Water-soluble Brown Carbon Research Articles

Aqueous Photolysis of Water-Soluble Brown Carbon from Simulated Prescribed and Wildfire Biomass Burning.

This work, as part of the Georgia Wildland fire Simulation Experiment (G-WISE) campaign, explores the aqueous photolysis of water-soluble brown carbon (W-BrC) in biomass burning aerosols from the combustion of fuel beds collected from three distinct ecoregions in Georgia: Piedmont, Coastal Plain, and Blue Ridge. Burns were conducted under conditions representative of wildfires, which are common unplanned occurrences in Southeastern forests (low fuel moisture content), and prescribed fires, which are commonly used in forest management (higher fuel moisture content). Upon exposure to radiation from UV lamps equivalent to approximately 5 h in the atmosphere, the absorption spectra of all six samples exhibited up to 40% photobleaching in the UV range (280-400 nm) and as much as 30% photo-enhancement in the visible range (400-500 nm). Together, these two effects reduced the absorption Ångström exponent (AAE), a measure of the wavelength dependence of the spectrum, from 6.0-7.9 before photolysis to 5.0-5.7 after. Electrospray ionization ultrahigh-resolution mass spectrometry analysis shows the potential formation of oligomeric chromophores due to aqueous photolysis. This work provides insight into the impacts that aqueous photolysis has on W-BrC in biomass burning aerosols and its dependence on fuel bed composition and moisture content.

Measurement report: Optical characterization, seasonality, and sources of brown carbon in fine aerosols from Tianjin, North China: year-round observations

Abstract. To investigate the optical characteristics and sources of brown carbon (BrC) in North China, where the atmospheric aerosol loadings are high and have severe impacts on Earth's climate system, we collected fine aerosols (PM2.5) at an urban site in Tianjin over a 1-year period. We measured the ultraviolet (UV) light absorption and excitation emission matrix (EEM) fluorescence of the water-soluble BrC (WSBrC) and the water-insoluble but methanol-soluble BrC (WI-MSBrC) in the PM2.5 using a three-dimensional fluorescence spectrometer. The average light absorption efficiency of both WSBrC (Abs365, WSBrC) and WI-MSBrC (Abs365, WI-MSBrC) at 365 nm was found to be highest in winter (10.4 ± 6.76 and 10.0 ± 5.13 Mm−1, respectively) and distinct from season to season. The averages of the fluorescence index (FI) and the biological index (BIX) of WSBrC were lower in summer than in the other seasons and opposite to that of the humification index (HIX), which implied that the secondary formation and further chemical processing of aerosols were more intensive during the summer period than in the other seasons. However, in winter, the higher HIX together with the higher FI and BIX of WI-MSBrC suggested that the BrC loading was mainly influenced by primary emissions from biomass burning and coal combustion. Based on the EEM, the types of fluorophores in WSBrC were divided into humic-like substances (HULIS), including low-oxygenated and high-oxygenated species and protein-like compounds (PLOM), though mostly PLOM in the WI-MSBrC. The direct radiation absorption by both WSBrC and WI-MSBrC in the range of 300–400 nm accounted for ∼ 40 % of that (SFEAbs, 4.97 ± 2.71 and 7.58 ± 5.75 W g−1, respectively) in the range 300–700 nm.

Brown Carbon From Biomass Burning Reinforces the Himalayas and Tibetan Plateau Warming

AbstractThe Himalayas and Tibetan Plateau (the HTP), referred to as “the third pole” with an excessive warming rate, exerts strong impacts on the global environment. As one of warming contributors, atmospheric brown carbon (BrC) remains limited scientific understanding in the HTP due to a scarcity of observations. In this study, we present a study of the light‐absorbing properties of methanol‐soluble brown carbon (MeS‐BrC) and water‐soluble brown carbon (WS‐BrC) during 2018–2021. Highly spatiotemporal variations of BrC light absorptions were observed. In the HTP marginal area, elevated BrC absorption coefficients at 365 nm (babs,365) and levoglucosan concentrations were obtained, and MeS‐BrC exhibits approximately 1.3–1.8 times higher absorption compared to WS‐BrC. We determined that BrC light absorptions was largely attributed to biomass burning (29%–35%). BrC can act as a potent warming agent in the HTP marginal area, with high direct solar absorption (25%–47% relative to black carbon).

Seasonal characterization of chemical and optical properties of water-soluble organic aerosol in Beijing

Water-soluble organic aerosol (WSOA) plays a crucial role in altering radiative forcing and impacting human health. However, our understanding of the seasonal variations of WSOA in Chinese megacities after the three-year clean air action plan is limited. In this study, we analyzed PM2.5 filter samples collected over one year (2020−2021) in Beijing to characterize the seasonal changes in the chemical and optical properties of WSOA using an offline aerosol mass spectrometer along with spectroscopy techniques. The mean mass concentration of WSOA during the observation period was 8.84 ± 7.12 μg m−3, constituting approximately 64–67 % of OA. Our results indicate the contribution of secondary OA (SOA) increased by 13–28 % due to a substantial reduction in primary emissions after the clean air action plan. The composition of WSOA exhibited pronounced seasonal variations, with a predominant contribution from less oxidized SOA in summer (61 %) and primary OA originating from coal combustion and biomass burning during the heating season (34 %). The mass absorption efficiency of WSOA at 365 nm in winter was nearly twice that in summer, suggesting that WSOA from primary emissions possesses a stronger light-absorbing capability than SOA. On average, water-soluble brown carbon accounted for 33–48 % of total brown carbon absorption. Fluorescence analysis revealed humic-like substances as the most significant fluorescence component of WSOA, constituting 82 %. Furthermore, both absorption and fluorescence chromophores were associated with nitrogen-containing compounds, highlighting the role of nitrogen-containing species in influencing the optical properties of WSOA. The results are important for chemical transport models to accurately simulate the WSOA and its climate effects.

Field evidence of brown carbon absorption enhancement linked to organic nitrogen formation in Indo-Gangetic Plain

Atmospheric brown carbon (BrC), a short-lived climate forcer, absorbs solar radiation and is a substantial contributor to the warming of the Earth's atmosphere. BrC composition, its absorption properties, and their evolution are poorly represented in climate models, especially during atmospheric aqueous events such as fog and clouds. These aqueous events, especially fog, are quite prevalent during wintertime in Indo-Gangetic Plain (IGP) and involve several stages (e.g., activation, formation, and dissipation, etc.), resulting in a large variation of relative humidity (RH) in the atmosphere. The huge RH variability allowed us to examine the evolution of water-soluble brown carbon (WS-BrC) diurnally and as a function of aerosol liquid water content (ALWC) and RH in this study. We explored links between the evolution of WS-BrC mass absorption efficiency at 365 nm (MAEWS-BrC-365) and chemical characteristics, viz., low-volatility organics and water-soluble organic nitrogen (WSON) to water-soluble organic carbon (WSOC) ratio (org-N/C), in the field (at Kanpur in central IGP) for the first time worldwide. We observed that WSON formation governed enhancement in MAEWS-BrC-365 diurnally (except during the afternoon) in the IGP. During the afternoon, the WS-BrC photochemical bleaching dwarfed the absorption enhancement caused by WSON formation. Further, both MAEWS-BrC-365 and org-N/C ratio increased with a decrease in ALWC and RH in this study, signifying that evaporation of fog droplets or bulk aerosol particles accelerated the formation of nitrogen-containing organic chromophores, resulting in the enhancement of WS-BrC absorptivity. The direct radiative forcing of WS-BrC relative to that of elemental carbon (EC) was ∼19 % during wintertime in Kanpur, and ∼ 40 % of this contribution was in the UV-region. These findings highlight the importance of further examining the links between the evolution of BrC absorption behavior and chemical composition in the field and incorporating it in the BrC framework of climate models to constrain the predictions.

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

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

Seasonal changes in water-soluble brown carbon (BrC) at Nanling background station in South China

Brown carbon (BrC) is an important light-absorbing component of organic carbon (OC), causing large uncertainty in aerosol radiative forcing evaluation and being related to health issues as well. Knowledge of BrC in an atmospheric background station is beneficial to understand its role in a changing climate. A year-long sampling campaign was conducted at Nanling background station to get a comprehensive knowledge of WS-BrC, a total of seventy-two PM2.5 samples throughout a year were used. Light absorption and fluorescence spectra of WSOC were analyzed synchronously using a fluorescence spectrophotometer. The low levels of PM2.5, OC, and elemental carbon (EC) conferred a background site. The optical properties of WS-BrC were characterized using excitation-emission matrix (EEM) fluorescence spectroscopy. The WS-BrC made a significant contribution (365 nm, 18% ± 10%) to total carbonaceous aerosol absorption. The mass absorption efficiency (MAE) of WS-BrC is 0.81 ± 0.34 m2 gC–1, and varies among seasons due to the different sources or atmospheric processing. Three EEM fluorescent components were identified by parallel factor (PAFAFAC) analysis, including two humic-like substances (HULIS, C1, C2), and one phenolic-like component. The HULIS components accounted for approximately 70% of the total fluorescence intensities. Primary combustion emissions showed enhanced activity during the winter and spring seasons, but there were no significant influences on WS-BrC in spring. Secondary sources contributed significantly to WS-BrC during winter, summer, and autumn (all exceeding 50%), except for spring. Photooxidation is a significant process in the formation of secondary WS-BrC in winter and autumn, but there may be another formation pathway in summer, i.e., the ammonia pathway. This study contributes to our understanding of BrC in the background atmosphere.

Effects of copper on chemical kinetics and brown carbon formation in the aqueous ˙OH oxidation of phenolic compounds.

Many phenolic compounds (PhCs) in biomass burning and fossil fuel combustion emissions can partition into atmospheric aqueous phases (e.g., cloud/fog water and aqueous aerosols) and undergo reactions to form secondary organic aerosols (SOAs) and brown carbon (BrC). Redox-active transition metals, particularly Fe and Cu, are ubiquitous species in atmospheric aqueous phases known to participate in Fenton/Fenton-like chemistry as a source of aqueous ˙OH. However, even though the concentrations of water-soluble Cu are close to those of water-soluble Fe in atmospheric aqueous phases in some areas, unlike Fe, the effects that Cu have on SOA and BrC formation in atmospheric aqueous phases have scarcely been studied and remain poorly understood. We investigated the effects of Cu(II) on PhC reaction rates and BrC formation during the aqueous oxidation of four PhCs (guaiacol, catechol, syringol, and vanillin) by ˙OH generated from Fenton-like chemistry under different pH conditions. While the PhCs reacted when both H2O2 and Cu(II) were present in the absence (i.e., dark oxidation) and presence (i.e., photooxidation) of light, the reaction rates were at least one order of magnitude higher during photooxidation. Higher PhC reaction rates were measured at higher pH during both dark oxidation and photooxidation as a result of higher ˙OH concentrations produced by Fenton-like chemistry. Only water-soluble BrC was formed during dark oxidation and photooxidation when Cu(II) was present. Mass absorption coefficients (103 to 104 cm2 g-1) comparable to those of biomass burning BrC were measured during dark oxidation and photooxidation when Cu(II) was present. Light absorption was enhanced at higher pH during dark oxidation and photooxidation, which indicated that higher quantities and/or more absorbing BrC chromophores were formed at higher pH. The effects that Cu(II) had on the PhC reaction rates and the composition of SOAs and BrC formed depended on the PhC base structure (i.e., benzenediol vs. methoxyphenol). Overall, these results show how aqueous reactions involving Cu(II), H2O2, and PhCs can be an efficient source of daytime and nighttime water-soluble BrC and SOAs, which can have significant implications for how the atmospheric fates of PhCs are modeled for areas with substantial concentrations of water-soluble Cu in highly to moderately acidic cloud/fog water and aqueous aerosols.

Characterization of water-soluble brown carbon chromophores from wildfire plumes in the western USA using size-exclusion chromatography

Abstract. Wildfires are an important source of carbonaceous aerosol in the atmosphere. Organic aerosol that absorbs light in the ultraviolet to visible spectral range is referred to as brown carbon (BrC), and its impact on Earth's radiative budget has not been well characterized. We collected water-soluble brown carbon using a particle-into-liquid sampler (PILS) on board a Twin Otter aircraft during the Fire Influence on Regional to Global Environments and Air Quality (FIREX-AQ) campaign. Samples were collected downwind of wildfires in the western United States from August to September 2019. We applied size-exclusion chromatography (SEC) with ultraviolet-visible spectroscopy to characterize the molecular size distribution of BrC chromophores. The wildfire plumes had transport ages of 0 to 5 h, and the absorption was dominated by chromophores with molecular weights <500 Da. With BrC normalized to a conserved biomass burning tracer, carbon monoxide, a consistent decrease in BrC absorption with plume age was not observed during FIREX-AQ. These findings are consistent with the variable trends in BrC absorption with plume age reported in recent studies. While BrC absorption trends were broadly consistent between the offline SEC analysis and the online PILS measurements, the absolute values of absorption and their spectral dependence differed. We investigate plausible explanations for the discrepancies observed between the online and offline analyses. This included solvent effects, pH, and sample storage. We suspect that sample storage impacted the absorption intensity of the offline measurements without impacting the molecular weight distribution of BrC chromophores.

Measurement report: Brown carbon aerosol in polluted urban air of the North China Plain – day–night differences in the chromophores and optical properties

Abstract. Brown carbon (BrC) aerosol is light-absorbing organic carbon that affects radiative forcing and atmospheric photochemistry. The BrC chromophoric composition and its linkage to optical properties at the molecular level, however, are still not well characterized. In this study, we investigate the day–night differences in the chromophoric composition (38 species) and optical properties of water-soluble and water-insoluble BrC fractions (WS-BrC and WIS-BrC) in aerosol samples collected in Shijiazhuang, one of the most polluted cities in China. We found that the light absorption contribution of WS-BrC to total BrC at 365 nm was higher during the day (62±8 %) than during the night (47±26 %), which is in line with the difference in chromophoric polarity between daytime (more polar nitrated aromatics) and nighttime (more less-polar polycyclic aromatic hydrocarbons, PAHs). The high polarity and water solubility of BrC in the daytime suggests the enhanced contribution of secondary formation to BrC during the day. There was a decrease in the mass absorption efficiency of BrC from nighttime to daytime (2.88±0.24 vs. 2.58±0.14 for WS-BrC and 1.43±0.83 vs. 1.02±0.49 m2 g C−1 for WIS-BrC, respectively). Large polycyclic aromatic hydrocarbons (PAHs) with four- to six-ring PAHs and nitrophenols contributed to 76.7 % of the total light absorption between 300–420 nm at nighttime, while nitrocatechols and two- to three-ring oxygenated PAHs accounted for 52.6 % of the total light absorption during the day. The total mass concentrations of the identified chromophores showed larger day–night difference during the low-pollution period (day-to-night ratio of 4.3) than during the high-pollution period (day-to-night ratio of 1.8). The large day–night difference in BrC composition and absorption, therefore, should be considered when estimating the sources, atmospheric processes, and impacts of BrC.

Characterizing water-soluble brown carbon in fine particles in four typical cities in northwestern China during wintertime: integrating optical properties with chemical processes

Abstract. Brown carbon (BrC) aerosol could impact atmospheric radiative forcing and play a crucial role in atmospheric photochemistry. In this study, fine particulate matter (PM2.5) filter samples were collected synchronously in four major cities in northwestern China during the winter season (December 2019–January 2020): Lanzhou (LZ), Xining (XN), Yinchuan (YC), and Ürümqi (UR), which are represented as energy-producing and heavy manufacturing cities in China. The primary aim of the study is to explore the optical properties, sources, and chemical processes of water-soluble BrC (WS-BrC). The average mass absorption efficiency at 365 nm (MAE365) of WS-BrC at these four cities was 1.24 ± 0.19 m2 g−1 (XN), 1.19 ± 0.12 m2 g−1 (LZ), 1.07 ± 0.23 m2 g−1 (YC), and 0.78 ± 0.16 m2 g−1 (UR). The properties of WS-BrC were further investigated by an acid–base titration experiment. The results showed that the MAE365 values in all cities increased with higher pH values (2–11), while the fluorescence intensities of water extracts fluctuated with pH values, being stronger under both highly acidic and basic conditions. The sensitivity to pH variation was most pronounced in the WS-BrC samples from YC and LZ, indicating the important contribution of acid or base functional group compounds in these locations. Additionally, the study revealed significant photo-enhancement (LZ) or photo-bleaching (YC and UR) phenomena of WS-BrC in different cities. These results suggest that the sources and/or chemical processes of WS-BrC varied among the cities. The sources and chemical processes of WS-BrC were further explored by a combination of parallel factor analysis (PARAFAC) on excitation–emission matrix (EEM) spectra of WS-BrC and positive matrix factorization analysis (PMF) on high-resolution mass spectra of water-soluble organic aerosol (WSOA). Six PARAFAC components were identified, including three humic-like substances (HULIS; two less oxygenated (LO) HULIS and one highly oxygenated (HO) HULIS), two protein-like or phenol-like substances (PLS), and one undefined substance. Four PMF factors were identified, including a water-soluble primary OA (WS-POA), a less oxidized oxygenated OA associated with coal combustion-induced WSOA (LO-OOA), and two highly oxidized oxygenated OAs resulting from photochemical oxidation and aqueous-phase oxidation transformations (HO-OOA1 and HO-OOA2). WS-POA was determined to be the most significant source of light absorption, accounting for 30 %–60 % based on multiple linear regression models, and it showed a significant correlation with PLS and LO-HULIS components. The loss of light absorption of WS-POA was found to occur through its conversion to LO-OOA and HO-OOAs through photochemical or aqueous reactions, with HO-OOAs being significantly correlated with the HO-HULIS component. These processes can be clearly illustrated by integrating optical properties and chemical composition using a Van Krevelen diagram and an EEM plot.

Emission of water soluble brown carbon from different combustion sources: optical properties and functional group characterisation

Brown carbon (BrC) has a large impact on the Earth’s radiative balance. This study examined BrC’s optical characteristics, chemical functional groups, and total organic carbon (TOC) in deposited particulate matter from combustion of biomass, fossil fuels, and mosquito coil. A UV–vis spectrophotometer was used to assess BrC’s optical properties, a TOC analyzer was used to quantify TOC, and attenuated total reflection-fourier transform infrared spectroscopy (ATR-FTIR) was used to identify functional group. The light absorption properties (absorption coefficient (babs-BrC), mass absorption efficiency (MAE365), absorption angstrom exponent (AAE), and refractive index (kabs-BrC)) were determined. Among biomasses, wheat straw exhibited the greatest value of babs-BrC (27.26 × 103 ± 4.09 × 103 Mm−1) whereas maize straw had the lowest value of babs-BrC (7.38 × 103 ± 1.11 × 103 Mm−1). A higher light absorption coefficient at 365 nm suggested that chromophores contributed more to the process. AAE followed this sequence - mosquito coil (5.46 ± 0.82) > biomass (5.13 ± 1.45) > fossil fuels (2.85 ± 0.32). The highest value of MAE365 (0.99 ± 0.15 m2 gC−1) and kabs-BrC (0.028 ± 0.004) was obtained in wheat straw, whereas the lowest value of MAE365 (0.07 ± 0.011 m2 gC−1) and kabs-BrC (0.002) was identified in octane. Biomasses samples showed a strong peak at ∼850, ∼1368, ∼1370, ∼1306, and near 1640 cm−1, indicating that the major component of BrC was organic nitrate R-ONO2 which is responsible to increase the light absorption properties. It also contains complex heterocyclic aromatic ring compounds, carbonyl group (C=O), and nitrogen-containing groups such as −NO 2, C≡N. The projected substantial contribution of BrC to overall light absorption is one illustration of the probable climatic effect of biomasses and fossil fuel burning in Southeast Asian region.

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.

Investigating the molecular weight distribution of atmospheric water-soluble brown carbon using high-performance size exclusion chromatography coupled with diode array and fluorescence detectors

Atmospheric brown carbon (BrC) contain amounts of organic species, but their molecular weight (MW) distributions is still poorly understood. This study applied high-performance size exclusion chromatography (HPSEC) coupled with a diode array detector (DAD) and fluorescence detector (FLD) to characterize the MW distributions of typical chromophores and fluorophores within water-soluble BrC. The investigation focused on the spring season, encompassing both typical urban and rural aerosols. Our results showed that chromophores (at 254 and 365 nm), and humic-like and protein-like fluorophores identified by excitation-emission matrix parallel factor analysis (EEM-PARAFAC) within BrC were broadly distributed along the MW continuum (∼50–20,000 Da). This suggests that BrC mainly comprises complex chromophores and fluorophores with heterogeneous molecular sizes. High-MW (HMW, >1 kDa) species (66%–74%) dominated the chromophores at 254 and 365 nm. However, the latter chromophores were enriched with more HMW species. This result suggested that the HMW chromophores might contribute more to BrC absorption at longer wavelengths. The PARAFAC-derived fluorescent components also exhibited different MW distributions. Three humic-like substances (HULIS) were all dominated by HMW fractions (51%–74%), but protein-like fluorescent component (PLOM) enriched low-MW (LMW, <1 kDa) species (60%–66%). Furthermore, the molecular size (i.e., weight-averaged and number-averaged MW) and the ratios between HMW and LMW species decreased in the order highly-oxygenated HULIS > less-oxygenated HULIS > PLOM, indicating that the fluorophores with longer Em were generally related to larger MW. To our knowledge, this is the first report on the molecular size of individual fluorescent components within aerosol BrC. The results obtained here enhanced our knowledge of heterogeneous composition, complex physicochemical properties, and potential atmospheric fates of aerosol BrC.

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

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

Insights into dissolved organics in non-urban areas - Optical properties and sources

Brown carbon aerosols show obvious light absorption properties in the ultraviolet–visible (UV–Vis) range, which has an important impact on photochemistry and climate. In this study, experimental samples originated from the North slope of the Qinling Mountains (at two remote suburb sites) to study the optical properties of water-soluble brown carbon (WS–BrC) in PM2.5. The WS-BrC of TY (a sampling site on the edge of Tangyu of Mei county) has a stronger light absorption ability than CH (a rural sampling site, near the Cuihua Mountains scenic spot). The direct radiation effect of WS-BrC relative to elemental carbon (EC) is 6.67 ± 1.36% in TY and 24.13 ± 10.84% in CH in the UV range, respectively. In addition, two humic-like and one protein-like fluorophore components in WS-BrC were identified by fluorescence spectrum and parallel factor (EEMs-PARAFAC). Humification index (HIX), biological index (BIX) and fluorescence index (FI) together showed that the WS-BrC in the two sites may originate from fresh aerosol emissions. Potential source analysis of Positive Matrix Factorization (PMF) model show that the combustion process, vehicle, secondary formation and road dust are the main contributors to WS-BrC.

More water-soluble brown carbon after the residential “coal-to-gas” conversion measure in urban Beijing

The implementation of air pollution reduction measures has significantly reduced the concentration of atmospheric fine particles (PM2.5) in Beijing, among which the “coal-to-gas” conversion measures may play a crucial role. However, the effect of this conversion measure on brown carbon (BrC) is not well known. Here, the chemical composition of BrC in humic-like fraction (HULIS-BrC) and water-insoluble fraction (WI-BrC) were characterized for ambient PM2.5 samples collected in Beijing before and after the “coal-to-gas” conversion measure. After the conversion measure, the number of HULIS-BrC compounds increased by ~14%, while the number of WI-BrC compounds decreased by ~8%. The intensity of over 90% of HULIS-BrC compounds also increased after the conversion measure, and correspondingly the O/C ratios of CHO and CHON compounds in HULIS-BrC fraction generally increased with the increase of intensity ratios after/before the conversion measure, indicating that there were more water-soluble highly oxygenated BrC compounds after “coal-to-gas” conversion measure. On the contrary, the intensity of more than 80% of WI-BrC compounds decreased after the conversion measure, and the O/C ratios of CHO and CHON compounds in WI-BrC fraction generally decreased with the decrease of intensity ratios after/before the conversion measure, indicating that after the “coal-to-gas” conversion measure the water-insoluble low oxygenated BrC compounds decreased. This work sheds light on the differences in the chemical composition of BrC between before and after the “coal-to-gas” conversion measure and suggests that future studies on the residential coal combustion BrC and secondary BrC deserve further exploration.

Water-soluble brown carbon in atmospheric aerosols from the resource-dependent cities: Optical properties, chemical compositions and sources

As a vital type of light-absorbing aerosol, brown carbon (BrC) presents inherent associations with atmospheric photochemistry and climate change. However, the understanding of the chemical and optical properties of BrC is limited, especially in some resource-dependent cities with long heating periods in northwest China. This study showed that the annual average abundances of Water-soluble BrC (WS-BrC) were 9.33±7.42 and 8.69±6.29 µg/m3 in Baotou and Wuhai and the concentrations, absorption coefficient (Abs365), and mass absorption efficiency (MAE365) of WS-BrC presented significant seasonal patterns, with high values in the heating season and low values in the non-heating season; while showing opposite seasonal trends for the Absorption Ångström exponent (AAE300-400). Comparatively, the levels of WS-BrC in developing regions (such as cities in Asia) were higher than those in developed regions (such as cities in Europe and Australia), indicating the significant differences in energy consumption in these regions. By combining fluorescence excitation-emission matrix (EEM) spectra with the parallel factor (PARAFAC) model, humic-like (C1 and C2) and protein-like (C3) substances were identified, and accounted for 61.40%±4.66% and 38.6%±3.78% at Baotou, and 60.33%±6.29% and 39.67%±4.17% at Wuhai, respectively. The results of source apportionment suggested that the potential source regions of WS-BrC varied in heating vs. non-heating seasons and that the properties of WS-BrC significantly depended on primary emissions (e.g., combustion emissions) and secondary formation.

Technical note: Chemical composition and source identification of fluorescent components in atmospheric water-soluble brown carbon by excitation–emission matrix spectroscopy with parallel factor analysis – potential limitations and applications

Abstract. Three-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy is an important method for the identification of the occurrence, chemical composition, and source of atmospheric chromophores. However, current knowledge on the identification and interpretation of fluorescent components is mainly based on aquatic dissolved organic matter and might not be applicable to atmospheric samples. Therefore, this study comprehensively investigated EEM data of different types of strong light-absorbing organic compounds, water-soluble organic matter (WSOM) in different aerosol samples (combustion source samples and ambient aerosols), soil dust, and purified fulvic and humic acids supplemented by parallel factor (PARAFAC) modeling. The results demonstrated that organic compounds with high aromaticity and strong electron-donating groups generally present strong fluorescence spectra at longer emission wavelengths, whereas organic compounds substituted with electron-withdrawing groups have relatively weaker fluorescence intensity. In particular, aromatic compounds containing nitro groups (i.e., nitrophenols), which show strong absorption and are the major component of atmospheric brown carbon, exhibited no significant fluorescence. The EEM–PARAFAC method identified three fluorescent components (i.e., C1, C2, and C3) in ambient WSOM. Although EEM–PARAFAC-derived C1 (Ex/Em = 235, 270/330 nm) in ambient WSOM is generally considered to be protein-like groups, our findings suggested that it is mainly composed of aromatic acids, phenolic compounds, and their derivatives, with only traces of amino acids. C2 is associated with the atmospheric chemical reaction of biomass burning and/or biogenic organic molecules, with a relatively lower degree of oxidation, which are more abundant in Guangzhou WSOM (56 %–69 %). C3, in contrast, is mainly attributed to highly oxygenated organic molecules derived from soil and atmospheric aging processes and has a relatively higher contribution in Chuzhou WSOM (23 %). These findings provide new insights into the analysis of chemical properties and sources of atmospheric fluorophores using the EEM method.

Aqueous-phase photochemical oxidation of water-soluble brown carbon aerosols arising from solid biomass fuel burning

The fate of BrC in aqueous systems such as clouds and fog droplets does not depend on solid biomass types.