WSOC and WIOC. Coal combustion contributed much more to fluorescent WIOC (40 %), whereas secondary formation contributed more to fluorescent WSOC (12 %). During aerosol pollution episodes, the increase in fluorescence efficiency was much greater for WIOC (25 %) than for WSOC (12 %), and WSOC and WIOC experienced a redshift and blueshift in emission wavelength, respectively. WSOC had more highly oxygenated HULIS, while WIOC had more less-oxygenated HULIS in aerosol episodes than the non-episodic periods. In addition, aerosol pollution was accompanied by the increased contributions of biomass burning and coal combustion to both fluorescent WSOC and WIOC, while the decreased relative contribution of secondary formation to fluorescent WSOC. Our findings highlighted the different fluorescence properties, compositions and sources of fluorescent WSOC and WIOC, providing a comprehensive view of BrC aerosols.

Physicochemical Characterization of the Particulate Matter in New Jersey/New York City Area, Resulting from the Canadian Quebec Wildfires in June 2023.

The global increase in wildfires, primarily driven by climate change, significantly affects air quality and health. Wildfire-emitted particulate matter (WFPM) is linked to adverse health effects, yet the toxicological mechanisms are not fully understood given its physicochemical complexity and the lack of spatiotemporal exposure data. This study focuses on the physicochemical characterization of WFPM from a Canadian wildfire in June 2023, which affected over 100 million people in the US Northeast, particularly around New Jersey/New York. Aerosol systems were deployed to characterize WFPM during the 3 day event, revealing unprecedented mass concentrations mainly in the WFPM0.1 and WFPM0.1-2.5 size fractions. Peak WFPM2.5 concentrations reached 317 µg/m3, nearly 10 times the National Ambient Air Quality Standard (NAAQS) 24 h average limit. Chemical analysis showed a high organic-to-total carbon ratio (96%), consistent with brown carbon wildfires nanoparticles. Large concentrations of high-molecular-weight PAHs were found predominantly bound to WFPM0.1, with retene, a molecular marker of biomass burning and a known teratogen, being the most abundant (>70%). Computational modeling estimated a total lung deposition of 9.15 mg over 72 h, highlighting the health risks of WFPM, particularly due to its long-distance travel capability and impact on densely populated areas.

Evaporation-Induced Transformations in Volatile Chemical Product-Derived Secondary Organic Aerosols: Browning Effects and Alterations in Oxidative Reactivity.

Volatile chemical products (VCPs) are increasingly recognized as significant sources of volatile organic compounds (VOCs) in urban atmospheres, potentially serving as key precursors for secondary organic aerosol (SOA) formation. This study investigates the formation and physicochemical transformations of VCP-derived SOA, produced through ozonolysis of VOCs evaporated from a representative room deodorant air freshener, focusing on the effects of aerosol evaporation on its molecular composition, light absorption properties, and reactive oxygen species (ROS) generation. Following aerosol evaporation, solutes become concentrated, accelerating reactions within the aerosol matrix that lead to a 42% reduction in peroxide content and noticeable browning of the SOA. This process occurs most effectively at moderate relative humidity (∼40%), reaching a maximum solute concentration before aerosol solidification. Molecular characterization reveals that evaporating VCP-derived SOA produces highly conjugated nitrogen-containing products from interactions between existing or transformed carbonyl compounds and reduced nitrogen species, likely acting as chromophores responsible for the observed brownish coloration. Additionally, the reactivity of VCP-derived SOA was elucidated through heterogeneous oxidation of sulfur dioxide (SO2), which revealed enhanced photosensitized sulfate production upon drying. Direct measurements of ROS, including singlet oxygen (1O2), superoxide (O2•-), and hydroxyl radicals (•OH), showed higher abundances in dried versus undried SOA samples under light exposure. Our findings underscore that drying significantly alters the physicochemical properties of VCP-derived SOA, impacting their roles in atmospheric chemistry and radiative balance.

Peatland Wildfires Enhance Nitrogen-Containing Organic Compounds in Marine Aerosols over the Western Pacific.

Peatland wildfires contribute significantly to the atmospheric release of light-absorbing organic carbon, often referred to as brown carbon. In this study, we examine the presence of nitrogen-containing organic compounds (NOCs) within marine aerosols across the Western Pacific Ocean, which are influenced by peatland fires from Southeast Asia. Employing ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in electrospray ionization (ESI) positive mode, we discovered that NOCs are predominantly composed of reduced nitrogenous bases, including CHN+ and CHON+ groups. Notably, the count of NOC formulas experiences a marked increase within plumes from peatland wildfires compared to those found in typical marine air masses. These NOCs, often identified as N-heterocyclic alkaloids, serve as potential light-absorbing chromophores. Furthermore, many NOCs demonstrate pyrolytic stability, engage in a variety of substitution reactions, and display enhanced hydrophilic properties, attributed to chemical processes such as methoxylation, hydroxylation, methylation, and hydrogenation that occur during emission and subsequent atmospheric aging. During the daytime atmospheric transport, aging of aromatic N-heterocyclic compounds, particularly in aliphatic amines prone to oxidation and reactions with amine, was observed. The findings underscore the critical role of peatland wildfires in augmenting nitrogen-containing organics in marine aerosols, underscoring the need for in-depth research into their effects on marine ecosystems and regional climatic conditions.

Atmospheric brown carbon in China haze is dominated by secondary formation.

Brown carbon (BrC) is a class of light-absorbing organic aerosols (OA) and has significant influence on atmospheric radiative forcing. However, the current limited understanding of the physicochemical properties of BrC restricts the accurate evaluation of its environmental effects. Here the optical characteristics and chemical composition of BrC during wintertime in the Yangtze River Delta (YRD) region, China were measured by using high-resolution aerosol mass spectrometry (HR-AMS) and UV-vis spectrometry. Our results showed that BrC in PM2.5 during the campaign was dominated by water-soluble organics, which consist of less oxidized oxygenated OA (LO-OOA), more oxidized oxygenated OA (MO-OOA), fossil fuel OA (FFOA) and biomass burning OA (BBOA). MO-OOA and BBOA were the strongest light absorbing BrC at 365 nm (Abs365), followed by LO-OOA and FFOA with a mass absorption coefficient (MAC) being 0.74 ± 0.04, 0.73 ± 0.03, 0.48 ± 0.04 and 0.39 ± 0.06 m2 g-1 during the campaign, respectively. In the low relative humidity (RH < 80 %) haze periods Abs365 of LO-OOA contributed to 44 % of the total light absorption at 365 nm, followed by MO-OOA (31 %), FFOA (21 %) and BBOA (4 %). In contrast, in the high-RH (RH > 80 %) haze periods Abs365 was dominated by MO-OOA, which accounted for 62 % of the total Abs365, followed by LO-OOA (17 %), BBOA (13 %) and FFOA (8 %). Chemical composition analysis further showed that LO-OOA and MO-OOA are produced from gas-phase photooxidation of VOCs and aerosol aqueous reactions, respectively, in which ammonia significantly enhanced the formation and light absorption of BrC in the high RH haze period. On average, >75 % of the total Abs365nm in the YRD region during the haze events was contributed by LO-OOA and MO-OOA, suggesting that atmospheric BrC in China haze periods is predominantly formed by secondary reactions.

Long-term spatial distribution and implication of black and brown carbon in the Tibetan Plateau.

Black carbon (BC) and brown carbon (BrC) over the high-altitude Tibetan Plateau (TP) can significantly influence regional and global climate change as well as glacial melting. However, obtaining plateau-scale in situ observations is challenging due to its high altitude. By integrating reanalysis data with on-site measurements, the spatial distribution of BC and BrC can be accurately estimated using the random forest algorithm (RF). In our study, the on-site observations of BC and BrC were successively conducted at four sites from 2018 to 2021. Ground-level BC and BrC concentrations were then obtained at a spatial resolution of 0.25° × 0.25° for three periods (including Periods-1980, 2000, and 2020) using RF and multi-source data. The highest annual concentrations of BC (1363.9 ± 338.7 ng/m3) and BrC (372.1 ± 96.2 ng/m3) were observed during Period-2000. BC contributed a dominant proportion of carbonaceous aerosol, with concentrations 3-4 times higher than those of BrC across the three periods. The ratios of BrC to BC decreased from Period-1980 to Period-2020, indicating the increasing importance of BC over the TP. Spatial distributions of plateau-scale BC and BrC concentrations showed heightened levels in the southeastern TP, particularly during Period-2000. These findings significantly enhance our understanding of the spatio-temporal distribution of light-absorbing carbonaceous aerosol over the TP.

Comparative study of atmospheric brown carbon at Shanghai and the East China Sea: Molecular characterization and optical properties.

The pollution burdens and compositions of atmospheric brown carbon (BrC) that determine their impacts on climate-health-ecosystems have not been well studied, particularly in some mega-economic coastal areas. Herein, atmospheric BrC samples synchronously collected from urban Shanghai (SH) and Huaniao Island (HNI) in the East China Sea during winter were characterized through ultrahigh-performance liquid chromatography-diode array detector-high resolution mass spectrometry (UHPLC-DAD-HRMS). The three polarity-dependent BrC fractions exhibited significant differences in both light absorption and chromophore composition. The average light absorption coefficients of BrC subfractions at 365 nm in SH were 2.6-3.7 times higher than those in HNI. The water-insoluble BrC (WIS-BrC) and humic-likes BrC (HULIS-BrC) dominated the total BrC absorption in SH (45 ± 7 %) and HNI (43 ± 6 %), respectively. Compared with SH, the higher O/Cw, lower molecule conjugation degree, and reduced mass absorption efficiency at 365 nm (MAE365) in HNI imply a potential bleaching mechanism during the transportation oxidation process. Thousands of BrC chromophores were detected at both sites. >20 major chromophores with strong absorption were unambiguously identified in HULIS-BrC and accounted for ∼40 % of the HULIS light absorption at 365 nm at both sites. These chromophores in SH HULIS-BrC featured oxygenated aromatics and nitroaromatics, while alkyl benzenesulfonic acids with emissions from cargo ships were found in HNI HULIS-BrC. Moreover, 22 major chromophores identified in WIS-BrC included alkaloids, polyaromatic hydrocarbons (PAHs), and carbonyl oxygenated PAHs, contributing 39 % and 49 % of the WIS-BrC light absorption at 365 nm in SH and HNI, respectively. Ascertaining the molecular-specific optical properties of BrC chromophores over the mega-economic coastal area is helpful for the predictive understanding of the sources and evolution of BrC, as well as its atmospheric behavior from land to sea.

Aqueous-Phase Photoreactions of Mixed Aromatic Carbonyl Photosensitizers Yield More Oxygenated, Oxidized, and less Light-Absorbing Secondary Organic Aerosol (SOA) than Single Systems.

Aromatic carbonyls have been mainly probed as photosensitizers for aqueous secondary organic aerosol (aqSOA) and light-absorbing organic aerosol (i.e., brown carbon or BrC) formation, but due to their organic nature, they can also undergo oxidation to form aqSOA and BrC. However, photochemical transformations of aromatic carbonyl photosensitizers, particularly in multicomponent systems, are understudied. This study explored aqSOA formation from the irradiation of aromatic carbonyl photosensitizers in mixed and single systems under cloud/fog conditions. Mixed systems consisting of phenolic carbonyls only (VL + ActSyr + SyrAld: vanillin [VL] + acetosyringone [ActSyr] + syringaldehyde [SyrAld]) and another composed of both nonphenolic and phenolic carbonyls (DMB + ActSyr + SyrAld: 3,4-dimethoxybenzaldehyde [DMB], a nonphenolic carbonyl, + ActSyr + SyrAld) were compared to single systems of VL (VL*) and DMB (DMB*), respectively. In mixed systems, the shorter lifetimes of VL and DMB indicate their diminished capacity to trigger the oxidation of other organic compounds (e.g., guaiacol [GUA], a noncarbonyl phenol). In contrast to the slow decay and minimal photoenhancement for DMB*, the rapid photodegradation and significant photoenhancement for VL* indicate efficient direct photosensitized oxidation (i.e., self-photosensitization). Relative to single systems, the increased oxidant availability promoted functionalization in VL + ActSyr + SyrAld and accelerated the conversion of early generation aqSOA in DMB + ActSyr + SyrAld. Moreover, the increased availability of oxidizable substrates countered by stronger oxidative capacity limited the contribution of mixed systems to aqSOA light absorption. This suggests a weaker radiative effect of BrC from mixed photosensitizer systems than BrC from single photosensitizer systems. Furthermore, more oxygenated and oxidized aqSOA was observed with increasing complexity of the reaction systems (e.g., VL* < VL + ActSyr + SyrAld < VL + ActSyr + SyrAld + GUA). This work offers new insights into aqSOA formation by emphasizing the dual role of organic photosensitizers as oxidant sources and oxidizable substrates.

Photochemical evolution of the molecular composition of dissolved organic carbon and dissolved brown carbon from wood smoldering.

Recently, extreme wildfires occur frequently around the world and emit substantial brown carbon (BrC) into the atmosphere, whereas the molecular compositions and photochemical evolution of BrC remain poorly understood. In this work, primary smoke aerosols were generated from wood smoldering, and secondary smoke aerosols were formed by the OH radical photooxidation in an oxidation flow reactor, where both primary and secondary smoke samples were collected on filters. After solvent extraction of filter samples, the molecular composition of dissolved organic carbon (DOC) was determined by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS). The molecular composition of dissolved BrC was obtained based on the constraints of DOC formulae. The proportion of dissolved BrC fractions accounted for approximately 1/3-1/2 molecular formulae of DOC. The molecular characteristics of dissolved BrC showed higher levels of carbon oxidation state, double bond equivalents, and modified aromaticity index than those of DOC, indicating that dissolved BrC fractions were a class of organic structures with relatively higher oxidation state, unsaturated and aromatic degree in DOC fractions. The comparative analysis suggested that aliphatic and olefinic structures dominated DOC fractions (contributing to 70.1%-76.9%), while olefinic, aromatic, and condensed aromatic structures dominated dissolved BrC fractions (contributing to 97.5%-99.9%). It is worth noting that dissolved BrC fractions only contained carboxylic-rich alicyclic molecules (CRAMs)-like structures, unsaturated hydrocarbons, aromatic structures, and highly oxygenated compounds. CRAMs-like structures were the most abundant species in both DOC and dissolved BrC fractions. Nevertheless, the specific molecular characteristics for DOC and dissolved BrC fractions varied with subgroups after aging. The results highlight the similarities and differences in the molecular compositions and characteristics of DOC and dissolved BrC fractions with aging. This work will provide insights into understanding the molecular composition of DOC and dissolved BrC in smoke.

South and Southeast Asia controls black carbon characteristics of Meili Snow Mountains in southeast Tibetan Plateau.

South and Southeast Asia (SSA) emitted black carbon (BC) exerts potential effects on glacier and snow melting and regional climate change in the Tibetan Plateau. In this study, online BC measurements were conducted for 1 year at a remote village located at the terminus of the Mingyong Glacier below the Meili Snow Mountains. The Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) was used to investigate the contribution and potential effect of SSA-emitted BC. In addition, variations in the light absorption characteristics of BC and brown carbon (BrC) were examined. The results indicated that the annual mean concentration of BC was 415 ± 372 ngm-3, with the highest concentration observed in April (monthly mean: 930 ± 484 ngm-3). BC exhibited a similar diurnal variation throughout the year, with two peaks observed in the morning (from 8:00 to 9:00 AM) and in the afternoon (from 4:00 to 5:00 PM), with even lower values at nighttime. At a short wavelength of 370 nm, the absorption coefficient (babs) reached its maximum value, and the majority of babs values were < 20 Mm-1, indicating that the atmosphere was not overloaded with BC. At the same wavelength, BrC substantially contributed to babs, with an annual mean of 25.2 % ± 12.8 %. SSA was the largest contributor of BC (annual mean: 51.1 %) in the study area, particularly in spring (65.6 %). However, its contributions reached 20.2 % in summer, indicating non-negligible emissions from activities in other regions. In the atmosphere, the SSA BC-induced radiative forcing (RF) over the study region was positive. While at the near surface, the RF exhibited a significant seasonal variation, with the larger RF values occurring in winter and spring. Overall, our findings highlight the importance of controlling BC emissions from SSA to protect the Tibetan Plateau against pollution-related glacier and snow cover melting.

Emission and optical characteristics of brown carbon in size-segregated particles from three types of Chinese ships.

Brown carbon (BrC) is one of the important light absorption substances that have high light absorption ability under short wavelength light. However, limit studies have focused on the BrC emission from ships. In this study, size-segregated particulate matters (PM) were collected from three different types of ships, light absorption characteristics and size distribution of methanol-soluble BrC and water-soluble BrC in PM from ship exhausts were investigated. Results showed that four-stroke low-power diesel fishing boat (4-LDF) had the highest mass concentrations of methanol-soluble organic carbon (MSOC) and water-soluble organic carbon (WSOC), followed by 2-stroke high-power heavy-fuel-oil vessel (2-HHV), and four-stroke high-power marine-diesel vessel (4-HMV). While 2-HHV had obviously higher light absorption coefficients of methanol-soluble BrC (Abs365,M) and water-soluble BrC (Abs365,W) in unit weight of PM than the other two types of ships. The tested ships presented comparable or higher absorption efficiency of BrC in water extracts (MAE365,W) compared with other BrC emission sources. Majority of BrC was concentrated in fine particles, and the particle size distributions of both Abs365,M and Abs365,W showed bimodal patterns, peaking at 0.43-0.65 µm and 4.7-5.8 µm, respectively. However, different particle size distributions were found for MAE365,M between diesel and heavy fuel oil ships. Besides, different wavelength dependence in particles with different size were also detected. Ship exhaust could be confirmed as a non-ignorable BrC emission source, and complex influencing factor could affect the light absorption characteristics of ship emissions. Particle size should also be considered when light absorption ability of BrC was evaluated.

Influence of Fuel Properties on the Light Absorption of Fresh and Laboratory-Aged Atmospheric Brown Carbon Produced from Realistic Combustion of Boreal Peat and Spruce Foliage.

Climate change has exacerbated fire activity in the boreal region. Consequently, smoldering boreal peatland fires are an increasingly important source of light-absorbing atmospheric organic carbon ("brown carbon"; BrC). To date, however, BrC from this source remains largely unstudied, which limits our ability to predict its climate impact. Here, we use size-exclusion chromatography coupled with diode array UV-vis detection to examine the molecular-size-dependent light absorption properties of fresh and photoaged aqueous BrC extracts collected during laboratory combustion of boreal peat and live spruce foliage. The atmospheric stability of BrC extracts varies with chromophore molecular size and fuel type: in particular, the high-molecular-weight fractions of both peat- and spruce-BrC are more resistant to photobleaching than their corresponding low-molecular-weight fractions, and total light absorption by peat-BrC persists over longer illumination timescales than that of spruce-BrC. Importantly, the BrC molecular size distribution itself varies with fuel properties (e.g., moisture content) and to an even greater extent with fuel type. Overall, our findings suggest that the accurate estimation of BrC radiative forcing, and the overall climate impact of wildfires, will require atmospheric models to consider the impact of regional diversity in vegetation/fuel types.

Variability in molecular composition and optical absorption of atmospheric brown carbon aerosols in two contrasting urban areas of China.

Atmospheric brown carbon (BrC) aerosols were investigated at two urban sites in southern (Hefei) and northern (Shijiazhuang) China during summer and winter of 2019-2020 to explore regional variability in their compositional and optical properties. Organic matter in ambient PM2.5 samples were characterized at molecular level using ultrahigh performance liquid chromatography coupled with a diode array detector and an Orbitrap mass spectrometer. Although the molecular composition of organic aerosols varied substantially over different ambient environments, they were mainly composed by CHO and CHON species in positive ionization mode while CHO and CHOS species in negative mode. The mass absorption coefficients of BrC aerosols at wavelength range 250-450 nm were relatively higher for winter samples in both cities and for Shijiazhuang samples in both seasons, partly attributed to the higher concentration levels of anthropogenic air pollutants in these environments. The absorption Ångström exponents further revealed that BrC aerosols in winter seasons and in Shijiazhuang had a greater capacity of absorption at shorter wavelengths. A total of 26 BrC species with strong absorption were unambiguously identified from different environments, which mainly consisted of CHO, CHON, and CHN species and had higher degrees of unsaturation and lower degrees of oxidation. The presence and abundance of these BrC species varied dynamically across the seasons and cities, with a greater number of species presented in the winter of Shijiazhuang. The BrC species together contributed 12-26 % in the total absorbance of light-absorbing organic components at 250-450 nm. This study highlights the regional differences in BrC properties influenced by the sources and atmospheric processes, which should be taken into account to assess their climate impacts.

Spatiotemporal distribution, light absorption characteristics, and source apportionments of black and brown carbon in China.

Black carbon (BC) and brown carbon (BrC) are aerosols that absorb light and thereby contribute to climate change. In this study, the light absorption properties and spatiotemporal distributions of equivalent BC (eBC) and BrC aerosols were determined based on continuous measurements of aerosol light absorption from January to August 2017, using a seven-channel aethalometer at 49 sampling sites in China. The source apportionments of BC and BrC were identified using the BC/PM2.5, absorption Ångström exponent, the concentration-weighted trajectory method, and the random forest model. Based on the results, BC was the dominant light absorber, whereas BrC was responsible for a higher proportion of the light absorption in northern compared to southern China. The light absorption of BrC was highest in winter (34.3 Mm-1), followed by spring (19.0 Mm-1) and summer (3.6 Mm-1). The combustion of liquid fuels accounted for over 50 % of the light absorption coefficient of BC in most cities and the importance of carbon monoxide (CO) and nitrogen dioxide (NO2) was over 10 % for BC emitted by liquid fuel combustion, based on the random forest model. The contribution of solid fuel combustion to BC in the north was larger than that in the southern regions as coal combustion and crop residue burning are important emission sources of BC in most northern cities. The contribution of primary BrC to light absorption was high in some northern cities, whereas that of secondary BrC was prevalent in some southern cities. The diurnal variations in secondary BrC were affected by changes in odd oxygen and relative humidity, which promoted the photobleaching of the chromophores and aqueous-phase reactions of secondary BrC.

Optical Variation and Molecular Transformation of Brown Carbon During Oxidation by NO3• in the Aqueous Phase.

The NO3•-driven nighttime aging of brown carbon (BrC) is known to greatly impact its atmospheric radiative forcing. However, the impact of oxidation by NO3• on the optical properties of BrC in atmospheric waters as well as the associated reaction mechanism remain unclear. In this work, we found that the optical variation of BrC proxies under environmentally relevant NO3• exposure depends strongly on their sources, with enhanced light absorptivity for biomass-burning BrC but bleaching for urban aerosols and humic substances. High-resolution mass spectrometry using FT-ICR MS shows that oxidation by NO3• leads to the formation of light-absorbing species (e.g., nitrated organics) for biomass-burning BrC while destroying electron donors (e.g., phenols) within charge transfer complexes in urban aerosols and humic substances, as evidenced by transient absorption spectroscopy and NaBH4 reduction experiments as well. Moreover, we found that the measured rate constants between NO3• with real BrCs (k = (1.8 ± 0.6) × 107 MC-1s-1, expressed as moles of carbon) are much higher than those of individual model organic carbon (OC), suggesting the reaction with OCs may be a previously ill-quantified important sink of NO3• in atmospheric waters. This work provides insights into the kinetics and molecular transformation of BrC during the oxidation by NO3•, facilitating further evaluation of BrC's climatic effects and atmospheric NO3• levels.