Brown Carbon Light Absorption Research Articles

Enhanced Light Absorption and Elevated Viscosity of Atmospheric Brown Carbon through Evaporation of Volatile Components.

Samples of brown carbon (BrC) material were collected from smoke emissions originating from wood pyrolysis experiments, serving as a proxy for BrC representative of biomass burning emissions. The acquired samples, referred to as "pyrolysis oil (PO1)," underwent subsequent processing by thermal evaporation of their volatile compounds, resulting in a set of three additional samples with volume reduction factors of 1.33, 2, and 3, denoted as PO1.33, PO2, and PO3. The chemical compositions of these POx samples and their BrC chromophore features were analyzed using a high-performance liquid chromatography instrument coupled with a photodiode array detector and a high-resolution mass spectrometer. The investigation revealed a noteworthy twofold enhancement of BrC light absorption observed for the progression of PO1 to PO3 samples, assessed across the spectral range of 300-500 nm. Concurrently, a decrease in the absorption Ångstrom exponent (AAE) from 11 to 7 was observed, indicating a weaker spectral dependence. The relative enhancement of BrC absorption at longer wavelengths was more significant, as exemplified by the increased mass absorption coefficient (MAC) measured at 405 nm from 0.1 to 0.5 m2/g. Molecular characterization further supports this darkening trend, manifesting as a depletion of small oxygenated, less absorbing monoaromatic compounds and the retention of relatively large, less polar, more absorbing constituents. Noteworthy alterations of the PO1 to PO3 mixtures included a reduction in the saturation vapor pressure of their components and an increase in viscosity. These changes were quantified by the mean values shifting from approximately 1.8 × 103 μg/m3 to 2.3 μg/m3 and from ∼103 Pa·s to ∼106 Pa·s, respectively. These results provide quantitative insights into the extent of BrC aerosol darkening during atmospheric aging through nonreactive evaporation. This new understanding will inform the refinement of atmospheric and chemical transport models.

Analysis of the Influencing Factors and Sources of Brown Carbon Light Absorption in a Typical Megacity of the Yangtze River Delta, China

Brown carbon (BrC) is a new term for organic aerosol (OA) with strong absorption ability from the visible to ultraviolet (UV) wavelengths, which plays a vital role in atmospheric visibility and climate change. Herein, we report field measurements from 1 March 2020 to 28 February 2021, sampled at urban Suzhou, Yangtze River Delta (YRD), China, to investigate the optical properties and sources of BrC. By analyzing the seasonal characteristics of the absorption of BrC at 370 nm (babs370), babs370 was found to be the highest (9.0 ± 7.2 Mm−1) in winter and the lowest (5.1 ± 3.3 Mm−1) in summer, respectively. The absorption Ångström exponent (AAE) value of BrC in winter was 1.22 ± 0.05, followed by 1.21 ± 0.05, 1.20 ± 0.05, and 1.19 ± 0.05 for fall, spring, and summer, respectively. The mass absorption cross-section (MAC) of secondary organic carbon (SOC) was 3.3 ± 0.2 m2g−1 in spring, 2.9 ± 0.1 m2g−1 in summer, 4.3 ± 0.1 m2g−1 in fall, and 2.8 ± 0.2 m2g−1 in winter, significantly lower than that of primary organic carbon (POC) at 370 nm, suggesting the aging process could weaken the light absorption of BrC. Five different BrC factors were identified by the positive matrix factorization (PMF) analysis, including biomass-burning-related, vehicle-related, sulfate-related, nitrate-related, and dust-related factors, which on average account for 7.4%, 73.4%, 11.9%, 1.9%, and 5.4% of babs370, respectively. Potential Source Contribution Factor (PSCF) analysis showed that those high babs370 periods were mainly contributed by air mass from the south. Moreover, for the influence degree of the potential source areas, the sequence was winter > spring > fall > summer. Our results improve the understanding of BrC in an important industrial city in YRD, which could reduce the uncertainty of the prediction of its climate effect in this region.

Variations in optical properties of water- and methanol-soluble organic carbon in PM2.5 in Tianjin and Handan over the Wintertime of 2018–2020

The impact of the Three-year Action Plan for winning the “blue sky defense battle” on the pollution levels and chemical characteristics of fine particulate matter has been intensively studied over the past few years. However, the effect of air pollution control on light absorption of brown carbon remains unclear. In this study, the light absorption and fluorescence properties of water- and methanol-soluble organic carbon (WSOC and MSOC) in PM2.5 in Tianjin and Handan in North China Plain were measured and evaluated for three consecutive winters during the Three-year Blue-Sky Action (2018–2020). Overall, the WSOC and MSOC mass concentrations and light absorption coefficients of WSOC and MSOC at 365 nm generally decreased from 2018 to 2020, indicating that the emission of solvent-soluble organic carbon has been effectively controlled with the implementation of pollution abatement measures, such as the enforcement of clean energy policies. The light absorption coefficient and mass absorption efficiency at 365 nm of MSOC were 1.41–3.82 and 1.13–1.72 times higher than that of WSOC, respectively. Fluorescent spectra coupled with parallel factor analysis indicated that less‑/highly‑oxygenated humic-like (LO-/HO-HULIS) and non-N aromatic species (non-Nas) were the major fluorophores in both WSOC and MSOC in the two cities, with LO-HULIS and HO-HULIS as two major contributors to WSOC light absorption, while both HULIS and non-Nas fluorophores had a strong correlation with MSOC light absorption. Correlation analysis with source tracers and fluorescent indices indicated that the influence of combustion emissions remains significant, and secondary formation made a non-negligible contribution to the light absorption and fluorescent components of WSOC and MSOC in both cities. This work will contribute to a better understanding of the evolution of concentration levels and optical properties of WSOC and MSOC during pollution abatement and will inform the subsequent development of measures to achieve a win-win situation for both air quality and climate change.

Insight into the Role of NH3/NH4+ and NOx/NO3- in the Formation of Nitrogen-Containing Brown Carbon in Chinese Megacities.

Particulate brown carbon (BrC) plays a crucial role in the global radiative balance due to its ability to absorb light. However, the effect of molecular formation on the light absorption properties of BrC remains poorly understood. In this study, atmospheric BrC samples collected from six Chinese megacities in winter and summer were characterized through ultrahigh-performance liquid chromatography coupled with Orbitrap mass spectrometry (UHPLC-Orbitrap MS) and light absorption measurements. The average values of BrC light absorption coefficient at a wavelength of 365 nm (babs365) in winter were approximately 4.0 times higher than those in summer. Nitrogen-containing organic molecules (CHNO) were identified as critical components of light-absorbing substances in both seasons, underscoring the importance of N-addition in BrC. These nitrogen-containing BrC chromophores were more closely related to nitro-containing compounds originating from biomass burning and nitrogen oxides (NOx)/nitrate (NO3-) reactions in winter. In summer, they were related to reduced N-containing compounds formed in ammonia (NH3)/ammonium (NH4+) reactions. The NH3/NH4+-mediated reactions contributed more to secondary BrC in summer than winter, particularly in southern cities. Compared with winter, the higher O/Cw, lower molecule conjugation indicator (double bond equivalent, DBE), and reduced BrC babs365 in summer suggest a possible bleaching mechanism during the oxidation process. These findings strengthen the connection between molecular composition and the light-absorbing properties of BrC, providing insights into the formation mechanisms of BrC chromophores across northern and southern Chinese cities in different seasons.

Contribution of Carbonyl Chromophores in Secondary Brown Carbon from Nighttime Oxidation of Unsaturated Heterocyclic Volatile Organic Compounds.

The light absorption properties of brown carbon (BrC), which are linked to molecular chromophores, may play a significant role in the Earth's energy budget. While nitroaromatic compounds have been identified as strong chromophores in wildfire-driven BrC, other types of chromophores remain to be investigated. Given the electron-withdrawing nature of carbonyls ubiquitous in the atmosphere, we characterized carbonyl chromophores in BrC samples from the nighttime oxidation of furan and pyrrole derivatives, which are important but understudied precursors of secondary organic aerosols primarily found in wildfire emissions. Various carbonyl chromophores were characterized and quantified in BrC samples, and their ultraviolet-visible spectra were simulated by using time-dependent density functional theory. Our findings suggest that chromophores with carbonyls bonded to nitrogen (i.e., imides and amides) derived from N-containing heterocyclic precursors substantially contribute to BrC light absorption. The quantified N-containing carbonyl chromophores contributed to over 40% of the total light absorption at wavelengths below 350 nm and above 430 nm in pyrrole BrC. The contributions of chromophores to total light absorption differed significantly by wavelength, highlighting their divergent importance in different wavelength ranges. Overall, our findings highlight the significance of carbonyl chromophores in secondary BrC and underscore the need for further investigation.

Impact of wildfires on regional ozone and PM2.5: Considering the light absorption of Brown carbon

The influence of wildfire brown carbon (BrC) in moderating the formation of O3 and fine particulate matter (PM2.5) due to its absorption of ultraviolet (UV) radiation is, for the first time, investigated using a modified community multiscale air quality (CMAQ) model. The wavelength-dependent imaginary refractive index of the organic carbon from wildfires, which are needed by the CMAQ model for its inline photolysis rate calculation, are generated experimentally from wood burning aerosols from a combustion chamber. On high emission days of the Bastrop County Complex fire in Texas in early September 2011, BrC UV absorption reduces the daytime average NO2 photolysis rate by up to 38% in the core region of the wildfire plume compared to the base scenario that does not consider BrC absorption. Consequently, O3 production in the smoke plume is suppressed compared to the base scenario due to reduced HOx radical concentrations. In the core region, the predicted O3 increase due to wildfire reaches as high as 47–123 ppb without considering BrC absorption, the predicted increase of O3 is 5–15% lower when BrC absorption is considered. Similarly, considering the BrC UV absorption leads to approximately 1% (or ∼2–3 μg m−3) lower estimation of the wildfire emissions’ impact on total PM2.5. This change is small because secondary aerosols, which are the components affected by BrC absorption, only account for a small fraction of the total PM2.5 in wildfire impacted regions in this study. In addition, our study shows that assumptions about aerosol mixing state (core-shell vs. homogeneous) in the inline photolysis rate calculation would not significantly affect out assessment of the impact of wildfire BrC light absorption on O3 and PM2.5.

Combined influences of sources and atmospheric bleaching on light absorption of water-soluble brown carbon aerosols

Light-absorbing Brown Carbon (BrC) aerosols partially offset the overall climate-cooling of aerosols. However, the evolution of BrC light-absorption during atmospheric transport is poorly constrained. Here, we utilize optical properties, ageing-diagnostic δ13C-BrC and transport time to deduce that the mass absorption cross-section (MACWS-BrC) is decreasing by ~50% during long-range oversea transport, resulting in a first-order bleaching rate of 0.24 day‒1 during the 3-day transit from continental East Asia to a south-east Yellow Sea receptor. A modern 14C signal points to a strong inverse correlation between BrC light-absorption and age of the source material. Combining this with results for South Asia reveals a striking agreement between these two major-emission regions of rapid photobleaching of BrC with a higher intrinsic absorptivity for BrC stemming from biomass burning. The consistency of bleaching parameters constrained independently for the outflows of both East and South Asia indicates that the weakening of BrC light absorption, thus primarily related to photochemical processes rather than sources, is likely a ubiquitous phenomenon.

Light absorption properties of brown carbon aerosol after following the switch from coal to natural gas policy in China: A case study of winter particulate matter over Xi'an, northwestern China

To control haze pollution, the Xi'an city in northwestern China replaced coal by natural gas in industrial and household heating at the end of 2017. Following this change we studied here the light absorption properties of brown carbon (BrC)in atmospheric particulate matter (PM2.5) over Xi'an in 2018. PM2.5 samples were collected from November 15 to December 25, 2018, and the light absorption properties of brown carbon in methanol-soluble organic carbon (MSOC) and water-soluble organic carbon (WSOC) were analyzed. Compared to a previous study from the coal combustion period, the mass absorption efficiency (MAE) increased in the sampling period while the radiation-forced absorption fraction of brown carbon relative to elemental carbon reduced, indicating that the light-absorbing capacity and efficiency of brown carbon has improved. Furthermore, highly positive linear relationships (r > 0.80) occur between the absorption coefficient and typical products of biomass burning and vehicle emission, except for coal combustion (r = 0.57). Additionally, an estimation from the positive matrix factorization and multivariable linear regression model results showed that biomass burning, motor vehicle emission, and secondary source took up approximately 89.53% of AbsWSOC,365. The contribution of coal combustion to light absorption BrC was the lowest (7.36% for AbsMSOC,365 and 10.24% for AbsWSOC,365) in our study, which differs from previous studies in Xi'an. Therefore, the emission source of bulk coal combustion has a relatively small influence on the light absorption of BrC in Xi'an.

Measurement report: Diurnal variations of brown carbon during two distinct seasons in a megacity in northeast China

Abstract. Brown carbon (BrC) represents an important target for the “win-win” strategy of mitigating climate change and improving air quality. However, estimating co-benefits of BrC control remains difficult for China, partially because current measurement results are insufficient to represent the highly variable emission sources and meteorological conditions across different regions. In this study, we investigated, for the first time, the diurnal variations of BrC during two distinct seasons in a megacity in northeast China. The winter campaign conducted in January 2021 was characterized by low temperatures rarely seen in other Chinese megacities (down to about −20 ∘C). The mass absorption efficiencies of BrC at 365 nm (MAE365) were found to be ∼ 10 % higher at night. The variations of MAE365 could not be explained by the influence of residential biomass burning emissions or secondary aerosol formation but were strongly associated with the changes of a diagnostic ratio for the relative importance of coal combustion and vehicle emissions (RS/N). Given that most coal combustion activities were uninterruptible, the higher nighttime MAE365 in winter were attributed primarily to increased emissions from heavy-duty diesel trucks. The spring campaign conducted in April 2021 was characterized by frequent occurrences of agricultural fires, as supported by the intensive fire hotspots detected around Harbin and the more-than-doubled ratios of levoglucosan to organic carbon (LG/OC) compared to the winter campaign. In spring, the MAE365 depended little on RS/N but exhibited a strong positive correlation with LG/OC, suggesting open burning emissions as the dominant influencing factor for BrC's light absorption capacity. MAE365 were ∼ 70 % higher at night for the spring campaign, pointing to the prevalence of nighttime agricultural fires, which were presumably in response to local bans on open burning. It is noteworthy that the agricultural-fire emissions resulted in a distinct peak at ∼ 365 nm for the light absorption spectra of BrC, and candidates for the compounds at play were inferred to be aromatic species with nitro-functional groups. The presence of the ∼ 365 nm peak complicated the determination of absorption Ångström exponents for the agricultural-fire-impacted samples. In addition, the ∼ 365 nm peak became much less significant during the day, likely due to photobleaching of the relevant chromophores.

Light absorption of brown carbon and nitrated phenols in aerosols in a city of South Asia: From sources to atmosphere

Nitrated phenols (NPs) are important components of the brown carbon (BrC) aerosols emitted from biomass burning and vehicle emissions. BrC affects the climate through the absorption of sunlight. Previous studies have reported the emission factors and optical properties of BrC from both primary sources and aerosols. However, the contribution of NPs to the absorption of radiation by BrC in aerosols from primary emission sources and ambient aerosols in South Asia, one of the most polluted regions worldwide, is not well known. We systematically investigated the optical properties and components of BrC from emission sources to atmosphere, and found that the major light-absorbing NPs in BrC from biomass burning (e.g., 4-nitrocatechol and methyl-nitrocatechols) were different from those from vehicle emissions (e.g., 2,6-dimethyl-4-nitrophenol and methyl-nitrophenols), which confirmed that the optical properties of BrC depend on the fuel type of the primary source. The contribution of ∑NPs to methanol-soluble brown carbon (MS-BrC) (f∑NPs/MS-BrC (365nm)) in ambient aerosols in Nepal (1–15%) was significantly higher than the value of f∑NPs/MS-BrC (365nm) from primary sources (0.1–2.0%). This indicates that future research should focus on the light absorption properties and climatic effects of NPs in ambient aerosols.

Characterization of water−soluble brown carbon in atmospheric fine particles over Xi'an, China: Implication of aqueous brown carbon formation from biomass burning

Brown carbon (BrC) aerosols can affect not only the climate but also human health, however, the light absorption, chemical compositions, and formation mechanisms of BrC are still uncertain, which leads to uncertainties in the accurate estimation of its climate and health impacts. In this study, highly time − resolved brown carbon (BrC) in fine particles was investigated in Xi'an using offline aerosol mass spectrometer analysis. The light absorption coefficient (babs365) and mass absorption efficiency (MAE365) at 365 nm of water−soluble organic aerosol (WSOA) generally increased with oxygen−to−carbon (O/C) ratios, indicating that oxidized OA could have more impacts on BrC light absorption. Meanwhile, the light absorption appeared to increase generally with the increases of nitrogen−to−carbon (N/C) ratios and water−soluble organic nitrogen; strong correlations (R of 0.76 for CxHyNp+ and R of 0.78 for CxHyOzNp+) between babs365 and the N − containing organic ion families were observed, suggesting that the N − containing compounds are the effective BrC chromophores. babs365 correlated relatively well with BBOA (r of 0.74) and OOA (R of 0.57), but weakly correlated with CCOA (R of 0.33), indicating that BrC in Xi'an was likely to be associated with biomass burning and secondary sources. A multiple linear regression model was applied to apportion babs365 to contributions of different factors resolved from positive matrix factorization on water-soluble organic aerosols (OA) and obtained MAE365 values of different OA factors. We found that biomass-burning organic aerosol (BBOA) dominated the babs365 (48.3 %), followed by oxidized organic aerosol (OOA, 33.6 %) and coal combustion organic aerosol (CCOA, 18.1 %). We further observed that nitrogen−containing organic matter (i.e., CxHyNp+ and CxHyOzNp+) increased with the increase of OOA/WSOA and the decrease of BBOA/WSOA, especially under high ALWC conditions. Our work offered proper observation evidence that BBOA is oxidized through the aqueous formation to produce BrC in Xi'an, China.

Mixing states and secondary formation processes of organic nitrogen-containing single particles in Guangzhou, China

Organic nitrogen (ON) compounds play a significant role in the light absorption of brown carbon and the formation of organic aerosols, however, the mixing state, secondary formation processes, and influencing factors of ON compounds are still unclear. This paper reports on the mixing state of ON-containing particles based on measurements obtained using a high-performance single particle aerosol mass spectrometer in January 2020 in Guangzhou. The ON-containing particles accounted for 21% of the total detected single particles, and the particle count and number fraction of the ON-containing particles were two times higher at night than during the day. The prominent increase in the content of ON-containing particles with the enhancement of NOx mainly occurred at night, and accompanied by high relative humidity and nitrate, which were associated with heterogeneous reactions between organics and gaseous NOx and/or NO3 radical. The synchronous decreases in ON-containing particles and the mass absorption coefficient of water-soluble extracts at 365 nm in the afternoon may be associated with photo-bleaching of the ON species in the particles. In addition, the positive matrix factorization analysis found five factors dominated the formation processes of ON particles, and the nitrate factor (33%) mainly contributed to the production of ON particles at night. The results of this study provide unique insights into the mixing states and secondary formation processes of the ON-containing particles.

Distribution characteristics and optical properties of carbonaceous aerosol: brown carbon and black carbon in Nanchang, inland China

PM2.5 samples were collected from October 31, 2019, to November 10, 2019, in Nanchang for 10 consecutive days. The mass concentrations of PM2.5 and carbon components were measured, and the distribution characteristics of carbonaceous aerosols were discussed. The optical properties of carbonaceous aerosols were quantified by the thermal-optical method and solvent extraction method, respectively. The results showed that the average concentrations of organic carbon (OC) and elemental carbon (EC) in aerosols in Nanchang were 11.79 ± 3.86 and 3.51 ± 1.59 μg m−3, respectively. The average OC/EC was 3.62, and OC2, OC3, OC4 and EC1 accounted for relatively large proportions (19.55, 24.96, 22.37 and 17.38%). Carbonaceous aerosols in Nanchang were greatly affected by coal combustion, vehicle exhaust emissions and secondary organic carbon (SOC) formation. For particulate brown carbon (BrC), the average light absorption coefficient (babs) and mass absorption efficiency (MAE) at 405 nm were 16.87 Mm−1 and 1.49 m2g−1, respectively. The average Absorption Ångström exponent (AAE) was 8.58. For water-soluble organic carbon (WSOC) and methanol-soluble organic carbon (MSOC), the average babs,365,WSOC and babs,365,MSOC were 14.79 and 22.51 Mm−1, respectively. The mean values of AAE300-600,WSOC and AAE300-600,MSOC were 4.17 and 4.84, respectively. The mean MAE365,WSOC and MAE365,MSOC were 1.83 and 2.18 m2 g−1, respectively. The mean value of MAEBC at 405 nm was 10.28 m2 g−1. The optical properties of particulate BrC and dissolved BrC were similar at 405 nm. The light absorption of BrC cannot be ignored, although BC was the main light absorption component.

Impact of biogenic secondary organic aerosol (SOA) loading on the molecular composition of wintertime PM2.5 in urban Tianjin: an insight from Fourier transform ion cyclotron resonance mass spectrometry

Abstract. Biomass burning is one of the key sources of urban aerosols in the North China Plain, especially during winter, when the impact of secondary organic aerosols (SOAs) formed from biogenic volatile organic compounds (BVOCs) is generally considered to be minor. However, little is known about the influence of biogenic SOA loading on the molecular composition of wintertime organic aerosols. Here, we investigated the water-soluble organic compounds in fine particulate matter (PM2.5) from urban Tianjin by ultrahigh-resolution Fourier transform ion cyclotron resonanc mass spectrometry (FT-ICR MS). Our results show that most of the CHO and CHON compounds are derived from biomass burning which are poor in oxygen and contain aromatic rings that probably contribute to light-absorbing brown carbon (BrC) chromophores. Under moderate to high SOA-loading conditions, the nocturnal chemistry is more efficient than photooxidation to generate secondary CHO and CHON compounds with high oxygen content. Under low SOA loading, secondary CHO and CHON compounds with low oxygen content are mainly formed by photochemistry. Secondary CHO compounds are mainly derived from oxidation of monoterpenes. However, nocturnal chemistry may be more productive to sesquiterpene-derived CHON compounds. In contrast, the number- and intensity-weight of S-containing groups (CHOS and CHONS) increased significantly with the increase of biogenic SOA loading, which agrees with the fact that a majority of the S-containing groups are identified as organosulfates (OSs) and nitrooxy–organosulfates (nitrooxy–OSs) that are derived from the oxidation of BVOCs. Terpenes may be potential major contributors to organosulfates and nitrooxy–organosulfates. While the nocturnal chemistry is more beneficial to the formation of organosulfates and nitrooxy–organosulfates under low SOA loading. The SOA loading is an important factor that is associated with the oxidation degree, nitrate group content and chemodiversity of nitrooxy-organosulfates. Furthermore, our study suggests that the hydrolysis of nitrooxy-organosulfates is a possible pathway for the formation of organosulfates.

Insights into the nitroaromatic compounds, formation, and light absorption contributing emissions from various geological maturity coals

Nitroaromatic compounds (NACs) are essential components of atmospheric organic aerosols. Coal combustion is a key source of atmospheric NACs. In this study, a triple-quadrupole liquid chromatography-mass spectrometry (LC-MS) system was used to identify ten individual NAC emitted in combustions of chunk coal and its briquette at different maturity levels. The Gaussian calculation was applied to quantify the absorption contribution of NACs to brown carbon (BrC). The emission factors (EFs) of total quantified NACs (ΣNACs) are 21.80–4429.55 μg/kg. 4-Nitrocatechol (4NC) is the most abundant NACs, accounting for 25.5–82.3 % of the ΣNACs and has the largest contribution to light absorption (0.34–29.23 %). The EFs for ΣNACs of chunk coal are 1.1–3.0 times those of its briquette, while the coal with volatile matter (VM) = 35.83 % shows the highest NAC emissions. The reaction pathway analysis demonstrates that NACs in briquette are generated through the pyrolysis of coal tar at an early stage of coal combustion, while volatile organic compounds (VOCs) that are emitted in chunk coal contribute greatly to the formations of NACs. The molecular properties analysis reveals that ΣNACs contribute 0.47–35.27 % to BrC light absorption. Anthracite coal (VM = 8.01 %) demonstrates the lowest light absorption coefficient (babs-365). Since bituminous coal (with VM = ~10 %–40 %) is popularly used for heating in rural China in winter, the results of this study could assist to evaluate the climate and environmental impacts on the NACs emission from coal combustion on a regional scale. Finally, the results highlighted that replacements of bituminous by clear fuel (such as chunk or briquette anthracite) could reduce NACs emission effectively.

Impacts of biomass burning and photochemical processing on the light absorption of brown carbon in the southeastern Tibetan Plateau

Abstract. Brown carbon (BrC) in the atmosphere can greatly influence aerosol's radiative forcing over the Tibetan Plateau (TP) because it has the non-negligible capacity of light absorption compared to black carbon (BC); however, our understanding of optical properties, sources, and atmospheric processes of BrC in this region remains limited. In this study, a multiple-wavelength Aethalometer coupled with a quadrupole aerosol chemical speciation monitor was deployed to investigate the highly time resolved BrC in the submicron aerosol at the southeastern edge of the TP during the pre-monsoon season. The results showed that BrC made substantial contributions (20.0 %–40.2 %) to the light absorption of submicron aerosol from 370 to 660 nm. Organic aerosol (OA), an alternative to BrC, was split into a biomass burning OA (BBOA) with aging processes and a photochemical-oxidation-processed oxygenated OA (po-OOA) by a hybrid environmental receptor model analysis. Combined with the light absorption coefficient of BrC (babs-BrC), the source-specific mass absorption cross sections of BBOA (0.61–2.78 m2 g−1) and po-OOA (0.30–1.43 m2 g−1) at 370–660 nm were retrieved. On average, babs-BrC from po-OOA (1.3–6.0 Mm−1) was comparable to that from BBOA (1.3–6.0 Mm−1) at all wavelengths. The concentration-weighted trajectory analysis showed that the most important potential source regions for babs-BrC values from BBOA and po-OOA were located in northern Myanmar and along the China–Myanmar border, indicating the cross-border transport of BrC from Southeast Asia. A “simple forcing efficiency” evaluation further illustrated the importance of the BrC radiative effect with the high fractional radiative forcing by two OAs relative to BC (48.8 ± 15.5 %). This study highlights a significant influence of BrC of biomass burning origin and secondary formation on climate change over the TP region during the pre-monsoon season.

Optical properties of vehicular brown carbon emissions: Road tunnel and chassis dynamometer tests

Brown carbon (BrC), as an important light-absorbing aerosol, significantly impacts regional and global climate. Vehicle emission is a nonnegligible source of BrC, but the optical properties of BrC emitted from vehicles remain poorly understood. This study evaluates the absorption Ångström exponent (AAE) of traffic-related light-absorbing aerosols (i.e., AAETr) and the absorption emission factor (EFabs) of vehicular BrC via chassis dynamometer tests and a road tunnel measurement in Tianjin, China. AAETr are estimated as 0.98–1.33 and 1.11 ± 0.001 for tested vehicles and on-road vehicle fleet, respectively. The AAE of vehicular BrC (AAEBrC) is 3.83 ± 0.092 for on-road vehicle fleet. The vehicle technology updates effectively reduce the EFabs of vehicular BrC. Among the four tested China 5 and China 6 gasoline vehicles in the chassis dynamometer tests, BrC EFabs of China 5 gasoline direct injection vehicle is the highest, while China 6 mixing fuel injection vehicle exhibits the lowest EFabs. The BrC EFabs of on-road vehicle fleet at 370 nm wavelength are 0.081 ± 0.0058 m2 kg−1 for mixed fleet, 0.074 ± 0.018 m2 kg−1 for gasoline vehicles (GVs), and 1.66 ± 0.71 m2 kg−1 for diesel vehicles (DVs) in the tunnel measurement. EFabs of GV fleet in the road tunnel is higher than China 5 and China 6 vehicles, as China 1–4 vehicles accounted for 26.8% of the total vehicle fleet in the tunnel. EFabs of vehicular BrC are lower than those from biomass burning and coal combustion emissions. The light absorption of BrC from GVs and DVs accounts for 7.2 ± 2.1% and 1.5 ± 0.77% of total traffic-related absorption at 370 nm, respectively. Our study provides optical features of BrC from vehicle source and could contribute to estimating the impacts of vehicular aerosol emissions on global and regional climate change.

Revisiting the Absorption Spectra of Polycyclic Aromatic Hydrocarbons over Porto (Portugal) by TD-DFT Calculations

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the “real-world” absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds.

Winter brown carbon over six of China's megacities: light absorption, molecular characterization, and improved source apportionment revealed by multilayer perceptron neural network

Abstract. Brown carbon (BrC) constitutes a large fraction of organic carbon and exhibits strong light absorption properties, thus affecting the global radiation budget. In this study, we investigated the light absorption properties, chemical functional bonds, and sources of BrC in six megacities in China, namely Beijing, Harbin, Xi'an, Chengdu, Guangzhou, and Wuhan. The average values of the BrC light absorption coefficient and the mass absorption efficiency at 365 nm in northern cities were higher than those in southern cities by 2.5 and 1.8 times, respectively, demonstrating the abundance of BrC present in northern China's megacities. Fourier transform infrared (FT-IR) spectra revealed sharp and intense peaks at 1640, 1458–1385, and 1090–1030 cm−1, which were ascribed to aromatic phenols, confirming the contribution of primary emission sources (e.g., biomass burning and coal combustion) to BrC. In addition, we noted peaks at 860, 1280–1260, and 1640 cm−1, which were attributed to organonitrate and oxygenated phenolic groups, indicating that secondary BrC also existed in the six megacities. Positive matrix factorization (PMF) coupled with multilayer perceptron (MLP) neural network analysis was used to apportion the sources of BrC light absorption. The results showed that primary emissions (e.g., biomass burning, tailpipe emissions, and coal combustion) made a major contribution to BrC in the six megacities. However, secondary formation processes made a greater contribution to light absorption in the southern cities (17.9 %–21.2 %) than in the northern cities (2.1 %–10.2 %). These results can provide a basis for the more effective control of BrC to reduce its impacts on regional climates and human health.

Potential underestimation of ambient brown carbon absorption based on the methanol extraction method and its impacts on source analysis

Abstract. The methanol extraction method was widely applied to isolate organic carbon (OC) from ambient aerosols, followed by measurements of brown carbon (BrC) absorption. However, undissolved OC fractions will lead to underestimated BrC absorption. In this work, water, methanol (MeOH), MeOH / dichloromethane (MeOH / DCM, 1:1, v/v), MeOH / DCM (1:2, v/v), tetrahydrofuran (THF), and N,N-dimethylformamide (DMF) were tested for extraction efficiencies of ambient OC, and the light absorption of individual solvent extracts was determined. Among the five solvents and solvent mixtures, DMF dissolved the highest fractions of ambient OC (up to ∼95 %), followed by MeOH and MeOH / DCM mixtures (<90 %), and the DMF extracts had significantly (p<0.05) higher light absorption than other solvent extracts. This is because the OC fractions evaporating at higher temperatures (>280∘) are less soluble in MeOH (∼80 %) than in DMF (∼90 %) and contain stronger light-absorbing chromophores. Moreover, the light absorption of DMF and MeOH extracts of collocated aerosol samples in Nanjing showed consistent temporal variations in winter when biomass burning dominated BrC absorption, while the average light absorption of DMF extracts was more than 2 times greater than the MeOH extracts in late spring and summer. The average light absorption coefficient at 365 nm of DMF extracts was 30.7 % higher (p<0.01) than that of MeOH extracts. Source apportionment results indicated that the MeOH solubility of BrC associated with biomass burning, lubricating oil combustion, and coal combustion is similar to their DMF solubility. The BrC linked with unburned fossil fuels and polymerization processes of aerosol organics was less soluble in MeOH than in DMF, which was likely the main reason for the large difference in time series between MeOH and DMF extract absorption. These results highlight the importance of testing different solvents to investigate the structures and light absorption of BrC, particularly for the low-volatility fraction potentially originating from non-combustion sources.