Fraction Of Brown Carbon Research Articles

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

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

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

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

Mass and Light Absorption Properties of Atmospheric Carbonaceous Aerosols over the Outflow Regions of Indo-Gangetic Plain

The uncertainty associated with carbonaceous aerosols in climate models becomes an obstacle to evaluating their harmful environmental effects. Brown Carbon (BrC) has recently become an eye-catching carbonaceous aerosol in ambient air because of its strong light absorption properties. The optical properties of soluble BrC are well studied in South Asia, one of the largest emitters. However, the absorption property of strong light-absorbing insoluble BrC is highly uncertain because of their complex mixing. Besides, the simultaneous apportionment of light-absorbing carbonaceous aerosol constituents as a function of wavelengths is seldom explored. The present study aims to study mass as well as apportionment of absorption properties of Black Carbon (BC) and different BrC chromophores using a multi-wavelength thermal-optical carbon analyzer over the least explored Eastern part of India to fill the knowledge gap. The output suggested that the primary emission sources dominate the carbonaceous aerosol mass; thus, the primary emission reductions will be helpful in improving the local air quality. The BrC is the dominant light-absorbing carbonaceous aerosol in the ultraviolet wavelengths. Besides, significant light absorption by BrC chromophores in near-infrared wavelengths (up to ∼50% of total aerosol absorption) suggested the absorption by BrC in longer wavelengths cannot be neglected. The insoluble fraction of BrC (Tar-BrC), which has a property identical to BC, contributes significantly to light absorption and is more than 50% of total absorption by aerosols in shorter ≤635 nm wavelengths. The present study also revealed that the contribution of Tar-BrC is more pronounced in the Indo-Gangetic Plain (IGP) outflow region than in the IGP emission source regions.

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.

Relationship between Land Use and Spatial Variability of Atmospheric Brown Carbon and Black Carbon Aerosols in Amazonia

The aerosol radiative effect is an important source of uncertainty in estimating the anthropogenic impact of global climate change. One of the main open questions is the role of radiation absorption by aerosols and its relation to land use worldwide, particularly in the Amazon Rainforest. Using AERONET (Aerosol Robotic Network) long-term measurements of aerosol optical depth (AOD) at a wavelength of 500 nm and absorption AOD (AAOD) at wavelengths of 440, 675, and 870 nm, we estimated the fraction and seasonality of the black carbon (BC) and brown carbon (BrC) contributions to absorption at 440 nm. This was conducted at six Amazonian sites, from central Amazon (Manaus and the Amazon Tall Tower Observatory—ATTO) to the deforestation arc (Rio Branco, Cuiabá, Ji-Paraná, and Alta Floresta). In addition, land use and cover data from the MapBiomas collection 6.0 was used to access the land transformation from forest to agricultural areas on each site. The results showed, for the first time, important geographical and seasonal variability in the aerosol optical properties, particularly the BC and BrC contributions. We observed a clear separation between dry and wet seasons, with BrC consistently accounting for an average of approximately 12% of the aerosol AAOD at 440 nm in the deforestation arc. In central Amazon, the contribution of BrC was approximately 25%. A direct relationship between the reduction in forests and the increase in the area dedicated to agriculture was detected. Moreover, places with lower fractions of forest had a smaller fraction of BrC, and regions with higher fractions of agricultural areas presented higher fractions of BC. Therefore, significant changes in AOD and AAOD are likely related to land-use transformations and biomass burning emissions, mainly during the dry season. The effects of land use change could introduce differences in the radiative balance in the different Amazonian regions. The analyses presented in this study allow a better understanding of the role of aerosol emissions from the Amazon Rainforest that could have global impacts.

Are fireworks a significant episodic source of brown carbon?

We hypothesize that firework events involving the combustion of charcoal fuel, organic binders, metal salts, and cellulose-based wrapping material could be significant transient sources of aerosol brown carbon (BrC). To test this, we couple high time-resolution (1min) measurements of black carbon (BC) and BrC absorption from a 7-wavelength aethalometer with time-integrated (12-24h) measurements of filter extracts, i.e., UV-visible, fluorescence, and Fourier-transformed infrared (FT-IR) signatures of BrC, total and water-soluble organic carbon (OC and WSOC), ionic species, and firework tracer metals during a sampling campaign covering the Diwali fireworks episode in India. In sharp contrast to BC, BrC absorption shows a distinct and considerable rise of 2-4 times during the Diwali period, especially during the hours of peak firework activity, as compared to the background. Fluorescence profiles suggest enrichment of humic-like substances (HULIS) in the firework plume, while the enhancement of BrC absorption in the 400-500nm range suggests the presence of nitroaromatic compounds (NACs). Considerable contributions of WSOC and secondary organics to OC (44.1% and 31.2%, respectively) and of the water-soluble fraction of BrC to total BrC absorption (71.0%) during the Diwali period point toward an atmospherically processed, polar signature of firework-related BrC, which is further confirmed by FT-IR profiles. This aqueous BrC exerts a short-lived but strong effect on atmospheric forcing (12.0% vis-à-vis BC in the UV spectrum), which could affect tropospheric chemistry via UV attenuation and lead to a stabilization of the post-Diwali atmosphere, resulting in enhanced pollutant build-up and exposure.

Columnar aerosol types and compositions over peninsular Southeast Asia based on long-term AERONET data

Aerosol chemical components such as black carbon (BC) and brown carbon (BrC) regulate aerosol optical properties, which in turn drive the atmospheric radiative forcing estimations due to aerosols. In this study, we used the long-term measurements from AERONET (Aerosol Robotic Network) to better understand the aerosol types and composition with respect to their seasonal and spatial variabilities in peninsular Southeast Asia (PSEA, here defined as Vietnam, Cambodia, Thailand, Laos, and Myanmar). Two methods (i.e., aerosol type cluster and aerosol component retrieval) were applied to determine the aerosol type and chemical composition during the biomass-burning (BB) season. AERONET sites in northern PSEA showed a higher AOD (aerosol optical depth) compared to that of southern PSEA. Differences in land use pattern, geographic location, and weather regime caused much of the aerosol variability over PSEA. Lower single-scattering albedo (SSA) and higher fine-mode fraction (FMF) values were observed in February and March, suggesting the predominance of BB type aerosols with finer and stronger absorbing particles during the dry season. However, we also found that the peak BB month (i.e., March) in northern PSEA may not coincide with the lowest SSA once dust particles have mixed with the other aerosols. Furthermore, we investigated two severe BB events in March of 2014 and 2015, revealing a significant BrC fraction during BB event days. On high AOD days, although the BC fraction was high, the BrC fraction remained low due to lack of aerosol aging. This study highlights the dominance of carbonaceous aerosols in the PSEA atmosphere during the BB season, while also revealing that transported dust particles and BrC aerosol aging may introduce uncertainties into the aerosol radiative forcing calculation.

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.

Water-Insoluble Organics Dominate Brown Carbon in Wintertime Urban Aerosol of China: Chemical Characteristics and Optical Properties.

The chromophores responsible for light absorption in atmospheric brown carbon (BrC) are not well characterized, which hinders our understanding of BrC chemistry, the links with optical properties, and accurate model representations of BrC to global climate and atmospheric oxidative capacity. In this study, the light absorption properties and chromophore composition of three BrC fractions of different polarities were characterized for urban aerosol collected in Xi'an and Beijing in winter 2013-2014. These three BrC fractions show large differences in light absorption and chromophore composition, but the chromophores responsible for light absorption are similar in Xi'an and Beijing. Water-insoluble BrC (WI-BrC) fraction dominates the total BrC absorption at 365 nm in both Xi'an (51 ± 5%) and Beijing (62 ± 13%), followed by a humic-like fraction (HULIS-BrC) and high-polarity water-soluble BrC. The major chromophores identified in HULIS-BrC are nitrophenols and carbonyl oxygenated polycyclic aromatic hydrocarbons (OPAHs) with 2-3 aromatic rings (in total 18 species), accounting for 10% and 14% of the light absorption of HULIS-BrC at 365 nm in Xi'an and Beijing, respectively. In comparison, the major chromophores identified in WI-BrC are PAHs and OPAHs with 4-6 aromatic rings (in total 16 species), contributing 6% and 8% of the light absorption of WI-BrC at 365 nm in Xi'an and Beijing, respectively.

Atmospheric evolution of molecular-weight-separated brown carbon from biomass burning

Abstract. Biomass burning is a major source of atmospheric brown carbon (BrC), and through its absorption of UV/VIS radiation, it can play an important role in the planetary radiative balance and atmospheric photochemistry. The considerable uncertainty of BrC impacts is associated with its poorly constrained sources, transformations, and atmospheric lifetime. Here we report laboratory experiments that examined changes in the optical properties of the water-soluble (WS) BrC fraction of laboratory-generated biomass burning particles from hardwood pyrolysis. Effects of direct UVB photolysis and OH oxidation in the aqueous phase on molecular-weight-separated BrC were studied. Results indicated that the majority of low-molecular-weight (MW) BrC (<400 Da) was rapidly photobleached by both direct photolysis and OH oxidation on an atmospheric timescale of approximately 1 h. High MW BrC (≥400 Da) underwent initial photoenhancement up to ∼15 h, followed by slow photobleaching over ∼10 h. The laboratory experiments were supported by observations from ambient BrC samples that were collected during the fire seasons in Greece. These samples, containing freshly emitted to aged biomass burning aerosol, were analyzed for both water- and methanol-soluble BrC. Consistent with the laboratory experiments, high-MW BrC dominated the total light absorption at 365 nm for both methanol and water-soluble fractions of ambient samples with atmospheric transport times of 1 to 68 h. These ambient observations indicate that overall, biomass burning BrC across all molecular weights has an atmospheric lifetime of 15 to 28 h, consistent with estimates from previous field studies – although the BrC associated with the high-MW fraction remains relatively stable and is responsible for light absorption properties of BrC throughout most of its atmospheric lifetime. For ambient samples of aged (>10 h) biomass burning emissions, poor linear correlations were found between light absorptivity and levoglucosan, consistent with other studies suggesting a short atmospheric lifetime for levoglucosan. However, a much stronger correlation between light absorptivity and total hydrous sugars was observed, suggesting that they may serve as more robust tracers for aged biomass burning emissions. Overall, the results from this study suggest that robust model estimates of BrC radiative impacts require consideration of the atmospheric aging of BrC and the stability of high-MW BrC.

Abundance and Light Absorption Properties of Brown Carbon Emitted from Residential Coal Combustion in China.

Brown carbon (BrC) fractions, including water-soluble organic carbon (WSOC), water-soluble humic-like substances (HULISw), alkaline soluble organic carbon (ASOC), and methanol soluble organic carbon (MSOC) were extracted from particles emitted from the residential combustion of coal with different geological maturities. The abundances and light absorption properties of these BrC fractions were comprehensively studied. The results showed that the abundances of the different constituents of the BrC fraction varied greatly with the extraction solvent, accounting for 4.3%-46%, 2.3%-23%, 3.2%-14%, and 76%-98% of the total carbon content in particles. The specific UV-vis absorbance (SUVA254) of BrC fractions followed the order of MSOC > ASOC > HULISw > WSOC. The WSOC and MSOC fractions from the combustion of low maturity coal had relatively low SUVA254 and high SR values. The mass absorption efficiencies (MAE365) for ASOC and MSOC were higher than for WSOC, and WSOC and MSOC from low maturity coal combustion had relatively low levels of light absorption. These findings indicated that coal combustion is a potential source of atmospheric BrC and the abundance and light absorption of the coal combustion-derived BrC fractions were strongly dependent on the extraction methods used and the coal maturity rather than the coal shapes.

Optical properties and oxidative potential of water- and alkaline-soluble brown carbon in smoke particles emitted from laboratory simulated biomass burning

Biomass burning (BB) is an important source of brown carbon (BrC) in atmospheric aerosols. The aim of this study is to investigate the light absorbing ability and oxidative potential of BB-derived BrC fractions (including not only the water soluble fraction but the water-insoluble ones). For this purpose, BrC fractions in the smoke particles (PM2.5) generated from burning of crop residues (rice straw, wheat straw, and corn straw) and wood stems (pine wood and Chinese fir) were sequentially extracted and fractionated into water- and alkaline-soluble extracts, and water- and alkaline-soluble humic-like substances (HULISWS and HULISAS). Their organic carbon (OC) contents, light absorption, and oxidative potential were comparably investigated. The results showed that the OC within water extracts (WSOC) and alkaline extracts (ASOC), and HULISWS and HULISAS accounted for 24.8%–28.5%, 10.7%–15.3%, 12.4%–16.6%, and 2.2%–5.6% of the BB smoke PM2.5 mass, respectively, thereby indicating that BB potentially influenced the atmospheric water-soluble and alkaline-soluble BrC levels. The BrC fractions had similar absorption patterns, but they also exhibited distinct features. BrC SUVA254 decreased in the order of: HULISAS (3.68–4.58 m2/gC) > HULISWS (2.99–3.72 m2/gC) > WSOC (2.54–2.80 m2/gC) > ASOC (1.30–2.06 m2/gC). BrC MAE365 was in the order of: HULISAS (1.95–2.40 m2/gC) > HULISWS (1.12–1.60 m2/gC) > WSOC (0.86–1.23 m2/gC) and ASOC (0.54–0.95 m2/gC). These results suggest that the HULIS fractions exhibited high aromaticity and strong light absorption. Moreover, BB extractable fractions exhibited a strong oxidative potential to generate reactive oxygen species, and the dithiothreitol activity followed the order of: water extracts (12.5–20.6 pmol/min/μg) > alkaline extracts (9.3–16.2 pmol/min/μg) > HULISWS (6.6–10.7 pmol/min/μg) > HULISAS (3.7–7.1 pmol/min/μg). The chemical characteristics of the BB BrC fractions also varied among the biomass types, where the crop residue smoke PM2.5 contained more BrC than wood smoke PM2.5, but the water-soluble BrC in the former generally exhibited weaker light absorption than the latter.

Light absorption by polar and non-polar aerosol compounds from laboratory biomass combustion

Abstract. Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of strongly light-absorbing black carbon (BC) and of organic carbon (OC) with its light-absorbing fraction – brown carbon (BrC). There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while the non-polar BrC fraction has been largely ignored. In the present study, the light absorption properties of polar and non-polar fractions of fresh and aged BB emissions were examined to estimate the contribution of different-polarity organic compounds to the light absorption properties of BB aerosols. In our experiments, four globally and regionally important fuels were burned under flaming and smoldering conditions in the Desert Research Institute (DRI) combustion chamber. To mimic atmospheric oxidation processes (5–7 days), BB emissions were aged using an oxidation flow reactor (OFR). Fresh and OFR-aged BB aerosols were collected on filters and extracted with water and hexane to study absorption properties of polar and non-polar organic species. Results of spectrophotometric measurements (absorption weighted by the solar spectrum and normalized to mass of fuel consumed) over the 190 to 900 nm wavelength range showed that the non-polar (hexane-soluble) fraction is 2–3 times more absorbing than the polar (water-soluble) fraction. However, for emissions from fuels that undergo flaming combustion, an increased absorbance was observed for the water extracts of oxidized/aged emissions while the absorption of the hexane extracts was lower for the aged emissions for the same type of fuels. Absorption Ångström exponent (AAE) values, computed based on absorbance values from spectrophotometer measurements, were changed with aging and the nature of this change was fuel dependent. The light absorption by humic-like substances (HULIS) was found to be higher in fuels characteristic of the southwestern USA. The absorption of the HULIS fraction was lower for OFR-aged BB emissions. Comparison of the light absorption properties of different-polarity extracts (water, hexane, HULIS) provides insight into the chemical nature of BB BrC and its transformation during oxidation processes.

The Brown–Black Continuum of Light-Absorbing Combustion Aerosols

Brown carbon (BrC) exhibits highly variable light-absorption properties, with the imaginary part of the refractive indices (k) varying over several orders of magnitude. This poorly understood variability poses a challenge to accurately determining the BrC climate effect. Here, we present a framework to explain the variability in BrC k. We hypothesize that a fraction of BrC is composed of black-carbon (BC) precursors whose transformation to BC is not complete, and that there is a continuum of light-absorption properties along which BC and BrC lie. To test this hypothesis, we performed controlled-combustion experiments using benzene and toluene. By systematically varying the combustion conditions, we isolated BrC components along the brown–black continuum progressing from light (k = 0.004 at 550 nm) to dark (k = 0.25 at 550 nm). Using laser-desorption-ionization mass spectrometry and thermodenuder measurements, we show that the BrC progression from light to dark is associated with an increase in molecular s...

Separation of brown carbon from black carbon for IMPROVE and Chemical Speciation Network PM2.5 samples

ABSTRACTThe replacement of the Desert Research Institute (DRI) model 2001 with model 2015 thermal/optical analyzers (TOAs) results in continuity of the long-term organic carbon (OC) and elemental carbon (EC) database, and it adds optical information with no additional carbon analysis effort. The value of multiwavelength light attenuation is that light absorption due to black carbon (BC) can be separated from that of brown carbon (BrC), with subsequent attribution to known sources such as biomass burning and secondary organic aerosols. There is evidence of filter loading effects for the 25% of all samples with the highest EC concentrations based on the ratio of light attenuation to EC. Loading corrections similar to those used for the seven-wavelength aethalometer need to be investigated. On average, nonurban Interagency Monitoring of PROtected Visual Environments (IMPROVE) samples show higher BrC fractions of short-wavelength absorption than urban Chemical Speciation Network (CSN) samples, owing to greater influence from biomass burning and aged aerosols, as well as to higher primary BC contributions from engine exhaust at urban sites. Sequential samples taken during an Everglades National Park wildfire demonstrate the evolution from flaming to smoldering combustion, with the BrC fraction increasing as smoldering begins to dominate the fire event.Implications: The inclusion of seven wavelengths in thermal/optical carbon analysis of speciated PM2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) samples allows contributions from biomass burning and secondary organic aerosols to be estimated. This separation is useful for evaluating control strategy effectiveness, identifying exceptional events, and determining natural visibility conditions.

Speciation and Sources of Brown Carbon in Precipitation at Seoul, Korea: Insights from Excitation-Emission Matrix Spectroscopy and Carbon Isotopic Analysis.

Brown carbon (BrC) plays a significant role in the Earth's radiative balance, yet its sources and chemical composition remain poorly understood. In this work, we investigated BrC in the atmospheric environment of Seoul by characterizing dissolved organic matter in precipitation using excitation-emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC). The two independent fluorescent components identified by PARAFAC were attributed to humic-like substance (HULIS) and biologically derived material based on their significant correlations with measured HULIS isolated using solid-phase extraction and total hydrolyzable tyrosine. The year-long observation shows that HULIS contributes to 66 ± 13% of total fluorescence intensity of our samples on average. By using dual carbon (13C and 14C) isotopic analysis conducted on isolated HULIS, the HULIS fraction of BrC was found to be primarily derived from biomass burning and emission of terrestrial biogenic gases and particles (>70%), with minor contributions from fossil-fuel combustion. The knowledge derived from this study could contribute to the establishment of a characterizing system of BrC components identified by EEM spectroscopy. Our work demonstrates that, EEM fluorescence spectroscopy is a powerful tool in BrC study, on the basis of its chromophore resolving power, allowing investigation into individual components of BrC by other organic matter characterization techniques.

Radiative forcing of organic aerosol in the atmosphere and on snow: Effects of SOA and brown carbon

Organic aerosols (OA) play an important role in climate change. However, very few calculations of global OA radiative forcing include secondary organic aerosol (SOA) or the light-absorbing part of OA (brown carbon). Here we use a global model to assess the radiative forcing associated with the change in primary organic aerosol (POA) and SOA between present-day and preindustrial conditions in both the atmosphere and the land snow/sea ice. Anthropogenic emissions are shown to substantially influence the SOA formation rate, causing it to increase by 29 Tg/yr (93%) since preindustrial times. We examine the effects of varying the refractive indices, size distributions for POA and SOA, and brown carbon fraction in SOA. The increase of SOA exerts a direct forcing ranging from −0.12 to −0.31 W m−2 and a first indirect forcing in warm-phase clouds ranging from −0.22 to −0.29 W m−2, with the range due to different assumed SOA size distributions and refractive indices. The increase of POA since preindustrial times causes a direct forcing varying from −0.06 to −0.11 W m−2, when strongly and weakly absorbing refractive indices for brown carbon are used. The change in the total OA exerts a direct forcing ranging from −0.14 to −0.40 W m−2. The atmospheric absorption from brown carbon ranges from +0.22 to +0.57 W m−2, which corresponds to 27%~70% of the black carbon (BC) absorption predicted in the model. The radiative forcing of OA deposited in land snow and sea ice ranges from +0.0011 to +0.0031 W m−2 or as large as 24% of the forcing caused by BC in snow and ice simulated by the model.