Light-absorbing aerosols, particularly black carbon (BC), have significant impacts on human health and the climate. They are also the least-studied fraction of atmospheric particles, particularly in residential areas of southern Africa. The optical characteristics of ground-based light-absorbing aerosols from Kwadela Township in South Africa are investigated in this study. Daily averaged ambient PM25 highest levels were 51.39 µg m–3 and 32.18 µg m–3, whereas hourly averages peaked at 61.31 µg m–3 and 34.69 µg m–3 during winter and summer, respectively. Levels of daily averaged light-absorbing aerosols were 2.9 times higher (1.89 ± 0.5 µg m–3) in winter 2014 than in summer 2015 (0.66 ± 0.2 µg m–3). In both seasons, hourly averaged levels showed bimodal diurnal cycles, which correlated with the PM2.5 diurnal patterns that indicated distinct peaks in the morning and evening. These diurnal cycle peak periods corresponded with the times of increased solid domestic fuel usage, road traffic, and also shallower boundary layer. On average, light-absorbing aerosols contributed a larger proportion of total ambient PM2.5 levels in winter (6.5 ± 1.0

During the SEAC(4)RS campaign in 2013, inflight measurements of light-absorption by aerosol in biomass burning and agriculture fire plumes were collected along with concomitant measurements of aerosol extinction, scattering, and black carbon mass concentration. Here, we compare three measurements of aerosol absorption coefficients: from a photoacoustic spectrometer (PAS), a particle soot absorption photometer (PSAP), and a continuous light absorption photometer (CLAP). Each of these absorption measurements was collected in three visible spectral regions: red, green, and blue (although the precise wavelength and bandwidth vary with each instrument). The absorption measurements were compared during the plumes, in the boundary layer, and in the free troposphere. The slopes from the comparison ranged from 0.6 to 1.24. For biomass burning plumes, the uncertainty in the absorption measurements translates into a range in single scattering albedos of 0.93-0.94 at a wavelength of 660 nm, 0.94-0.95 at 532 nm and 0.92-0.95 at 405 nm. Overall, the aerosol absorption instruments agreed within their stated accuracies. Comparisons with simultaneous measurements of refractive black carbon mass concentration (collected by a single particle soot photometer), were used to derive the mass absorption coefficients (MAC). For all wavelengths, the MAC was high by greater than a factor of three compared to the expected MAC for black carbon.

Abstract. Optical properties of flame-generated black carbon (BC) containing soot particles were quantified at multiple wavelengths for particles produced using two different flames, a methane diffusion flame and an ethylene premixed flame. Measurements were made for: (i) nascent soot particles, (ii) thermally denuded nascent particles, and (iii) particles that were coated then thermally denuded, leading to collapse of the initially lacy, fractal-like morphology. The measured mass absorption coefficients (MAC) depended on soot maturity and generation, but were similar between flames for similar conditions. For mature soot, here corresponding to particles with volume-equivalent diameters > ~ 160 nm, the MAC and absorption Angstrom exponent values were independent of particle collapse while the single scatter albedo increased. The MAC values for these larger particles were also size-independent. Effective, theory-specific complex refractive index (RI) values are derived from the observations with two widely-used methods: Lorenz-Mie theory and the Rayleigh-Debye-Gans (RDG) approximation. Mie theory systematically under-predicts the observed absorption cross-sections at all wavelengths for larger particles (with x > 0.9) independent of the complex RI used, while RDG provides good agreement. Importantly, this implies that the use of Mie theory within air quality and climate models, as is common, likely leads to under-predictions in the absorption by BC, with the extent of under-prediction depending on the assumed BC size distribution and complex RI used. We suggest that it is more appropriate to assume a constant, size-independent (but wavelength-specific) MAC to represent absorption by uncoated BC particles within models.

A wide range of globally significant biomass fuels were burned during the fourth Fire Lab at Missoula Experiment (FLAME-4). A multi-channel photoacoustic absorption spectrometer (PAS) measured dry absorption at 405, 532, and 660 nm and thermally denuded (250 °C) absorption at 405 and 660 nm. Absorption coefficients were broken into contributions from black carbon (BC), brown carbon (BrC), and lensing following three different methodologies, with one extreme being a method that assumes the thermal denuder effectively removes organics and the other extreme being a method based on the assumption that black carbon (BC) has an Ångström exponent of unity. The methodologies employed provide ranges of potential importance of BrC to absorption but, on average, there was a difference of a factor of 2 in the ratio of the fraction of absorption attributable to BrC estimated by the two methods. BrC absorption at shorter visible wavelengths is of equal or greater importance to that of BC, with maximum contributions of up to 92 % of total aerosol absorption at 405 nm and up to 58 % of total absorption at 532 nm. Lensing is estimated to contribute a maximum of 30 % of total absorption, but typically contributes much less than this. Absorption enhancements and the estimated fraction of absorption from BrC show good correlation with the elemental-carbon-to-organic-carbon ratio (EC ∕ OC) of emitted aerosols and weaker correlation with the modified combustion efficiency (MCE). Previous studies have shown that BrC grows darker (larger imaginary refractive index) as the ratio of black to organic aerosol (OA) mass increases. This study is consistent with those findings but also demonstrates that the fraction of total absorption attributable to BrC shows the opposite trend: increasing as the organic fraction of aerosol emissions increases and the EC ∕ OC ratio decreases.

Single-scattering albedo (SSA) and absorption Ångström exponent (AAE) are two critical parameters in determining the impact of absorbing aerosol on the Earth's radiative balance. Aerosol emitted by biomass burning represent a significant fraction of absorbing aerosol globally, but it remains difficult to accurately predict SSA and AAE for biomass burning aerosol. Black carbon (BC), brown carbon (BrC), and non-absorbing coatings all make substantial contributions to the absorption coefficient of biomass burning aerosol. SSA and AAE cannot be directly predicted based on fuel type because they depend strongly on burn conditions. It has been suggested that SSA can be effectively parameterized via the modified combustion efficiency (MCE) of a biomass burning event and that this would be useful because emission factors for CO and CO2, from which MCE can be calculated, are available for a large number of fuels. Here we demonstrate, with data from the FLAME-4 experiment, that for a wide variety of globally relevant biomass fuels, over a range of combustion conditions, parameterizations of SSA and AAE based on the elemental carbon (EC) to organic carbon (OC) mass ratio are quantitatively superior to parameterizations based on MCE. We show that the EC ∕ OC ratio and the ratio of EC ∕ (EC + OC) both have significantly better correlations with SSA than MCE. Furthermore, the relationship of EC ∕ (EC + OC) with SSA is linear. These improved parameterizations are significant because, similar to MCE, emission factors for EC (or black carbon) and OC are available for a wide range of biomass fuels. Fitting SSA with MCE yields correlation coefficients (Pearson's r) of ∼ 0.65 at the visible wavelengths of 405, 532, and 660 nm while fitting SSA with EC / OC or EC / (EC + OC) yields a Pearson's r of 0.94–0.97 at these same wavelengths. The strong correlation coefficient at 405 nm (r = 0.97) suggests that parameterizations based on EC / OC or EC / (EC + OC) have good predictive capabilities even for fuels in which brown carbon absorption is significant. Notably, these parameterizations are effective for emissions from Indonesian peat, which have very little black carbon but significant brown carbon (SSA = 0.990 ± 0.001 at 532 and 660 nm, SSA = 0.937 ± 0.011 at 405 nm). Finally, we demonstrate that our parameterization based on EC / (EC + OC) accurately predicts SSA during the first few hours of plume aging with data from Yokelson et al. (2009) gathered during a biomass burning event in the Yucatán Peninsula of Mexico.

AbstractThe mass accommodation coefficient for uptake of water vapor to liquid water, αM, has been constrained using photoacoustic measurements of aqueous absorbing aerosol. Measurements performed over a range of relative humidities and pressures were compared to detailed model calculations treating coupled heat and mass transfer occurring during photoacoustic laser heating cycles. The strengths and weaknesses of this technique are very different to those for droplet growth/evaporation experiments that have typically been applied to these measurements, making this a useful complement to existing studies. Our measurements provide robust evidence that αM is greater than 0.1 for all humidities tested and greater than 0.3 for data obtained at relative humidities greater than 88% where the aerosol surface was most like pure water. These values of αM are above the threshold at which kinetic limitations are expected to impact the activation and growth of aerosol particles in warm cloud formation.

Aircraft observations of meteorological, trace gas, and aerosol properties were made between May and September 2013 in the southeastern United States (US). Regionally representative aggregate vertical profiles of median and interdecile ranges of the measured parameters were constructed from 37 individual aircraft profiles made in the afternoon when a well-mixed boundary layer with typical fair-weather cumulus was present (Wagner et al., 2015). We use these 0–4 km aggregate profiles and a simple model to calculate the sensitivity of aerosol optical depth (AOD) to changes in dry aerosol mass, relative humidity, mixed-layer height, the central diameter and width of the particle size distribution, hygroscopicity, and dry and wet refractive index, while holding the other parameters constant. The calculated sensitivity is a result of both the intrinsic sensitivity and the observed range of variation in these parameters. These observationally based sensitivity studies indicate that the relationship between AOD and dry aerosol mass in these conditions in the southeastern US can be highly variable and is especially sensitive to relative humidity (RH). For example, calculated AOD ranged from 0.137 to 0.305 as the RH was varied between the 10th and 90th percentile profiles with dry aerosol mass held constant. Calculated AOD was somewhat less sensitive to aerosol hygroscopicity, mean size, and geometric standard deviation, σg. However, some chemistry–climate models prescribe values of σg substantially larger than we or others observe, leading to potential high biases in model-calculated AOD of ∼ 25 %. Finally, AOD was least sensitive to observed variations in dry and wet aerosol refractive index and to changes in the height of the well-mixed surface layer. We expect these findings to be applicable to other moderately polluted and background continental air masses in which an accumulation mode between 0.1–0.5 µm diameter dominates aerosol extinction.

Aircraft observations of meteorological, trace gas, and aerosol properties were made during May–September 2013 in the southeastern United States (US) under fair-weather, afternoon conditions with well-defined planetary boundary layer structure. Optical extinction at 532 nm was directly measured at relative humidities (RHs) of ∼ 15, ∼ 70, and ∼ 90 % and compared with extinction calculated from measurements of aerosol composition and size distribution using the κ-Köhler approximation for hygroscopic growth. The calculated enhancement in hydrated aerosol extinction with relative humidity, f(RH), calculated by this method agreed well with the observed f(RH) at ∼ 90 % RH. The dominance of organic aerosol, which comprised 65 ± 10 % of particulate matter with aerodynamic diameter < 1 µm in the planetary boundary layer, resulted in relatively low f(RH) values of 1.43 ± 0.67 at 70 % RH and 2.28 ± 1.05 at 90 % RH. The subsaturated κ-Köhler hygroscopicity parameter κ for the organic fraction of the aerosol must have been < 0.10 to be consistent with 75 % of the observations within uncertainties, with a best estimate of κ = 0.05. This subsaturated κ value for the organic aerosol in the southeastern US is broadly consistent with field studies in rural environments. A new, physically based, single-parameter representation was developed that better described f(RH) than did the widely used gamma power-law approximation.

Natural emissions of ozone-and-aerosol-precursor gases such as isoprene and monoterpenes are high in the southeastern US. In addition, anthropogenic emissions are significant in the southeastern US and summertime photochemistry is rapid. The NOAA-led SENEX (Southeast Nexus) aircraft campaign was one of the major components of the Southeast Atmosphere Study (SAS) and was focused on studying the interactions between biogenic and anthropogenic emissions to form secondary pollutants. During SENEX, the NOAA WP-3D aircraft conducted 20 research flights between 27 May and 10 July 2013 based out of Smyrna, TN.Here we describe the experimental approach, the science goals and early results of the NOAA SENEX campaign. The aircraft, its capabilities and standard measurements are described. The instrument payload is summarized including detection limits, accuracy, precision and time resolutions for all gas-and-aerosol phase instruments. The inter-comparisons of compounds measured with multiple instruments on the NOAA WP-3D are presented and were all within the stated uncertainties, except two of the three NO2 measurements.The SENEX flights included day-and nighttime flights in the southeastern US as well as flights over areas with intense shale gas extraction (Marcellus, Fayetteville and Haynesville shale). We present one example flight on 16 June 2013, which was a daytime flight over the Atlanta region, where several crosswind transects of plumes from the city and nearby point sources, such as power plants, paper mills and landfills, were flown. The area around Atlanta has large biogenic isoprene emissions, which provided an excellent case for studying the interactions between biogenic and anthropogenic emissions. In this example flight, chemistry in and outside the Atlanta plumes was observed for several hours after emission. The analysis of this flight showcases the strategies implemented to answer some of the main SENEX science questions.

C. A. Brock, N. L. Wagner, B. E. Anderson, A. Beyersdorf, P. Campuzano-Jost, D. A. Day, G. S. Diskin, T. D. Gordon, J. L. Jimenez, D. A. Lack, J. Liao, M. Markovic, A. M. Middlebrook, A. E. Perring, M. S. Richardson, J. P. Schwarz, A. Welti, L. D. Ziemba, and D. M. Murphy NOAA Earth System Research Laboratory, Boulder, Colorado, USA Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA NASA Langley Research Center, Hampton, Virginia, USA Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado, USA now at: TEAC Consulting, Brisbane, Australia

Introduction Conclusions References

Vertical profiles of submicron aerosol from in situ aircraft-based measurements were used to construct aggregate profiles of chemical, microphysical, and optical properties. These vertical profiles were collected over the southeastern United States (SEUS) during the summer of 2013 as part of two separate field studies: the Southeast Nexus (SENEX) study and the Study of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS). Shallow cumulus convection was observed during many profiles. These conditions enhance vertical transport of trace gases and aerosol and create a cloudy transition layer on top of the sub-cloud mixed layer. The trace gas and aerosol concentrations in the transition layer were modeled as a mixture with contributions from the mixed layer below and the free troposphere above. The amount of vertical mixing, or entrainment of air from the free troposphere, was quantified using the observed mixing ratio of carbon monoxide (CO). Although the median aerosol mass, extinction, and volume decreased with altitude in the transition layer, they were ~10 % larger than expected from vertical mixing alone. This enhancement was likely due to secondary aerosol formation in the transition layer. Although the transition layer enhancements of the particulate sulfate and organic aerosol (OA) were both similar in magnitude, only the enhancement of sulfate was statistically significant. The column integrated extinction, or aerosol optical depth (AOD), was calculated for each individual profile, and the transition layer enhancement of extinction typically contributed less than 10 % to the total AOD. Our measurements and analysis were motivated by two recent studies that have hypothesized an enhanced layer of secondary aerosol aloft to explain the summertime enhancement of AOD (2–3 times greater than winter) over the southeastern United States. The first study attributes the layer aloft to secondary organic aerosol (SOA) while the second study speculates that the layer aloft could be SOA or secondary particulate sulfate. In contrast to these hypotheses, the modest enhancement we observed in the transition layer was not dominated by OA and was not a large fraction of the summertime AOD.

Emissions factors (EFs) for gas and sub-micron particle-phase species were measured in intercepted plumes as a function of vessel speed from an underway research vessel, the NOAA ship Miller Freeman, operating a medium-speed diesel engine on low-sulfur marine gas oil (fuel sulfur content ~0.1% by weight). The low-sulfur fuel in use conforms to the MARPOL fuel sulfur limit within emission control areas set to take effect in 2015 and to California-specific limits set to take effect in 2014. For many of the particle-phase species, EFs were determined using multiple measurement methodologies, allowing for an assessment of how well EFs from different techniques agree. The total sub-micron PM (PM1) was dominated by particulate black carbon (BC) and particulate organic matter (POM), with an average POM / BC ratio of 1.3. Consideration of the POM / BC ratios observed here with literature studies suggests that laboratory and in-stack measurement methods may overestimate primary POM EFs relative to those observed in emitted plumes. Comparison of four different methods for black carbon measurement indicates that careful attention must be paid to instrument limitations and biases when assessing EFBC. Particulate sulfate (SO42−) EFs were extremely small and the particles emitted by Miller Freeman were inefficient as cloud condensation nuclei (CCN), even at high super saturations, consistent with the use of very low-sulfur fuel and the overall small emitted particle sizes. All measurement methodologies consistently demonstrate that the measured EFs (fuel mass basis) for PM1 mass, BC and POM decreased as the ship slowed. Particle number EFs were approximately constant across the speed change, with a shift towards smaller particles being emitted at slower speeds. Emissions factors for gas-phase CO and formaldehyde (HCHO) both increased as the vessel slowed, while EFs for NOx decreased and SO2 EFs were approximately constant.

Black carbon (BC) mass emission factors (EFBC; g BC (kg fuel)−1) from a variety of ocean-going vessels have been determined from measurements of BC and carbon dioxide (CO2) concentrations in ship plumes intercepted by the R/V Atlantis during the 2010 California Nexus (CalNex) campaign. The ships encountered were all operating within 24 nautical miles of the California coast and were utilizing relatively low sulphur fuels (average fuel sulphur content of 0.4%, 0.09% and 0.03% for vessels operating slow-speed, medium-speed and high-speed diesel engines, respectively). Black carbon concentrations within the plumes, from which EFBC values are determined, were measured using four independent instruments: a photoacoustic spectrometer and a particle soot absorption photometer, which measure light absorption, and a single particle soot photometer and soot particle aerosol mass spectrometer, which measure the mass concentration of refractory BC directly. These measurements have been used to assess the level of agreement between these different techniques for the determination of BC emission factors from ship plumes. Also, these measurements greatly expand upon the number of individual ships for which BC emission factors have been determined during real-world operation. The measured EFBC's have been divided into vessel type categories and engine type categories, from which averages have been determined. The geometric average EFBC (excluding outliers) determined from over 71 vessels and 135 plumes encountered was 0.31 &pm; 0.31 g BC (kg fuel)−1, where the standard deviation represents the variability between individual vessels. The most frequent engine type encountered was the slow-speed diesel (SSD), and the most frequent SSD vessel type was the cargo ship sub-category. Average and median EFBC values from the SSD category are compared with previous observations from the Texas Air Quality Study (TexAQS) in 2006, during which the ships encountered were predominately operating on high-sulphur fuels (average fuel sulphur content of 1.6%). There is a statistically significant difference between the EFBC values from CalNex and TexAQS for SSD vessels and for the cargo and tanker ship types within this engine category. The CalNex EFBC values are lower than those from TexAQS, suggesting that operation on lower sulphur fuels is associated with smaller EFBC values.