The chemical composition of aerosol particles (Dp ≤ 1.5 μm) was measured over the southeast Pacific Ocean during the VAMOS (Variability of the American Monsoon Systems) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-Rex) between 16 October and 15 November 2008 using the US Department of Energy (DOE) G-1 aircraft. The objective of these flights was to gain an understanding of the sources and evolution of these aerosols, and of how they interact with the marine stratus cloud layer that prevails in this region of the globe. Our measurements showed that the marine boundary layer (MBL) aerosol mass was dominated by non-sea-salt SO42−, followed by Na+, Cl−, Org (total organics), NH4+, and NO3−, in decreasing order of importance; CH3SO3− (MSA), Ca2+, and K+ rarely exceeded their limits of detection. Aerosols were strongly acidic with a NH4+ to SO42− equivalents ratio typically < 0.3. Sea-salt aerosol (SSA) particles, represented by NaCl, exhibited Cl− deficits caused by both HNO3 and H2SO4, but for the most part were externally mixed with particles, mainly SO42−. SSA contributed only a small fraction of the total accumulation mode particle number concentration. It was inferred that all aerosol species (except SSA) were of predominantly continental origin because of their strong land-to-sea concentration gradient. Comparison of relative changes in median values suggests that (1) an oceanic source of NH3 is present between 72° W and 76° W, (2) additional organic aerosols from biomass burns or biogenic precursors were emitted from coastal regions south of 31° S, with possible cloud processing, and (3) free tropospheric (FT) contributions to MBL gas and aerosol concentrations were negligible. The very low levels of CH3SO3− observed as well as the correlation between SO42− and NO3− (which is thought primarily anthropogenic) suggest a limited contribution of DMS to SO42− aerosol production during VOCALS.

Utilizing the unique characteristics of the cloud over the Southeast Pacific (SEP) off the coast of Chile during the VOCALS field campaign, we compared satellite remote sensing of cloud microphysical properties against in-situ data from multi-aircraft observations, and studied the extent to which these retrieved properties are sufficiently constrained and consistent to reliably quantify the influence of aerosol loading on cloud droplet sizes. After constraining the spatial-temporal coincidence between satellite retrievals and in-situ measurements, we selected 17 non-drizzle comparison pairs. For these cases the mean aircraft profiling times were within one hour of Terra overpasses at both projected and un-projected (actual) aircraft positions for two different averaging domains of 5 km and 25 km. Retrieved quantities that were averaged over a larger domain of 25 km compared better statistically with in-situ observations than averages over a smaller domain of 5 km. Comparison at projected aircraft positions was slightly better than un-projected aircraft positions for some parameters. Overall, both MODIS-retrieved effective radius and LWP were larger but highly correlated with the in-situ measured effective radius and LWP, e. g., for averaging domains of 5 km, the biases are up to 1.75 mu m and 0.02 mm whilst the correlation coefficients are about 0.87 and 0.85, respectively. The observed effective radius difference between the two decreased with increasing cloud drop number concentration (CDNC), and increased with increasing cloud geometrical thickness. Compared to the absolute effective radius difference, the correlations between the relative effective radius difference and CDNC or cloud geometric thickness are weaker. For averaging domains of 5 km and 25 km, the correlation coefficients between MODIS-retrieved and in-situ measured CDNC are 0.91 and 0.93 with fitting slopes of 1.23 and 1.27, respectively. If the cloud adiabaticity is taken into account, better agreements are achieved for both averaging domains (the fitting slopes are 1.04 and 1.07, respectively). Our comparison and sensitivity analysis of simulated retrievals demonstrate that both cloud geometrical thickness and cloud adiabaticity are important factors in satellite retrievals of effective radius and cloud drop number concentration. The large variabilities in cloud geometrical thickness and adiabaticity, the dependencies of cloud microphysical properties on both quantities (as demonstrated in our sensitivity study of simulated retrievals), and the inability to accurately account for either of them in retrievals lead to some uncertainties and biases in satellite retrieved cloud effective radius, cloud liquid water path, and cloud drop number concentration. However, strong correlations between satellite retrievals and in-situ measurements suggest that satellite retrievals of cloud effective radius, cloud liquid water path, and cloud drop number concentration can be used to investigate aerosol indirect effects qualitatively.

Abstract. Utilizing the unique characteristics of the cloud over the Southeast Pacific (SEP) off the coast of Chile during the VOCALS field campaign, we validated satellite remote sensing of cloud microphysical properties against in situ data from multi-aircraft observations, and studied the extent to which these retrieved properties are sufficiently constrained and consistent to reliably quantify the influence of aerosol loading on cloud droplet sizes. After constraining the spatial-temporal coincidence between satellite retrievals and in situ measurements, we selected 17 non-drizzle comparison pairs. For these cases the mean aircraft profiling times were within one hour of Terra overpass at both projected and un-projected (actual) aircraft positions for two different averaging domains of 5 km and 25 km. Retrieved quantities that were averaged over a larger domain of 25 km compared better statistically with in situ observations than averages over a smaller domain of 5 km. Validation at projected aircraft positions was slightly better than un-projected aircraft positions for some parameters. Overall, both MODIS-retrieved effective radius and LWP were larger but highly correlated with the in situ measured effective radius and LWP. The observed effective radius difference between the two decreased with increasing cloud drop number concentration, and increased with increasing cloud geometrical thickness. Also, MODIS retrievals for adiabatic clouds agreed better with the in situ measurements than for sub-adiabatic clouds. Our validation and sensitivity analysis of simulated retrievals demonstrate that both cloud geometrical thickness and cloud adiabaticity are important factors in satellite retrievals of effective radius and cloud drop number concentration. The large variabilities in cloud geometric thickness and adiabaticity, the dependencies of cloud microphysical properties on both quantities (as demonstrated in our sensitivity study of simulated retrievals), and the inability to accurately account for either of them in retrievals lead to substantial uncertainties and biases in satellite retrieved cloud effective radius, cloud liquid water path, and cloud drop number concentration. However, strong correlations between satellite retrievals and in situ measurements suggest that satellite retrievals of cloud effective radius, cloud liquid water path, and cloud drop number concentration can be used to investigate aerosol indirect effects qualitatively.

During the VOCALS Regional Experiment, the DOE G-1 aircraft was used to sample a varying aerosol environment pertinent to properties of stratocumulus clouds over a longitude band extending 800 km west from the Chilean coast at Arica. Trace gas and aerosol measurements are presented as a function of longitude, altitude, and dew point in this study. Spatial distributions are consistent with an upper atmospheric source for O3 and South American coastal sources for marine boundary layer (MBL) CO and aerosol, most of which is acidic sulfate. Pollutant layers in the free troposphere (FT) can be a result of emissions to the north in Peru or long range transport from the west. At a given altitude in the FT (up to 3 km), dew point varies by 40 °C with dry air descending from the upper atmospheric and moist air having a boundary layer (BL) contribution. Ascent of BL air to a cold high altitude results in the condensation and precipitation removal of all but a few percent of BL water along with aerosol that served as CCN. Thus, aerosol volume decreases with dew point in the FT. Aerosol size spectra have a bimodal structure in the MBL and an intermediate diameter unimodal distribution in the FT. Comparing cloud droplet number concentration (CDNC) and pre-cloud aerosol (Dp>100 nm) gives a linear relation up to a number concentration of ~150 cm−3, followed by a less than proportional increase in CDNC at higher aerosol number concentration. A number balance between below cloud aerosol and cloud droplets indicates that ~25 % of aerosol with Dp>100 nm are interstitial (not activated). A direct comparison of pre-cloud and in-cloud aerosol yields a higher estimate. Artifacts in the measurement of interstitial aerosol due to droplet shatter and evaporation are discussed. Within each of 102 constant altitude cloud transects, CDNC and interstitial aerosol were anti-correlated. An examination of one cloud as a case study shows that the interstitial aerosol appears to have a background, upon which is superimposed a high frequency signal that contains the anti-correlation. The anti-correlation is a possible source of information on particle activation or evaporation.

This study assesses the ability of the recent chemistry version (v3.3) of the Weather Research and Forecasting (WRF-Chem) model to simulate boundary layer structure, aerosols, stratocumulus clouds, and energy fluxes over the Southeast Pacific Ocean. Measurements from the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) and satellite retrievals (i.e., products from the MODerate resolution Imaging Spectroradiometer (MODIS), Clouds and Earth's Radiant Energy System (CERES), and GOES-10) are used for this assessment. The Morrison double-moment microphysics scheme is newly coupled with interactive aerosols in the model. The 31-day (15 October–16 November 2008) WRF-Chem simulation with aerosol-cloud interactions (AERO hereafter) is also compared to a simulation (MET hereafter) with fixed cloud droplet number concentrations in the microphysics scheme and simplified cloud and aerosol treatments in the radiation scheme. The well-simulated aerosol quantities (aerosol number, mass composition and optical properties), and the inclusion of full aerosol-cloud couplings lead to significant improvements in many features of the simulated stratocumulus clouds: cloud optical properties and microphysical properties such as cloud top effective radius, cloud water path, and cloud optical thickness. In addition to accounting for the aerosol direct and semi-direct effects, these improvements feed back to the simulation of boundary-layer characteristics and energy budgets. Particularly, inclusion of interactive aerosols in AERO strengthens the temperature and humidity gradients within the capping inversion layer and lowers the marine boundary layer (MBL) depth by 130 m from that of the MET simulation. These differences are associated with weaker entrainment and stronger mean subsidence at the top of the MBL in AERO. Mean top-of-atmosphere outgoing shortwave fluxes, surface latent heat, and surface downwelling longwave fluxes are in better agreement with observations in AERO, compared to the MET simulation. Nevertheless, biases in some of the simulated meteorological quantities (e.g., MBL temperature and humidity) and aerosol quantities (e.g., underestimations of accumulation mode aerosol number) might affect simulated stratocumulus and energy fluxes over the Southeastern Pacific, and require further investigation. The well-simulated timing and outflow patterns of polluted and clean episodes demonstrate the model's ability to capture daily/synoptic scale variations of aerosol and cloud properties, and suggest that the model is suitable for studying atmospheric processes associated with pollution outflow over the ocean. The overall performance of the regional model in simulating mesoscale clouds and boundary layer properties is encouraging and suggests that reproducing gradients of aerosol and cloud droplet concentrations and coupling cloud-aerosol-radiation processes are important when simulating marine stratocumulus over the Southeast Pacific.

The VAMOS Ocean-Cloud-Atmosphere-Land Regional Experiment (VOCALS-REx) was conducted from 15 October to 15 November 2008 in the South East Pacific (SEP) region to investigate interactions between land, sea and atmosphere in this unique tropical eastern ocean environment and to improve the skill of global and regional models in representing the region. This study synthesises selected aircraft, ship and surface site observations from VOCALS-REx to statistically summarise and characterise the atmospheric composition and variability of the Marine Boundary Layer (MBL) and Free Troposphere (FT) along the 20° S parallel between 70° W and 85° W. Significant zonal gradients in mean MBL sub-micron aerosol particle size and composition, carbon monoxide, sulphur dioxide and ozone were seen over the campaign, with a generally more variable and polluted coastal environment and a less variable, more pristine remote maritime regime. Gradients in aerosol and trace gas concentrations were observed to be associated with strong gradients in cloud droplet number. The FT was often more polluted in terms of trace gases than the MBL in the mean; however increased variability in the FT composition suggests an episodic nature to elevated concentrations. This is consistent with a complex vertical interleaving of airmasses with diverse sources and hence pollutant concentrations as seen by generalised back trajectory analysis, which suggests contributions from both local and long-range sources. Furthermore, back trajectory analysis demonstrates that the observed zonal gradients both in the boundary layer and the free troposphere are characteristic of marked changes in airmass history with distance offshore – coastal boundary layer airmasses having been in recent contact with the local land surface and remote maritime airmasses having resided over ocean for in excess of ten days. Boundary layer composition to the east of 75° W was observed to be dominated by coastal emissions from sources to the west of the Andes, with evidence for diurnal pumping of the Andean boundary layer above the height of the marine capping inversion. Analysis of intra-campaign variability in atmospheric composition was not found to be significantly correlated with observed low-frequency variability in the large scale flow pattern; campaign-average interquartile ranges of CO, SO2 and O3 concentrations at all longitudes were observed to dominate over much smaller differences in median concentrations calculated between periods of different flow regimes. The campaign climatology presented here aims to provide a valuable dataset to inform model simulation and future process studies, particularly in the context of aerosol-cloud interaction and further evaluation of dynamical processes in the SEP region for conditions analogous to those during VOCALS-REx. To this end, our results are discussed in terms of coastal, transitional and remote spatial regimes in the MBL and FT and a gridded dataset are provided as a resource.

The Cumulus Humilis Aerosol Processing Study (CHAPS) provided a unique opportunity to study aerosol and cloud processing. Clouds play an active role in the processing and cycling of atmospheric constituents. Gases and particles can partition to cloud droplets by absorption and condensation as well as activation and impact scavenging. The U.S. Department of Energy (DOE) G-1 aircraft was used as one of the main platforms in CHAPS. Flight tracks were designed and implemented to characterize freshly emitted aerosols at cloud top and cloud base as well as within the cloud, i.e., cumulus humilis (or fair-weather cumulus), in the vicinity of Oklahoma City. Measurements of interstitial aerosols and residuals of activated condensation cloud nuclei were conducted simultaneously. The interstitial aerosols were measured downstream of an isokinetic inlet, and the activated particles downstream of a counter-flow virtual impactor (CVI). The sampling line to the Aerodyne Aerosol Mass Spectrometer (AMS) was switched between the isokinetic inlet and the CVI to allow characterization of non-activated interstitial particles outside of clouds in contrast to particles activated in clouds. Trace gases including ozone, carbon monoxide, sulfur dioxide, and a series of volatile organic compounds (VOCs) were also measured, as were key meteorological state parameters including liquid water content, cloud drop size, and dew point. We will report on the CCN properties in cumulus humilis. Several approaches will be taken. The first is single-particle analysis of particles collected by the Time-Resolved Aerosol Sampler (TRAC) by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) coupled with energy disperse X-ray spectroscopy (EDX). Specifically, we examine differences between activated and interstitial ones, such as differences in chemical composition and morphology. The second analysis will link in situ measurements by AMS and PTRMS with the observations by TRAC. For instance, by comparing the characteristic m/z obtained by AMS and the CO or isoprene, one can gain more insight into the role of primary and secondary organic aerosols in CCN and background aerosols. Combined with observations of cloud properties, our goal is to provide an improved picture of CCN activation in cumulus humilis.

As part of the MILAGRO field campaign, the DOE G-1 aircraft was used to make measurements over and downwind of Mexico City with the objective of determining growth characteristics of aerosols from a megacity urban source. This study focuses on number concentration and size distributions. It is found that a 5-fold increase in aerosol volume is accompanied by about a 5-fold increase in accumulation mode number concentration. There is growth in aerosol volume because there are more accumulation mode particles, not because of an increase in the average size of accumulation particles. Condensation and volume growth laws were examined to see whether either is consistent with observations. Condensation calculations show that the growth of Aitken mode particles into the accumulation mode size range gives the required increase in number concentration. There are minimal changes in the accumulation mode size distribution with age, consistent with observations. Volume-growth in contrast yields a population of large particles, distinctly different from what is observed. Detailed model calculations are required to translate our observations into specific information on the volatility and properties of secondary organic aerosol.

The time evolution of aerosol concentration and chemical composition in a megacity urban plume was determined based on 8 flights of the DOE G-1 aircraft in and downwind of Mexico City during the March 2006 MILAGRO field campaign. A series of selection criteria are imposed to eliminate data points with non-urban emission influences. Biomass burning has urban and non-urban sources that are distinguished on the basis of CH3CN and CO. In order to account for dilution in the urban plume, aerosol concentrations are normalized to CO which is taken as an inert tracer of urban emission, proportional to the emissions of aerosol precursors. Time evolution is determined with respect to photochemical age defined as −Log10 (NOx/NOy). The geographic distribution of photochemical age and CO is examined, confirming the picture that Mexico City is a source region and that pollutants become more dilute and aged as they are advected towards T1 and T2, surface sites that are located at the fringe of the City and 35 km to the NE, respectively. Organic aerosol (OA) per ppm CO is found to increase 7 fold over the range of photochemical ages studied, corresponding to a change in NOx/NOy from nearly 100% to 10%. In the older samples the nitrate/CO ratio has leveled off suggesting that evaporation and formation of aerosol nitrate are in balance. In contrast, OA/CO increases with age in older samples, indicating that OA is still being formed. The amount of carbon equivalent to the deduced change in OA/CO with age is 56 ppbC per ppm CO. At an aerosol yield of 5% and 8% for low and high yield aromatic compounds, it is estimated from surface hydrocarbon observations that only ~9% of the OA formation can be accounted for. A comparison of OA/CO in Mexico City and the eastern U.S. gives no evidence that aerosol yields are higher in a more polluted environment.

Effects of aerosol organics on cloud condensation nucleus (CCN) concentration and first indirect aerosol effect J. Wang, Y.-N. Lee, P. H. Daum, J. Jayne, and M. L. Alexander Brookhaven National Laboratory, 75 Rutherford Drive, Upton, NY 11973-5000, USA Aerodyne Research Inc. 45 Manning Road, Billerica, MA 01821-3976, USA Pacific Northwest National Laboratory, P.O. Box 999, K8-88 Richland, WA 99352, USA Received: 9 April 2008 – Accepted: 16 April 2008 – Published: 28 May 2008 Correspondence to: J. Wang (jian@bnl.gov) Published by Copernicus Publications on behalf of the European Geosciences Union.