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Modeling SOA formation from the oxidation of intermediate volatility n-alkanes

The chemical mechanism leading to SOA formation and ageing is expected to be a multigenerational process, i.e. a successive formation of organic compounds with higher oxidation degree and lower vapor pressure. This process is here investigated with the explicit oxidation model GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere). Gas phase oxidation schemes are generated for the C8–C24 series of n-alkanes. Simulations are conducted to explore the time evolution of organic compounds and the behavior of secondary organic aerosol (SOA) formation for various preexisting organic aerosol concentration (COA). As expected, simulation results show that (i) SOA yield increases with the carbon chain length of the parent hydrocarbon, (ii) SOA yield decreases with decreasing COA, (iii) SOA production rates increase with increasing COA and (iv) the number of oxidation steps (i.e. generations) needed to describe SOA formation and evolution grows when COA decreases. The simulated oxidative trajectories are examined in a two dimensional space defined by the mean carbon oxidation state and the volatility. Most SOA contributors are not oxidized enough to be categorized as highly oxygenated organic aerosols (OOA) but reduced enough to be categorized as hydrocarbon like organic aerosols (HOA), suggesting that OOA may underestimate SOA. Results show that the model is unable to produce highly oxygenated aerosols (OOA) with large yields. The limitations of the model are discussed.
Hemispheric transport and influence of meteorology on global aerosol climatology

Based on a 10-yr simulation with the global air quality modeling system GEM-AQ/EC, the northern hemispheric aerosol transport with the inter-annual and seasonal variability as well as the mean climate was investigated. The intercontinental aerosol transport is predominant in the zonal direction from west to east with the ranges of inter-annual variability between 14% and 63%, and is 0.5–2 orders of magnitude weaker in the meridional direction but with larger inter-annual variability. The aerosol transport is found to fluctuate seasonally with a factor of 5–8 between the maximum in late winter and spring and the minimum in late summer and fall. Three meteorological factors controlling the intercontinental aerosol transport and its inter-annual variations are identified from the modeling results: (1) Anomalies in the mid-latitude westerlies in the troposphere. (2) Variations of precipitation over the intercontinental transport pathways and (3) Changes of meteorological conditions within the boundary layer. Changed only by the meteorology, the aerosol column loadings in the free troposphere over the source regions of Europe, North America, South and East Asia vary inter-annually with the highest magnitudes of 30–37% in January and December and the lowest magnitudes of 16–20% in August and September, and the inter-annual aerosol variability within the boundary layer influencing the surface concentrations with the magnitudes from 6% to 20% is more region-dependent. As the strongest climatic signal, the El Niño-Southern Oscillation (ENSO) can lead the anomalies in the intercontinental aerosols in El Niño- and La Niña-years respectively with the strong and weak transport of the mid-latitude westerlies and the low latitude easterlies in the Northern Hemisphere (NH).
On the robustness of aerosol effects on an idealized supercell storm simulated with a cloud system-resolving model

A cloud system-resolving model (the Weather Research and Forecasting model) with 1 km horizontal grid spacing is used to investigate the response of an idealized supercell storm to increased cloud droplet concentrations associated with polluted conditions. The primary focus is on exploring robustness of simulated aerosol effects in the face of complex process interactions and feedbacks between the cloud microphysics and dynamics. Simulations are run using sixteen different model configurations with various microphysical or thermodynamic processes modified or turned off. Robustness of the storm response to polluted conditions is also explored for each configuration by performing additional simulations with small perturbations to the initial conditions. Differences in the domain-mean accumulated surface precipitation and convective mass flux between polluted and pristine conditions are small for almost all model configurations, with relative differences in each quantity generally less than 15%. Configurations that produce a decrease (increase) in cold pool strength in polluted conditions also tend to simulate a decrease (increase) in surface precipitation and convective mass flux. Combined with an analysis of the dynamical and thermodynamic fields, these results indicate the importance of interactions between microphysics, cold pool evolution, and dynamics along outflow boundaries in explaining the system response. Several model configurations, including the baseline, produce an overall similar storm response (weakening) in polluted conditions despite having different microphysical or thermodynamic processes turned off. With hail initiation turned off or the hail fallspeed-size relation set to that of snow, the model produces an invigoration instead of weakening of the storm in polluted conditions. These results highlight the difficulty of foreseeing impacts of changes to model parameterizations and isolating process interactions that drive the system response to aerosols. Overall, these findings are robust, in a qualitative sense, to small perturbations in the initial conditions. However, there is sensitivity in the magnitude, and in some cases sign, of the storm response to polluted conditions with small perturbations in the temperature of the thermal used to initiate convection (less than &pm;0.5 K) or the vertical shear of the environmental wind (&pm;5%). It is concluded that reducing uncertainty in simulations of aerosol effects on individual deep convective storms will likely require ensemble methods in addition to continued improvement of model parameterizations.
Corrigendum to "The HNO3 forming branch of the HO2 + NO reaction: pre-industrial-to-present trends in atmospheric species and radiative forcings" published in Atmos. Chem. Phys., 11, 8929–8943, 2011
Single particle characterization of black carbon aerosol in the Northeast Tibetan Plateau, China

Refractory black carbon (rBC) mass, size distribution, and mixing state were measured with a ground-based Single Particle Soot Photometer (SP2) at Qinghai Lake (QHL), a rural area in the Northeastern Tibetan Plateau of China, during October 2011. The average measured rBC mass concentration of 0.36 μg STP-m−3 is significantly higher than the concentrations measured in background and remote regions around the globe. The diurnal variation of rBC concentration showed nocturnal peak and afternoon low concentrations and showed a loose anticorrelation to the variation of mixed layer depths, indicating nighttime trapping of emissions and daytime ventilation. The high rBC values and their diurnal behavior strongly suggest that the QHL area was heavily influenced by local rBC sources. The mass size distribution of rBC showed a primary mode peak at 175-nm diameter and a small secondary mode peak at 495 nm volume-equivalent diameter assuming 2 g cm−3 void free density. About 40% of the observed rBC particles within the detectable size range were mixed with large amounts of non-refractory materials present as a thick coating. A comparison of the Aethalometer and SP2 measurements suggests that there are non-BC species strongly affecting the Aethalometer measurement and, therefore, the Aethalometer measurements are not reliable for rBC determinations in the Tibetan Plateau region without artifact corrections. The apparent black-carbon specific, mass-absorption cross section derived from the Aethalometer and SP2 data was 37.5 m2 g−1 at a wavelength of 880 nm. A strong correlation was found between rBC and CO with a slope of 1.5 ± 0.1 ng STP-m−3 ppbv−1, similar to values of mixed rural emissions.
Hydration or dehydration: competing effects of upper tropospheric cloud radiation on the TTL water vapor

A tropical channel version of the Weather Research and Forecasting (WRF) model is used to investigate the radiative impacts of upper tropospheric clouds on water vapor in the tropical tropopause layer (TTL). The WRF simulations of cloud radiative effects and water vapor in the upper troposphere and lower stratosphere show reasonable agreement with observations, including approximate reproduction of the water vapor "tape recorder" signal. By turning on and off the upper tropospheric cloud radiative effect (UTCRE) above 200 hPa, we find that UTCRE induces a warming of 0.76 K and a moistening of 9% in the upper troposphere at 215 hPa. However, UTCRE cools and dehydrates the TTL, with a cooling of 0.82 K and a dehydration of 16% at 100 hPa. The enhanced vertical ascent due to UTCRE contributes substantially to mass transport and the dehydration in the TTL. The hydration due to the enhanced vertical transport is counteracted by the dehydration from adiabatic cooling associated with the enhanced vertical motion. UTCRE also substantially changes the horizontal winds in the TTL, resulting in shifts of the strongest dehydration away from the lowest temperature anomalies in the TTL. UTCRE increases in-situ cloud formation in the TTL. A seasonal variation is shown in the simulated UTCRE, with stronger impact in the moist phase from June to November than in the dry phase from December to May.
Observations of middle atmospheric H2O and O3 during the 2010 major sudden stratospheric warming by a network of microwave radiometers

In this study, we present middle atmospheric water vapor (H2O) and ozone (O3) measurements obtained by ground-based microwave radiometers at three European locations in Bern (47° N), Onsala (57° N) and Sodankylä (67° N) during Northern winter 2009/2010. In January 2010, a major sudden stratospheric warming (SSW) occurred in the Northern Hemisphere whose signatures are evident in the ground-based observations of H2O and O3. The observed anomalies in H2O and O3 are mostly explained by the relative location of the polar vortex with respect to the measurement locations. The SSW started on 26 January 2010 and was most pronounced by the end of January. The zonal mean temperature in the middle stratosphere (10 hPa) increased by approximately 25 Kelvin within a few days. The stratospheric vortex weakened during the SSW and shifted towards Europe. In the mesosphere, the vortex broke down, which lead to large scale mixing of polar and midlatitudinal air. After the warming, the polar vortex in the stratosphere split into two weaker vortices and in the mesosphere, a new, pole-centered vortex formed with maximum wind speed of 70 m s−1 at approximately 40° N. The shift of the stratospheric vortex towards Europe was observed in Bern as an increase in stratospheric H2O and a decrease in O3. The breakdown of the mesospheric vortex during the SSW was observed at Onsala and Sodankylä as a sudden increase in mesospheric H2O. The following large-scale descent inside the newly formed mesospheric vortex was well captured by the H2O observations in Sodankylä. In order to combine the H2O observations from the three different locations, we applied the trajectory mapping technique on our H2O observations to derive synoptic scale maps of the H2O distribution. Based on our observations and the 3-D wind field, this method allows determining the approximate development of the stratospheric and mesospheric polar vortex and demonstrates the potential of a network of ground-based instruments.
Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation

We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h−1, among the highest found in urban atmospheres. The largest primary ROx source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h−1 and 1.7 ppbv h−1, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h−1, much larger than that of O1D+H2O (0.4 ppbv h−1). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h−1), followed by formation of RO2NO2 (1.0 ppbv h−1) and RONO2 (0.7 ppbv h−1). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h−1 and 6.2 ppbv h−1, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O3 pollution.
Technical Note: Latitude-time variations of atmospheric column-average dry air mole fractions of CO2, CH4 and N2O

We present a comparison of an atmospheric general circulation model (AGCM)-based chemistry-transport model (ACTM) simulation with total column measurements of CO2, CH4 and N2O from the Total Carbon Column Observing Network (TCCON). The model is able to capture observed trends, seasonal cycles and inter hemispheric gradients at most sampled locations for all three species. The model-observation agreements are best for CO2, because the simulation uses fossil fuel inventories and an inverse model estimate of non-fossil fuel fluxes. The ACTM captures much of the observed seasonal variability in CO2 and N2O total columns (~81 % variance, R>0.9 between ACTM and TCCON for 19 out of 22 cases). These results suggest that the transport processes in troposphere and stratosphere are well represented in ACTM. Thus the poor correlation between simulated and observed CH4 total columns, particularly at tropical and extra-tropical sites, have been attributed to the uncertainties in surface emissions and loss by hydroxyl radicals. While the upward-looking total column measurements of CO2 contains surface flux signals at various spatial and temporal scales, the N2O measurements are strongly affected by the concentration variations in the upper troposphere and stratosphere.
Measurements of the movement of the jet streams at mid-latitudes, in the Northern and Southern Hemispheres, 1979 to 2010

Previous studies have shown that the mean latitude of the sub-tropical jet streams in both hemispheres have shifted toward the poles over the last few decades. This paper presents a study of the movement of both the subtropical and Polar fronts, the location of the respective jet streams, between 1979 and 2010 at mid-latitudes, using total ozone measurements to identify the sharp horizontal boundary that occurs at the position of the fronts. Previous studies have shown that the two fronts are the boundaries of three distinct regimes in the stratosphere, corresponding to the Hadley, Ferrel, and polar meridionally overturning circulation cells in the troposphere. Over the period of study the horizontal area of the Hadley cell has increased at latitudes between 20 and 60 degrees while the area of the Polar cell has decreased. A linear regression analysis was performed to identify the major factors associated with the movement of the subtropical jet streams. These were: (1) changes in the Tropical land plus ocean temperature, (2) direct radiative forcing from greenhouse gases in the troposphere, (3) changes in the temperature of the lower tropical stratosphere, (4) the Quasi-Biennial Oscillation, and (5) volcanic eruptions. The dominant mechanism was the direct radiative forcing from greenhouse gases. Between 1979 and 2010 the poleward movement of the subtropical jet streams was 3.7 ± 0.3 degrees in the Northern Hemisphere and 6.5 ± 0.2 degrees in the Southern Hemisphere. Previous studies have shown that weather systems tend to follow the jet streams. The observed poleward movement in both hemispheres over the past thirty years represents a significant change in the position of the sub-tropical jet streams, which should lead to significant latitudinal shifts in the global weather patterns and the hydrologic cycle.