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A two-habit model for the microphysical and optical properties of ice clouds

To provide a better representation of natural ice clouds, a novel ice cloud model is developed by assuming an ice cloud to consist of an ensemble of hexagonal columns and 20-element aggregates with specific habit fractions at each particle size bin. The microphysical and optical properties of this two-habit model (THM) are compared with both laboratory and in situ measurements, and its performance in downstream satellite remote sensing applications is assessed. The ice water contents and median mass diameters calculated based on the THM closely agree with in situ measurements made during 11 field campaigns. In this study, the scattering, absorption, and polarization properties of ice crystals are calculated with a combination of the invariant imbedding T matrix, pseudo-spectral time domain, and improved geometric-optics methods over an entire practical range of particle sizes. The phase functions, calculated based on the THM, show close agreement with counterparts from laboratory and in situ measurements and from satellite-based retrievals. When the THM is applied to the retrievals of cloud microphysical and optical properties from MODIS (the Moderate Resolution Imaging Spectroradiometer) observations, excellent spectral consistency is achieved; specifically, the retrieved cloud optical thicknesses based on the visible/near infrared bands and the thermal infrared bands agree quite well. Furthermore, a comparison between the polarized reflectivities observed by the PARASOL satellite and from theoretical simulations illustrates that the THM can be used to represent ice cloud polarization properties.
The impact of polar stratospheric ozone loss on Southern Hemisphere stratospheric circulation and climate

The impact of polar stratospheric ozone loss resulting from chlorine activation on polar stratospheric clouds is examined using a pair of model integrations run with the fully coupled chemistry climate model UM-UKCA. Suppressing chlorine activation through heterogeneous reactions is found to produce modelled ozone differences consistent with observed ozone differences between the present and pre-ozone hole period. Statistically significant high-latitude Southern Hemisphere (SH) ozone loss begins in August and peaks in October–November, with > 75% of ozone destroyed at 50 hPa. Associated with this ozone destruction is a > 12 K decrease of the lower polar stratospheric temperatures and an increase of > 6 K in the upper stratosphere. The heating components of this temperature change are diagnosed and it is found that the temperature dipole is the result of decreased short-wave heating in the lower stratosphere and increased dynamical heating in the upper stratosphere. The cooling of the polar lower stratosphere leads, through thermal wind balance, to an acceleration of the polar vortex and delays its breakdown by ~ 2 weeks. A link between lower stratospheric zonal wind speed, the vertical component of the Eliassen–Palm (EP) flux, Fz and the residual mean vertical circulation, w*, is identified. In November and December, increased westerly winds and a delay in the breakup of the polar vortex lead to increases in Fz, indicating increased wave activity entering the stratosphere and propagating to higher altitudes. The resulting increase in wave breaking, diagnosed by decreases to the EP flux divergence, drives enhanced downwelling over the polar cap. Many of the stratospheric signals modelled in this study propagate down to the troposphere, and lead to significant surface changes in December.
Chemical characterization of SOA formed from aqueous-phase reactions of phenols with the triplet excited state of carbonyl and hydroxyl radical

Phenolic compounds, which are emitted in significant amounts from biomass burning, can undergo fast reactions in atmospheric aqueous phases to form secondary organic aerosol (aqSOA). In this study, we investigate the reactions of phenol (compound with formula C6H5OH)), guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol) with two major aqueous-phase oxidants – the triplet excited states of an aromatic carbonyl (3C*) and hydroxyl radical (· OH). We thoroughly characterize the low-volatility species produced from these reactions and interpret their formation mechanisms using aerosol mass spectrometry (AMS), nanospray desorption electrospray ionization mass spectrometry (nano-DESI MS), and ion chromatography (IC). A large number of oxygenated molecules are identified, including oligomers containing up to six monomer units, functionalized monomer and oligomers with carbonyl, carboxyl, and hydroxyl groups, and small organic acid anions (e.g., formate, acetate, oxalate, and malate). The average atomic oxygen-to-carbon (O / C) ratios of phenolic aqSOA are in the range of 0.85–1.23, similar to those of low-volatility oxygenated organic aerosol (LV-OOA) observed in ambient air. The aqSOA compositions are overall similar for the same precursor, but the reactions mediated by 3C* are faster than · OH-mediated reactions and produce more oligomers and hydroxylated species at the point when 50% of the phenolic compound has reacted. Profiles determined using a thermodenuder indicate that the volatility of phenolic aqSOA is influenced by both oligomer content and O / C ratio. In addition, the aqSOA shows enhanced light absorption in the UV–visible region, suggesting that aqueous-phase reactions of phenols may contribute to formation of secondary brown carbon in the atmosphere, especially in regions influenced by biomass burning.
High spatial resolution aerosol retrievals used for daily particulate matter monitoring over Po valley, northern Italy

The Moderate Resolution Imaging Spectroradiometer (MODIS) Collection 5.1 Aerosol Optical Depth (AOD) data retrieved at 0.55 μm with spatial resolution of 10 km (MYD04) and the new 1 km Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm from MODIS is investigated in this work. We focus on evaluating the ability of these two products to characterize the spatial distribution of aerosols within urban areas. This is done through the comparison with PM10 measurements from 126 of the Italian Regional Agency for Environmental Protection (ARPA) ground monitoring stations during 2012. The Po Valley area (northern Italy) was chosen as the study domain since urban air pollution is one of the most important concerns in this region. Population and industrial activities are located within a large number of urban areas within the valley. We find that the annual correlations between PM10 and AOD are R2 = 0.90 and R2 = 0.62 for MYD04 and for MAIAC respectively. When the depth of the planetary boundary layer (PBL) is used to normalize the AOD, we find a significant improvement in the PM–AOD correlation. The introduction of the PBL information is needed for AOD to capture the seasonal cycle of the observed PM10 over the Po valley and significantly improves the PM vs. AOD relationship, leading to a correlation of R2 = 0.98 for both retrievals when they are normalized by the PBL depth. The results show that the normalized MAIAC retrieval provides a higher resolution depiction of the AOD within the Po Valley and performs as well in a statistical sense as the normalized standard MODIS retrieval for the same days and locations.
Seasonal characteristics of fine particulate matter (PM) based on high-resolution time-of-flight aerosol mass spectrometric (HR-ToF-AMS) measurements at the HKUST Supersite in Hong Kong

Atmospheric particulate matter (PM) remains poorly understood due to the lack of comprehensive measurements at high time resolution for tracking its dynamic features and the lack of long-term observation for tracking its seasonal variability. Here, we present highly time-resolved and seasonal compositions and characteristics of non-refractory components in PM with a diameter less than 1 μm (NR-PM1) at a suburban site in Hong Kong. The measurements were made with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) at the Hong Kong University of Science and Technology (HKUST) Air Quality Research Supersite for 4 months, with one in each season of the year. The average NR-PM1 concentration of ~ 15 μg m−3 is higher than those AMS measurements made in South Korea and Japan, but lower than those in North China, the Yangtze River Delta and the nearby Pearl River Delta. The seasonal dependence of the total NR-PM1 monthly averaged concentrations was small, but that of the fractions of the species in NR-PM1 was significant. Site characteristic plays an important role in the relative fractions of species in NR-PM1 and our results are generally consistent with measurements at other non-urban sites in this regard. Detailed analyses were conducted on the AMS data in the aspects of (1) species concentrations, (2) size distributions, (3) degree of oxygenation of organics, and (4) positive matrix factorization (PMF)-resolved organic factors in a seasonal context, as well as with air mass origin from back-trajectory analysis. Sulfate had the highest fraction in NR-PM1 (> 40%), and the surrogates of secondary organic species – semi-volatile oxygenated organic aerosol (SVOOA) and low-volatility oxygenated organic aerosol (LVOOA) – prevailed (~ 80%) in the organic portion of NR-PM1. Local contributions to the organic portion of NR-PM1 at this suburban site was strongly dependent on season. The hydrocarbon-like organic aerosol (HOA) factor related to local traffic emissions contributed > 10% to organic aerosols in spring and summer but only 6–7% in autumn and winter. The cooking organic aerosol (COA) factor contributed > 10% to organic aerosols in winter. With the aid of highly time-resolved data, diurnal patterns of the degree of oxygenation of organic aerosols were used to determine the sources and formation processes of the least understood organic portion of PM. The oxygen-to-carbon atomic ratio (O : C) and average carbon oxidation state OS C) showed little variation in autumn and winter, when the long-range transport of oxidized organics dominated, whereas they peaked in the afternoon in spring and summer, when locally produced secondary organic aerosol prevailed. Air mass origin, in contrast, had a strong influence on both NR-PM1 concentrations and the fractions of species in NR-PM1. The findings of the current study provide a better understanding of the role of air mass origin in the seasonal characteristics of the PM composition and the relative importance of local vs. transported organic aerosols in this region.
Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 1: Aging processes of oligomers

It has recently been established that unsaturated water-soluble organic compounds (UWSOCs) might efficiently form oligomers in polluted fogs and wet aerosol particles, even for weakly soluble ones like methyl vinyl ketone (MVK). The atmospheric relevance of these processes is explored by means of multiphase process model studies in a companion paper. In the present study, we investigate the aging of these aqueous-phase MVK oligomers formed via •OH oxidation, as well as their ability to form secondary organic aerosol (SOA) upon water evaporation. The comparison between aqueous-phase composition and aerosol composition after nebulization of the corresponding solutions shows similar trends for oligomer formation and aging. The measurements reveal that oligomer aging leads to the formation of organic diacids. Quantification of the SOA mass formed after nebulization is performed, and the obtained SOA mass yields seem to depend on the spectral irradiance of the light used to initiate the photochemistry. Investigating a large range of initial MVK concentrations (0.2–20 mM), the results show that their •OH oxidation undergoes competition between functionalization and oligomerization that is dependent on the precursor concentration. At high initial MVK concentrations (≥ 2 mM), oligomerization prevails over functionalization, while at lower initial concentrations, oligomerization is not the major process, and functionalization dominates, resulting in small carbonyls, dicarbonyls and monoacids. The atmospheric implications of these processes are discussed.
Corrigendum to "Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles" published in Atmos. Chem. Phys., 14, 4661–4678, 2014
Tracing the second stage of ozone recovery in the Antarctic ozone-hole with a "big data" approach to multivariate regressions

This study presents a sensitivity analysis of multivariate regressions of recent springtime Antarctic vortex ozone trends using a "big data" ensemble approach. Our results indicate that the poleward heat flux (Eliassen–Palm flux) and the effective chlorine loading respectively explain most of the short-term and long-term variability in different Antarctic springtime total ozone records. The inclusion in the regression of stratospheric volcanic aerosols, solar variability and the quasi-biennial oscillation is shown to increase rather than decrease the overall uncertainty in the attribution of Antarctic springtime ozone because of large uncertainties in their respective records. Calculating the trend significance for the ozone record from the late 1990s onwards solely based on the fit of the effective chlorine loading is not recommended, as this does not take fit residuals into account, resulting in too narrow uncertainty intervals, while the fixed temporal change of the effective chlorine loading does not allow for any flexibility in the trends. When taking fit residuals into account in a piecewise linear trend fit, we find that approximately 30–60% of the regressions in the full ensemble result in a statistically significant positive springtime ozone trend over Antarctica from the late 1990s onwards. Analysis of choices and uncertainties in time series show that, depending on choices in time series and parameters, the fraction of statistically significant trends in parts of the ensemble can range from negligible to a complete 100% significance. We also find that, consistent with expectations, the number of statistically significant trends increases with increasing record length. Although our results indicate that the use multivariate regressions is a valid approach for assessing the state of Antarctic ozone hole recovery, and it can be expected that results will move towards more confidence in recovery with increasing record length, uncertainties in choices currently do not yet support formal identification of recovery of the Antarctic ozone hole.
Constraints on Asian ozone using Aura TES, OMI and Terra MOPITT

Rapid industrialization in Asia in the last two decades has resulted in a significant increase in Asian ozone (O3) precursor emissions with likely a corresponding increase in the export of O3 and its precursors. However, the relationship between this increasing O3, the chemical environment, O3 production efficiency, and the partitioning between anthropogenic and natural precursors is unclear. In this work, we use satellite measurements of O3, CO and NO2 from TES (Tropospheric Emission Spectrometer), MOPITT (Measurement of Pollution In The Troposphere) and OMI (Ozone Monitoring Instrument) to quantify O3 precursor emissions for 2006 and their impact on free tropospheric O3 over northeastern Asia, where pollution is typically exported globally due to strong westerlies. Using the GEOS-Chem (Goddard Earth Observing System Chemistry) global chemical transport model, we test the modeled seasonal and interannual variation of O3 based on prior and updated O3 precursor emissions where the updated emissions of CO and NOx are based on satellite measurements of CO and NO2. We show that the observed TES O3 variability and amount are consistent with the model for these updated emissions. However, there is little difference in the modeled ozone between the updated and prior emissions. For example, for the 2006 June time period, the prior and posterior NOx emissions were 14% different over China but the modeled ozone in the free troposphere was only 2.5% different. Using the adjoint of GEOS-Chem we partition the relative contributions of natural and anthropogenic sources to free troposphere O3 in this region. We find that the influence of lightning NOx in the summer is comparable to the contribution from surface emissions but smaller for other seasons. China is the primary contributor of anthropogenic CO, emissions and their export during the summer. While the posterior CO emissions improved the comparison between model and TES by 32%, on average, this change also had only a small effect on the free tropospheric ozone. Our results show that the influence of India and southeastern Asia emissions on O3 pollution export to the northwestern Pacific is sizeable, comparable with Chinese emissions in winter, about 50% of Chinese emissions in spring and fall, and approximately 20% of the emissions in the summer.
Global and regional modeling of clouds and aerosols in the marine boundary layer during VOCALS: the VOCA intercomparison

A diverse collection of models are used to simulate the marine boundary layer in the southeast Pacific region during the period of the October–November 2008 VOCALS REx (VAMOS Ocean Cloud Atmosphere Land Study Regional Experiment) field campaign. Regional models simulate the period continuously in boundary-forced free-running mode, while global forecast models and GCMs (general circulation models) are run in forecast mode. The models are compared to extensive observations along a line at 20° S extending westward from the South American coast. Most of the models simulate cloud and aerosol characteristics and gradients across the region that are recognizably similar to observations, despite the complex interaction of processes involved in the problem, many of which are parameterized or poorly resolved. Some models simulate the regional low cloud cover well, though many models underestimate MBL (marine boundary layer) depth near the coast. Most models qualitatively simulate the observed offshore gradients of SO2, sulfate aerosol, CCN (cloud condensation nuclei) concentration in the MBL as well as differences in concentration between the MBL and the free troposphere. Most models also qualitatively capture the decrease in cloud droplet number away from the coast. However, there are large quantitative intermodel differences in both means and gradients of these quantities. Many models are able to represent episodic offshore increases in cloud droplet number and aerosol concentrations associated with periods of offshore flow. Most models underestimate CCN (at 0.1% supersaturation) in the MBL and free troposphere. The GCMs also have difficulty simulating coastal gradients in CCN and cloud droplet number concentration near the coast. The overall performance of the models demonstrates their potential utility in simulating aerosol–cloud interactions in the MBL, though quantitative estimation of aerosol–cloud interactions and aerosol indirect effects of MBL clouds with these models remains uncertain.