Mixture Of Black Carbon Research Articles

Solubility Considerations for Cloud Condensation Nuclei (CCN) Activity Analysis of Pure and Mixed Black Carbon Species

Black carbon (BC) is an aerosol that is released into the atmosphere due to the incomplete burning of biomass and can affect the climate directly or indirectly. BC commonly mixes with other primary or secondary aerosols to undergo aging, thereby changing its radiative properties and cloud condensation nuclei (CCN) activity. The composition of aged BC species in the atmosphere is difficult to measure with high confidence, so their associated CCN activity can be uncertain. In this work, the CCN activity analysis of BC was performed using laboratory measurements of proxy aged BC species. Vulcan XC72R carbon black was used as the representative of BC, and three structural isomers of benzenedicarboxylic acid─phthalic acid (PTA), isophthalic acid (IPTA), and terephthalic acid (TPTA)─were mixed with BC to generate three different proxies of aged BC species. Most studies related to CCN activity analysis of BC aerosols use the traditional Köhler theory or an adsorption theory (such as the Frenkel-Halsey-Hill adsorption theory). PTA, IPTA, and TPTA fall in the sparingly water-soluble range and therefore do not fully obey either of the aforementioned theories. Consequently, a novel hybrid activity model (HAM) was used for the CCN activity analysis of the BC mixtures studied in this work. HAM combines the features of adsorption theory via the adsorption isotherm with the features of Köhler theory by incorporating solubility partitioning. The results in this work showed that HAM improves the representation of CCN activity of pure and mixed BC aerosol species with high certainty, evident from generally better goodness of fit, R2 > 0.9. This work implies that the hygroscopicity parameterization based on HAM captures the size-dependent variability in the CCN activity of the pure and aged BC species.

Carbonaceous aerosols remote sensing from geostationary satellite observation, Part I: Algorithm development using critical reflectance

Current aerosol remote sensing without using multi-view satellite sensors still fail to retrieve its components directly, such as black carbon (BC) and organic carbon (OC) simultaneously due to the limitations on available observations. In this study, A new general carbonaceous aerosol retrieval strategy for geostationary single-view satellite observations is implemented based on a method of critical reflectance, to retrieve the parameters of BC and extra OC concentration from measured radiance without prior quantification of Aerosol Optical Thickness (AOT). The method is based on measuring the change in upward reflectance between clear and hazy days over a varying surface reflectance, with the aim of finding a balance between brightening due to scattering and darkening due to absorption. Since aerosols in the proposed algorithm are considered as a mixture of BC, OC and clustered shell aerosols, this balance can be used to retrieve concentration parameters of these components via radiative transfer models. Sensitivity tests indicate that different scenarios of BC and OC volume fractions can introduce certain sensitivity pattern on critical reflectance. The retrieval is achieved by minimizing the differences between measured critical reflectance and a set of look-up tables (LUTs). Random sampling consensus (RANSAC) is also used in the strategy to reduce the influence of clouds and anomalous pixels on the retrievals. Since critical reflectance should be calculated by comparing geometrically consistent clear and hazy images, the algorithm is more suitable for geostationary satellites with constant viewing geometries. An initial validation and application applied to Himawari images over the North China Plain (NCP) shows that the carbonaceous aerosol retrievals are highly consistent with the expectations in terms of spatial and temporal patterns. The retrievals of BC and OC concentration follow the daily fluctuations of the Aethalometers observations and feature small differences in mean values throughout the month. Additionally, the AOTs at 0.55 μm can be also satisfactorily reproduced based on the carbonaceous aerosol retrievals, resulting in a mean absolute error of 0.089 and a correlation coefficient of 0.870. The main errors in the method arise from shell model assumptions, RANSAC fitting bias, inconsistent clear reference AOT in LUT, and geometric inconsistency between the clear reference and hazy images. This work indicates that the BC and OC concentration in high resolution can be acquired through the geostationary single-view remote sensing for the further air quality and climate studies.

Recent Progress in Impacts of Mixing State on Optical Properties of Black Carbon Aerosol

Black carbon (BC) exerts profound impacts on air quality and climate because of its high-absorption cross section over a broad band of solar spectrum. Non-BC materials coated on BC could alter the mixing state of BC particles and can considerably enhance its mass absorption coefficient. Quantification of this absorption enhancement remains a challenge due to incomplete understanding of the complex physical and chemical properties related to mixing states. In this paper, we summarize the recent progress in measurement and modeling studies on the BC mixing state and their effects on optical properties. Laboratory and field-based observations have shown that the transformation of a mixing state from a highly fractal nature to a more compact shape exhibits a decrease in electric mobility diameter but an increase in fractal dimension and effective density. Meanwhile, the transition behavior is also obviously influenced by emission source which can determine the components of BC mixtures. Based on the empirically determined parameters, accurate numerical modeling shows great capability on calculating BC optical properties. However, considering the significant uncertainties related to BC microphysical properties, proper parameterization considering realistic BC aggregates and coating fraction can help to understand the progress from an externally to internally mixed state.

Automated Aerosol Classification from Spectral UV Measurements Using Machine Learning Clustering

In this study, we present an aerosol classification technique based on measurements of a double monochromator Brewer spectrophotometer during the period 1998–2017 in Thessaloniki, Greece. A machine learning clustering procedure was applied based on the Mahalanobis distance metric. The classification process utilizes the UV Single Scattering Albedo (SSA) at 340 nm and the Extinction Angstrom Exponent (EAE) at 320–360 nm that are obtained from the spectrophotometer. The analysis is supported by measurements from a CIMEL sunphotometer that were deployed in order to establish the training dataset of Brewer measurements. By applying the Mahalanobis distance algorithm to the Brewer timeseries, we automatically assigned measurements in one of the following clusters: Fine Non Absorbing Mixtures (FNA): 64.7%, Black Carbon Mixtures (BC): 17.4%, Dust Mixtures (DUST): 8.1%, and Mixed: 9.8%. We examined the clustering potential of the algorithm by reclassifying the training dataset and comparing it with the original one and also by using manually classified cases. The typing score of the Mahalanobis algorithm is high for all predominant clusters FNA: 77.0%, BC: 63.9%, and DUST: 80.3% when compared with the training dataset. We obtained high scores as well FNA: 100.0%, BC: 66.7%, and DUST: 83.3% when comparing it with the manually classified dataset. The flags obtained here were applied in the timeseries of the Aerosol Optical Depth (AOD) at 340 nm of the Brewer and the CIMEL in order to compare between the two and also stress the future impact of the proposed clustering technique in climatological studies of the station.

Molecular Fingerprinting of14C Dated Soil Organic Matter Fractions from Archaeological Settings in NW Spain

AbstractThis paper evaluates the complexities of radiocarbon (14C) dates from soil organic matter (SOM) in archaeological scenarios. The aqueous NaOH-insoluble residual SOM from Neolithic to medieval sites in NW Spain produced consistently older calibrated14C ages than NaOH-extractable SOM. Using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS), we analyzed the molecular composition of these SOM fractions, aiming to understand the differences in14C ages and to gain insight on SOM dynamics in relation to age fractionation. The molecular composition of the NaOH-extractable SOM, which accounts for roughly two-thirds of total SOM, has a larger proportion of microbial detritus than the NaOH-insoluble SOM. This might suggest that the discrepancies between the two fractions is due to microbial rejuvenation in the extractable fraction, leading to14C results that are younger than the activity that is to be dated. However, archaeological evidence presented here unambiguously shows that the14C age of the extractable SOM provides the more accurate age for the targeted activity, and that the insoluble fraction contains inherited old carbon. After statistical data evaluation using Partial Least Squares-Regression (PLS-R), it is concluded that this inherited SOM is a mixture of Black Carbon from wild and/or domestic fires and recalcitrant aliphatic SOM.

Retrieval of Aerosol Components Using Multi-Wavelength Mie-Raman Lidar and Comparison with Ground Aerosol Sampling

We verified an algorithm using multi-wavelength Mie-Raman lidar (MMRL) observations to retrieve four aerosol components (black carbon (BC), sea salt (SS), air pollution (AP), and mineral dust (DS)) with in-situ aerosol measurements, and determined the seasonal variation of aerosol components in Fukuoka, in the western region of Japan. PM2.5, PM10, and mass concentrations of BC and SS components are derived from in-situ measurements. MMRL provides the aerosol extinction coefficient (α), particle linear depolarization ratio (δ), backscatter coefficient (β), and lidar ratio (S) at 355 and 532 nm, and the attenuated backscatter coefficient (βatt) at 1064 nm. We retrieved vertical distributions of extinction coefficients at 532 nm for four aerosol components (BC, SS, AP, and DS) using 1α532 + 1β532 + 1βatt,1064 + 1δ532 data of MMRL. The retrieved extinction coefficients of the four aerosol components at 532 nm were converted to mass concentrations using the theoretical computed conversion factor assuming the prescribed size distribution, particle shape, and refractive index for each aerosol component. MMRL and in-situ measurements confirmed that seasonal variation of aerosol optical properties was affected by internal/external mixing of various aerosol components, in addition to hygroscopic growth of water-soluble aerosols. MMRL overestimates BC mass concentration compared to in-situ observation using the pure BC model. This overestimation was reduced drastically by introducing the internal mixture model of BC and water-soluble substances (Core-Gray Shell (CGS) model). This result suggests that considering the internal mixture of BC and water-soluble substances is essential for evaluating BC mass concentration in this area. Systematic overestimation of BC mass concentration was found during summer, even when we applied the CGS model. The observational facts based on in-situ and MMRL measurements suggested that misclassification of AP as CGS particles was due to underestimation of relative humidity (RH) by the numerical model in lidar analysis, as well as mismatching of the optical models of AP and CGS assumed in the retrieval with aerosol properties in the actual atmosphere. The time variation of lidar-derived SS was generally consistent with in-situ measurement; however, we found some overestimation of SS during dust events. The cause of this SS overestimation is mainly due to misclassifying internally mixing DS as SS, implying that to consider internal mixing between DS and water-soluble substances leads to better estimation. The time-variations of PM2.5 and PM10 generally showed good agreement with in-situ measurement although lidar-derived PM2.5 and PM10 overestimated in dust events.

The influence of different black carbon and sulfate mixing methods on their optical and radiative properties

Three different internal mixing methods (Core–Shell, Maxwell-Garnett, and Bruggeman) and one external mixing method are used to study the impact of mixing methods of black carbon (BC) with sulfate aerosol on their optical properties, radiative flux, and heating rate. The optical properties of a mixture of BC and sulfate aerosol particles are considered for three typical bands. The results show that mixing methods, the volume ratio of BC to sulfate, and relative humidity have a strong influence on the optical properties of mixed aerosols. Compared to internal mixing, external mixing underestimates the particle mass absorption coefficient by 20–70% and the particle mass scattering coefficient by up to 50%, whereas it overestimates the particle single scattering albedo by 20–50% in most cases. However, the asymmetry parameter is strongly sensitive to the equivalent particle radius, but is only weakly sensitive to the different mixing methods. Of the internal methods, there is less than 2% difference in all optical properties between the Maxwell-Garnett and Bruggeman methods in all bands; however, the differences between the Core–Shell and Maxwell-Garnett/Bruggeman methods are usually larger than 15% in the ultraviolet and visible bands.A sensitivity test is conducted with the Beijing Climate Center Radiation transfer model (BCC-RAD) using a simulated BC concentration that is typical of east-central China and a sulfate volume ratio of 75%. The results show that the internal mixing methods could reduce the radiative flux more effectively because they produce a higher absorption. The annual mean instantaneous radiative force due to BC–sulfate aerosol is about –3.18W/m2 for the external method and –6.91W/m2 for the internal methods at the surface, and –3.03/–1.56/–1.85W/m2 for the external/Core–Shell/(Maxwell-Garnett/Bruggeman) methods, respectively, at the tropopause.

A Comparative Study of Pigments from the Wall Paintings of Two Greek Byzantine Churches

The goal of this study was to characterize pigments used in the murals of two Byzantine churches, from Kastoria, northern Greece. The identification of the iconographer was also investigated by comparing the pigments applied in the wall paintings of the churches. Pigment microsamples of various colors were collected and analyzed by environmental scanning electron microscopy coupled with an energy dispersive system to characterize the elemental composition. Raman spectroscopy was employed to collect molecular spectra for characterization of mineralogical phases. Hematite, cinnabar, and minium were identified in red surfaces. Brown and yellow colors were assigned to mixtures of iron oxides, iron hydroxides, and calcite. Mixtures of iron, lead, and mercury compounds were used to produce different hues in the murals. Black tones were prepared primarily using charcoal and bone black. Grey colors were produced by a mixture of black carbon with calcite; blue hues, by a mixture of iron oxides, calcite, and black carbon. The minerals used were similar for both churches. However, the green color was prepared either by green earth or mixtures of iron oxides and calcite. A modern pigment, lithopone, was also determined, demonstrating restoration or overpainting and thus complicating possible correlations. Based on these preliminary results, the wall paintings could not be ascribed to a specific iconographer.

Measurements of submicron aerosols at the California–Mexico border during the Cal–Mex 2010 field campaign

We present measurements of submicron aerosols in Tijuana, Mexico during the Cal–Mex 2010 field campaign. A suite of aerosol instrumentations were deployed, including a hygroscopic–volatility tandem differential mobility analyzer (HV–TDMA), aerosol particle mass analyzer (APM), condensation particle counter (CPC), cavity ring-down spectrometer (CRDS), and nephelometer to measure the aerosol size distributions, effective density, hygroscopic growth factors (HGF), volatility growth factors (VGF), and optical properties. The average mass concentration of PM0.6 is 10.39 ± 7.61 μg m−3, and the derived average black carbon (BC) mass concentration is 2.87 ± 2.65 μg m−3. There is little new particle formation or particle growth during the day, and the mass loading is dominated by organic aerosols and BC, which on average are 37% and 27% of PM1.0, respectively. For four particle sizes of 46, 81, 151, and 240 nm, the measured particle effective density, HGFs, and VGFs exhibit distinct diurnal trends and size-dependence. For smaller particles (46 and 81 nm), the effective density distribution is unimodal during the day and night, signifying an internally mixed aerosol composition. In contrast, larger particles (151 and 240 nm) exhibit a bi-modal effective density distribution during the daytime, indicating an external mixture of fresh BC and organic aerosols, but a unimodal distribution during the night, corresponding to an internal mixture of BC and organic aerosols. The smaller particles show a noticeable diurnal trend in the effective density distribution, with the highest effective density (1.70 g cm−3) occurring shortly after midnight and the lowest value (0.90 g cm−3) occurring during the afternoon, corresponding most likely to primary organic aerosols and BC, respectively. Both HGFs and VGFs measured are strongly size-dependent. HGFs increase with increasing particle size, indicating that the largest particles are more hygroscopic. VGFs decrease with increasing particle size, indicating that larger particles are more volatile. The hygroscopicity distributions of smaller particles (46 and 81 nm) are unimodal, with a HGF value close to unity. Large particles typically exhibit a bi-modal distribution, with a non-hygroscopic mode and a hygroscopic mode. For all particle sizes, the VGF distributions are bimodal, with a primary non-volatile mode and a secondary volatile mode. The average extinction, scattering, and absorption coefficients are 86.04, 63.07, and 22.97 Mm−1, respectively, and the average SSA is 0.75. Our results reveal that gasoline and diesel vehicles produce a significant amount of black carbon particles in this US–Mexico border region, which impacts the regional environment and climate.

Influence of the Interactions Between Black Carbon and Soil Constituents on the Sorption of Pyrene

Biochar (a kind of black carbon (BC)) has been advocated as a promising additive to farmland, thus it is crucial to understand the influence of BC on the fate of hydrophobic organic chemicals (HOCs) when they exist in soil. This study explored the sorption of pyrene onto a BC sample obtained by pyrolyzing pine sawdust, two soils, clay (kaolinite), and the mixtures thereof to investigate the influence of the interactions between BC and soil constituents on the sorption of HOCs and the mechanisms therein. Sorption of pyrene onto soil−BC mixtures was significantly less than that predicted by the sum of the individual soil and BC sorption, indicating that the sorption of pyrene onto soil and BC did not occur independently. The reduction of BC sorption capacity in soil seemed primarily to be caused by soil dissolved organic matter (DOM), which attenuated pyrene sorption onto BC by 18.7%−40.3% (within pyrene equilibrium concentration range of 0.05−0.5 S w). These were likely due to the blockage of micropores, reduced accessibility of sorption sites, and binding of pyrene by DOM in aqueous solution. In addition to the DOM effect, kaolinite also diminished pyrene sorption onto BC to some extent, which suggested additional interaction between BC and soil particles. Pyrene sorption onto the soil−BC mixtures varied with water content and contact time. The influence of wet versus dry conditions and contact time on the Koc of pyrene was more obvious when pyrene equilibrium concentrations were lower. The effect of aging also varied with soil properties. In summary, BC could not behave independently in soil, and its sorption capacity was changed by its interactions with soil constituents, which may be influenced by soil properties, environmental condition, and contact time.

Brown carbon and internal mixing in biomass burning particles

Biomass burning (BB) contributes large amounts of black carbon (BC) and particulate organic matter (POM) to the atmosphere and contributes significantly to the earth's radiation balance. BB particles can be a complicated optical system, with scattering and absorption contributions from BC, internal mixtures of BC and POM, and wavelength-dependent absorption of POM. Large amounts of POM can also be externally mixed. We report on the unique ability of multi-wavelength photo-acoustic measurements of dry and thermal-denuded absorption to deconstruct this complicated wavelength-dependent system of absorption and mixing. Optical measurements of BB particles from the Four Mile Canyon fire near Boulder, Colorado, showed that internal mixtures of BC and POM enhanced absorption by up to 70%. The data supports the assumption that the POM was very weakly absorbing at 532nm. Enhanced absorption at 404nm was in excess of 200% above BC absorption and varied as POM mass changed, indicative of absorbing POM. Absorption by internal mixing of BC and POM contributed 19(±8)% to total 404-nm absorption, while BC alone contributed 54(±16)%. Approximately 83% of POM mass was externally mixed, the absorption of which contributed 27(±15)% to total particle absorption (at 404nm). The imaginary refractive index and mass absorption efficiency (MAE) of POM at 404nm changed throughout the sampling period and were found to be 0.007±0.005 and 0.82±0.43m(2)g(-1), respectively. Our analysis shows that the MAE of POM can be biased high by up to 50% if absorption from internal mixing of POM and BC is not included.

Parameterization of cloud optical properties for semidirect radiative forcing

[1] A parameterization of liquid cloud optical properties with a mixture of black carbon is proposed. It is found that the changes in cloud optical properties due to mixture of black carbon can be treated as a perturbation to existing cloud optical property parameterizations in climate models. The advantage of the proposed scheme is that current cloud optical property parameterizations used in climate models can be kept. It is shown that the dominant factor with respect to radiative forcing due to the inclusion of black carbon in cloud droplets is the resulting change in single-scattering albedo values. Therefore, a simple scheme to modify only the single-scattering albedo is considered. The additional consideration of the modification of asymmetry factor only applies to the case of very large black carbon volume fraction. The results in a one-dimensional radiation model show that internal mixtures of black carbon can have a significant impact on solar flux and heating rates. For a black carbon volume fraction of 10−7, the reduction in solar flux at the top of the atmosphere can be over 0.5 Wm−2 and the heating rate can increase by about 0.08 Kd−1 for a solar zenith angle of 53°.

Size distributions and mixtures of dust and black carbon aerosol in Asian outflow: Physiochemistry and optical properties

During Transport and Chemical Evolution over the Pacific (TRACE‐P) and Asian Aerosol Characterization Experiment (ACE‐Asia) we measured the dry size distribution of Asian aerosols, their state of mixing, and the optical properties of dust, black carbon (BC) and other aerosol constituents in combustion and/or dust plumes. Optical particle sizing in association with thermal heating extracted volatile components and resolved sizes for dust and refractory soot that usually dominated light absorption. BC was internally mixed with volatile aerosol in ∼85% of accumulation mode particles and constituted ∼5–15% of their mass. These optically effective sizes constrained the soot and dust size distributions and the imaginary part of the dust refractive index, k, to 0.0006 ± 0.0001. This implies a single‐scatter albedo, ϖ (550 nm), for dust ranging from 0.99+ for Dp<1 μm to ∼0.90 at Dp = 10 μm and a size‐integrated campaign average near 0.97 ± 0.01. The typical mass scattering efficiency for the dust was ∼0.3 m2 g−1, and the mass absorption efficiency (MAE) was 0.009 m2 g−1. Less dust south of 25°N and stronger biomass burning signatures resulted in lower values for ϖ of ∼0.82 in plumes aloft. Chemically inferred elemental carbon was moderately correlated with BC light absorption (R2 = 0.40), while refractory soot volume between 0.1 and 0.5 μm was highly correlated (R2 = 0.79) with absorption. However, both approaches yield an MAE for BC mixtures of ∼7 ± 2 m2 g−1 and higher than calculated MAE values for BC of 5 m2 g−1. The increase in the mass fraction of soot and BC in pollution aerosol in the presence of elevated dust appears to be due to uptake of the volatile components onto the coarse dust. This predictably lowered ϖ for the accumulation mode from 0.84 in typical pollution to ∼0.74 in high‐dust events. A chemical transport model revealed good agreement between model and observed BC absorption for most of SE Asia and in biomass plumes but underestimated BC for combustion sources north of 25°N by a factor of ∼3.

Radiative Absorption Capability of Asian Dust with Black Carbon Contamination

[1] Radiative forcing by mineral dust is one of the major uncertainties in assessing the impact of aerosols on the climate. Coagulation and condensation of pollutants on dust particles can further complicate the problem by altering their optical properties. During four Asian dust events in the spring 2002, concentration and size distribution of aerosols were measured in Taipei, Taiwan. Black carbon (BC), organic carbon (OC) and optical properties of the dust aerosols were measured. We found that both the mass specific absorption efficiency and imaginary refractive index of the aerosols decreased significantly during the dust events because of reduced black carbon concentrations. In addition the black carbon in aerosols was found to have significantly higher absorption efficiency than that adopted in current climate models. We suggest that the higher absorption efficiency is due to the formation of an internal mixture of BC and other particulate matter.

Wavelength Dependence of the Absorption of Black Carbon Particles: Predictions and Results from the TARFOX Experiment and Implications for the Aerosol Single Scattering Albedo

Measurements are presented of the wavelength dependence of the aerosol absorption coefficient taken during the Tropical Aerosol Radiative Forcing Observational Experiment (TARFOX) over the northern Atlantic. The data show an approximate lamda(exp -1) variation between 0.40 and 1.0 micrometers. The theoretical basis of the wavelength variation of the absorption of solar radiation by elemental carbon [or black carbon (BC)] is explored. For a wavelength independent refractive index the small particle absorption limit simplifies to a lambda(exp -1) variation in relatively good agreement with the data. This result implies that the refractive indices of BC were relatively constant in this wavelength region, in agreement with much of the data on refractive indices of BC. However, the result does not indicate the magnitude of the refractive indices. The implications of the wavelength dependence of BC absorption for the spectral behavior of the aerosol single scattering albedo are discussed. It is shown that the single scattering albedo for a mixture of BC and nonabsorbing material decreases with wavelength in the solar spectrum (i.e., the percentage amount of absorption increases). This decease in the single scattering albedo with wavelength for black carbon mixtures is different from the increase in single scattering allied for most mineral aerosols (dusts). This indicates that, if generally true, the spectral variation of the single- scattering albedo can be used to distinguish aerosol types. It also highlights the importance of measurements of the spectral variation of the aerosol absorption coefficient and single scattering albedo.