Black Carbon Mass Size Distributions Research Articles

Measurement report: Size-resolved mass concentration of equivalent black carbon-containing particles larger than 700 nm and their role in radiation

Abstract. Black carbon (BC) mass size distribution (BCMSD) is crucial in both the environment and the climate system due to BC's intense size-dependent absorption of solar radiation. BC-containing particles larger than 700 nm (BC>700) could contribute to more than half of bulk BC mass concentration. Unfortunately, previous methods concentrated on BC-containing particles of less than 700 nm because of technical limitations. The contribution of BC to absorption and the radiative effect might be underestimated without consideration of BC>700. In this study, equivalent BCMSD (eBCMSD) from 150 nm up to 1.5 µm was measured at high time resolution of 1 h for the first time by an aerodynamic aerosol classifier in tandem with an aethalometer in two field campaigns over eastern China, namely Changzhou located in the Yangtze River Delta and Beijing located in the North China Plain. The results revealed that the pattern of eBCMSD in Changzhou (Beijing) was mostly bimodal (unimodal) peaking at 240 and 1249 nm (427 nm). The peak diameter of eBCMSD in Changzhou did not shift significantly with increasing pollution (240 to 289 nm). In contrast, the peak diameter of eBCMSD in Beijing shifted towards larger sizes, from 347 to 527 nm, with increasing pollution, indicating that the aging process at the urban site was different from that at the regional background site. eBCMSD in both Changzhou and Beijing had a significant diurnal cycle with a smaller (larger) value of eBCMSD during daytime (nighttime). Equivalent BC>700 (eBC>700) was ubiquitous and varied significantly with different locations and pollution levels. The campaign-averaged contribution of eBC>700 to bulk eBC mass concentration (meBC,bulk), bulk absorption coefficient (σab,bulk) and estimated direct radiative forcing of eBC (DRFeBC) in Changzhou and Beijing were 27.8 % (20.9 %–36.5 %) and 24.1 % (17.5 %–34.2 %), 19.6 % (15.8 %–24.6 %) and 25.9 % (19.6 %–33.7 %) and 20.5 % (18.4 %–22.2 %) and 21.0 % (16.3 %–26.1 %), respectively. meBC,bulk, σab,bulk and DRFeBC of eBC>700 in Changzhou (Beijing) increased by a factor of 3.6 (5.1) from 0.11 (0.07) to 0.40 (0.36) µg m−3, by a factor of 3.2 (5.5) from 0.54 (0.63) to 1.75 (3.45) Mm−1 and by a factor of 2.4 (4.7) from 0.1 (0.1) to 0.24 (0.47) W m−2, respectively, with the aggravation of pollution. The contribution of eBC>700 to meBC,bulk and σab,bulk had a significant diurnal cycle with a higher (lower) fraction during daytime (nighttime) in both Changzhou and Beijing. A case study indicated that the contribution of eBC>700 to meBC,bulk, σab,bulk and DRFeBC could reach up to 50 %, 50 % and 40 %, respectively. It was highly recommended to consider the whole size range of BC-containing particles in model estimation of the BC radiative effect.

Black carbon content of traffic emissions significantly impacts black carbon mass size distributions and mixing states

Abstract. Both the size and mixing state of black carbon (BC)-containing aerosols are crucial in estimating the environmental, health and climate impacts of BC. Traffic emissions are a major global source of BC; however, parameterization of BC mass size distributions and mixing states associated with traffic remains lacking due to its dependence on vehicle types and driving conditions. To investigate BC mass size distributions and mixing states associated with traffic emissions, a field campaign was conducted in the Guangzhou urban area during winter, which used a system coupling a differential mobility analyzer (DMA) and a single-particle soot photometer (SP2) to measure BC mass size distributions in the range of 100 to 700 nm. The resolved primary organic aerosols were hydrocarbon-like organic aerosols (HOA) and cooking-like organic aerosols (COA), as well as refractory BC (rBC), which was detected by the DMA–SP2 and correlated highly with HOA (R2=0.88), confirming that traffic emissions are the dominant source of atmospheric BC during the observations. The BC mass size distribution was found to be best fitted by a lognormal distribution, with a geometric mean (Dg,BC) of 258±16 nm, varying between 200 and 300 nm. During daytime, active formation of secondary nitrate and organic aerosols was observed, but it had little effect on the variations of BC mass size distributions. Further analyses revealed that Dg,BC was moderately correlated with rBC / HOA (R2=0.41) in a linear form of Dg,BC=34×rBC/HOA+177, demonstrating that the BC content of traffic emissions significantly impacts the BC mass size distributions. In addition, the size-dependent fractions of BC-containing aerosols in all types of aerosols (fBCc) and the fraction of identified externally mixed (bare/thinly coated) BC particles in all BC-containing aerosols (fext) were also characterized. It was found that the daytime secondary aerosol formation reduced both fBCc and fext, with the decrease in fext being more pronounced for larger particles, possibly due to the higher relative coating thickness. Variations in fext during nighttime were mainly controlled by the emission conditions. For example, fext for 600 nm particles decreased from 0.82 to 0.46 as rBC / HOA increased from 1 to 3.5, while the mass ratios of secondary aerosols to rBC varied little, demonstrating that the BC content also significantly affects the mixing states of freshly emitted BC from traffic emissions. This study suggests that BC content can be used as the key factor to parameterize both the BC mass size distribution and mixing states from traffic emissions, which warrants future comprehensive investigation. In addition, other sources such as biomass burning and coal combustion also contribute substantially to BC emissions, and it was important to investigate whether BC content of other major BC sources than traffic is also important in determining BC mass size distributions and mixing states. Overall, results of this study have significant implications for accurate representation of BC from different sources when modeling the impacts of BC.

New method to determine black carbon mass size distribution

Abstract. Black carbon (BC) is an important atmospheric component with strong light absorption. Many attempts have been made to measure BC mass size distribution (BCMSD) for its significant impact on climate and public health. Larger-coverage BCMSD, ranging from upper submicron particles sizes to larger than 1 µm, contributes to a substantial proportion of total BC mass and absorption. However, the current time resolution of larger-coverage BCMSD measurement was limited to 1 d, which was insufficient to characterize variation of larger-coverage BCMSD. In this study, a new method to determine equivalent BCMSD (eBCMSD) was proposed from size-resolved absorption coefficient measured by an aerodynamic aerosol classifier in tandem with an aethalometer. The proposed method could measure larger-coverage eBCMSD with a time resolution as high as 1 h and was validated by comparing the measurement results with refractory BCMSD (rBCMSD) measured by a differential mobility analyzer in tandem with a single-particle soot photometer (DMA–SP2) for particle sizes larger than 300 nm during a field measurement in the Yangtze River Delta. Bulk refractory BC mass concentration (mrBC,bulk) by DMA–SP2 was underestimated by 33 % compared to bulk equivalent BC mass concentration (meBC,bulk) by this method because of the limited size range of measurement for DMA–SP2. Uncertainty analysis of this method was performed with respect to mass absorption cross-section (MAC), transfer function inversion, number fraction of BC-containing particle and instrumental noise. The results indicated that MAC was the main uncertainty source, leading to meBC,bulk values that varied from −20 % to 28 %. With the advantage of a wide size coverage up to 1.5 µm, high time resolution, easy operation and low cost, this method is expected to have wide applications in field measurement for better estimating the radiative properties and climate effects of BC.

Seasonal contrast in size distributions and mixing state of black carbon and its association with PM<sub>1.0</sub> chemical composition from the eastern coast of India

Abstract. Over the Indian region, aerosol absorption is considered to have a potential impact on the regional climate, monsoon and hydrological cycle. Black carbon (BC) is the dominant absorbing aerosol, whose absorption potential is determined mainly by its microphysical properties, including its concentration, size and mixing state with other aerosol components. The Indo-Gangetic Plain (IGP) is one of the regional aerosol hot spots with diverse sources, both natural and anthropogenic, but still the information on the mixing state of the IGP aerosols, especially BC, is limited and a significant source of uncertainty in understanding their climatic implications. In this context, we present the results from intensive measurements of refractory BC (rBC) carried out over Bhubaneswar, an urban site in the eastern coast of India, which experiences contrasting air masses (the IGP outflow or coastal/marine air masses) in different seasons. This study helps to elucidate the microphysical characteristics of BC over this region and delineates the IGP outflow from the other air masses. The observations were carried out as part of South West Asian Aerosol Monsoon Interactions (SWAAMI) collaborative field experiment during July 2016–May 2017, using a single-particle soot photometer (SP2) that uses a laser-induced incandescence technique to measure the mass and mixing state of individual BC particles and an aerosol chemical speciation monitor (ACSM) to infer the possible coating material. Results highlighted the distinctiveness in aerosol microphysical properties in the IGP air masses. BC mass concentration was highest during winter (December–February) (∼1.94±1.58 µg m−3), when the prevailing air masses were mostly of IGP origin, followed by post-monsoon (October–November) (mean ∼1.34±1.40 µg m−3). The mass median diameter (MMD) of the BC mass size distributions was in the range 0.190–0.195 µm, suggesting mixed sources of BC, and, further, higher values (∼ 1.3–1.8) of bulk relative coating thickness (RCT) (ratio of optical and core diameters) were seen, indicating a significant fraction of highly coated BC aerosols in the IGP outflow. During the pre-monsoon (March–May), when marine/coastal air masses prevailed, BC mass concentration was lowest (∼0.82±0.84 µg m−3), and larger BC cores (MMD > 0.210 µm) were seen, suggesting distinct source processes, while RCT was ∼ 1.2–1.3, which may translate into higher extent of absolute coating on BC cores, which may have crucial regional climate implications. During the summer monsoon (July–September), BC size distributions were dominated by smaller cores (MMD ≤ 0.185 µm), with the lowest coating indicating fresher BC, likely from fossil fuel sources. A clear diurnal variation pattern of BC and RCT was noticed in all the seasons, and daytime peak in RCT suggested enhanced coating on BC due to the condensable coating material originating from photochemistry. Examination of submicrometre aerosol chemical composition highlighted that the IGP outflow was dominated by organics (47 %–49 %), and marine/coastal air masses contained higher amounts of sulfate (41 %–47 %), while ammonium and nitrate were seen in minor amounts, with significant concentrations only during the IGP air mass periods. The diurnal pattern of sulfate resembled that of the RCT of rBC particles, whereas organic mass showed a pattern similar to that of the rBC mass concentration. Seasonally, the coating on BC showed a negative association with the mass concentration of sulfate during the pre-monsoon season and with organics during the post-monsoon season. These are the first experimental data on the mixing state of BC from a long time series over the Indian region and include new information on black carbon in the IGP outflow region. These data help in improving the understanding of regional BC microphysical characteristics and their climate implications.

Role of black carbon mass size distribution in the direct aerosol radiative forcing

Abstract. Large uncertainties exist when estimating radiative effects of ambient black carbon (BC) aerosol. Previous studies about the BC aerosol radiative forcing mainly focus on the BC aerosols' mass concentrations and mixing states, while the effects of BC mass size distribution (BCMSD) were not well considered. In this paper, we developed a method of measuring the BCMSD by using a differential mobility analyzer in tandem with an Aethalometer. A comprehensive method of multiple charging corrections was proposed and implemented in measuring the BCMSD. Good agreement was obtained between the BC mass concentration integrated from this system and that measured in the bulk phase, demonstrating the reliability of our proposed method. Characteristics of the BCMSD and corresponding radiative effects were studied based on a field measurement campaign conducted in the North China Plain by using our own measurement system. Results showed that the BCMSD had two modes and the mean peak diameters of the modes were 150 and 503 nm. The BCMSD of the coarser mode varied significantly under different pollution conditions with peak diameter varying between 430 and 580 nm, which gave rise to significant variation in aerosol bulk optical properties. The direct aerosol radiative forcing was estimated to vary by 8.45 % for different measured BCMSDs of the coarser mode, which shared the same magnitude with the variation associated with assuming different aerosol mixing states (10.5 %). Our study reveals that the BCMSD as well as its mixing state in estimating the direct aerosol radiative forcing matters. Knowledge of the BCMSD should be fully considered in climate models.

A size-segregation method for monitoring the diurnal characteristics of atmospheric black carbon size distribution at urban traffic sites

Understanding the characteristics of the size distribution of ambient black carbon (BC) in distinct environments is critical because the influence of BC aerosols on climate, visibility, and human health depends strongly on the distribution of BC aerosols over the particle size spectrum. In this study, a novel method for determining the mass size distribution of BC in atmospheric aerosols was developed. This size-segregation method relies on measuring BC in parallel using two aethalometers, one of which is used to measure the total BC (BCT) mass concentration as a reference level and the other is used to measure the BC (BCi) mass concentration for BC sizes below specific particle sizes that are selected using a size cut-off inlet. In this study, this method was applied to measure BC in atmospheric samples at an urban traffic site. The aethalometers were operated continually from December 15, 2012 to January 31, 2013, and from February 15, 2013 to March 31, 2013. The measurement results presented in this paper are for the diurnal variation patterns, average concentrations, mass fractions, and size distributions of BC aerosols. The results indicate that BCT mass concentration is approximately 2.8 μg m−3 in the Taipei urban area. The levels of BC at this sampling site were affected markedly by traffic emission levels and local wind speed. At the sampling site, the average BC2.5/BCT, BC1.0/BCT, BC0.5/BCT, BC0.25/BCT, and BC0.1/BCT were 0.96 ± 0.04, 0.92 ± 0.07, 0.89 ± 0.04, 0.73 ± 0.10, and 0.18 ± 0.08, respectively. The results indicate that approximately 90% of the BC aerosols were smaller than 0.5 μm, that most of the BC aerosols (55%) were in the size range of 0.1–0.25 μm, and that approximately 18% of the BC aerosols were ultrafine. Moreover, the daily average mass size distribution of BC exhibited a single accumulation mode at 0.16 μm at this sampling site. The mode of the BC mass size distribution at rush hour (9 AM) was only 0.14 μm, which is smaller than the daily average. Moreover, the mode of the BC mass size distribution at an early morning hour (3 AM) was 0.18 μm, and a minor coarse mode was also observed during this period. The results further revealed that the geometric diameter (Dpg) of the BC aerosols varied between 0.14 and 0.22 μm and the geometric standard deviation (σg) of these BC aerosols ranged between 1.4 and 2.3 during the sampling period. Because BC exhibits extremely low chemical reactivity; the size distribution of BC in the atmosphere does not change substantially except through coagulation.

Black carbon mass size distributions of diesel exhaust and urban aerosols measured using differential mobility analyzer in tandem with Aethalometer

Black carbon (BC) is the dominant component of the light absorbing aerosols in the atmosphere, changing earth's radiative balance and affecting the climate. The mixing state and size distribution of atmospheric BC are largely unknown and cause uncertainties in climate models. BC is also a major component of diesel PM emissions, recently classified by World Health Organization as Category I Carcinogen, and has been associated with various adverse health effects. This study presents a novel approach of direct and continuous measurement of BC mass size distribution by tandem operation of a differential mobility spectrometry and a refined Aethalometer. A condensation particle counter was deployed in parallel with the Aethalometer to determine particle number size distribution. A wide range of particle sizes (20–600 nm) was investigated to determine the BC modal characteristics in fresh diesel engine tailpipe emissions and in different urban environments including a typical urban ambient site and a busy roadside. The study provided a demonstration of a new analytic approach and showed the evolution of BC mass size distribution from fresh engine emissions to the aged aerosols in the roadside and ambient environments. The results potentially can be used to refine the input for climate modeling to determine the effect of particle-bound atmospheric BC on the global climate.

Single Particle Soot Photometer intercomparison at the AIDA chamber

Abstract. Soot particles, consisting of black carbon (BC), organic carbon (OC), inorganic salts, and trace elements, are emitted into the atmosphere during incomplete combustion. Accurate measurements of atmospheric BC are important as BC particles cause adverse health effects and impact the climate. Unfortunately, the accurate measurement of the properties and mass concentrations of BC particles remains difficult. The Single Particle Soot Photometer (SP2) can contribute to improving this situation by measuring the mass of refractory BC in individual particles as well as its mixing state. Here, the results of the first detailed SP2 intercomparison, involving 6 SP2s from 6 different research groups, are presented, including the most evolved data products that can presently be calculated from SP2 measurements. It was shown that a detection efficiency of almost 100% down to 1 fg BC per particle can readily be achieved, and that this limit can be pushed down to ∼0.2 fg BC with optimal SP2 setup. Number and mass size distributions of BC cores agreed within ±5% and ±10%, respectively, in between the SP2s, with larger deviations in the range below 1 fg BC. The accuracy of the SP2's mass concentration measurement depends on the calibration material chosen. The SP2 has previously been shown to be equally sensitive to fullerene soot and ambient BC from sources where fossil fuel was dominant and less sensitive to fullerene soot than to Aquadag. Fullerene soot was therefore chosen as the standard calibration material by the SP2 user community; however, many data sets rely solely on Aquadag calibration measurements. The difference in SP2 sensitivity was found to be almost equal (fullerene soot to Aquadag response ratio of ∼0.75 at 8.9 fg BC) for all SP2s. This allows the calculation of a fullerene soot equivalent calibration curve from a measured Aquadag calibration, when no fullerene soot calibration is available. It could be shown that this approach works well for all SP2s over the mass range of 1–10 fg. This range is suitable for typical BC mass size distributions in the ambient air far from sources. The number size distribution of purely scattering particles optically measured by the 6 SP2s also agreed within 15%. Measurements of the thickness of non-refractory coatings (i.e. product from α-pinene ozonolysis) on the BC particles, relying on BC mass optical size and on an additional particle position measurement, also compared well (within ±17%). The estimated coating thickness values were consistent with thermo-optical analysis of OC and elemental carbon (EC) content, though absolutely accurate values cannot be expected given all the assumptions that have to be made regarding refractive index, particle morphology, etc. This study showed that the SP2 provides accurate and reproducible data, but also that high data quality is only achieved if the SP2 is carefully tuned and calibrated. It has to be noted that the agreement observed here does not account for additional variability in output data that could result from the differences in the potentially subjective assumptions made by different SP2 users in the data processing.

Black carbon measurements in the boundary layer over western and northern Europe

Abstract. Europe is a densely populated region that is a significant global source of black carbon (BC) aerosol, but there is a lack of information regarding the physical properties and spatial/vertical distribution of rBC in the region. We present the first aircraft observations of sub-micron refractory BC (rBC) aerosol concentrations and physical properties measured by a single particle soot photometer (SP2) in the lower troposphere over Europe. The observations spanned a region roughly bounded by 50° to 60° N and from 15° W to 30° E. The measurements, made between April and September 2008, showed that average rBC mass concentrations ranged from about 300 ng m−3 near urban areas to approximately 50 ng m−3 in remote continental regions, lower than previous surface-based measurements. rBC represented between 0.5 and 3% of the sub-micron aerosol mass. Black carbon mass size distributions were log-normally distributed and peaked at approximately 180 nm, but shifted to smaller diameters (~160 nm) near source regions. rBC was correlated with carbon monoxide (CO) but had different ratios to CO depending on location and air mass. Light absorption coefficients were measured by particle soot absorption photometers on two separate aircraft and showed similar geographic patterns to rBC mass measured by the SP2. We summarize the rBC and light absorption measurements as a function of longitude and air mass age and also provide profiles of rBC mass concentrations and size distribution statistics. Our results will help evaluate model-predicted regional rBC concentrations and properties and determine regional and global climate impacts from rBC due to atmospheric heating and surface dimming.