ALBERT

Description: Aerosol loading in the marine environment is investigated using aerosol composition measurements from several research ship campaigns (ICEALOT, MAP, RHaMBLe, VOCALS and OOMPH), observations of total AOD column from satellite (MODIS) and ship-based instruments (Maritime Aerosol Network, MAN), and a global chemical transport model (GEOS-Chem). This work represents the most comprehensive evaluation of oceanic OM emission inventories to date, by employing aerosol composition measurements obtained from campaigns with wide spatial and temporal coverage. The model underestimates AOD over the remote ocean on average by 0.02 (21 %), compared to satellite observations, but provides an unbiased simulation of ground-based Maritime Aerosol Network (MAN) observations. Comparison with cruise data demonstrates that the GEOS-Chem simulation of marine sulfate, with the mean observed values ranging between 0.22 μg m−3 and 1.34 μg m−3, is generally unbiased, however surface organic matter (OM) concentrations, with the mean observed concentrations between 0.07 μg m−3 and 0.77 μg m−3, are underestimated by a factor of 2–5 for the standard model run. Addition of a sub-micron marine OM source of approximately 9 TgC yr−1 brings the model into agreement with the ship-based measurements, however this additional OM source does not explain the model underestimate of marine AOD. The model underestimate of marine AOD is therefore likely the result of a combination of satellite retrieval bias and a missing marine aerosol source (which exhibits a different spatial pattern than existing aerosol in the model).

Description: Ambient particles collected on teflon filters at the Peak of Whistler Mountain, British Columbia (2182 m a.s.l.) during spring and summer 2009 were measured by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFG). The project mean and standard deviation of organic aerosol mass concentrations (OM) for all samples was 3.2±3.3 (μg m−3). Measurements of aerosol mass fragments, size, and number concentrations were used to separate fossil-fuel combustion and burning and non-burning forest sources of the measured organic aerosol. The OM was composed of the same anthropogenic and non-burning forest components observed at Whistler mid-valley in the spring of 2008; during the 2009 campaign, biomass burning aerosol was additionally observed from fire episodes occurring between June and September. On average, organic hydroxyl, alkane, carboxylic acid, ketone, and primary amine groups represented 31 %±11 %, 34 %±9 %, 23 %±6 %, 6 %±7 %, and 6 %±3 % of OM, respectively. Ketones in aerosols were associated with burning and non-burning forest origins, and represented up to 27 % of the OM. The organic aerosol fraction resided almost entirely in the submicron fraction without significant diurnal variations. OM/OC mass ratios ranged mostly between 2.0 and 2.2 and O/C atomic ratios between 0.57 and 0.76, indicating that the organic aerosol reaching the site was highly aged and possibly formed through secondary formation processes.

Description: The Cloud Aerosol LIdar with Orthogonal Polarization (CALIOP), on board the CALIPSO platform, has measured profiles of total attenuated backscatter coefficient (level 1 products) since June 2006. CALIOP's level 2 products, such as the aerosol backscatter and extinction coefficient profiles, are retrieved using a complex succession of automated algorithms. The goal of this study is to help identify potential shortcomings in the CALIOP version 2 level 2 aerosol extinction product and to illustrate some of the motivation for the changes that have been introduced in the next version of CALIOP data (version 3, released in June 2010). To help illustrate the potential factors contributing to the uncertainty of the CALIOP aerosol extinction retrieval, we focus on a one-day, multi-instrument, multiplatform comparison study during the CALIPSO and Twilight Zone (CATZ) validation campaign on 4 August 2007. On that day, we observe a consistency in the Aerosol Optical Depth (AOD) values recorded by four different instruments (i.e. space-borne MODerate Imaging Spectroradiometer, MODIS: 0.67 and POLarization and Directionality of Earth's Reflectances, POLDER: 0.58, airborne High Spectral Resolution Lidar, HSRL: 0.52 and ground-based AErosol RObotic NETwork, AERONET: 0.48 to 0.73) while CALIOP AOD is a factor of two lower (0.32 at 532 nm). This case study illustrates the following potential sources of uncertainty in the CALIOP AOD: (i) CALIOP's low signal-to-noise ratio (SNR) leading to the misclassification and/or lack of aerosol layer identification, especially close to the Earth's surface; (ii) the cloud contamination of CALIOP version 2 aerosol backscatter and extinction profiles; (iii) potentially erroneous assumptions of the aerosol extinction-to-backscatter ratio (Sa) used in CALIOP's extinction retrievals; and (iv) calibration coefficient biases in the CALIOP daytime attenuated backscatter coefficient profiles. The use of version 3 CALIOP extinction retrieval for our case study seems to partially fix factor (i) although the aerosol retrieved by CALIOP is still somewhat lower than the profile measured by HSRL; the cloud contamination (ii) appears to be corrected; no particular change is apparent in the observation-based CALIOP Sa value (iii). Our case study also showed very little difference in version 2 and version 3 CALIOP attenuated backscatter coefficient profiles, illustrating a minor change in the calibration scheme (iv).

Description: Dynamical downscaling has been extensively used to study regional climate forced by large-scale global climate models. During the downscaling process, however, the simulation of regional climate models (RCMs) tends to drift away from the driving fields. Developing a solution that addresses this issue, by retaining the large scale features (from the large-scale fields) and the small-scale features (from the RCMs) has led to the development of "nudging" techniques. Here, we examine the performance of two nudging techniques, grid and spectral nudging, in the downscaling of NCEP/NCAR data with the Weather Research and Forecasting (WRF) Model. The simulations are compared against the results with North America Regional Reanalysis (NARR) data set at different scales of interest using the concept of similarity. We show that with the appropriate choice of wave numbers, spectral nudging outperforms grid nudging in the capacity of balancing the performance of simulation at the large and small scales.

Description: Direct measurements of N2O5 reactivity on ambient aerosol particles were made during September 2009 at the Scripps Institution of Oceanography (SIO) Pier facility located in La Jolla, CA. N2O5 reactivity measurements were made using a custom flow reactor and the particle modulation technique alongside measurements of aerosol particle size distributions and non-refractory composition. The pseudo-first order rate coefficients derived from the particle modulation technique and the particle surface area concentrations were used to determine the population average N2O5 reaction probability, γ(N2O5), approximately every 50 min. Insufficient environmental controls within the instrumentation trailer led us to restrict our analysis primarily to nighttime measurements. Within this subset of data, γ(N2O5) ranged from 〈0.001 to 0.029 and showed significant day-to-day variations. We compare these data to a recent parameterization that utilizes aerosol composition measurements and an aerosol thermodynamics model. The parameterization captures several aspects of the measurements with similar general trends over the time series. However, the parameterization persistently overestimates the measurements by a factor of 1.5–3 and does not illustrate the same extent of variability. Assuming chloride is internally mixed across the particle population leads to the largest overestimates. Removing this assumption only partially reduces the discrepancies, suggesting that other particle characteristics that can suppress γ(N2O5) are important, such as organic coatings or non-aqueous particles. The largest apparent driver of day-to-day variability in the measured γ(N2O5) at this site was the particle nitrate loading, as inferred from both the measured particle composition and the parameterizations. The relative change in measured γ(N2O5) as a function of particle nitrate loading appears to be consistent with expectations based on laboratory data, providing direct support for the atmospheric importance of the so-called "nitrate effect".

Description: We report properties of marine aerosol and clouds measured in the shipping lanes between Monterey Bay and San Francisco off the coast of Central California. Using a suite of aerosol instrumentation onboard the CIRPAS Twin Otter aircraft, these measurements represent a unique set of data contrasting the properties of clean and ship-impacted marine air masses in dry aerosol and cloud droplet residuals. Below-cloud aerosol exhibited average mass and number concentrations of 2 μg m−3 and 510 cm−3, respectively, which are consistent with previous studies performed off the coast of California. Enhancements in vanadium and cloud droplet number concentrations are observed concurrently with a decrease in cloud water pH, suggesting that periods of high aerosol loading are primarily linked to increased ship influence. Mass spectra from a compact time-of-flight Aerodyne aerosol mass spectrometer reveal an enhancement in the fraction of organic at m/z 42 (f42) and 99 (f99) in ship-impacted clouds. These ions are well correlated to each other (R2〉0.64) both in and out of cloud and constitute 14% (f44) and 3% (f99) of organic mass during periods of enhanced sulfate. High-resolution mass spectral analysis of these masses from ship measurements suggests that the ions responsible for this variation were oxidized, possibly due to cloud processing. We propose that the organic fractions of these ions be used as a metric for determining the extent to which cloud-processed ship emissions impact the marine atmosphere where (f42 〉 0.15; f99 〉 0.04) would imply heavy influence from shipping emissions, (0.05 〈 f42 〈 0.15; 0.01 〈 f99 〈 0.04) would imply moderate, but persistent, influences from ships, and (f42 〈 0.05; f99 〈 0.01) would imply clean, non-ship-influenced air.

Description: Soluble iron in fine atmospheric particles has been identified as a public health concern by participating in reactions that generate reactive oxygen species (ROS). The mineralogy and oxidation state (speciation) of iron have been shown to influence fractional iron solubility (soluble iron/total iron). In this study, iron speciation was determined in single particles at urban and rural sites in Georgia USA using synchrotron-based techniques, such as X-ray Absorption Near-Edge Structure (XANES) spectroscopy and microscopic X-ray fluorescence measurements. Soluble and total iron content (soluble + insoluble iron) of these samples was measured using spectrophotometry and synchrotron-based techniques, respectively. These bulk measurements were combined with synchrotron-based measurements to investigate the relationship between iron speciation and fractional iron solubility in ambient aerosols. XANES measurements indicate that iron in the single particles was present as a mixture of Fe(II) and Fe(III), with Fe(II) content generally between 5 and 35% (mean: ~25%). XANES and elemental analyses (e.g. elemental molar ratios of single particles based on microscopic X-ray fluorescence measurements) indicate that a majority (74%) of iron-containing particles are best characterized as Al-substituted Fe-oxides, with a Fe/Al molar ratio of 4.9. The next most abundant group of particles (12%) was Fe-aluminosilicates, with Si/Al molar ratio of 1.4. No correlation was found between fractional iron solubility (soluble iron/total iron) and the abundance of Al-substituted Fe-oxides and Fe-aluminosilicates present in single particles at any of the sites during different seasons, suggesting solubility largely depended on factors other than differences in major iron phases.

Description: We present the development of ANISORROPIA, the discrete adjoint of the ISORROPIA thermodynamic equilibrium model that treats the Na+-SO42−- HSO4−-NH4+ -NO3−-Cl−-H2O aerosol system, and we demonstrate its sensitivity analysis capabilities. ANISORROPIA calculates sensitivities of an inorganic species in aerosol or gas phase with respect to the total concentrations of each species present with less than a two-fold increase in computational time over the concentration calculations. Due to the highly nonlinear and discontinuous solution surface of ISORROPIA, evaluation of the adjoint required a new, complex-variable version of the model, which determines first-order sensitivities with machine precision and avoids cancellation errors arising from finite difference calculations. The adjoint is verified over an atmospherically relevant range of concentrations, temperature, and relative humidity. We apply ANISORROPIA to recent field campaign results from Atlanta, GA, USA, and Mexico City, Mexico, to characterize the inorganic aerosol sensitivities of these distinct urban air masses. The variability in the relationship between fine mode inorganic aerosol mass and precursor concentrations shown has important implications for air quality and climate.

Description: The first dataset for summertime boreal forest concentrations of two atmospherically relevant α-dicarbonyl compounds, glyoxal (Gly) and methylglyoxal (Mgly) on PM2.5 aerosol was obtained during the HUMPPA-COPEC-2010 field measurement intensive in Hyytiälä, Finland. Anthropogenic influences over the course of the campaign were identified using trace gas signatures and aerosol particle chemical composition analysis. The data evaluation allowed the identification of different events such as urban pollution plumes, biomass burning and sawmill emissions as sources of high Gly and Mgly concentrations. Mean aerosol concentrations during periods of biogenic influence were 0.81 ng m−3 for Gly and 0.31 ng m−3 for Mgly. Mgly was generally less abundant in PM2.5, probably due to its shorter photolysis lifetime and less effective partitioning into the particle phase due to its smaller effective Henry's Law constant compared to Gly. This is in contrast with previous urban studies which show significantly more Mgly than Gly. Peak concentrations for Gly coincided with nearby sources, e.g. high VOC emissions from nearby sawmills, urban pollution plumes from the city of Tampere located 50 km southwest of the sampling site and biomass burning emissions from wildfires. Calculated ratios of Gly in PM2.5 and total organic matter in PM1 aerosols indicate higher values in less aged aerosols. Irreversible processing of Gly in the particle phase, e.g. via oxidation by OH radicals, organo sulfate or imidazole formation are processes currently discussed in the literature which could likely explain these findings.

Description: We introduce a method for deriving aerosol spectral radiative forcing along with single scattering albedo, asymmetry parameter, and surface albedo from airborne vertical profile measurements of shortwave spectral irradiance and spectral aerosol optical thickness. The new method complements the traditional, direct measurement of aerosol radiative forcing efficiency from horizontal flight legs below gradients of aerosol optical thickness, and is particularly useful over heterogeneous land surfaces and for homogeneous aerosol layers where the horizontal gradient method is impractical. Using data collected by the Solar Spectral Flux Radiometer (SSFR) and the Ames Airborne Tracking Sunphotometer (AATS-14) during the MILAGRO (Megacity Initiative: Local and Global Research Observations) experiment, we validate an over-ocean spectral aerosol forcing efficiency from the new method by comparing with the traditional method. Retrieved over-land aerosol optical properties are compared with in-situ measurements and AERONET retrievals. The spectral forcing efficiencies over ocean and land are remarkably similar and agree with results from other field experiments.