Light-absorbing Organic Carbon Research Articles

Characteristics of light absorption and environmental effects of Brown carbon aerosol in Chongqing during summer and winter based on online measurement: Implications of secondary formation

Light-absorbing organic carbon (i.e., brown carbon, BrC) significantly contributes to light absorption and radiative forcing in the atmospheric particles. However, the secondary formation of BrC and optical properties of secondary BrC are poorly understood. In this study, we analyzed and evaluated the light absorption and environmental effects of BrC and secondary BrC from July 1st to 31st, 2022 (summer) and January 20th to February 20th, 2023 (winter) in Chongqing. BrC and secondary BrC light absorption were estimated via a seven-wavelength aethalometer and the statistical approach. The average values of secondary BrC light absorption (AbsBrC,sec,λ) accounted for 46.2–56.5% of AbsBrC. AbsBrC,370 and AbsBrC,sec,370 were significantly higher during winter (26.2 ± 13.2 and 9.1 ± 5.2 Mm−1 respectively) than that during summer (7.2 ± 4.1 and 5.2 ± 3.5 Mm−1 respectively) (p < 0.001), suggesting secondary formation played an essential role in BrC. A diurnal cycle of AbsBrC,sec,370 was explained by the photobleaching of light-absorbing chromophores under the oxidizing conditions in the daytime, and the formation of chromophores via aqueous reactions with NH4+ and NOx after sunset during winter. PSCF analysis showed that transport of anthropogenic emissions from the northeastern and southeastern areas of Chongqing was the important source of the secondary BrC in PP during winter. During winter, the average values of SFEBrC and SFEBrC,sec were 31.9 and 27.4 W g−1 lower than that during summer (64.7 and 44.5 W g−1), respectively. In contrast, J[NO2] values of SFEBrC and SFEBrC,sec decreased by 23.3% and 8.7% during winter higher than that during summer (19.9% and 5.6%), indicating that BrC and secondary BrC cause substantial radiative effects and atmospheric photochemistry. Overall, this study is helpful in understanding the characterization and secondary formation of BrC and accurately evaluating the environmental effects of BrC in Chongqing.

Rapid aqueous-phase dark reaction of phenols with nitrosonium ions: Novel mechanism for atmospheric nitrosation and nitration at low pH.

Dark aqueous-phase reactions involving the nitrosation and nitration of aromatic organic compounds play a significant role in the production of light-absorbing organic carbon in the atmosphere. This process constitutes a crucial aspect of tropospheric chemistry and has attracted growing research interest, particularly in understanding the mechanisms governing nighttime reactions between phenols and nitrogen oxides. In this study, we present new findings concerning the rapid dark reactions between phenols containing electron-donating groups and inorganic nitrite in acidic aqueous solutions with pH levels <3.5. This reaction generates a substantial amount of nitroso- and nitro-substituted phenolic compounds, known for their light-absorbing properties and toxicity. In experiments utilizing various substituted phenols, we demonstrate that their reaction rates with nitrite depend on the electron cloud density of the benzene ring, indicative of an electrophilic substitution reaction mechanism. Control experiments and theoretical calculations indicate that the nitrosonium ion (NO+) is the reactive nitrogen species responsible for undergoing electrophilic reactions with phenolate anions, leading to the formation of nitroso-substituted phenolic compounds. These compounds then undergo partial oxidation to form nitro-substituted phenols through reactions with nitrous acid (HONO) or other oxidants like oxygen. Our findings unveil a novel mechanism for swift atmospheric nitrosation and nitration reactions that occur within acidic cloud droplets or aerosol water, providing valuable insights into the rapid nocturnal formation of nitrogen-containing organic compounds with significant implications for climate dynamics and human health.

Dark brown carbon from wildfires: a potent snow radiative forcing agent?

Deposition of wildfire smoke on snow contributes to its darkening and accelerated snowmelt. Recent field studies have identified dark brown carbon (d-BrC) to contribute 50–75% of shortwave absorption in wildfire smoke. d-BrC is a distinct class of water-insoluble, light-absorbing organic carbon that co-exists in abundance with black carbon (BC) in snow across the world. However, the importance of d-BrC as a snow warming agent relative to BC remains unexplored. We address this gap using aerosol-snow radiative transfer calculations on datasets from laboratory and field measurement. We show d-BrC increases the annual mean snow radiative forcing between 0.6 and 17.9 W m−2, corresponding to different wildfire smoke deposition scenarios. This is a 1.6 to 2.1-fold enhancement when compared with BC-only deposition on snow. This study suggests d-BrC is an important contributor to snowmelt in midlatitude glaciers, where ~40% of the world’s glacier surface area resides.

Peatland Wildfires Enhance Nitrogen-Containing Organic Compounds in Marine Aerosols over the Western Pacific.

Peatland wildfires contribute significantly to the atmospheric release of light-absorbing organic carbon, often referred to as brown carbon. In this study, we examine the presence of nitrogen-containing organic compounds (NOCs) within marine aerosols across the Western Pacific Ocean, which are influenced by peatland fires from Southeast Asia. Employing ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) in electrospray ionization (ESI) positive mode, we discovered that NOCs are predominantly composed of reduced nitrogenous bases, including CHN+ and CHON+ groups. Notably, the count of NOC formulas experiences a marked increase within plumes from peatland wildfires compared to those found in typical marine air masses. These NOCs, often identified as N-heterocyclic alkaloids, serve as potential light-absorbing chromophores. Furthermore, many NOCs demonstrate pyrolytic stability, engage in a variety of substitution reactions, and display enhanced hydrophilic properties, attributed to chemical processes such as methoxylation, hydroxylation, methylation, and hydrogenation that occur during emission and subsequent atmospheric aging. During the daytime atmospheric transport, aging of aromatic N-heterocyclic compounds, particularly in aliphatic amines prone to oxidation and reactions with amine, was observed. The findings underscore the critical role of peatland wildfires in augmenting nitrogen-containing organics in marine aerosols, underscoring the need for in-depth research into their effects on marine ecosystems and regional climatic conditions.

Quantifying the Light-Absorption Properties and Molecular Composition of Brown Carbon Aerosol from Sub-Saharan African Biomass Combustion.

Sub-Saharan Africa is a hotspot for biomass burning (BB)-derived carbonaceous aerosols, including light-absorbing organic (brown) carbon (BrC). However, the chemically complex nature of BrC in BB aerosols from this region is not fully understood. We generated smoke in a chamber through smoldering combustion of common sub-Saharan African biomass fuels (hardwoods, cow dung, savanna grass, and leaves). We quantified aethalometer-based, real-time light-absorption properties of BrC-containing organic-rich BB aerosols, accounting for variations in wavelength, fuel type, relative humidity, and photochemical aging conditions. In filter samples collected from the chamber and Botswana in the winter, we identified 182 BrC species, classified into lignin pyrolysis products, nitroaromatics, coumarins, stilbenes, and flavonoids. Using an extensive set of standards, we determined species-specific mass and emission factors. Our analysis revealed a linear relationship between the combined BrC species contribution to chamber-measured BB aerosol mass (0.4-14%) and the mass-absorption cross-section at 370 nm (0.2-2.2 m2 g-1). Hierarchical clustering resolved key molecular-level components from the BrC matrix, with photochemically aged emissions from leaf and cow-dung burning showing BrC fingerprints similar to those found in Botswana aerosols. These quantitative findings could potentially help refine climate model predictions, aid in source apportionment, and inform effective air quality management policies for human health and the global climate.

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.

Shortwave absorption by wildfire smoke dominated by dark brown carbon

Wildfires emit large amounts of black carbon and light-absorbing organic carbon, known as brown carbon, into the atmosphere. These particles perturb Earth’s radiation budget through absorption of incoming shortwave radiation. It is generally thought that brown carbon loses its absorptivity after emission in the atmosphere due to sunlight-driven photochemical bleaching. Consequently, the atmospheric warming effect exerted by brown carbon remains highly variable and poorly represented in climate models compared with that of the relatively nonreactive black carbon. Given that wildfires are predicted to increase globally in the coming decades, it is increasingly important to quantify these radiative impacts. Here we present measurements of ensemble-scale and particle-scale shortwave absorption in smoke plumes from wildfires in the western United States. We find that a type of dark brown carbon contributes three-quarters of the short visible light absorption and half of the long visible light absorption. This strongly absorbing organic aerosol species is water insoluble, resists daytime photobleaching and increases in absorptivity with night-time atmospheric processing. Our findings suggest that parameterizations of brown carbon in climate models need to be revised to improve the estimation of smoke aerosol radiative forcing and associated warming.

Size-resolved light-absorbing organic carbon and organic molecular markers in Nanjing, east China: Seasonal variations and sources

Owing to the potential influence of light-absorbing organic carbon (OC), also termed “brown carbon” (BrC), on the planetary radiation budget, many studies have focused on its absorption in single-sized ranges of particulate matter (PM). However, the size distribution and organic tracer-based source apportionment of BrC absorption have not been extensively investigated. In this study, size-resolved PM samples were collected using multi-stage impactors from eastern Nanjing during each season in 2017. The light absorption of methanol-extractable OC at 365 nm (Abs365, Mm−1) was determined using spectrophotometry, and a series of organic molecular markers (OMMs) was measured using a gas chromatography-mass spectrometer. Fine PM with an aerodynamic diameter <2.1 μm (PM2.1) dominated Abs365 (79.8 ± 10.4%) of the total size ranges with maxima and minima in winter and summer, respectively. The distributions of Abs365 shifted to larger PM sizes from winter to spring and summer due to lower primary emissions and increased BrC chromophores in dust. Except for low-volatility (po,*L < 10−10 atm) polycyclic aromatic hydrocarbons (PAHs), the non-polar OMMs, including n-alkanes, PAHs, oxygenated PAHs, and steranes, showed a bimodal distribution pattern. Secondary products of biogenic precursors and biomass burning tracers presented a unimodal distribution peaking at 0.4–0.7 μm, while sugar alcohols and saccharides were enriched in coarse PM. Their seasonal variations in average concentrations reflected intense photochemical reactions in summer, more biomass burning emissions in winter, and stronger microbial activity in spring and summer. Positive matrix factorization was used for the source apportionment of Abs365 in fine and coarse PM samples. Biomass burning contributed an average of 53.9% to the Abs365 of PM2.1 extracts. The Abs365 of coarse PM extracts was associated with various dust-related sources where the aging processes of aerosol organics could occur.

Compensatory effect of biomass burning on black carbon concentrations during COVID-19 lockdown at a high-altitude station in SW India

The characteristics of black carbon (BC) aerosols, their sources, and their impact on atmospheric radiative forcing were extensively studied during the COVID-19 lockdown (28th March–31st May 2020) at a high-altitude rural site over the Western Ghats in southwest India. BC concentration and the contribution of BC originating from biomass burning (BCbb) estimated from the aethalometer model during the lockdown period were compared with the same periods in 2017 and 2018 and with the pre-lockdown period (1st February to March 20, 2020). BC concentrations were 44, 19, and 17% lower during the lockdown period compared with the pre-lockdown periods of 2020 and similar periods (28th March to 31st May) of 2017 and 2018, respectively. BCbb contributed ∼50% to total BC during the lockdown period of 2020 and compensated for the decrease in BC concentration due to lower traffic emissions. The characteristics of light-absorbing organic carbon (brown carbon; BrC) absorption at 370 nm were evaluated during the lockdown and the pre-lockdown periods of 2020, 2017, and 2018. The BrC was estimated to be the highest during the lockdown period of 2020. Finally, atmospheric radiative forcing was calculated using the mean BC concentration during the pre-lockdown, lockdown, and similar periods (28th March to 31st May) of 2017 and 2018.

Global brown carbon emissions from combustion sources

Light-absorbing organic carbon (OC), sometimes known as Brown Carbon (BrC), has been recognized as an important fraction of carbonaceous aerosols substantially affecting radiative forcing. This study firstly developed a bottom-up estimate of global primary BrC, and discussed its spatiotemporal distribution and source contributions from 1960 to 2010. The global total primary BrC emission from both natural and anthropogenic sources in 2010 was 7.26 (5.98–8.93 as an interquartile range) Tg, with 43.5% from anthropogenic sources. High primary BrC emissions were in regions such as Africa, South America, South and East Asia with natural sources (wild fires and deforestation) contributing over 70% in the former two regions, while in East Asia, anthropogenic sources, especially residential solid fuel combustion, accounted for over 80% of the regional total BrC emissions. Globally, the historical trend was mainly driven by anthropogenic sources, which increased from 1960 to 1990 and then started to decline. Residential emissions significantly impacted on emissions and temporal trends that varied by region. In South and Southeast Asia, the emissions increased obviously due to population growth and a slow transition from solid fuels to clean modern energies in the residential sector. It is estimated that in primary OC, the global average was about 20% BrC, but this ratio varied from 13% to 47%, depending on sector and region. In areas with high residential solid fuel combustion emissions, the ratio was generally twice the value in other areas. Uncertainties in the work are associated with the concept of BrC and measurement technologies, pointing to the need for more studies on BrC analysis and quantification in both emissions and the air.

An overestimation of light absorption of brown carbon in ambient particles caused by using filters with large pore size

As an important component of carbonaceous particles, organic carbon (OC) plays a significant role in radiative forcing in the atmosphere. Recently, the warming effect of light-absorbing OC has been emphasized. Water-soluble organic carbon (WSOC) is commonly used as a surrogate to investigate the light absorption of OC. Thus far, filters with 0.45 μm (PS1) and 0.20 μm pore sizes (PS2) are both used to investigate the light absorption of WSOC, which may cause large divergent results. In this study, we found that the light absorption ability of WSOC treated with PS1 was higher than that of PS2 due to the extinction of suspended particles (e.g., black carbon) with particle size between 0.20 μm and 0.45 μm, although the concentrations of WSOC treated with PS1 and PS2 were very close. This phenomenon was more remarkable at visible wavelengths, resulting in an overestimation of the warming effect of WSOC by 9%–22% for aerosol samples treated by PS1, with the highest values occurring in samples heavily influenced by fossil fuel burning emissions. An overestimation of WSOC light absorption treated by PS1 occurred in the investigated ambient aerosol samples from three sites, so it may be a general phenomenon that also exists in other regions of the world. Therefore, to achieve the actual solar radiative forcing of OC in the atmosphere, it is recommended to use PS2 in the future, and reported data of WSOC treated by PS1 should be re-evaluated.

Source-specific light absorption by carbonaceous components in the complex aerosol matrix from yearly filter-based measurements

Abstract. Understanding the sources of light-absorbing organic (brown) carbon (BrC) and its interaction with black carbon (BC) and other non-refractory particulate matter (NR-PM) fractions is important for reducing uncertainties in the aerosol direct radiative forcing. In this study, we combine multiple filter-based techniques to achieve long-term, spectrally resolved, source- and species-specific atmospheric absorption closure. We determine the mass absorption efficiency (MAE) in dilute bulk solutions at 370 nm to be equal to 1.4 m2 g−1 for fresh biomass smoke, 0.7 m2 g−1 for winter-oxygenated organic aerosol (OA), and 0.13 m2 g−1 for other less absorbing OA. We apply Mie calculations to estimate the contributions of these fractions to total aerosol absorption. While enhanced absorption in the near-UV has been traditionally attributed to primary biomass smoke, here we show that anthropogenic oxygenated OA may be equally important for BrC absorption during winter, especially at an urban background site. We demonstrate that insoluble tar balls are negligible in residential biomass burning atmospheric samples of this study and thus could attribute the totality of the NR-PM absorption at shorter wavelengths to methanol-extractable BrC. As for BC, we show that the mass absorption cross-section (MAC) of this fraction is independent of its source, while we observe evidence for a filter-based lensing effect associated with the presence of NR-PM components. We find that bare BC has a MAC of 6.3 m2 g−1 at 660 nm and an absorption Ångström exponent of 0.93 ± 0.16, while in the presence of coatings its absorption is enhanced by a factor of ∼ 1.4. Based on Mie calculations of closure between observed and predicted total light absorption, we provide an indication for a suppression of the filter-based lensing effect by BrC. The total absorption reduction remains modest, ∼ 10 %–20 % at 370 nm, and is restricted to shorter wavelengths, where BrC absorption is significant. Overall, our results allow an assessment of the relative importance of the different aerosol fractions to the total absorption for aerosols from a wide range of sources and atmospheric ages. When integrated with the solar spectrum at 300–900 nm, bare BC is found to contribute around two-thirds of the solar radiation absorption by total carbonaceous aerosols, amplified by the filter-based lensing effect (with an interquartile range, IQR, of 8 %–27 %), while the IQR of the contributions by particulate BrC is 6 %–13 % (13 %–20 % at the rural site during winter). Future studies that will directly benefit from these results include (a) optical modelling aiming at understanding the absorption profiles of a complex aerosol composed of BrC, BC and lensing-inducing coatings; (b) source apportionment aiming at understanding the sources of BC and BrC from the aerosol absorption profiles; (c) global modelling aiming at quantifying the most important aerosol absorbers.

Measurement report: PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt;-bound nitrated aromatic compounds in Xi'an, Northwest China – seasonal variations and contributions to optical properties of brown carbon

Abstract. Nitrated aromatic compounds (NACs) are a group of key chromophores for brown carbon (light-absorbing organic carbon, i.e., BrC) aerosol, which affects radiative forcing. The chemical composition and sources of NACs and their contributions to BrC absorption, however, are still not well understood. In this study, PM2.5-bound NACs in Xi'an, Northwest China, were investigated for 112 daily PM2.5 filter samples from 2015 to 2016. Both the total concentrations and contributions from individual species of NACs show distinct seasonal variations. The seasonally averaged concentrations of NACs are 2.1 (spring), 1.1 (summer), 12.9 (fall), and 56 ng m−3 (winter). Thereinto, 4-nitrophenol is the major NAC component in spring (58 %). The concentrations of 5-nitrosalicylic acid and 4-nitrophenol dominate in summer (70 %), and the concentrations of 4-nitrocatechol and 4-nitrophenol dominate in fall (58 %) and winter (55 %). The NAC species show different seasonal patterns in concentrations, indicating differences in emissions and formation pathways. Source apportionment results using positive matrix factorization (PMF) further show large seasonal differences in the sources of NACs. Specifically, in summer, NACs were highly influenced by secondary formation and vehicle emissions (∼ 80 %), while in winter, biomass burning and coal combustion contributed the most (∼ 75 %). Furthermore, the light absorption contributions of NACs to BrC are wavelength-dependent and vary greatly by season, with maximum contributions at ∼ 330 nm in winter and fall and ∼ 320 nm in summer and spring. The differences in the contribution to light absorption are associated with the higher mass fractions of 4-nitrocatechol (λmax⁡= 345 nm) and 4-nitrophenol (λmax⁡= 310 nm) in fall and winter, 4-nitrophenol in spring, and 5-nitrosalicylic acid (λmax⁡= 315 nm) and 4-nitrophenol in summer. The mean contributions of NACs to BrC light absorption at a wavelength of 365 nm in different seasons are 0.14 % (spring), 0.09 % (summer), 0.36 % (fall), and 0.91 % (winter), which are about 6–9 times higher than their mass fractional contributions of carbon in total organic carbon. Our results indicate that the composition and sources of NACs have profound impacts on the BrC light absorption.

Light-absorbing Properties and Sources of PM2.5 Organic Components at a Suburban Site in Northern Nanjing

The light absorption of organic components in PM2.5 was investigated at a suburban site in northern Nanjing from September 2018 to September 2019, and PM2.5 compositional data and principal component analysis (PCA) were used to identify the sources of light-absorbing organic carbon (brown carbon, BrC). The results showed that the average light absorption coefficients of water-soluble organic carbon (WSOC) and methanol extractable organic carbon (MEOC) were (3.22±2.18) Mm-1 (Abs365,w) and (7.69±4.93) Mm-1(Abs365,m), respectively. Significant correlations were observed between Abs365,w and mass concentrations of WSOC (r=0.72, P<0.01) and between Abs365,m and mass concentrations of MEOC (r=0.62, P=0.04). Both Abs365,w and Abs365,m exhibited seasonal variations, with higher values during winter than during summer,and higher diel variations at night than during the day. This can be attributed to meteorological characteristics during the winter and nighttime, i.e., decreased boundary layer height and increased atmospheric stability, enhanced primary emissions in winter,and stronger photobleaching effects during the summer and during the day. The annual average Abs365,m/Abs365,w ratio (2.60±0.92) was much larger than the average mass ratio of MEOC/WSOC (1.37±0.30), indicating that the water-insoluble fraction of MEOC had a stronger light absorption effect and dominated BrC absorption. No strong correlation (r<0.60) was observed between WSOC, MEOC, Abs365,m, and mass concentrations of K+, indication that biomass burning was not the main source of BrC in the study location. The mass absorption efficiency of WSOC (MAE365,w) and MEOC (MAE365,m) and their ratios (MAE365,m/MAE365,w) showed similar seasonal variations to Abs365. The average MAE365 value of the water-insoluble fraction of MEOC (4.10±5.15) m2·g-1 was 6.0 and 2.9 times higher than that of MAE365,w and MAE365,m, respectively, suggested that BrC absorption was primarily attributable to water-insoluble components. In comparison to the absorption Ångström exponent of WSOC (ÅWSOC), ÅMEOC displayed marked temporal variability, which might be related to the seasonal variation in the emission of water-insoluble chromophores. According to the PCA results, the light absorption of PM2.5 organic was mainly attributed to secondary formation and anthropogenic primary emissions rather than biomass burning.

Brown carbon light absorption over an urban environment in northern peninsular Southeast Asia.

Light-absorbing organic carbon (or brown carbon, BrC) has been recognized as a critical driver in regional-to-global climate change on account of its significant contribution to light absorption. BrC sources vary from primary combustion processes (burning of biomass, biofuel, and fossil fuel) to secondary formation in the atmosphere. This paper investigated the light-absorbing properties of BrC such as site-specific mass absorption cross-section (MACBrC), absorption Ångström exponent (AAEBrC), and the absorbing component of the refractive index (kBrC) by using light absorption measurements from a 7-wavelength aethalometer over an urban environment of Chiang Mai, Thailand in northern peninsular Southeast Asia (PSEA), from March to April 2016. The contribution of BrC to total aerosol absorption (mean ± SD) was 46±9%, 29±7%, 24±6%, 20±4%, and 15±3% at 370, 470, 520, 590, and 660nm, respectively, highlighting the significant influence of BrC absorption on the radiative imbalance over northern PSEA. Strong and significant associations between BrC light absorption and biomass-burning (BB) organic tracers highlighted the influence of primary BB emissions. The median MACBrC and kBrC values at 370nm were 2.4m2g-1 and 0.12, respectively. The fractional contribution of solar radiation absorbed by BrC relative to BC (mean ± SD) in the 370-950nm range was estimated to be 34±7%, which can significantly influence the regional radiation budget and consequently atmospheric photochemistry. This study provides valuable information to understand BrC absorption over northern PSEA and can be used in model simulations to reassess the regional climatic impact with greater accuracy.

Deposition of brown carbon onto snow: changes in snow optical and radiative properties

Abstract. Light-absorbing organic carbon aerosol – colloquially known as brown carbon (BrC) – is emitted from combustion processes and has a brownish or yellowish visual appearance, caused by enhanced light absorption at shorter visible and ultraviolet wavelengths (0.3 µm≲λ≲0.5 µm). Recently, optical properties of atmospheric BrC aerosols have become the topic of intense research, but little is known about how BrC deposition onto snow surfaces affects the spectral snow albedo, which can alter the resulting radiative forcing and in-snow photochemistry. Wildland fires in close proximity to the cryosphere, such as peatland fires that emit large quantities of BrC, are becoming more common at high latitudes, potentially affecting nearby snow and ice surfaces. In this study, we describe the artificial deposition of BrC aerosol with known optical, chemical, and physical properties onto the snow surface, and we monitor its spectral radiative impact and compare it directly to modeled values. First, using small-scale combustion of Alaskan peat, BrC aerosols were artificially deposited onto the snow surface. UV–Vis absorbance and total organic carbon (TOC) concentration of snow samples were measured for samples with and without artificial BrC deposition. These measurements were used to first derive a BrC (mass) specific absorption (m2 g−1) across the UV–Vis spectral range. We then estimate the imaginary part of the refractive index of deposited BrC aerosol using a volume mixing rule. Single-particle optical properties were calculated using Mie theory, and these values were used to show that the measured spectral snow albedo of snow with deposited BrC was in general agreement with modeled spectral snow albedo using calculated BrC optical properties. The instantaneous radiative forcing per unit mass of total organic carbon deposited to the ambient snowpack was found to be 1.23 (+0.14/-0.11) W m−2 per part per million (ppm). We estimate the same deposition onto a pure snowpack without light-absorbing impurities would have resulted in an instantaneous radiative forcing per unit mass of 2.68 (+0.27/-0.22) W m−2 per ppm of BrC deposited.

Biomass-burning-derived particles from a wide variety of fuels – Part 1: Properties of primary particles

Abstract. Relationships between various optical, physical, and chemical properties of biomass-combustion-derived particles are characterized for particles produced in the laboratory from a wide range of fuels and burn conditions. The modified combustion efficiency (MCE), commonly used to parameterize biomass particle emissions and properties, is shown to generally have weak predictive capabilities, especially for more efficient combustion conditions. There is, however, a strong relationship between many intensive optical properties (e.g., single-scatter albedo, Ångström absorption exponent, mass absorption efficiency) and the organic aerosol-to-black carbon ([OA] ∕ [BC]) mass ratio over a wider range than previously considered (0.3 to 105). The properties of brown carbon (BrC, i.e., light-absorbing organic carbon) also vary with [OA] ∕ [BC]. Coating-induced enhancements (i.e., “lensing” effects) contribute only a minor amount to BC absorption for all of the burns despite some burns producing particles having large ensemble-average coating-to-core mass ratios. The BC–OA mixing state varies strongly with [OA] ∕ [BC]; the fraction of OA that is internally mixed with BC decreases with [OA] ∕ [BC] while the relative amount of OA coated on BC increases. In contrast, there is little relationship between many OA bulk chemical properties and [OA] ∕ [BC], with the O : C and H : C atomic ratios and the relative abundance of a key marker ion (m/z=60, linked to levoglucosan) all showing no dependence on [OA] ∕ [BC]. In contrast, both the organic nitrate fraction of OA and the OA volatility do depend on the [OA] ∕ [BC]. Neither the total particle nor BC-specific size distributions exhibit any clear dependence on the burn conditions or [OA] ∕ [BC], although there is perhaps a dependence on fuel type. Overall, our results expand on existing knowledge to contribute new understanding of the properties of particles emitted from biomass combustion.

Composition and light absorption of N-containing aromatic compounds in organic aerosols from laboratory biomass burning.

This study seeks to understand the compositional details of N-containing aromatic compounds (NACs) emitted during biomass burning (BB) and their contribution to light-absorbing organic carbon (OC), also termed brown carbon (BrC). Three laboratory BB experiments were conducted with two U.S. pine forest understory fuels typical of those consumed during prescribed fires. During the experiments, submicron aerosol particles were collected on filter media and subsequently extracted with methanol and examined for their optical and chemical properties. Significant correlations (p < 0.05) were observed between BrC absorption and elemental carbon (EC)/OC ratios for individual burns data. However, the pooled experimental data indicated that the BB BrC absorption depends on more than the BB fire conditions as represented by the EC/OC ratio. Fourteen NAC formulas were identified in the BB samples, most of which were also observed in simulated secondary organic aerosol (SOA) from photo-oxidation of aromatic VOCs with NOX. However, the molecular structures associated with the identical NAC formula from BB and SOA are different. In this work, the identified NACs from BB are featured by methoxy and cyanate groups, and are predominately generated during the flaming phase. The mass concentrations of identified NACs were quantified using authentic and surrogate standards, and their contributions to bulk light absorption of solvent extractable OC were also calculated. The contributions of identified NACs to organic matter (OM) and BrC absorption were significantly higher in flaming-phase samples than those in smoldering-phase samples, and correlated with EC/OC ratio (p < 0.05) for both individual burns and pooled experimental data, indicating that the formation of NACs from BB largely depends on burn conditions. The average contributions of identified NACs to overall BrC absorption at 365 nm ranged from 0.087 ± 0.024 to 1.22 ± 0.54%, 3 - 10 times higher than their mass contributions to OM (0.023 ± 0.0089 to 0.18 ± 0.067%), so the NACs with light absorption identified in this work from BB are likely strong BrC chromophores. Further studies are warranted to identify more light-absorbing compounds to explain the unknown fraction (> 98%) of BB BrC absorption.

Brown carbon in the continental outflow to the North Indian Ocean.

In this paper, we synthesize the size distribution and optical properties of the atmospheric water-soluble fraction of light-absorbing organic carbon (brown carbon; BrC) in the continental outflow from the Indo-Gangetic Plain (IGP) in South Asia to the North Indian Ocean. A comparison of the mass absorption coefficient of water-soluble BrC (babs-WSBrC-365nm) in PM2.5 with that in PM10 sampled over the Bay of Bengal reveals the dominance of BrC in fine mode. Furthermore, the babs-BrC-365nm shows a significant linear relationship with mass concentrations of airborne particulate matter, water-soluble organic carbon and non-sea-salt-K+ in the continental outflow from the IGP. This observation emphasizes the ubiquitous nature and significant contribution of water-soluble BrC from biomass burning emissions (BBEs). Comparing the absorption properties from this study with global datasets, it is discernible that BBEs dominate BrC absorption. Furthermore, the imaginary refractive index of water-soluble BrC (kWSBrC-365nm) in marine aerosols sampled over the North Indian Ocean during November is significantly higher than during December to January. Thus, significant temporal variability is associated with crop-residue burning emissions in the IGP on the composition of BrC over the North Indian Ocean. Our estimates show that the babs-WSBrC-365nm and kWSBrC-365nm from post-harvest crop-residue burning emissions in the IGP are much higher than the BBEs from the southeastern United States and Amazonian forest fires. Another major finding of this study is the lack of significant relationship between kWSBrC-365nm and the mass ratio of elemental carbon to particulate organic matter, as previously suggested by chamber experiments to model varying BrC absorption properties in ambient aerosols. Therefore, considerable spatio-temporal variability prevails among emission sources (wood burning vs. crop-residue burning), which needs to be considered when assessing the regional radiative forcing of BrC relative to major absorbing elemental carbon.

Production of particulate brown carbon during atmospheric aging of residential wood-burning emissions

Abstract. We investigate the optical properties of light-absorbing organic carbon (brown carbon) from domestic wood combustion as a function of simulated atmospheric aging. At shorter wavelengths (370–470 nm), light absorption by brown carbon from primary organic aerosol (POA) and secondary organic aerosol (SOA) formed during aging was around 10 % and 20 %, respectively, of the total aerosol absorption (brown carbon plus black carbon). The mass absorption cross section (MAC) determined for black carbon (BC, 13.7 m2 g−1 at 370 nm, with geometric standard deviation GSD =1.1) was consistent with that recommended by Bond et al. (2006). The corresponding MAC of POA (5.5 m2 g−1; GSD =1.2) was higher than that of SOA (2.4 m2 g−1; GSD =1.3) at 370 nm. However, SOA presents a substantial mass fraction, with a measured average SOA ∕ POA mass ratio after aging of ∼5 and therefore contributes significantly to the overall light absorption, highlighting the importance of wood-combustion SOA as a source of atmospheric brown carbon. The wavelength dependence of POA and SOA light absorption between 370 and 660 nm is well described with absorption Ångström exponents of 4.6 and 5.6, respectively. UV-visible absorbance measurements of water and methanol-extracted OA were also performed, showing that the majority of the light-absorbing OA is water insoluble even after aging.