Water-soluble Brown Carbon Research Articles

Molecular compositions and optical properties of water-soluble brown carbon during the autumn and winter in Guangzhou, China

Brown carbon (BrC) has attracted increasing attention due to its significant effects on the atmospheric environment and climate. In this study, we investigated the seasonal variations of the optical and molecular properties of water-soluble BrC in Guangzhou and the key factors affecting its light absorption and fluorescence properties. The mass absorption efficiency at 365 nm (MAE365) indicated that water-soluble BrC had a stronger light absorption capacity in winter than in autumn. An excitation emission matrix-parallel factor analysis (EEM-PARAFAC) identified four fluorescent components (C1–C4) in the water-soluble organic compound (WSOC) fraction, of which the humic-like components (C1, C2, and C4) were the dominant fluorophores. More C1 and C4 components were detected in autumn WSOC, whereas more C3 component in winter WSOC, which was mainly due to the differences in the sources and oxidation processes of WSOC in different seasons. The molecular composition of WSOC also indicated significant seasonal variations as revealed by an electrospray ionization ultrahigh-resolution mass spectrometry (ESI-UHRMS) analysis. The autumn WSOC had a higher degree of oxidation, whereas the winter WSOC had a higher aromaticity. Furthermore, a principal component analysis (PCA) and the Pearson correlation coefficients indicated that the light absorption of water-soluble BrC over Guangzhou was mainly affected by their aromaticity and N-containing species, with aromatic CHO and CHON compounds being the most important chromophores. The fluorescent components C1 and C4 were characterized by a relatively high oxidation level, which may be more relevant to aged organic aerosols with a high aromaticity and oxidation. The fluorescent component C3 may be more relevant to the primary emission of organic aerosols or fresh organic aerosols with low oxidation, and some non-nitrogen-containing species also had associations with previously assigned protein-like components (C3).

Molecular characteristics and compositions affecting light absorption features of cloud water revealed by Fourier transform ion cyclotron resonance mass spectrometry

In-cloud brown carbon (BrC) can change cloud lifetimes and radiative effects. However, little is known regarding its molecular-level composition. Herein, the molecular characteristics of water-soluble organic matter (WSOM) in cloud water were analyzed by Fourier transform ion cyclotron resonance mass spectrometry coupled with electrospray ionization (ESI) in negative mode. CHON formulas were dominant in WSOM and exhibited the highest level of aromaticity. Combined with the water-soluble BrC (WS-BrC) light-absorption coefficient (Abs365), the principal component analysis indicated that WS-BrC light absorption was mainly affected by unsaturation, aromaticity, highly oxygenated compounds, and N-containing formulas. Thirteen important potential WS-BrC were identified based on a random forest regression model, which could explain 61.7% of the variation in Abs365. Among them, C7H6N2O5, C8H8N2O5, C9H10N2O5, C10H12N2O5, C8H10O5S, and C8H9NO7S were identified as WS-BrC for the first time in clouds, and these may belong to dinitrophenols or nitrotyrosine, organosulfates, and their derivatives. These findings would improve our understanding of cloud WS-BrC composition.

Molecular characterization of humic-like substances (HULIS) in atmospheric particles (PM2.5) in offshore Eastern China Sea (OECS) using solid-phase extraction coupled with ESI FT-ICR MS

Humic-like substances (HULIS) are organic macromolecular compounds (water-soluble brown carbon) that have an important effect on climate change due to their strong light absorption. However, the molecular composition of HULIS in atmospheric particles in the offshore Eastern China Sea (OECS) has scarcely been investigated. In this study, solid-phase extraction (SPE) was performed to collect HULIS from water extracts. The molecular compositions of samples were characterized by negative-ion electrospray ionization (ESI) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). A total of 1197–1828 molecular formulas of HULIS were identified in collected samples, and three of them with higher intensities near Shanghai city, Zhejiang province, and Fujian province were discussed in detail. The identified molecular formulas were classified into four major subgroups, including CHO, CHNO, CHOS, and CHNOS compounds. S-containing formulas (CHOS and CHNOS) represented the dominant components (21.0–76.7% relative abundance), followed by CHO (16.5–64.3%), while CHNO compounds constituted 6.1–18.1% of the identified formulas. High fractions of CHO formulas were found in the list of α-pinene ozonolysis yields and S-containing formulas with olefinic structures were abundant in atmospheric particles, suggesting enhanced SOA formation. The samples had a relative abundance-weighted average O/C of 0.25–0.67 and a double bond equivalent of 3.49–4.96. Most identified formulas (>89%) were assigned to aliphatic and olefinic species. The CHNO and S-containing formulas identified in the samples were primarily contributed by –ONO2 functional groups and organosulfates. Biogenic volatile organic compounds (α-pinene or monoterpene) were the dominant precursors of HULIS in the samples. Lignin-like species (41–46%) and protein/amino sugars (28–30%) were the major species among substance classes. The results provide an improved understanding of the molecular composition of HULIS in the Eastern China Sea.

Characterization of nitrated aromatic compounds in fine particles from Nanjing, China: Optical properties, source allocation, and secondary processes

Recently, nitrated aromatic compounds (NACs) have received much attention due to their role as key chromophores of brown carbon (BrC) and their impact on human health and the climate. In this study, a method for detection of 12 NACs in the atmosphere was developed and applied to the detection of 191 atmospheric samples in the northern suburbs of Nanjing in 2017. The average concentration of total NACs in Nanjing was 26.48 ng m−3, which was lower than that in North China. The total NACs also showed obvious seasonal variation, with the highest concentration in winter (51.99 ng m−3) and the lowest concentration in summer (11.26 ng m−3). Moreover, the contribution of subcomponents of NACs also changed with the seasons. Nitrophenols (NPs) and nitrocatechols (NCs) were most abundant in winter, while nitrosalicylic acids (NSAs) were more abundant in summer, accounting for 30%, 27%, and 85%, respectively. The reason for this result may be due to the different sources of dominance of NACs in different seasons. The light absorption of NACs to water-soluble BrC was mainly concentrated in the 300–400 nm range, and its contribution reached the maximum at 310 nm. NPs and NCs had the highest contribution to BrC among all NACs in winter, with a range of 25–54% and 3–59%, respectively. The Positive Matrix Factorization (PMF) was used to analyze the main sources of NACs in different seasons. Secondary generation was the largest source in summer, accounting for 43.5%, and biomass combustion contributed the most in autumn, accounting for 36.7%. NACs are affected by temperature, especially in summer, and the subcomponents vary in temperature dependence. The secondary generation process of NACs is affected by NO2 and O3, especially when NO2 is greater than 40 μg m−3 and O3 is less than 220 μg m−3.

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.

Examination of brown carbon absorption from wildfires in the western US during the WE-CAN study

Abstract. Light absorbing organic carbon, or brown carbon (BrC), can be a significant contributor to the visible light absorption budget. However, the sources of BrC and the contributions of BrC to light absorption are not well understood. Biomass burning is thought to be a major source of BrC. Therefore, as part of the WE-CAN (Western Wildfire Experiment for Cloud Chemistry, Aerosol Absorption and Nitrogen) study, BrC absorption data were collected on board the National Science Foundation/National Center for Atmospheric Research (NSF/NCAR) C-130 aircraft as it intercepted smoke from wildfires in the western US in July–August 2018. BrC absorption measurements were obtained in near real-time using two techniques. The first coupled a particle-into-liquid sampler (PILS) with a liquid waveguide capillary cell and a total organic carbon analyzer for measurements of water-soluble BrC absorption and WSOC (water-soluble organic carbon). The second employed a custom-built photoacoustic aerosol absorption spectrometer (PAS) to measure total absorption at 405 and 660 nm. The PAS BrC absorption at 405 nm (PAS total Abs 405 BrC) was calculated by assuming the absorption determined by the PAS at 660 nm was equivalent to the black carbon (BC) absorption and the BC aerosol absorption Ångström exponent was 1. Data from the PILS and PAS were combined to investigate the water-soluble vs. total BrC absorption at 405 nm in the various wildfire plumes sampled during WE-CAN. WSOC, PILS water-soluble Abs 405, and PAS total Abs 405 tracked each other in and out of the smoke plumes. BrC absorption was correlated with WSOC (R2 value for PAS =0.42 and PILS =0.60) and CO (carbon monoxide) (R2 value for PAS =0.76 and PILS =0.55) for all wildfires sampled. The PILS water-soluble Abs 405 was corrected for the non-water-soluble fraction of the aerosol using the calculated UHSAS (ultra-high-sensitivity aerosol spectrometer) aerosol mass. The corrected PILS water-soluble Abs 405 showed good closure with the PAS total Abs 405 BrC with a factor of ∼1.5 to 2 difference. This difference was explained by particle vs. bulk solution absorption measured by the PAS vs. PILS, respectively, and confirmed by Mie theory calculations. During WE-CAN, ∼ 45 % (ranging from 31 % to 65 %) of the BrC absorption was observed to be due to water-soluble species. The ratio of BrC absorption to WSOC or ΔCO showed no clear dependence on fire dynamics or the time since emission over 9 h.

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.

Impacts of severe residential wood burning on atmospheric processing, water-soluble organic aerosol and light absorption, in an inland city of Southeastern Europe

This study examines the concentrations and characteristics of carbonaceous aerosols (including saccharides) and inorganic species measured by PM2.5 filter sampling and a multi-wavelength Aethalometer during two campaigns in a mountainous, medium-sized, Greek city (Ioannina). The first campaign was conducted in summer and used as a baseline of low concentrations, while the second took place in winter under intensive residential wood burning (RWB) emissions. Very high winter-mean OC concentrations (26.0 μg m−3) were observed, associated with an OC/EC ratio of 9.9, and mean BCwb and PM2.5 levels of 4.5 μg m−3 and 57.5 μg m−3, respectively. Simultaneously, record-high levoglucosan (Lev) concentrations (mean: 6.0 μg m−3; max: 15.9 μg m−3) were measured, revealing a severely biomass burning (BB)-laden environment. The water-soluble OC component (WSOC) accounted for 56 ± 9% of OC in winter, exhibiting high correlations (R2 = 0.93–0.97) with BB tracers (nss-K+, BCwb, Lev), nitrate and light absorption, potentially indicating the formation of water-soluble brown carbon (BrC) from fast oxidation processes. The examination of diagnostic ratios involving BB tracers indicated the prevalence of hardwood burning, while the mean Lev/OC ratio (22%) was remarkably higher than literature values. Applying a mono-tracer method based on levoglucosan, we estimated very high BB contributions to OC (∼92%), EC (∼64%) and WSOC (∼87%) during winter. On the contrary, low levels were registered during summer for all carbonaceous components, with winter/summer ratios of 4–5 for PM2.5 and BC, 10 for OC, 30 for BCwb and ∼1100 for levoglucosan. The absence of local BB sources in summer, combined with the photochemical processing and aging of regional organic aerosols, resulted in higher WSOC/OC fractions (64 ± 13%). The results indicate highly soluble fine carbonaceous aerosol fraction year-round, which when considered alongside the extreme concentration levels in winter can have important implications for short- and long-term health effects.

Seasonal variation of water-soluble brown carbon in Qingdao, China: Impacts from marine and terrestrial emissions

Brown carbon (BrC) has been attracting more and more attention owing to its significant effects on climate. However, the limited knowledge on its chemical composition and sources limits the precision of aerosol radiative forcing estimated by climate models. In this study, the chemical components of PM2.5 and optical properties of water-soluble BrC (WS–BrC) were investigated from atmospheric particles collected in summer and winter in Qingdao, China. On the whole, though there were slight diurnal variations, seasonal differences were more obvious. Due to the influence of emission sources and meteorological conditions, the heavier pollution of carbonaceous aerosols occurred in winter. By comparison, the absorption Ångström exponent (AAE) and mass absorption efficiency of WS-BrC at 365 nm (MAE365) showed that WS-BrC in winter had stronger wavelength dependence and light absorption capacity, which might be associated with biomass burning source contributions. This was further confirmed by a strong correlation between the light absorption coefficient at 365 nm (Abs365) and non-sea salt K+, an indicator for biomass burning emissions. Four fluorescent components (C1∼C4) with high unsaturation in water-soluble organic carbon (WSOC) were identified by excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis method, which showed that WSOC in Qingdao was mainly related to humic-like chromophores. It is worth noting that C1 was similar to the water-soluble chromophore of simulated marine aerosols, which proved that marine emissions do have a certain impact on atmospheric particulate matter in coastal areas. In addition, the results of source analysis showed that WS-BrC originated from different terrestrial sources in different seasons. The current results may help to improve the knowledge of optical properties of WS-BrC in coastal cities, optimize the global climate model and formulate air management policies.

Seasonal variability of nitroaromatic compounds in ambient aerosols: Mass size distribution, possible sources and contribution to water-soluble brown carbon light absorption

Nitroaromatic compounds (NACs) as important constituents of atmospheric humic-like substances (HULIS) and brown carbon (BrC) affect the Earth's climate and pose a serious environmental hazard. We investigated seasonal size-segregated NACs in aerosol samples from the urban background environment in Ljubljana, Slovenia. Total concentrations of twenty NACs in PM15.6 were on average from 0.51 ng m−3 (summer) to 109 ng m−3 (winter), and contributed the most to submicron aerosols (more than 74%). Besides 4-nitrocatechol (4NC) as the prevailing species, methylnitrocatechols (MNCs) and nitrophenols (NPs), we reported on some very rarely mentioned, but also on five novel NACs (i.e., 3H4NBA: 3-hydroxy-4-nitrobenzoic acid, 3MeO4NP: 3-methoxy-4-nitrophenol, 4Et5NC: 4-ethyl-5-nitrocatechol, 3Et5NC: 3-ethyl-5-nitrocatechol and 3MeO5NC: 3-methoxy-5-nitrocatechol). Concentrations of 3MeO5NC, 4Et5NC and 3Et5NC were enhanced during cold seasons, contributing up to 11% to total NAC in winter. In cold season, NAC size distributions were characterized with the peaks in the broader size range of 0.305–1.01 μm (accumulation mode), with 4NC and alkyl-nitrocatechols (∑(M/Et)NC) as the most abundant, followed by 4-nitrosyringol, nitrophenols and nitroguaiacols. In spring, a pronounced peak of ∑(M/Et)NC was observed in the accumulation mode (0.305–0.56 μm) as well as in the coarse one. A strong correlation of all NACs with ∑(M/Et)NC and levoglucosan indicates that primary emissions of wood burning were the most important source of NACs, but their secondary formation (e.g., aqueous-phase at higher ambient RH) in cold season could also be a significant one. In warmer season, NACs may be mostly derived from traffic-related aromatic VOCs. The contribution of NACs to the light absorption of the aqueous extracts was up to 10-times higher (contribution to Abs365 up to 31%) than their mass contributions to WSOC (up to 3%) of corresponding size-segregated aerosols, confirming that most of the identified NACs are strong BrC chromophores.

Molecular Characterization of Water-Soluble Brown Carbon Chromophores in Snowpack from Northern Xinjiang, China

This study reports molecular-level characterization of brown carbon (BrC) attributed to water-soluble organic carbon in six snowpack samples collected from northern Xinjiang, China. The molecular composition and light-absorbing properties of BrC chromophores were unraveled by application of high-performance liquid chromatography (HPLC) coupled to a photodiode array (PDA) detector and high-resolution mass spectrometry. The chromophores were classified into five major types, that is, (1) phenolic/lignin-derived compounds, (2) flavonoids, (3) nitroaromatics, (4) oxygenated aromatics, and (5) other chromophores. Identified chromophores account for ∼23-64% of the total light absorption measured by the PDA detector in the wavelength range of 300-370 nm. In the representative samples from urban and remote areas, oxygenated aromatics and nitroaromatics dominate the absorption in the wavelengths below and above 320 nm, respectively. The highly polluted urban sample shows the most complex HPLC-PDA chromatogram, and more other chromophores contribute to the bulk absorption. Phenolic/lignin-derived compounds are the most light-absorbing species in the soil-influenced sample. Chromophores in two remote samples exhibit ultraviolet-visible features distinct from other samples, which are attributed to flavonoids. Identification of individual chromophores and quantitative analysis of their optical properties are helpful for elucidating the roles of BrC in snow radiative balance and photochemistry.

Brown carbon from biomass burning imposes strong circum-Arctic warming

Brown carbon from biomass burning imposes strong circum-Arctic warming

Significant coal combustion contribution to water-soluble brown carbon during winter in Xingtai, China: Optical properties and sources

To understand the characteristics of atmospheric brown carbon (BrC), daily PM2.5 samples in Xingtai, a small city in North China Plain (NCP), during the four seasons of 2018-2019, were collected and analyzed for optical properties and chemical compositions. The light absorption at 365 nm (absλ=365 nm) displayed a strong seasonal variation with the highest value in winter (29.0±14.3 M/m), which was 3.2∼5.4-fold of that in other seasons. A strong correlation of absλ=365 nm with benzo(b)fluoranthene (BbF) was only observed in winter, indicating that coal combustion was the major source for BrC in the season due to the enhanced domestic heating. The mass absorbing efficiency of BrC also exhibited a similar seasonal pattern, and was found to correlate linearly with the aerosol pH, suggesting a positive effect of aerosol acidity on the optical properties and formation of BrC in the city. Positive matrix factorization (PMF) analysis further showed that on a yearly basis the major source for BrC was biomass burning, which accounted for 34% of the total BrC, followed by secondary formation (26.7%), coal combustion (21.3%) and fugitive dust (18%). However, the contribution from coal combustion was remarkably enhanced in winter, accounting for ∼40% of the total. Our work revealed that more efforts of “shifting coal to clean energy” are necessary in rural areas and small cities in NCP in order to further mitigate PM2.5 pollution in China.

Emerging Major Role of Organic Aerosols in Explaining the Occurrence, Frequency, and Magnitude of Haze and Fog Episodes during Wintertime in the Indo Gangetic Plain.

Aerosols are an important part of Earth’s atmosphere. They can absorb, scatter, or reflect the incoming solar radiation, which results in heating or cooling of Earth, thus impacting its climate. It affects the health of exposed human population adversely, reduces visibility, disturbs environmental systems, and causes material damage. This study summarizes the research carried out to understand the role of aerosol load and its physicochemical characteristics on occurrence, frequency, and magnitude of haze and fog events during wintertime within the Indo Gangetic Plain (IGP) in the past decade. For most species, the highest concentration was measured during foggy events at night-time over the winter season. A few species such as water-soluble organic and inorganic carbon (WSOC and WSIC), K+, SO42–, and NO3–, owing to their hygroscopic nature, were efficiently scavenged, resulting in their lower concentration within the interstitial aerosol during fog episodes. Oligomerization with hydroxy and carbonyl functional groups during AFP (activating fog period) and DFP (dissipating fog period), respectively, accompanied by acidic aerosol (having catalytic ability) and high aerosol liquid water content conditions was found to be significant. Whereas the fragmentation process was dominant along with functionalization of −RCOOH or carbonyl (aldehyde/ketone) and −RCOOH moieties during FP (fog period) and PoFP (post-fog period), respectively. Transition metals play an important role in aqueous production of secondary organic aerosol (SOA) especially during the night-time. Crustal sources had the highest scavenging efficiency along with WSOC playing an important role in nucleation scavenging. Fine droplets had a higher concentration of species with a larger fraction of highly oxidized organic matter (OM) as compared to coarse or medium size droplets. Also, a new approach to calculate absorption by black carbon (BC) and brown carbon (BrC) was proposed, which found the water-soluble brown carbon (WSBrC) absorption value in aerosol to be up to 1.8 times higher than that measured in their corresponding aqueous extracts. Organic aerosol plays a vital role in facilitating fog formation and is responsible for the longer residence time in the ambient atmosphere. Ammonia plays an important role in stabilizing organic aerosol and aids to this recurring haze–fog–haze cycle that is dominant during wintertime in the IGP. Therefore, controlling the major anthropogenic sources of organic aerosol and ammonia should be our top priority in this part of the world.

Water-Soluble Brown Carbon in Pm2.5 at Two Typical Sites in Guanzhong Basin: Optical Properties, Sources, and Implications

Water-Soluble Brown Carbon in Pm2.5 at Two Typical Sites in Guanzhong Basin: Optical Properties, Sources, and Implications

Light absorption properties of brown carbon from biomass burning emissions.

A laboratory-scale experiment was conducted to determine the light absorption properties of brown carbon (BrC) produced from theincomplete combustion of 14 different biomasses. Particulate matters (PM) emitted from biomass burning were collected on the quartz fiber filters with a low volume sampler. BrC from filter samples was extracted with two different solvents (methanol and water), and absorption characteristics of BrC were determined using a UV-Vis spectrophotometer. The absorption coefficient (babs-BrC), mass absorption efficiency (MAEBrC), absorption angstrom exponent (AAEBrC), and absorbing portion of refractive index (kabs-BrC) were calculated for each biomass from the absorbance of the extracted solution. Methanol-soluble BrC (MeS-BrC) showed higher absorbance than water-soluble BrC (WS-BrC) in all biomasses. MeS-BrC has higher babs-BrC than WS-BrC, suggesting that the rate of light absorption on BrC extracted in methanol was higher. The absorption coefficients (babs-BrC) were varied among biomasses-rain tree had the highest value of babs-BrC, whereas jute stick had the lowest. The mass absorption efficiency of BrC (MAEBrC) was evaluated in both water and methanol extracts, and it was found that the MAEBrC for MeS-BrC in the biomasses was greater than that of WS-BrC. The highest MAEBrC value (13.02 m2g-1) wasidentified in the jackfruit tree, whereas the lowest MAEBrC value (0.1 m2g-1) wasobserved in thejute stick. The absorption angstrom exponent (AAE) of both WS-BrC and MeS-BrC was determined which represents the light absorption capacity of the aerosol particles. The highest AAE value was found in cow dung, and the lowest was found in rain tree. The increasing pH of the WS-BrC solution increased its optical absorption. However, this study revealed that the light absorption properties of brown carbon emitted from commonly used biomasses were varied significantly.

Concentration, optical characteristics, and emission factors of brown carbon emitted by on-road vehicles

Atmospheric brown carbon (BrC) is a light-absorbing component that affects radiative forcing; however, this effect requires further clarification, particularly with respect to BrC emission sources, chromophores, and optical properties. In the present study, the concentrations, optical properties, and emission factors of organic carbon (OC), water-soluble OC (WSOC), and humic-like substances (HULIS) in fine particulate matter (PM2.5) emitted from vehicles in three road tunnels (the Wucun, Xianyue, and Wenxing tunnels in Xiamen, China) were investigated. The mass concentrations and light absorption of OC, WSOC, and HULIS were higher at the exits of each tunnel than at entrances, demonstrating that vehicle emissions were a BrC source. At each tunnel's exit, the average light absorption contributed by HULIS-BrC to water-soluble BrC (WS-BrC) and total BrC at 365 nm was higher than the corresponding carbon mass concentration contributed by HULIS (HULIS-C) to WSOC and OC, indicating that the chromophores of HULIS emitted from vehicles had a disproportionately high effect on the light absorption characteristics of BrC. The emission factors (EFs) of HULIS-C and WSOC mass concentrations were highest at the Xianyue tunnel; however, the EFs of HULIS-BrC and WS-BrC light absorption were highest at the Wenxing tunnel, indicating that the chromophore composition of BrC was different among the tunnels and that the mass concentration EFs did not correspond directly to the light absorption EFs.

Assessment of online water-soluble brown carbon measuring systems for aircraft sampling

Abstract. Brown carbon (BrC) consists of particulate organic species that preferentially absorb light at visible and ultraviolet wavelengths. Ambient studies show that as a component of aerosol particles, BrC affects photochemical reaction rates and regional to global climate. Some organic chromophores are especially toxic, linking BrC to adverse health effects. The lack of direct measurements of BrC has limited our understanding of its prevalence, sources, evolution, and impacts. We describe the first direct, online measurements of water-soluble BrC on research aircraft by three separate instruments. Each instrument measured light absorption over a broad wavelength range using a liquid waveguide capillary cell (LWCC) and grating spectrometer, with particles collected into water by a particle-into-liquid sampler (CSU PILS-LWCC and NOAA PILS-LWCC) or a mist chamber (MC-LWCC). The instruments were deployed on the NSF C-130 aircraft during WE-CAN 2018 as well as the NASA DC-8 and the NOAA Twin Otter aircraft during FIREX-AQ 2019, where they sampled fresh and moderately aged wildfire plumes. Here, we describe the instruments, calibrations, data analysis and corrections for baseline drift and hysteresis. Detection limits (3σ) at 365 nm were 1.53 Mm−1 (MC-LWCC; 2.5 min sampling time), 0.89 Mm−1 (CSU PILS-LWCC; 30 s sampling time), and 0.03 Mm−1 (NOAA PILS-LWCC; 30 s sampling time). Measurement uncertainties were 28 % (MC-LWCC), 12 % (CSU PILS-LWCC), and 11 % (NOAA PILS-LWCC). The MC-LWCC system agreed well with offline measurements from filter samples, with a slope of 0.91 and R2=0.89. Overall, these instruments provide soluble BrC measurements with specificity and geographical coverage that is unavailable by other methods, but their sensitivity and time resolution can be challenging for aircraft studies where large and rapid changes in BrC concentrations may be encountered.

Chemical composition, optical properties, and oxidative potential of water- and methanol-soluble organic compounds emitted from the combustion of biomass materials and coal

Abstract. Biomass burning (BB) and coal combustion (CC) are important sources of brown carbon (BrC) in ambient aerosols. In this study, six biomass materials and five types of coal were combusted to generate fine smoke particles. The BrC fractions, including water-soluble organic carbon (WSOC), humic-like substance carbon (HULIS-C), and methanol-soluble organic carbon (MSOC), were subsequently fractionated, and their optical properties and chemical structures were then comprehensively investigated using UV–visible spectroscopy, proton nuclear magnetic resonance spectroscopy (1H NMR), and fluorescence excitation–emission matrix (EEM) spectroscopy combined with parallel factor (PARAFAC) analysis. In addition, the oxidative potential (OP) of BB and CC BrC was measured with the dithiothreitol (DTT) method. The results showed that WSOC, HULIS-C, and MSOC accounted for 2.3 %–22 %, 0.5 %–10 %, and 6.4 %–73 % of the total mass of combustion-derived smoke PM2.5, respectively, with MSOC extracting the highest concentrations of organic compounds. The MSOC fractions had the highest light absorption capacity (mass absorption efficiency at 365 nm (MAE365): 1.0–2.7 m2/gC) for both BB and CC smoke, indicating that MSOC contained more of the strong light-absorbing components. Therefore, MSOC may represent the total BrC better than the water-soluble fractions. Some significant differences were observed between the BrC fractions emitted from BB and CC with more water-soluble BrC fractions with higher MAE365 and lower absorption Ångström exponent values detected in smoke emitted from BB than from CC. EEM-PARAFAC identified four fluorophores: two protein-like, one humic-like, and one polyphenol-like fluorophores. The protein-like substances were the dominant components of WSOC (47 %–80 %), HULIS-C (44 %–87 %), and MSOC (42 %–70 %). The 1H-NMR results suggested that BB BrC contained more oxygenated aliphatic functional groups (H-C-O), whereas CC BrC contained more unsaturated fractions (H-C-C= and Ar−H). The DTT assays indicated that BB BrC generally had a stronger oxidative potential (DTTm, 2.6–85 pmol/min/µg) than CC BrC (DTTm, 0.4–11 pmol/min/µg), with MSOC having a stronger OP than WSOC and HULIS-C. In addition, HULIS-C contributed more than half of the DTT activity of WSOC (63.1 % ± 15.5 %), highlighting that HULIS was a major contributor of reactive oxygen species (ROS) production in WSOC. Furthermore, the principal component analysis and Pearson correlation coefficients indicated that highly oxygenated humic-like fluorophore C4 may be the important DTT active substances in BrC.

Diurnal variability in the spectral characteristics and sources of water-soluble brown carbon aerosols over Delhi

It is well established that light-absorbing organic aerosols (commonly known as brown carbon, BrC) impact climate. However, uncertainties remain as their contributions to absorption at different wavelengths are often ignored in climate models. Further, BrC exhibits differences in absorption at different wavelengths due to the variable composition including varying sources and meteorological conditions. However, diurnal variability in the spectral characteristics of water-soluble BrC (hereafter BrC) is not yet reported. This study presents unique measurement hitherto lacking in the literature. Online measurements of BrC were performed using an assembled system including a particle-into-liquid sampler, portable UV–Visible spectrophotometer with liquid waveguid capillary cell, and total carbon analyzer (PILS-LWCC-TOC). This system measured the absorption of ambient aerosol extracts at the wavelengths ranging from 300 to 600 nm with 2 min integration time and water-soluble organic carbon (WSOC) with 4 min integration time over a polluted megacity, New Delhi. Black carbon, carbon monoxide (CO), nitrogen oxides (NOx), and the chemical composition of non-refractory submicron aerosols were also measured in parallel. Diurnal variability in absorption coefficient (0.05 to 65 Mm−1), mass absorption efficiency (0.01 to 3.4 m−2 gC−1) at 365 nm, and absorption angstrom exponent (AAE) of BrC for different wavelength range (AAE300–400: 4.2–5.8; AAE400–600: 5.5–8.0; and AAE300–600: 5.3–7.3) is discussed. BrC chromophores absorbing at any wavelength showed minimum absorption during afternoon hours, suggesting the effects of boundary layer expansion and their photo-sensitive/volatile nature. On certain days, a considerable presence of BrC absorbing at 490 nm was observed during nighttime that disappears during the daytime. It appeared to be associated with secondary BrC. Observations also infer that BrC species emitted from the biomass and coal burning are more absorbing among all sources. A fraction of BrC is likely associated with trash burning, as inferred from the spectral characteristics of Factor-3 from the PMF analysis of BrC spectra. Such studies are essential in understanding the BrC characteristics and their further utilization in climate models.