Refractory Black Carbon Aerosol Research Articles

Size–resolved mixing state of ambient refractory black carbon aerosols in Beijing during the XXIV Olympic winter games

Atmospheric loading of black carbon aerosols influences air quality and visibility, and their mixing state and aerosol chemistry were sensitive to both emission scenarios and regional transport. In this study, the aerodynamic size-resolved mixing state of refractory black carbon aerosols (rBC) was investigated using a novel tandem system consisting of an aerodynamic aerosol classifier (AAC), a single particle soot photometer (SP2), and single-particle-aerosol mass spectrometry (SPA-MS) during the XXIV Olympic Winter Games (OWG) at an urban site in Beijing. Particles with aerodynamic diameter (Dae) of 200 nm and 300 nm were selected by AAC to focus on the effect of relative differences in morphology on the coating thickness, coating compositions, and optical properties of rBC particles. We found that rBC-containing particles with Dae of 300 nm were characterized by a rBC core with a count median diameter (CMD) of 108 ± 4 nm that typically have regular morphology (χ:mean∼1), higher relative coating thickness (RCT: mean ∼1.9), and strong light absorption enhancement (Eabs: mean ∼1.5). The rBC-containing particles with Dae = 200 nm normally had irregular shapes (χ:mean∼1.4) and weak Eabs (Eabs: mean ∼1.37). Classification based on air mass clustering and air pollution level revealed that the coating thickness of rBC particles only exhibited unimodal patterns under clean air conditions and distinct bimodal distributions under heavy pollution conditions, implying multiple origins of rBC particles, even during OWG periods. The coating thickness and Eabs of rBC particles were greater when influenced by the higher RH air from east. Furthermore, the chemical compositions of the rBC coating quantitatively determined by SPA-MS were used to estimate the possible origins of the Dae = 300 nm, featured by a thicker coating thickness and stronger light absorption enhancement. Our results showed that rBC particles were primarily mixed with organics, nitrate, and sulfate during the XXIV OWG period. The organic components have a limited role in increasing rBC coatings under polluted conditions, while the alkali metal ions (K and Na) associated with traffic emissions and the secondary inorganic species favor the formation of thick coatings. Higher RH makes limited contributions to rBC mixed with sulfate and organics only (BCOC*_S) and pure BC. The relatively fresh BC could directly mix with organics and sulfate at low RH levels while evolving to mix with nitrate at high RH conditions. In addition to high concentrations of locally emitted precursors and high RH that tend to form thick coatings of nitrate-related rBC aerosols, secondary transport from the west and southwest also contributes to rBC aerosols mixed with nitrate with relatively thick coatings.

Refractory black carbon aerosols in rainwater in the summer of 2019 in Beijing: Mass concentration, size distribution and wet scavenging ratio

Black carbon (BC) aerosols in the atmosphere play a significant role in climate systems due to their strong ability to absorb solar radiation. The lifetime of BC depends on atmospheric transport, aging and consequently on wet scavenging processes (in-cloud and below-cloud scavenging). In this study, sequential rainwater samples in eight rainfall events collected in 2 mm interval were measured by a tandem system including a single particle soot photometer (SP2) and a nebulizer. The results showed that the volume-weighted average (VWA) mass concentrations of refractory black carbon (rBC) in each rainfall event varied, ranging from 10.8 to 78.9 µg/L. The highest rBC concentrations in the rainwater samples typically occurred in the first fraction from individual rainfall events. The geometric mean median mass-equivalent diameter (MMD) decreased under precipitation, indicating that rBC with larger sizes was relatively aged and preferentially removed by wet scavenging. A positive correlation (R2 = 0.73) between the VWA mass concentrations of rBC in rainwater and that in ambient air suggested the important contribution of scavenging process. Additionally, the contributions of in-cloud and below-cloud scavenging were distinguished and accounted for 74% and 26% to wet scavenging, respectively. The scavenging ratio of rBC particles was estimated to be 0.06 on average. This study provides helpful information for better understanding the mechanism of rBC wet scavenging and reducing the uncertainty of numerical simulations of the climate effects of rBC.

Mixing state of refractory black carbon in fog and haze at rural sites in winter on the North China Plain

Abstract. The variability of the mixing state of refractory black carbon aerosol (rBC) and the corresponding complicated light absorption capacity imposes great uncertainty for its climate forcing assessment. In this study, field observations using a single-particle soot photometer (SP2) were conducted to investigate the mixing state of rBC under different meteorological conditions at a rural site on the North China Plain. The results showed that the hourly mass concentration of rBC during the observation periods was 2.6±1.5 µg m−3 on average, with a moderate increase (3.1±0.9) during fog episodes. The mass-equivalent size distribution of rBC exhibited an approximately lognormal distribution with a mass median diameter (MMD) of 213 nm. We found that the count median diameter (CMD) of rBC particles during snowfall episodes was larger than that before snowfall, and the number of rBC particles with Dc<121 nm were reduced by 28.4 % after snow. This may indicate that rBC-containing particles with small core sizes (Dc) were much more effectively removed by snow with light snow intensity (0.23 mm h−1). Based on the Mie scattering theory simulation, the relative and absolute coating thicknesses of rBC-containing particles were estimated to be ∼1.6 and ∼52 nm for the rBC core with a mass-equivalent diameter (Dc) of 170 to 190 nm, respectively, which indicates that most of the rBC-containing particles were thinly coated. Furthermore, a moderate light absorption enhancement (Eabs=1.3) and relatively low absorption cross section (MAC = 5.5 m2 g−1) at 880 nm were observed at the Gucheng (GC) site in winter compared with other typical rural sites. The relationship between the microphysical properties of rBC and meteorological conditions was also studied. Relatively warm and high-RH environments (RH>50 %, -4∘C<T<4∘C) were more favorable to rBC aging than dry and cold environments (RH<60 %, T<-8∘C). And the increase in ambient RH at the same temperature favors rBC aging. An increasing mass fraction of secondary inorganic aerosols (SIAs; especially sulfate and nitrate) and a decreasing mass fraction of organic aerosols in the environment support the formation of thick coatings by rBC. The RH dependence of absorption enhancement (Eabs) was likely caused by the relative coating thickness (RCT) as supported by the gradual increase in the mass concentration and mass fraction of secondary components as a function of RH in the ambient air. The mass fractions of aqueous-phase formation of secondary components had a limited effect on Eabs under a high-RH environment. The measured rBC concentrations and the mixing state of rBC in different meteorological environments will be useful for evaluating the radiative forcing of rBC in regional climate models.

Vertical profile of aerosol characteristics including activation over a rain shadow region in India

Unique airborne observations of aerosol size spectral and chemical characteristics over the peninsular Indian region are illustrated in this case study. Multimodal lognormal distributions were required to fit the observed in situ aerosol size distribution. The aerosol composition and mixing state was deduced from the single-particle analyses of aerosols using the transmission electron microscope and soot photometer coupled with satellite retrieved aerosol classification, and back trajectory analyses. Organic carbon was the most prominent aerosol type found at all altitudes. Refractory black carbon aerosols which constituted about 10–12% of the aerosols in the boundary layer were primarily internally mixed with both inorganic and organic coating. Other major aerosol types were dust and sea salt, with the latter primarily found below 2 km. Further, the cloud forming ability of in-situ aerosols is tested through a cloud condensation nuclei closure analysis. The effective hygroscopicity decreased above cloud base due to the absence of sea salt aerosols. The change in large-scale winds with altitude affected the aerosol composition and hygroscopicity. The multimodal aerosol size distribution and hygroscopicity parameter (κ = 0.18) obtained for the cloud base aerosols over the rain shadow region are useful for studying aerosol-cloud interactions using regional cloud-resolving models.

Mixing state of refractory black carbon aerosol in the South Asian outflow over the northern Indian Ocean during winter

Abstract. Regional climatic implications of aerosol black carbon (BC), which has a wide variety of anthropogenic sources in large abundance, are well recognized over South Asia. Significant uncertainties remain in its quantification due to a lack of sufficient information on the microphysical properties (its concentration, size, and mixing state with other aerosol components) that determine the absorption potential of BC. In particular, the information on the mixing state of BC is extremely sparse over this region. In this study, the first observations of the size distribution and mixing state of individual refractory black carbon (rBC) particles in the South Asian outflow to the south-eastern Arabian Sea and the northern and equatorial Indian Ocean regions are presented based on measurements using a single particle soot photometer (SP2) aboard the Integrated Campaign for Aerosols, gases, and Radiation Budget (ICARB-2018) ship during winter 2018 (16 January to 13 February). The results revealed significant spatial heterogeneity of BC characteristics. The highest rBC mass concentrations (∼938±293 ng m−3) with the highest relative coating thickness (RCT; the ratio of BC core to its coating diameters) of ∼2.16±0.19 are found over the south-east Arabian Sea (SEAS) region, which is in the proximity of the continental outflow. As we move to farther oceanic regions, though the mass concentrations decreased by nearly half (∼546±80 ng m−3), BC still remained thickly coated (RCT∼2.05±0.07). The air over the remote equatorial Indian Ocean, which received considerable marine air masses compared to the other regions, showed the lowest rBC mass concentrations (∼206±114 ng m−3) with a moderately thick coating (RCT∼1.73±0.16). Even over oceanic regions far from the landmass, regions that received the outflow from the more industrialized east coast/the Bay of Bengal had a thicker coating (∼104 nm) compared to regions that received outflow from the west coast and/or peninsular India (∼86 nm). Although different regions of the ocean depicted contrasting concentrations and mixing state parameters due to the varied extent and nature of the continental outflow as well as the atmospheric lifetime of air masses, the modal parameters of rBC mass–size distributions (mean mass median diameters ∼ 0.19–0.20 µm) were similar over all regions. The mean fraction of BC-containing particles (FBC) varied in the range of 0.08–0.12 (suggesting significant amounts of non-BC particles), whereas the bulk mixing ratio of coating mass to rBC mass was highest (8.31±2.40) over the outflow regions compared to the remote ocean (4.24±1.45), highlighting the role of outflow in providing condensable material for coatings on rBC. These parameters, along with the information on the size-resolved mixing state of BC cores, throw light on the role of sources and secondary processing of their complex mixtures for coatings on BC under highly polluted conditions. Examination of the non-refractory sub-micrometre aerosol chemical composition obtained using the aerosol chemical speciation monitor (ACSM) suggested that the overall aerosol system was sulfate-dominated over the far-oceanic regions. In contrast, organics were equally prominent adjacent to the coastal landmass. An association between the BC mixing state and aerosol chemical composition suggested that sulfate was the probable dominant coating material on rBC cores.

Mid carbon (C6+-C29+) in refractory black carbon aerosols is a potential tracer of open burning of rice straw: Insights from atmospheric observation and emission source studies

Abstract Biomass burning (BB) is one of the major sources of atmospheric aerosols. These aerosols cause global and regional issues such as adverse effects on human health, as well as contributing to climate change. Refractory black carbon (rBC) is a major chemical component emitted from BB. Recent studies indicate that the mass spectra distribution of carbon cluster ions (Cn+) in rBC reflects burning materials and combustion temperatures. Therefore, emissions apportionment is in principle possible with respect to rBC. However, emissions data for Cn+ are still not widely available. In this study, a combustion experiment using rice straw was conducted to identify the mass spectra of Cn+ measured using a soot particle aerosol mass spectrometer. Further, to confirm the results, atmospheric observations were conducted during the harvest season in a suburban area surrounded by rice fields because intentional open burning of rice straw (agricultural residues) is often conducted. Source apportionment of airborne ambient rBC generated from open burning of rice straw is carried out by a positive matrix factorization (PMF) method applied to hourly mean data for rBC and Cn+, as well as organic aerosols. During the atmospheric observation period, there was an intensive day of open burning of rice straw, confirmed by visual inspections around the observation site. Concentrations of PM2.5 reached up to 100 μg/m3 and the contribution of BB to rBC increased by up to 50% on that day. Tracers of BB (C2H4O2+ which is a fragment ion of levoglucosan and refractory K+ ions) were also enriched at that time. This study also found that the signal fraction of mid carbon (C6+-C29+) to total carbon (C1+-C35+) in rBC was 0.21 for dry rice straw burning. Correspondingly, the BB-related PMF factor in atmospheric observations (0.18) was close to the emission source data. Rice straw burning tends to occur at a low combustion temperature and generates amorphous (immature) soot, which was further confirmed by a larger value (0.41) for wet rice straw burning with low modification combustion efficiency. On the other hand, the mid carbon fraction of rBC from automobile exhausts (diesel and gasoline) was low (below 0.02) in laboratory studies and the automobile exhaust-related PMF factor was also relatively low (0.08) in atmospheric observations. These emissions are likely generated as graphite (mature) soot under a high combustion temperature. This study also quantifies and explores the atmospheric aging of BB aerosols. Decay rates of mid carbon were about 2 times slower than that of levoglucosan estimated from atmospheric observations. In sum, the mid carbon fraction can be used to differentiate sources of rBC emissions between open burning of rice straw at low combustion temperatures and other rBC sources at high combustion temperatures (such as internal combustion engines) on the one hand and estimate the decay rates of aerosols emitted from BB on the other hand.

Mixing characteristics of refractory black carbon aerosols at an urban site in Beijing

Abstract. Black carbon aerosols play an important role in climate change because they directly absorb solar radiation. In this study, the mixing state of refractory black carbon (rBC) at an urban site in Beijing in the early summer of 2018 was studied with a single-particle soot photometer (SP2) as well as a tandem observation system with a centrifugal particle mass analyzer (CPMA) and a differential mobility analyzer (DMA). The results demonstrated that the mass-equivalent size distribution of rBC exhibited an approximately lognormal distribution with a mass median diameter (MMD) of 171 nm. When the site experienced prevailing southerly winds, the MMD of rBC increased notably, by 19 %. During the observational period, the ratio of the diameter of rBC-containing particles (Dp) to the rBC core (Dc) was 1.20 on average for Dc=180 nm, indicating that the majority of rBC particles were thinly coated. The Dp∕Dc value exhibited a clear diurnal pattern, with a maximum at 14:00 LST and a Dp growth rate of 2.3 nm h−1; higher Ox conditions increased the coating growth rate. The microphysical properties of rBC were also studied. Bare rBC particles were mostly found in fractal structures with a mass fractal dimensions (Dfm) of 2.35, with limited variation during both clean and polluted periods. The morphology of rBC changed with coating thickness increasing. When the mass ratio of nonrefractory matter to rBC (MR) was <1.5, rBC-containing particles were primarily found in external fractal structures, and they changed to a core–shell structure when MR>6, at which point the measured scattering cross section of rBC-containing particles was consistent with that based on the Mie-scattering simulation. We found that only 28 % of the rBC-containing particles were in core–shell structures with a particle mass of 10 fg in the clean period but that proportion increased considerably, to 45 %, in the polluted period. Due to the morphology change, the absorption enhancement (Eabs) was 12 % lower than that predicted for core–shell structures.

Emission characteristics of refractory black carbon aerosols from fresh biomass burning: a perspective from laboratory experiments

Abstract. The emission characteristics of refractory black carbon (rBC) from biomass burning are essential information for numerical simulations of regional pollution and climate effects. We conducted combustion experiments in the laboratory to investigate the emission ratio and mixing state of rBC from the burning of wheat straw and rapeseed plants, which are the main crops cultivated in the Yangtze River Delta region of China. A single particle soot photometer (SP2) was used to measure rBC-containing particles at high temporal resolution and with high accuracy. The combustion state of each burning case was indicated by the modified combustion efficiency (MCE), which is calculated using the integrated enhancement of carbon dioxide and carbon monoxide concentrations relative to their background values. The mass size distribution of the rBC particles showed a lognormal shape with a mode mass equivalent diameter (MED) of 189 nm (ranging from 152 to 215 nm), assuming an rBC density of 1.8 g cm−3. rBC particles less than 80 nm in size (the lower detection limit of the SP2) accounted for ∼ 5 % of the total rBC mass, on average. The emission ratios, which are expressed as ΔrBC ∕ ΔCO (Δ indicates the difference between the observed and background values), displayed a significant positive correlation with the MCE values and varied between 1.8 and 34 ng m−3 ppbv−1. Multi-peak fitting analysis of the delay time (Δt, or the time of occurrence of the scattering peak minus that of the incandescence peak) distribution showed that rBC-containing particles with rBC MED = 200 ± 10 nm displayed two peaks at Δt = 1.7 µs and Δt = 3.2 µs, which could be attributed to the contributions from both flaming and smoldering combustion in each burning case. Both the Δt values and the shell / core ratios of the rBC-containing particles clearly increased as the MCE decreased from 0.98 (smoldering-dominant combustion) to 0.86 (flaming-dominant combustion), implying the great importance of the rapid condensation of semi-volatile organics. This laboratory study found that the mixing state of rBC particles from biomass burning strongly depends on its combustion processes, and overall MCE should be taken carefully into consideration while the climate effect of rBC particles from open biomass burning is simulated.

Size distribution and mixing state of refractory black carbon aerosol from a coastal city in South China

An intensive measurement campaign was conducted in the coastal city of Xiamen, China to investigate the size distribution and mixing state of the refractory black carbon (rBC) aerosol. The average rBC concentration for the campaign, measured with a ground-based single particle soot photometer (SP2), was 2.3±1.7μgm−3, which accounted for ~4.3% of the PM2.5 mass. A potential source contribution function model indicated that emissions from coastal cities to the southwest were the most important source for the rBC and that shipping traffic was another likely source. The mass size distribution of the rBC particles was mono-modal and approximately lognormal, with a mass median diameter (MMD) of ~185nm. Larger MMDs (~195nm) occurred during polluted conditions compared with non-polluted times (~175nm) due to stronger biomass burning activities during pollution episodes. Uncoated or thinly-coated particles composed the bulk of the rBC aerosol, and on average ~31% of the rBC was internally-mixed or thickly-coated. A positive matrix factorization model showed that organic materials were the predominant component of the rBC coatings and that mixing with nitrate increased during pollution conditions. These findings should lead to improvements in the parameterizations used to model the radiative effects of rBC.

Characteristics of Black Carbon Aerosol during the Chinese Lunar Year and Weekdays in Xi’an, China

Black carbon (BC) aerosol plays an important role in climate forcing. The net radiative effect is strongly dependent on the physical properties of BC particles. A single particle soot photometer and a carbon monoxide analyser were deployed during the Chinese Lunar Year (CLY) and on weekdays at Xi’an, China, to investigate the characteristics of refractory black carbon aerosol (rBC). The rBC mass on weekdays (8.4 μg·m−3) exceeds that during the CLY (1.9 μg·m−3), presumably due to the lower anthropogenic emissions during the latter. The mass size distribution of rBC shows a primary mode peak at ~205 nm and a small secondary mode peak at ~102-nm volume-equivalent diameter assuming 2 g·cm−3 in void-free density in both sets of samples. More than half of the rBC cores are thickly coated during the CLY (fBC = 57.5%); the percentage is slightly lower (fBC = 48.3%) on weekdays. Diurnal patterns in rBC mass and mixing state differ for the two sampling periods, which are attributed to the distinct anthropogenic activities. The rBC mass and CO mixing ratios are strongly correlated with slopes of 0.0070 and 0.0016 μg·m−3·ppbv−1 for weekdays and the CLY, respectively.

Characterizing elemental, equivalent black, and refractory black carbon aerosol particles: a review of techniques, their limitations and uncertainties.

Elemental-, equivalent black- and refractory black-carbon are terms that have been defined in order to dissect the more general term, black carbon, into its component parts related to its specific chemical and optical properties and its impact on climate and health. Recent publications have attempted to clarify the meaning of these terms with respect to their environmental impact, particularly on climate. Here, we focus on the measurement aspects, reviewing the most commonly implemented techniques for the direct and indirect derivation of black carbon properties, their strengths, limitations, and uncertainties, and provide a non-exhaustive bibliography where the reader can find more detailed information. This review paper is designed as a guide for those wishing to learn about the current state of black carbon measurement instrumentation, how calibration is carried out, when one instrument may have the advantage over another, and where new techniques are needed to fill important knowledge gaps.

Changes in black carbon deposition to Antarctica from two high-resolution ice core records, 1850–2000 AD

Abstract. Refractory black carbon aerosols (rBC) emitted by biomass burning (fires) and fossil fuel combustion, affect global climate and atmospheric chemistry. In the Southern Hemisphere (SH), rBC is transported in the atmosphere from low- and mid-latitudes to Antarctica and deposited to the polar ice sheet preserving a history of emissions and atmospheric transport. Here, we present two high-resolution Antarctic rBC ice core records drilled from the West Antarctic Ice Sheet divide and Law Dome on the periphery of the East Antarctic ice sheet. Separated by ~3500 km, the records span calendar years 1850–2001 and reflect the rBC distribution over the Indian and Pacific ocean sectors of the Southern Ocean. Concentrations of rBC in the ice cores displayed significant variability at annual to decadal time scales, notably in ENSO-QBO and AAO frequency bands. The delay observed between rBC and ENSO variability suggested that ENSO does not directly affect rBC transport, but rather continental hydrology, subsequent fire regimes, and aerosol emissions. From 1850 to 1950, the two ice core records were uncorrelated but were highly correlated from 1950 to 2002 (cross-correlation coefficient at annual resolution: r = 0.54, p < 0.01) due to a common decrease in rBC variability. The decrease in ice-core rBC from the 1950s to late 1980s displays similarities with inventories of SH rBC grass fires and biofuel emissions, which show reduced emission estimates over that period.

Variability of black carbon deposition to the East Antarctic Plateau, 1800–2000 AD

Abstract. Refractory black carbon aerosols (rBC) from biomass burning and fossil fuel combustion are deposited to the Antarctic ice sheet and preserve a history of emissions and long-range transport from low- and mid-latitudes. Antarctic ice core rBC records may thus provide information with respect to past combustion aerosol emissions and atmospheric circulation. Here, we present six East Antarctic ice core records of rBC concentrations and fluxes covering the last two centuries with approximately annual resolution (cal. yr. 1800 to 2000). The ice cores were drilled in disparate regions of the high East Antarctic ice sheet, at different elevations and net snow accumulation rates. Annual rBC concentrations were log-normally distributed and geometric means of annual concentrations ranged from 0.10 to 0.18 μg kg−1. Average rBC fluxes were determined over the time periods 1800 to 2000 and 1963 to 2000 and ranged from 3.4 to 15.5 μg m−2 a−1 and 3.6 to 21.8 μg m−2 a−1, respectively. Geometric mean concentrations spanning 1800 to 2000 increased linearly with elevation at a rate of 0.025 μg kg−1/500 m. Spectral analysis of the records revealed significant decadal-scale variability, which at several sites was comparable to decadal ENSO variability.