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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 and then thermally denuded, leading to the collapse of the initially lacy, fractal-like morphology. The measured mass absorption coefficients (MACs) 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 > ∼ 160nm, the MAC and absorption Ångström exponent (AAE) values were independent of particle collapse while the single-scatter albedo increased. The MAC values for these larger particles were also size-independent. The mean MAC value at 532nm for larger particles was 9.1±1.1m2g-1, about 17% higher than that recommended by Bond and Bergstrom (2006), and the AAE was close to unity. 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 underpredicts 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. (The dimensionless size parameter x = π dp/λ, where dp is particle diameter and λ is wavelength.) Importantly, this implies that the use of Mie theory within air quality and climate models, as is common, likely leads to underpredictions in the absorption by BC, with the extent of underprediction 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.

Oxidation flow reactors (OFRs) allow the concentration of a given atmospheric oxidant to be increased beyond ambient levels in order to study secondary organic aerosol (SOA) formation and aging over varying periods of equivalent aging by that oxidant. Previous studies have used these reactors to determine the bulk OA mass and chemical evolution. To our knowledge, no OFR study has focused on the interpretation of the evolving aerosol size distributions. In this study, we use size-distribution measurements of the OFR and an aerosol microphysics model to learn about size-dependent processes in the OFR. Specifically, we use OFR exposures between 0.09 and 0.9 equivalent days of OH aging from the 2011 BEACHON-RoMBAS and GoAmazon2014/5 field campaigns. We use simulations in the TOMAS (TwO-Moment Aerosol Sectional) microphysics box model to constrain the following parameters in the OFR: (1) the rate constant of gas-phase functionalization reactions of organic compounds with OH, (2) the rate constant of gas-phase fragmentation reactions of organic compounds with OH, (3) the reactive uptake coefficient for heterogeneous fragmentation reactions with OH, (4) the nucleation rate constants for three different nucleation schemes, and (5) an effective accommodation coefficient that accounts for possible particle diffusion limitations of particles larger than 60nm in diameter. We find the best model-to-measurement agreement when the accommodation coefficient of the larger particles (Dp>60nm) was 0.1 or lower (with an accommodation coefficient of 1 for smaller particles), which suggests a diffusion limitation in the larger particles. When using these low accommodation-coefficient values, the model agrees with measurements when using a published H2SO4-organics nucleation mechanism and previously published values of rate constants for gas-phase oxidation reactions. Further, gas-phase fragmentation was found to have a significant impact upon the size distribution, and including fragmentation was necessary for accurately simulating the distributions in the OFR. The model was insensitive to the value of the reactive uptake coefficient on these aging timescales. Monoterpenes and isoprene could explain 24%-95% of the observed change in total volume of aerosol in the OFR, with ambient semivolatile and intermediate-volatility organic compounds (S/IVOCs) appearing to explain the remainder of the change in total volume. These results provide support to the mass-based findings of previous OFR studies, give insight to important size-distribution dynamics in the OFR, and enable the design of future OFR studies focused on new particle formation and/or microphysical processes.

ABSTRACT Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated [...]

Low-cost gas and particulate matter sensor packages offer a compact, lightweight, and easily transportable solution to address global gaps in air quality (AQ) observations. However, regions that would benefit most from widespread deployment of low-cost AQ monitors often lack the reference-grade equipment required to reliably calibrate and validate them. In this study, we explore approaches to calibrating and validating three integrated sensor packages before a 1-year deployment to rural Malawi using colocation data collected at a regulatory site in North Carolina, USA. We compare the performance of five computational modeling approaches to calibrate the electrochemical gas sensors: k -nearest neighbors (k NN) hybrid, random forest (RF) hybrid, high-dimensional model representation (HDMR), multilinear regression (MLR), and quadratic regression (QR). For the CO, O x , NO, and NO 2 sensors, we found that k NN hybrid models returned the highest coefficients of determination and lowest error metrics when validated. Hybrid models were also the most transferable approach when applied to deployment data collected in Malawi. We compared k NN hybrid calibrated CO observations from two regions in Malawi to remote sensing data and found qualitative agreement in spatial and annual trends. However, ARISense monthly mean surface observations were 2 to 4 times higher than the remote sensing data, partly due to proximity to residential biomass combustion activity not resolved by satellite imaging. We also compared the performance of the integrated Alphasense OPC-N2 optical particle counter to a filter-corrected nephelometer using colocation data collected at one of our deployment sites in Malawi. We found the performance of the OPC-N2 varied widely with environmental conditions, with the worst performance associated with high relative humidity (RH >70 %) conditions and influence from emissions from nearby residential biomass combustion. We did not find obvious evidence of systematic sensor performance decay after the 1-year deployment to Malawi. Data recovery (30 %–80 %) varied by sensor and season and was limited by insufficient power and access to resources at the remote deployment sites. Future low-cost sensor deployments to rural, low-income settings would benefit from adaptable power systems, standardized sensor calibration methodologies, and increased regional regulatory-grade monitoring infrastructure. [ABSTRACT FROM AUTHOR]

This study compares the optical coefficients of size-selected soot particles measured at a wavelength of 870 nm with those predicted by three theories, namely, Rayleigh-Debye-Gans (RDG) approximation, volume-equivalent Mie theory, and integral equation formulation for scattering (IEFS). Soot particles, produced by a premixed ethene flame, were size-selected using two differential mobility analyzers in series, and their scattering and absorption coefficients were measured with nephelometry and photo-acoustic spectroscopy. Scanning electron microscopy and image processing techniques were used for the parameterization of the structural properties of the fractal-like soot aggregates. The aggregate structural parameters were used to evaluate the predictions of the optical coefficients based on the three light-scattering and absorption theories. Our results show that the RDG approximation agrees within 10% with the experimental results and the exact electromagnetic calculations of the IEFS theory. Volume-equivalent Mie theory overpredicts the experimental scattering coefficient by a factor of ~3.2. The optical coefficients predicted by the RDG approximation showed pronounced sensitivity to changes in monomer mean diameter, the count median diameter of the aggregates, and the geometric standard deviation of the aggregate number size distribution. OCIS codes: 010.1290, 290.5850.

Low-cost gas and particulate sensor packages offer a compact, lightweight, and easily transportable solution to address global gaps in air quality (AQ) observations. However, regions that would benefit most from widespread deployment of low-cost AQ monitors often lack the reference grade equipment required to reliably calibrate and validate them. In this study, we explore approaches to calibrating and validating three integrated sensor packages before a 1-year deployment to rural Malawi using collocation data collected at a regulatory site in North Carolina, USA. We compare the performance of five computational modelling approaches to calibrate the electrochemical gas sensors: k-Nearest Neighbor (kNN) hybrid, random forest (RF) hybrid, high-dimensional model representation (HDMR), multilinear regression (MLR), and quadratic regression (QR). For the CO, Ox, NO, and NO2 sensors, we found that kNN hybrid models returned the highest coefficients of determination and lowest error metrics when validated; they also appeared to be the most transferable approach when applied to field data collected in Malawi. We compared calibrated CO observations to remote sensing data in two regions in Malawi and found qualitative agreement in spatial and annual trends. However, the monthly mean surface observations were 2 to 4 times higher than the remote sensing data, possibly due to proximity to small-scale combustion activity not resolved by satellite imaging. We also compared the performance of the integrated Alphasense OPC-N2 optical particle counter to a filter-corrected nephelometer using collocation data collected at one of our deployment sites in Malawi. We found the performance of the OPC-N2 varied widely with environmental conditions, with the worst performance associated with high relative humidity (RH > 70 %) conditions and influence from emissions from nearby biomass cookstoves. We did not find obvious evidence of systematic sensor performance decay after the 1-year deployment to Malawi; however, overall data recovery was limited by insufficient power and access to technical resources at deployment sites. Future low-cost sensor deployments to rural Sub-Saharan Africa would benefit from adaptable power systems, standardized sensor calibration methodologies, and increased regulatory grade regional infrastructure. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The high atmospheric concentrations of toxic gases, particulate matter, and acids in the areas immediately surrounding volcanoes can have negative impacts on human and ecological health. To better understand the atmospheric fate of volcanogenic emissions in the near field (in the first few hours after emission), we have carried out real-time measurements of key chemical components of the volcanic plume from Kilauea on the Island of Hawai'i. Measurements were made at two locations, one ~3 km north-northeast of the vent and the other 31 km to the southwest, with sampling at each site spanning a range of meteorological conditions and volcanic influence. Instrumentation included a sulfur dioxide monitor and an Aerosol Chemical Speciation Monitor, allowing for a measurement of the partitioning between the two major sulfur species (gas-phase SO2 and particulate sulfate) every 5 min. During trade wind conditions, which sent the plume toward the southwest site, sulfur partitioning exhibited a clear diurnal pattern, indicating photochemical oxidation of SO2 to sulfate; this enabled the quantitative determination of plume age (5 h) and instantaneous SO2 oxidation rate (2.4 × 10-6 s-1 at solar noon). Under stagnant conditions near the crater, the extent of SO2 oxidation was substantially higher, suggesting faster oxidation. The particles within the plume were extremely acidic, with pH values (controlled largely by ambient relative humidity) as low as -0.8 and strong acidity (controlled largely by absolute sulfate levels) up to 2200 nmol/m³. The high variability of sulfur partitioning and particle composition underscores the chemically dynamic nature of volcanic plumes, which may have important implications for human and ecological health. [ABSTRACT FROM AUTHOR]