Mass Absorption Efficiency Research Articles

Characterization and source apportionment for light absorption amplification of black carbon at an urban site in eastern China

The mass absorption efficiency (MAE) of black carbon (BC) could be amplified by both internal mixing and the lensing effect from non-absorbing coating, which could intensify the global warming effect of BC. In this study, a two-year-long continuous campaign with measurements of aerosol optical properties and chemical composition were conducted in Nanjing, a typical polluted city in the Yangtze River Delta (YRD) region. Relatively large MAE values were observed in 2016, and the high BC internal mixing level could be the main cause. The strong positive correlation between the ratio of non-absorbing particulate matter (NAPM) over elemental carbon (EC) and the MAE value indicated that the coating thickness of BC largely promotes its light absorption ability. The impacts of chemical component coating on MAE amplification in autumn and winter were greater than in other seasons. Multiple linear regression was performed to estimate the MAE amplification effect by internal mixing and the coating of different chemical components. Nitrate coating had the strongest impact on MAE amplification, followed by organic matter. The effects of organic matter and nitrate coatings on MAE amplification increased with the internal mixing index (IMI). Based on the positive matrix factorization (PMF) model, it was found that large decrease in the contribution of industrial emissions and coal combustion to PM2.5 from 2016 to 2017 was the main cause for MAE reduction. The novel statistical model developed in this study could be a useful tool to separate the impacts of internal mixing and non-absorbing coating.

Chromophores and chemical composition of brown carbon characterized at an urban kerbside by excitation–emission spectroscopy and mass spectrometry

Abstract. The optical properties, chemical composition, and potential chromophores of brown carbon (BrC) aerosol particles were studied during typical summertime and wintertime at a kerbside in downtown Karlsruhe, a city in central Europe. The average absorption coefficient and mass absorption efficiency at 365 nm (Abs365 and MAE365) of methanol-soluble BrC (MS-BrC) were lower in the summer period (1.6 ± 0.5 Mm−1, 0.5 ± 0.2 m2 g−1) than in the winter period (2.8 ± 1.9 Mm−1, 1.1 ± 0.3 m2 g−1). Using a parallel factor (PARAFAC) analysis to identify chromophores, two different groups of highly oxygenated humic-like substances (HO-HULIS) dominated in summer and contributed 96 ± 6 % of the total fluorescence intensity. In contrast, less-oxygenated HULIS (LO-HULIS) dominated the total fluorescence intensity in winter with 57 ± 12 %, followed by HO-HULIS with 31 ± 18 %. Positive matrix factorization (PMF) analysis of organic compounds detected in real time by an online aerosol mass spectrometer (AMS) led to five characteristic organic compound classes. The statistical analysis of PARAFAC components and PMF factors showed that LO-HULIS chromophores were most likely emitted from biomass burning in winter. HO-HULIS chromophores could be low-volatility oxygenated organic aerosol from regional transport and oxidation of biogenic volatile organic compounds (VOCs) in summer. Five nitro-aromatic compounds (NACs) were identified by a chemical ionization mass spectrometer (C7H7O3N, C7H7O4N, C6H5O5N, C6H5O4N, and C6H5O3N), which contributed 0.03 ± 0.01 % to the total organic mass but can explain 0.3 ± 0.1 % of the total absorption of MS-BrC at 365 nm in winter. Furthermore, we identified 316 potential brown carbon molecules which accounted for 2.5 ± 0.6 % of the organic aerosol mass. Using an average mass absorption efficiency (MAE365) of 9.5 m2g−1 for these compounds, we can estimate their mean light absorption to be 1.2 ± 0.2 Mm−1, accounting for 32 ± 15 % of the total absorption of MS-BrC at 365 nm. This indicates that a small fraction of brown carbon molecules dominates the overall absorption. The potential BrC molecules assigned to the LO-HULIS component had a higher average molecular weight (265 ± 2 Da) and more nitrogen-containing molecules (62 ± 1 %) than the molecules assigned to the HO-HULIS components. Our analysis shows that the LO-HULIS, with a high contribution of nitrogen-containing molecules originating from biomass burning, dominates aerosol fluorescence in winter, and HO-HULIS, with fewer nitrogen-containing molecules as low-volatility oxygenated organic aerosol from regional transport and oxidation of biogenic volatile organic compounds (VOC), dominates in summer.

Brown carbon absorption and radiative effects under intense residential wood burning conditions in Southeastern Europe: New insights into the abundance and absorptivity of methanol-soluble organic aerosols

Biomass burning is a major source of Brown Carbon (BrC), strongly contributing to radiative forcing. In urban areas of the climate-sensitive Southeastern European region, where strong emissions from residential wood burning (RWB) are reported, radiative impacts of carbonaceous aerosols remain largely unknown. This study examines the absorption properties of water- and methanol-soluble organic carbon (WSOC, MeS_OC) in a city (Ioannina, Greece) heavily impacted by RWB. Measurements were performed during winter (December 2019 – February 2020) and summer (July – August 2019) periods, characterized by RWB and photochemical processing of organic aerosol (OA), respectively. PM2.5 filter extracts were analyzed spectrophotometrically for water- and methanol-soluble BrC (WS_BrC, MeS_BrC) absorption. WSOC concentrations were quantified using TOC analysis, while those of MeS_OC were determined using a newly developed direct quantification protocol, applied for the first time to an extended series of ambient samples. The direct method led to a mean MeS_OC/OC of 0.68 and a more accurate subsequent estimation of absorption efficiencies. The mean winter WS_BrC and MeS_BrC absorptions at 365 nm were 13.9 Mm−1 and 21.9 Mm−1, respectively, suggesting an important fraction of water-insoluble OA. Mean winter WS_BrC and MeS_BrC absorptions were over 10 times those observed in summer. MeS_OC was more absorptive than WSOC in winter (mean mass absorption efficiencies – MAE365: 1.81 vs 1.15 m2 gC−1) and especially in summer (MAE: 1.12 vs 0.27 m2 gC−1) due to photo-dissociation and volatilization of BrC chromophores. The winter radiative forcing (RF) of WS_BrC and MeS_BrC relative to elemental carbon (EC) was estimated at 8.7 % and 16.7 %, respectively, in the 300–2500 nm band. However, those values increased to 48.5 % and 60.2 % at 300–400 nm, indicating that, under intense RWB, BrC forcing becomes comparable to that of soot. The results highlight the consideration of urban BrC emissions in radiative transfer models, as a considerable climate forcing factor.

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.

Measurement report: Contrasting elevation-dependent light absorption by black and brown carbon: lessons from in situ measurements from the highly polluted Sichuan Basin to the pristine Tibetan Plateau

Abstract. Scientific knowledge about light absorption by aerosols is extremely limited at the eastern slope of the Tibetan Plateau (ESTP). We conducted the first aerosol field experiment at six sites (Chengdu, Sanbacun, Wenchuan, Lixian, Maerkang, Hongyuan) along the ESTP, ranging in elevation from 500 to 3500 m. The fraction of light absorption by brown carbon (BrC) to total carbon increases from 20 % to 50 % with altitude, and the mass absorption efficiency (MAE) of BrC over the Tibetan Plateau (TP) is 2–3 times higher than that inside the Sichuan Basin (SCB), especially in winter. In contrast, the MAE of elemental carbon (EC) in winter decreases with altitude. The contrasting variation of EC and BrC MAE with altitude is mainly attributed to source differences between the TP and SCB. Emissions from the more urban sources (motor vehicles, industries, etc.) inside the SCB fail to be transported to the TP due to the stable air in winter inside the basin, which is also favourable for aerosol ageing to enhance absorption efficiency. The radiative forcing of BrC relative to EC varies from 0.10 to 0.42 as altitude increases with the higher organic carbon (OC) to EC ratio over the TP than SCB. Thus, the reason for the enhanced relative BrC to EC radiative forcing from polluted SCB to pristine TP is that the BrC concentration decreases more slowly than the EC concentration with altitude. This study contributes to the understanding of the difference in light absorption by EC and BrC with altitude, from polluted lower-altitude basins to the pristine TP, and provides a data set for regional climate model validation.

Water-soluble brown carbon in PM2.5 at two typical sites in Guanzhong Basin: Optical properties, sources, and implications

Brown carbon (BrC) is a light-absorbing aerosol component that has a significant impact on atmospheric photochemistry and climate effects. Many studies on light absorbing characteristics of BrC (such as a fraction of water-soluble and/or water-insoluble) have been carried out in cities over the Guanzhong Basin, including radiative forcing, optical properties and sources. However, research on the Qinling Mountains is still lacking. Therefore, PM2.5 samples were collected at the northern piedmont of Qinling Mountains (QL) and Xi'an (XN) in the winter of 2020, and the optical properties and radiation effects of water extracts were analyzed and evaluated. The mass absorption efficiency (MAE) of water-soluble organic carbon (WSOC) at 365 nm (MAE365) obtained in QL and XN were 0.18 ± 0.03 m2 g−1 and 0.78 ± 0.96 m2 g−1, respectively. In the ultraviolet range, the relative light absorption of WSOC relative to elemental carbon (EC) was 6.76% and 33.41% in QL and XN, respectively, and the simple forcing efficiency (SFE280–400) were 0.71 ± 0.43 and 2.82 ± 1.71 W g−1 in QL and XN. It may have important effects on the radiation balance of regional climate systems. The chromophores in WSOC of XN and QL are mainly composed of humic-like and protein-like substances, and humus-like substances play a dominant role in two sites (52.61% and 71.13%). Biomass combustion has a limited contribution to chromophore abundance in WSOC of QL, which is more affected by urban transmission. The fluorescence index revealed that the chromophores in WSOC had autogenous characteristics and that the organic matter was mostly newly generated. Furthermore, the molecular weight and aromatic degree in XN samples were higher than that in QL, indicating a greater capacity for light absorption. This work will be instrumental in assessing the interaction and influence between the city and the northern piedmont of the Qinling Mountains and improve the capability of air pollution prevention and control of Guanzhong Basin.

Measurement report: Investigation of pH- and particle-size-dependent chemical and optical properties of water-soluble organic carbon: implications for its sources and aging processes

Abstract. Knowledge of the chemical structures and optical properties of water-soluble organic carbon (WSOC) is critical considering its involvement in many key aerosol-associated chemical reactions and its potential impacts on climate radiative forcing. This study investigates the coupled effects of pH and particle size on the chemical structures (functional groups) and optical properties (UV/fluorescence properties) of WSOC and further explores the source and aging of WSOC constituents. The results showed that the specific UV absorbance at a wavelength of 254 nm (SUVA254) and mass absorption efficiency at a wavelength of 365 nm (MAE365) were higher in smaller than larger particles, revealing the relatively higher aromaticity/molecular weight and more freshness of WSOC in smaller particles. A decrease in aromaticity/molecular weight of WSOC in larger particles was caused by the degradation reaction that occurred during the aging process. The carboxylic groups tend to be enriched in larger particles, whereas the contribution of phenolic groups was generally higher in smaller particles. The changes in the fluorescence peak position suggested that hydroxyl groups play a leading role in pH-responsive fluorescence in summer, while carboxylic and nitro groups play a dominant role in winter. Overall, the chromophores in smaller particles showed a more pronounced pH dependence, which might be related to the higher content of aromatic species in WSOC in these particle size ranges. Specifically, the climate impact of WSOC would be enhanced with increasing pH. The pH- and particle-size-dependent chemical and optical properties of WSOC provide insights into the structure, source, and aging of WSOC, which will ultimately improve the accuracy of assessing the climate effects of WSOC.

Potential influence of fine aerosol chemistry on the optical properties in a semi-arid region

The current understanding regarding the potential influence of aerosol chemistry on the optical properties does not satisfy accurate evaluation of aerosol radiative effects and precise determination of aerosol sources. We conducted a comprehensive study of the potential influence of aerosol chemistry on the optical properties in a semi-arid region based on various observations. Organic matter was the main contributor to the scattering coefficients followed by secondary inorganic aerosols in all seasons. We further related aerosol absorption to elemental carbon, organic matter, and mineral dust. Results showed that organic matter and mineral dust contributed to >40% of the aerosol absorption in the ultraviolet wavelengths. Therefore, it is necessary to consider the absorption of organic matter and mineral dust in addition to that of elemental carbon. We further investigated the potential influence of chemical composition, especially of organic matter and mineral dust on the optical parameters. Mineral dust contributed to higher absorption efficiency and lower scattering efficiency in winter. The absorption Ångström exponent (AAE) was mostly sensitive to organic matter and mineral dust in winter and spring, respectively; it was relatively high (i.e., 1.68) in winter and moderate (i.e., 1.42) in spring. Unlike in the other seasons, mineral dust contributed to higher mass absorption efficiency in winter. This work reveals the complexity of the relationship between aerosol chemistry and optical properties, and especially the influence of organic matter and mineral dust on aerosol absorption. The results are highly important regarding both regional air pollution and climate.

Contrasting mass absorption efficiency of carbonaceous aerosols between PM1 and PM2.5 in urban Beijing

Carbonaceous aerosol, mainly comprising elemental carbon (EC) and organic carbon (OC), plays an important role in aerosol–climate interaction owing to its light-absorbing feature. The radiative forcing of carbonaceous aerosol is largely determined by its mass absorption efficiency (MAE). To depict the MAE of carbonaceous aerosol and its variations with aerosol size and chemical composition, light absorption coefficients and the main chemical composition of PM1 and PM2.5 were comparably measured in a winter field campaign in urban Beijing. On average, aerosol absorption by PM1 at 880 nm wavelength contributes to approximately half of aerosol absorption by PM2.5, mainly because aerosol absorption at this wavelength was dominated by EC and nearly half of the total EC mass in PM2.5 existed in PM1. The average MAE of EC at 880 nm (MAEEC,880nm) was 3.9 ± 0.7 m2 g−1 for PM2.5, lower than that for PM1 (4.4 ± 0.8 m2 g−1) likely because of the larger EC cores and lower coating degrees of EC particles in PM1–2.5. Variation in MAEEC,880nm was related to the bulk mass fractions of nitrate in PM1 and PM2.5, implying the important impact of secondary nitrate formation on the modification of EC mixing states and enhancing EC absorption efficiency in Beijing. Absorption by OC took up about 40% of the absorption coefficients for PM1 and PM2.5 at 370 nm. The mean MAE of OC at 370 nm (MAEOC,370nm) was 2.4 ± 0.9 m2 g−1 for PM1, higher than that of for PM2.5 (1.9 ± 0.6 m2 g−1). The high value of MAEOC,370nm might be associated with regionally transported aerosols during clean and polluted periods. Enlarged particle sizes might have considerably weakened MAEOC,370nm for PM2.5 while exerting negligible impact on MAEOC,370nm for PM1.

Light absorption potential of water-soluble organic aerosols in the two polluted urban locations in the central Indo-Gangetic Plain

PM2.5 (particulate matter having aerodynamic diameter ≤2.5 μm) samples were collected during wintertime from two polluted urban sites (Allahabad and Kanpur) in the central Indo-Gangetic Plain (IGP) to comprehend the sources and atmospheric transformations of light-absorbing water-soluble organic aerosol (WSOA). The aqueous extract of each filter was atomized and analyzed in a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Water-soluble organic carbon (WSOC) and WSOA concentrations at Kanpur were ∼1.2 and ∼1.5 times higher than that at Allahabad. The fractions of WSOC and secondary organic carbon (SOC) to total organic carbon (OC) were also significantly higher ∼53% and 38%, respectively at Kanpur compared to Allahabad. This indicates a higher abundance of oxidized WSOA at Kanpur. The absorption coefficient (babs-365) of light-absorbing WSOA measured at 365 nm was 46.5 ± 15.5 Mm−1 and 73.2 ± 21.6 Mm−1 in Allahabad and Kanpur, respectively, indicating the dominance of more light-absorbing fractions in WSOC at Kanpur. The absorption properties such as mass absorption efficiency (MAE365) and imaginary component of refractive index (kabs-365) at 365 nm at Kanpur were also comparatively higher than Allahabad. The absorption forcing efficiency (Abs SFE; indicates warming effect) of WSOA at Kanpur was ∼1.4 times higher than Allahabad. Enhancement in light absorption capacity was observed with the increase in f44/f43 (fraction of m/z 44 (f44) to 43 (f43) in organic mass spectra) and O/C (oxygen to carbon) ratio of WSOA at Kanpur while no such trend was observed for the Allahabad site. Moreover, the correlation between carbon fractions and light absorption properties suggested the influence of low-volatile organic compounds (OC3 + OC4 fraction obtained from thermal/optical carbon analyzer) in increasing the light absorption capacity of WSOA in Kanpur.

Optical properties and potential sources of water-soluble and methanol-soluble organic aerosols in Taipei, Taiwan

The optical properties and sources of brown carbon (BrC) have been poorly constrained in climate models due to the variability of spatiotemporal characteristics, impeding the accurate understanding of its impact on air quality and climate. In this study, daily PM2.5 samples, which were collected from January to November 2021 in urban Taipei, Taiwan, and seasonal variations of optical properties of water-soluble and methanol-soluble organic carbon (WSOC and MSOC) were evaluated. The light absorption coefficients at 365 nm (Abs365) of both extracts, which strongly correlated with WSOC and MSOC mass concentrations, displayed distinct seasonal variations with the highest in winter and the lowest in summer. The Absorption Ångström Exponent of WSOC and MSOC ranged from 4.16 to 7.75 and 4.03–6.83, with averages of 6.05 ± 0.56 and 5.29 ± 0.61, respectively. The mass absorption efficiency (MAE365), which normalizes the Abs365 of both extracts to the mass of WSOC and MSOC, showed significant seasonal difference with the high MAE365, WSOC of 0.96 ± 0.29 m2 g−1 in winter and the lowest in summer of 0.49 ± 0.07 m2 g−1, whereas contrasting with the largest MAE365, MSOC of 0.99 ± 0.46 m2 g−1 in summer and the lowest in winter of 0.66 ± 0.28 m2 g−1, respectively. Fossil fuel combustion, such as traffic emission, and biomass burning, such as crematorium, were identified to be important contributors to light-absorbing substances. The estimated fractional radiative forcing by WSOC and MSOC to elemental carbon was most significant during winter (8.15 ± 3.77%) and spring (13.90 ± 4.38%), respectively, which may greatly affect the atmospheric photochemistry and climate. This study suggests that the impact of BrC in Taiwan on the local and regional air quality and climate is non-negligible.

Abundance, chemical structure, and light absorption properties of humic-like substances (HULIS) and other organic fractions of forest aerosols in Hokkaido

Atmospheric organic aerosol (OA) are considered as a significant contributor to the light absorption of OA, but its relationship with abundance, composition and sources are not understood well. In this study, the abundance, chemical structural characteristics, and light absorption property of HULIS and other low-to-high polar organics in PM0.95 collected in Tomakomai Experimental Forest (TOEF) were investigated with consideration of their possible sources. HULIS were the most abundant (51%), and correlation analysis revealed that biogenic secondary organic aerosols significantly contribute to HULIS. The mass spectra obtained using a high-resolution aerosol mass spectrometer (HR-AMS) showed that HULIS and highly polar water-soluble organic matter (HP-WSOM) were substantially oxygenated organic aerosol fractions, whereas water-insoluble organic matter (WISOM) had a low O/C ratio and more hydrocarbon-like structures. The WISOM fraction was the predominant light-absorbing organics. HULIS and WISOM showed a noticeable seasonal change in mass absorption efficiency (MAE365), which was highest in winter. Further, HULIS were shown to be less absorbing than those reported for urban sites. The findings in this study provide insights into the contribution of biogenic secondary OA on aerosol property and radiative forcing under varying contributions from other types of OA.

Effect of photooxidation on size distribution, light absorption, and molecular compositions of smoke particles from rice straw combustion

Organic aerosol (OA) emitted from biomass burning (BB) impacts air quality and global radiation balance. However, the comprehensive characterization of OA remains poorly understood because of the complex evolutionary behavior of OA in atmospheric processes. In this work, smoke particles were generated from rice straw combustion. The effect of OH radicals photooxidation on size distribution, light absorption, and molecular compositions of smoke particles was systematically investigated. The results showed that the median diameters of smoke particles increased by a factor of approximately 1.2 after photooxidation. In the particle compositions, although both non-polar fractions (n-hexane-soluble organic carbon, HSOC) and polar fractions (water-soluble organic carbon, WSOC) underwent photobleaching after aging, the photobleaching properties of HSOC (1.87–2.19) was always higher than that of WSOC (1.52–1.33). Besides, the light-absorbing properties of HSOC were higher than that of WSOC, showing a factor of approximately 1.75 times for mass absorption efficiency at 365 nm (MAE365). Consequently, the simple forcing efficiency (SFE) caused by absorption showed that HSOC has higher radiation effects than WSOC. After photooxidation, the concentration of 16 PAHs in HSOC fractions significantly decreased by 15.3%–72.5%. In WSOC fractions, the content of CHO, CHONS, and CHOS compounds decreased slightly, while the content of CHON compounds increased. Meantime, the variations in molecular properties supported the decrease in light absorption of WSOC fractions. These results reveal the aging behavior of smoke particles, then stress the importance of non-polar organic fractions in particles, providing new insights into understanding the atmospheric pollution caused by BB smoke particles.

Chemical Composition, Optical Properties and Sources of PM2.5 From a Highly Urbanized Region in Northeastern Mexico

Here, we report the chemical composition and optical properties of the fine particles (PM2.5) and water-soluble organic carbon (WSOC) of these particles. Additionally, the potential sources of WSOC emission were determined through the study on fluorescence excitation–emission matrix spectra and parallel factor analysis (EEM-PARAFAC). Samples were collected in an urban site of the Monterrey Metropolitan Area in Mexico during summer and winter and characterized using attenuated total reflectance-Fourier-transform infrared spectroscopy (ATR-FTIR), ultraviolet-visible-near infrared-diffuse reflectance spectroscopy (UV–Vis-NIR-DRS), fluorescence spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) techniques. The ATR-FTIR analyses allowed the identification of inorganic ions (e.g., CO32−, SO42−, and NO3−), organic functional groups [e.g., carbonyls (C=O), organic hydroxyl (C-OH), carboxylic acid (COOH)], and aromatic and unsaturated aliphatic hydrocarbons. The results obtained by XRD and XPS revealed the presence of organic and inorganic chemical species in PM2.5. The diffuse reflectance spectra of PM2.5 provided the absorption bands in the UV region for CaSO4, CaCO3, and aluminosilicates. The absorption coefficient at 365 nm (Abs365) and Ångström absorption exponent (AAE) values obtained for the aqueous extracts suggest that many of the water-soluble organic compounds corresponded to brown carbon (BrC) chromophores. The mass absorption efficiency values at 365 nm (MAE365) were higher in the winter than summer samples, suggesting the presence of more BrC compounds in the winter samples. The fluorescence indices combined with EEM-PARAFAC analysis showed that the WSOC fraction was mainly composed of humic-like substances (HULIS) which are both of terrestrial and microbial origin.

Evolution of light absorption properties during photochemical aging of straw open burning aerosols

Straw burning comprises more than 30% of all types of burned biomass in Asia, while the estimation of the emitted aerosols' direct radiative forcing effect suffers from large uncertainties, especially when atmospheric aging processes are considered. In this study, the light absorption properties of primary and aged straw burning aerosols in open fire were characterized at 7 wavelengths ranging from 370 nm to 950 nm in a chamber. The primary rice, corn and wheat straw burning bulk aerosols together had a mass absorption efficiency (MAE) of 2.43 ± 1.36 m2 g−1 at 520 nm and an absorption Ångström exponent (AAE) of 1.93 ± 0.71, while the primary sorghum straw burning bulk aerosols were characterized by a relatively lower MAE of 0.95 ± 0.54 m2 g−1 and a higher AAE of 4.80 ± 0.68. Both the MAE and AAE of primary aerosols can be well parameterized by the (PM-BC)/BC ratio (in wt.). The MAE of black carbon (BC) increased by 11–190% during photoreactions equivalent to 16–60 h of atmospheric aging, which was positively correlated with the (PM-BC)/(BC) ratio. The MAE of organic aerosols first slightly increased or leveled off, and then decreased. Specifically, at 370 nm, the first growth/plateau stage lasted until OH exposure reached 0.47–1.29 × 1011 molecule cm−3 s, and the following period exhibited decay rates of 1.0–2.8 × 10−12 cm3 molecule−1 s−1 against the OH radical, corresponding to half-lives of 46–134 h in a typical ambient condition. During photoreactions, competition among the lensing effect, growth/bleach of organic chromophores, and particle mass and size growth complicated the evolution of the direct radiative forcing effect. It is concluded that rice and corn straw burning aerosols maintained a warming effect after aging, while the cooling effect of fresh sorghum straw burning aerosols increased with aging.

Deconvolving light absorption properties and influencing factors of carbonaceous aerosol in Shanghai

Black carbon (BC) and brown carbon (BrC) have intensive impacts on atmospheric visibility and global climate change. In this study, PM2.5 samples were collected at Pudong (PD) and Qingpu (QP) of Shanghai in 2017, and characterized typical organic molecular tracers by gas chromatography-mass spectrometer. The light absorption (Abs) of carbonaceous aerosol and water-soluble organic matter was analyzed by a multi-wavelength thermal/optical carbon analyzer and a long-range ultraviolet-visible spectrophotometer. An improved two-component model integrated with both optical and chemical fingerprints of carbonaceous aerosol was applied to analyze the Abs of BC, water-soluble organic carbon (WSOC) and water-insoluble organic carbon (WISOC), with which the potential influencing factors including emission source and atmospheric aging were investigated. Results indicated that BrC contributed 19% at PD and 16% at QP of the total light absorption of the carbonaceous aerosol at 405 nm wavelength. Meanwhile, AbsWSOC(405)/AbsBrC(405) showed significant seasonal variations (27–50%) at both sites. Positive matrix factorization (PMF) analysis showed that vehicle emissions (60–61%) and biomass combustion (38–39%) were the major contributors to AbsBC(405), while biomass burning (34–40%), nitrate-relevant secondary processes (22–23%), vehicle emissions (18–19%) and biogenic SOA (13–19%) were major contributors to AbsWSOC(405). Hybrid combustion source (94–96%) had a predominant contribution to AbsWISOC(405). Statistical analysis showed that biomass burning had a great impact on the enhancement of AbsWISOC. Absorption Ångström exponent (AAE) and mass absorption efficiency (MAE) of each factor (source) using PMF analysis indicated that WSOC from combustion sources had higher AAEWSOC(350–550) values (8.11 and 8.29 for coal and biomass burning, respectively) and MAEWSOC(365) values (0.63–0.99) compared to other sources. Atmospheric aging process can lower the MAEWSOC(365) value (0.24–0.52). Overall, our study facilitates a better understanding of the relationships among source, optical properties, and atmospheric transformation processes of the carbonaceous aerosols in Shanghai.

The Sources, Molecular Compositions, and Light Absorption Properties of Water‐Soluble Organic Carbon in Marine Aerosols From South China Sea to the Eastern Indian Ocean

AbstractWater‐soluble organic carbon (WSOC) is a substantial component of carbonaceous aerosols in South/East Asia. However, the poorly constrained sources, molecular compositions, and light absorption properties of WSOC over South/East Asian marine regions lead to large uncertainty in climate effects. Herein, we collected marine aerosol samples from South China Sea to the eastern Indian Ocean to investigate the sources, molecular compositions, and light absorption properties of WSOC. The δ13C of Marine‐influenced WSOC (−20.6 ± 1.4‰) was higher than those in Continent‐influenced (South Asia‐influenced: −24.4 ± 1.1‰ and Southeast Asia‐influenced: −22.7 ± 1.0‰, p < 0.01) regions. Additionally, combining with 5‐day back trajectories and the relationships of δ13C‐WSOC with chemical tracers (Cl−/Na+ and nonsea salt K+/K+), we found that the Marine‐influenced WSOC was mostly related to oceanic emissions, which was more enriched in saturated primary marine biological compounds with lower oxidation level. In contrast, the Continent‐influenced WSOC was significantly affected by C3 biomass burning and secondary organic aerosols formation, and it has a higher fraction of aromatic and highly oxidized compounds. Moreover, the high aromatic level of Continental‐influenced WSOC may result in high mass absorption efficiency at 365 nm (MAE365) but low absorption Ångström exponent (AAE) values. Taken together with previous WSOC light absorption properties studies, we found that the MAE365 of WSOC in urban, rural and background, and marine regions correlated well with AAE. However, the response and correlation coefficients of MAE365 to AAE were highest in urban regions, followed by rural and background and marine regions, which is likely associated with different aromatic compound contents. Therefore, in the future, more attention should be paid to the sources and atmospheric processes of condensed aromatic compounds.

Measurement report: Optical properties and sources of water-soluble brown carbon in Tianjin, North China – insights from organic molecular compositions

Abstract. Brown carbon (BrC) aerosols exert vital impacts on climate change and atmospheric photochemistry due to their light absorption in the wavelength range from near-ultraviolet (UV) to visible light. However, the optical properties and formation mechanisms of ambient BrC remain poorly understood, limiting the estimation of their radiative forcing. In the present study, fine particles (PM2.5) were collected during 2016–2017 on a day/night basis over urban Tianjin, a megacity in northern China. Light absorption and fluorescence properties of water extracts of PM2.5 were investigated to obtain seasonal and diurnal patterns of atmospheric water-soluble BrC. There were obvious seasonal, but no evident diurnal, variations in the light absorption properties of BrC. In winter, BrC showed much stronger light-absorbing ability, with a mass absorption efficiency at 365 nm (MAE365) in winter (1.54±0.33 m2 gC−1) that was 1.8 times larger than MAE365 in summer (0.84±0.22 m2 gC−1). Direct radiative effects by BrC absorption relative to black carbon in the UV range were 54.3±16.9 % and 44.6±13.9 % in winter and summer, respectively. In addition, five fluorescent components in BrC, including three humic-like fluorophores and two protein-like fluorophores were identified with excitation–emission matrix fluorescence spectrometry and parallel factor (PARAFAC) analysis. The less oxygenated components contributed more to winter and nighttime samples, while more oxygenated components increased in summer and daytime samples. The higher humification index (HIX), together with lower biological index (BIX) and fluorescence index (FI), suggests that the chemical compositions of BrC were associated with a high aromaticity degree in summer and daytime due to photobleaching. Fluorescent properties indicate that wintertime BrC were predominantly affected by primary emissions and fresh secondary organic aerosol (SOA), while summer ones were more influenced by aging processes. Results of source apportionments using organic molecular compositions of the same set of aerosols reveal that fossil fuel combustion and aging processes, primary bioaerosol emission, biomass burning, and biogenic and anthropogenic SOA formation were the main sources of BrC. Biomass burning contributed much more to BrC in winter and at nighttime, while biogenic SOA contributed more in summer and during the daytime. In particular, our study highlights that primary bioaerosol emission is an important source of BrC in urban Tianjin in summer.

Optical properties, chemical functional group, and oxidative activity of different polarity levels of water-soluble organic matter in PM2.5 from biomass and coal combustion in rural areas in Northwest China

Biomass and coal combustion are major sources of water-soluble organic matter (WSOM) in PM2.5. This study investigated the carbon content, light absorption capacity, molecular structures, and oxidative activity of three types of WSOM (neutral humic-like substances (HULIS-n), acidic HULIS (HULIS-a), and high-polarity WSOM (HP-WSOM)) produced from biomass and coal combustion in Northwest China. The carbon emission factors of HULIS-n, HULIS-a, and HP-WSOM were 5.52 ± 4.29, 3.82 ± 2.83, and 3.24 ± 2.85 g/kg from biomass burning, and 1.77 ± 0.65, 4.41 ± 1.24, and 3.94 ± 1.78 g/kg from coal combustion, respectively. HULIS-n had the highest light absorption coefficient at 365 nm (babs-365) and the mass absorption efficiency at 365 nm (MAE365) both for biomass and coal burning, suggesting that HULIS-n contains more chromophores than the others. The Fourier transform infrared spectra results revealed that aromatic substances and polysaccharides were predominated in HULIS-n and HP-WSOM. Reactive oxygen species (ROS) in coal combustion followed a decreasing order of HULIS-n > HP-WSOM > HULIS-a. In terms of WSOM from biomass combustion, the highest ROS was in HULIS-n for corn straw and wheat straw in fire kangs but the highest ROS was in HP-WSOM for pepper rod and sesame rod in hanging stoves as well as wood block fire. HULIS-a produced by HS of biomass burning had higher ROS activity, and oxidative activity of HULIS-n produced by burning biomass by HB and SS did not differ greatly. High ROS and strong light absorption of HULIS-n in both biomass burning and coal burning may attribute to its molecular structures such as abundance of R–ONO2 organic nitrate. Our results also highlighted that the carbon content of HULIS-n occupied only 17.5% to HULIS + HP-WSOM in coal combustion, whereas HULIS-n contributed up to 58.3% and 64.8% of the total light absorption and ROS. Overall, this study revealed the complex emission properties of WSOM, which would improve the assessment of their environmental and climate impacts at a regional scale.

Characteristics of water-soluble organic carbon (WSOC) in PM2.5 in inland and coastal cities, China

Water-soluble organic carbon (WSOC) can have direct and indirect impacts on global climate change by absorbing sunlight and altering the hygroscopic properties of aerosols. In this study, PM2.5 samples were collected simultaneously in Jinan (inland city) and Weihai (coastal city) in spring 2018 to examine the optical properties and sources of WSOC. The WSOC concentration in Jinan (9.20 ± 3.04 μg m−3) was significantly higher than that in Weihai (2.95 ± 1.54 μg m−3). The coefficient of divergence (COD) (0.41) showed that the chemical compositions of PM2.5 in Jinan and Weihai had a moderate level of discrepancy. Based on linear regression analysis, biomass burning and secondary formation by liquid phase reactions had important influence on WSOC in Jinan and Weihai, and dust source also made a non-negligible contribution to WSOC in Jinan. Short/regional transport air masses derived from the southern region of the sampling sites were dominant and carried out the most abundant WSOC. The main potential source regions for Jinan covered a larger area than that in Weihai. The absorption Ångstrom exponent (AAE) in Jinan (4.4) was higher than that in Weihai (3.86) but was lower than previous studies. The strong correlation coefficients between light absorption at 365 nm (Abs365) and WSOC indicated water-soluble BrC and WSOC might have similar emission sources. The average mass absorption efficiency at 365 nm (MAE365) in Jinan was 0.65 m2 g−1, which was much lower than that in Weihai (1.18 m2 g−1).