CCN Data Interpretation Under Dynamic Operation Conditions

We have developed a new numerical model for the non-steadystate operation of the Droplet Measurement Technologies (DMT) Cloud Condensation Nuclei (CCN) counter. The model simulates the Scanning Flow CCN Analysis (SFCA) instrument mode, where a wide supersaturation range is continuously scanned by cycling the flowrate over 20–120 s. Model accuracy is verified using a broad set of data which include ammonium sulfate calibration data (under conditions of low CCN concentration) and airborne measurements where either the instrument pressure was not controlled or where exceptionally high CCN loadings were observed. It is shown here for the first time that small pressure and flow fluctuations can have a disproportionately large effect on the instrument supersaturation due to localized compressive/expansive heating and cooling. The model shows that, for fast scan times, these effects can explain the observed shape of the SFCA supersaturation-flow calibration curve and transients in the outlet droplet sizes. The extent of supersaturation depletion from the presence of CCN during SFCA operation is also examined; we found that depletion effects can be neglected below 4000 cm−3 for CCN number

Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol^(−1) for the LO-OOA, 89 ± 10 kJ mol^(−1) for the MO-OOA, 55 ± 11 kJ mol^(−1) for the BBOA, and 63 ± 15 kJ mol^(−1) for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O  :  C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties

Organic aerosol in the summertime southeastern United States: components and their link to volatility distribution, oxidation state and hygroscopicity

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centreville, Alabama) was constrained using measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a thermodenuder (TD). Positive matrix factorization (PMF) analysis was applied on both the ambient and thermodenuded high-resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiol (IEPOX)-related factor (isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol^(−1) for the LO-OOA, 89 ± 10 kJ mol^(−1) for the MO-OOA, 55 ± 11 kJ mol^(−1) for the BBOA, and 63 ± 15 kJ mol^(−1) for the isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O  :  C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due to its low enthalpy of vaporization according to the model. The isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties

Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO(2) and NO(x) in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NO(x) is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NO(x) can mediate 43–70% of total measured organic aerosol (29–49% of submicron particulate matter, PM(1)) in the southeastern US during summer. These measurements imply that future reduction in SO(2) and NO(x) emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic−biogenic interactions and consequently improve air quality and climate simulations

Worldwide data sets constrain the water vapor uptake coefficient in cloud formation

Cloud droplet formation depends on the condensation of water vapor on ambient aerosols, the rate of which is strongly affected by the kinetics of water uptake as expressed by the condensation (or mass accommodation) coefficient, α_c. Estimates of α_c for droplet growth from activation of ambient particles vary considerably and represent a critical source of uncertainty in estimates of global cloud droplet distributions and the aerosol indirect forcing of climate. We present an analysis of 10 globally relevant data sets of cloud condensation nuclei to constrain the value of αc for ambient aerosol. We find that rapid activation kinetics (α_c > 0.1) is uniformly prevalent. This finding resolves a long-standing issue in cloud physics, as the uncertainty in water vapor accommodation on droplets is considerably less than previously thought

Linking aerosol hygroscopicity, volatility, and oxidation with cloud condensation nuclei activity: From laboratory to ambient particles

The indirect effect of atmospheric aerosol on climate remains a large source of uncertainty in anthropogenic climate change prediction. An important fraction of this uncertainty arises from the impacts of organic aerosol on cloud droplet formation. Conventional thinking says that organic aerosol hygroscopicity, typically represented by the hygroscopicity parameter κ, increases with oxidation, most commonly represented by the oxygen to carbon ratio of the aerosol, O:C. Furthermore, these quantities are expected to increase as aerosol volatility decreases. Results indicate that the link between organic aerosol hygroscopicity and oxidation is not always straightforward, and in some cases, the average carbon oxidation state OSc appears to be a better indicator of oxidation than the oxygen to carbon ratio, O:C. In chamber and ambient studies, the least volatile fraction of the aerosol also appeared to be the least hygroscopic, contradictory to current thinking; however, in both cases, thermally-denuded aerosol showed greater oxidation, in terms of OSc, than non-denuded aerosol. When these findings are placed in the context of numerous published studies from a variety of different environment, the overall trend of increasing organic hygroscopicity with O:C still holds. This is also true for volatilized aerosol, though the magnitude of organic hygroscopicity is generally lower than that of non-denuded aerosol.Ph.D

Toward the Determination of Joint Volatility-Hygroscopicity Distributions: Development and Response Characterization for Single-Component Aerosol

<div><p>This work presents the development and characterization of a thermodenuder for the study and interpretation of aerosol volatility. Thermodenuder measurements are further combined with a continuous-flow streamwise thermal gradient CCN counter to obtain the corresponding aerosol hygroscopicity. The thermodenuder response function is characterized with monodisperse aerosol of variable volatility and hygroscopicity. The measurements are then interpreted with a comprehensive instrument model embedded within an optimization framework to retrieve aerosol properties with constrained uncertainty. Special attention is given to the interpretation of the size distribution of the thermodenuded aerosol, deconvoluting the effects of impurities and multiple charging, and to simplifications on the treatment of thermodenuder geometry, temperature, the cooling section, and the effects of curvature and accommodation coefficient on inferred particle volatility. Retrieved vapor pressures are consistent with published literature and shown to be most sensitive to uncertainty in the accommodation coefficient.</p> <p>Copyright 2014 American Association for Aerosol Research</p> </div

Effects of anthropogenic emissions on aerosol formation from isoprene and monoterpenes in the southeastern United States

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO(2) and NO(x) in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NO(x) is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NO(x) can mediate 43–70% of total measured organic aerosol (29–49% of submicron particulate matter, PM(1)) in the southeastern US during summer. These measurements imply that future reduction in SO(2) and NO(x) emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic−biogenic interactions and consequently improve air quality and climate simulations