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Model investigation of NO3 secondary organic aerosol (SOA) source and heterogeneous organic aerosol (OA) sink in the western United States

The relative importance of NO3-initiated source and heterogeneous sink of organic aerosol in the western United States is investigated using the WRF/Chem regional weather and chemistry model. The model is run for the four individual months, representing the four seasons, of January, May, August, and October, to produce hourly spatial maps of surface concentrations of NO3, organic aerosol (OA), and reactive organic gases (ROG, a sum of alkene species tracked in the lumped chemical mechanism employed). These "baseline" simulations are used in conjunction with literature data on secondary organic aerosol (SOA) mass yields, average organic aerosol composition, and reactive uptake coefficients for NO3 on organic surfaces to predict SOA source and OA heterogeneous loss rates due to reactions initiated by NO3. We find both source and sink rates maximized downwind of urban centers, therefore with a varying location that depends on wind direction. Both source and sink terms are maximum in summer, and SOA source dominates over OA loss by approximately three orders of magnitude, with large day-to-day variability. The NO3 source of SOA (peak production rates of 0.4–3.0 μg kg−1 h−1) is found to be significantly larger than the heterogeneous sink of OA via NO3 surface reactions (peak loss rates of 0.5–8 × 10−4 μg kg−1 h−1).
Particle size distribution of nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) on traffic and suburban sites of a European megacity: Paris (France)

The size distribution of particulate nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) was determined during two field campaigns at a traffic site in summer 2010 and at a suburban site during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) experiment in summer 2009. Both, OPAHs and NPAHs were strongly associated (>85%) to fine particles (Dp< 2.5 μm) increasing the interest of their study on a sanitary point of view. Results showed really different NPAH and OPAH particle size distributions between both sites. At traffic site, clearly bimodal (notably for NPAHs) particle size distributions (Dp = 0.14 and 1.4 μm) were observed, while the particle size distributions were more scattered at the suburban site, especially for OPAHs. Bimodal particle size distribution observed at traffic site for the NPAH could be assigned to the vehicle emissions and the particle resuspension. Broadest distribution observed at the suburban site could be attributed to the mass transfer of compounds by volatilization/sorption processes during the transport of particles in the atmosphere. Results also showed that the combination of the study of particle size distributions applied to marker compounds (primary: 1-nitropyrene; secondary: 2-nitrofluoranthene) and to NPAH or OPAH chemical profiles bring some indications on their primary and/or secondary origin. Indeed, 1,4-anthraquinone seemed only primary emitted by vehicles while 7-nitrobenz[a]anthracene, benz[a]antracen7,12-dione and benzo[b]fluorenone seemed secondarily formed in the atmosphere.
Analysis of stratospheric NO2 trends above Jungfraujoch using ground-based UV-visible, FTIR, and satellite nadir observations

The trend in stratospheric NO2 column at the NDACC (Network for the Detection of Atmospheric Composition Change) station of Jungfraujoch (46.5° N, 8.0° E) is assessed using ground-based FTIR and zenith-scattered visible sunlight SAOZ measurements over the period 1990 to 2009 as well as a composite satellite nadir data set constructed from ERS-2/GOME, ENVISAT/SCIAMACHY, and METOP-A/GOME-2 observations over the 1996–2009 period. To calculate the trends, a linear least squares regression model including explanatory variables for a linear trend, the mean annual cycle, the quasi-biennial oscillation (QBO), solar activity, and stratospheric aerosol loading is used. For the 1990–2009 period, statistically indistinguishable trends of −3.7 ± 1.1% decade−1 and −3.6 ± 0.9% decade−1 are derived for the SAOZ and FTIR NO2 column time series, respectively. SAOZ, FTIR, and satellite nadir data sets show a similar decrease over the 1996–2009 period, with trends of −2.4 ± 1.1% decade−1, −4.3 ± 1.4% decade−1, and −3.6 ± 2.2% decade−1, respectively. The fact that these declines are opposite in sign to the globally observed +2.5% decade−1 trend in N2O, suggests that factors other than N2O are driving the evolution of stratospheric NO2 at northern mid-latitudes. Possible causes of the decrease in stratospheric NO2 columns have been investigated. The most likely cause is a change in the NO2/NO partitioning in favor of NO, due to a possible stratospheric cooling and a decrease in stratospheric chlorine content, the latter being further confirmed by the negative trend in the ClONO2 column derived from FTIR observations at Jungfraujoch. Decreasing ClO concentrations slows the NO + ClO → NO2 + Cl reaction and a stratospheric cooling slows the NO + O3 → NO2 + O2 reaction, leaving more NOx in the form of NO. The slightly positive trends in ozone estimated from ground- and satellite-based data sets are also consistent with the decrease of NO2 through the NO2 + O3 → NO3 + O2 reaction. Finally, we cannot rule out the possibility that a strengthening of the Dobson-Brewer circulation, which reduces the time available for N2O photolysis in the stratosphere, could also contribute to the observed decline in stratospheric NO2 above Jungfraujoch.
Impact of natural and anthropogenic aerosols on stratocumulus and precipitation in the Southeast Pacific: a regional modelling study using WRF-Chem

Cloud-system resolving simulations with the chemistry version of the Weather Research and Forecasting (WRF-Chem) model are used to quantify the relative impacts of regional anthropogenic and oceanic emissions on changes in aerosol properties, cloud macro- and microphysics, and cloud radiative forcing over the Southeast Pacific (SEP) during the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) (15 October–16 November 2008). Two distinct regions are identified. The near-coast polluted region is characterized by low surface precipitation rates, the strong suppression of non-sea-salt particle activation due to sea-salt particles, a predominant albedo effect in aerosol indirect effects, and limited impact of aerosols associated with anthropogenic emissions on clouds. Opposite sensitivities to natural marine and anthropogenic aerosol perturbations are seen in cloud properties (e.g., cloud optical depth and cloud-top and cloud-base heights), precipitation, and the top-of-atmosphere and surface shortwave fluxes over this region. The relatively clean remote region is characterized by large contributions of aerosols from non-regional sources (lateral boundaries) and much stronger drizzle at the surface. Under a scenario of five-fold increase in regional anthropogenic emissions, this relatively clean region shows large cloud responses, for example, a 13% increase in cloud-top height and a 9% increase in albedo in response to a moderate increase (25% of the reference case) in cloud condensation nuclei (CCN) concentration. The reduction of precipitation due to this increase in anthropogenic aerosols more than doubles the aerosol lifetime in the clean marine boundary layer. Therefore, the aerosol impacts on precipitation are amplified by the positive feedback of precipitation on aerosol, which ultimately alters the cloud micro- and macro-physical properties, leading to strong aerosol-cloud-precipitation interactions. The high sensitivity is also related to an increase in cloud-top entrainment rate (by 16% at night) due to the increased anthropogenic aerosols. The simulated aerosol-cloud-precipitation interactions due to the increased anthropogenic aerosols have a stronger diurnal cycle over the clean region compared to the near-coast region with stronger interactions at night. During the day, solar heating results in more frequent decoupling of the cloud and sub-cloud layers, thinner clouds, reduced precipitation, and reduced sensitivity to the increase in anthropogenic emissions. This study shows the importance of natural aerosols in accurately quantifying anthropogenic forcing within a regional modeling framework. The results of this study also imply that the energy balance perturbations from increased anthropogenic emissions are larger in the more susceptible clean environment than in already polluted environment and are larger than possible from the first indirect effect alone.
On the dependence of the OH* Meinel emission altitude on vibrational level: SCIAMACHY observations and model simulations

Measurements of the OH Meinel emissions in the terrestrial nightglow are one of the standard ground-based techniques to retrieve upper mesospheric temperatures. It is often assumed that the emission peak altitudes are not strongly dependent on the vibrational level, although this assumption is not based on convincing experimental evidence. In this study we use Envisat/SCIAMACHY (Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY) observations in the near-IR spectral range to retrieve vertical volume emission rate profiles of the OH(3-1), OH(6-2) and OH(8-3) Meinel bands in order to investigate whether systematic differences in emission peak altitudes can be observed between the different OH Meinel bands. The results indicate that the emission peak altitudes are different for the different vibrational levels, with bands originating from higher vibrational levels having higher emission peak altitudes. It is shown that this finding is consistent with the majority of the previously published results. The SCIAMACHY observations yield differences in emission peak altitudes of up to about 4 km between the OH(3-1) and the OH(8-3) band. The observations are complemented by model simulations of the fractional population of the different vibrational levels and of the vibrational level dependence of the emission peak altitude. The model simulations reproduce the observed vibrational level dependence of the emission peak altitude well – both qualitatively and quantitatively – if quenching by atomic oxygen as well as multi-quantum collisional relaxation by O2 is considered. If a linear relationship between emission peak altitude and vibrational level is assumed, then a peak altitude difference of roughly 0.5 km per vibrational level is inferred from both the SCIAMACHY observations and the model simulations.
Some effects of ice crystals on the FSSP measurements in mixed phase clouds

In this paper, we show that in mixed phase clouds, the presence of ice crystals may induce wrong FSSP 100 measurements interpretation especially in terms of particle size and subsequent bulk parameters. The presence of ice crystals is generally revealed by a bimodal feature of the particle size distribution (PSD). The combined measurements of the FSSP-100 and the Polar Nephelometer give a coherent description of the effect of the ice crystals on the FSSP-100 response. The FSSP-100 particle size distributions are characterized by a bimodal shape with a second mode peaked between 25 and 35 μm related to ice crystals. This feature is observed with the FSSP-100 at airspeed up to 200 m s−1 and with the FSSP-300 series. In order to assess the size calibration for clouds of ice crystals the response of the FSSP-100 probe has been numerically simulated using a light scattering model of randomly oriented hexagonal ice particles and assuming both smooth and rough crystal surfaces. The results suggest that the second mode, measured between 25 μm and 35 μm, does not necessarily represent true size responses but corresponds to bigger aspherical ice particles. According to simulation results, the sizing understatement would be neglected in the rough case but would be significant with the smooth case. Qualitatively, the Polar Nephelometer phase function suggests that the rough case is the more suitable to describe real crystals. Quantitatively, however, it is difficult to conclude. A review is made to explore different hypotheses explaining the occurrence of the second mode. However, previous cloud in situ measurements suggest that the FSSP-100 secondary mode, peaked in the range 25–35 μm, is likely to be due to the shattering of large ice crystals on the probe inlet. This finding is supported by the rather good relationship between the concentration of particles larger than 20 μm (hypothesized to be ice shattered-fragments measured by the FSSP) and the concentration of (natural) ice particles (CPI data). In mixed cloud, a simple estimation of the number of ice crystals impacting the FSSP inlet shows that the ice crystal shattering effect is the main factor in observed ice production.
Methyl hydroperoxide (CH3OOH) in urban, suburban and rural atmosphere: ambient concentration, budget, and contribution to the atmospheric oxidizing capacity

Methyl hydroperoxide (MHP), one of the most important organic peroxides in the atmosphere, contributes to the tropospheric oxidizing capacity either directly as an oxidant or indirectly as a free radical precursor. In this study we report measurements of MHP from seven field campaigns at urban, suburban and rural sites in China in winter 2007 and summer 2006/2007/2008. MHP was usually present in the order of several hundreds of pptv level, but the average mixing ratios have shown a wide range depending on the season and measuring site. Primary sources and sinks of MHP are investigated to understand the impact of meteorological and chemical parameters on the atmospheric MHP budget. The MHP/(MHP+H2O2) ratio is also presented here to examine different sensitivities of MHP and H2O2 to certain atmospheric processes. The diurnal cycle of MHP/(MHP+H2O2), which is out of phase with that of both H2O2 and MHP, could imply that MHP production is more sensitive to the ambient NO concentration, while H2O2 is more strongly influenced by the wet deposition and the subsequent aqueous chemistry. It is interesting to note that our observation at urban Beijing site in winter 2007 provides evidence for the occasional transport of MHP-containing air masses from the marine boundary layer to the continent. Furthermore, the contribution of MHP as an atmospheric oxidant to the oxidizing capacity of an air parcel is assessed based on the "Counter Species" concept.
CO2(ν2)-O quenching rate coefficient derived from coincidental SABER/TIMED and Fort Collins lidar observations of the mesosphere and lower thermosphere

Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(ν2) vibrational levels by collisions with O atoms plays an important role. However, there is a factor of 3–4 discrepancy between the laboratory measurements of the CO2-O quenching rate coefficient, kVT, and its value estimated from the atmospheric observations. In this study, we retrieve kVT in the altitude region 85–105 km from the coincident SABER/TIMED and Fort Collins sodium lidar observations by minimizing the difference between measured and simulated broadband limb 15 μm radiation. The averaged kVT value obtained in this work is 6.5 ± 1.5 × 10−12 cm3 s−1 that is close to other estimates of this coefficient from the atmospheric observations. However, the retrieved kVT also shows altitude dependence and varies from 5.5 ± 1.1 × 10−12 cm3 s−1 at 90 km to 7.9 ± 1.2 × 10−12 cm3 s−1 at 105 km. Obtained results demonstrate the deficiency in current non-LTE modeling of the atmospheric 15 μm radiation, based on the application of the CO2-O quenching and excitation rates, which are linked by the detailed balance relation. We discuss the possible model improvements, among them accounting for the interaction of the "non-thermal" oxygen atoms with CO2 molecules.
Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of unspeciated low-volatility organics (semi-volatile and intermediate volatile organic compounds) emitted by combustion systems. It is formulated using the volatility basis-set approach. Unspeciated low-volatility organics are classified by volatility and then allowed to react with the hydroxyl radical. The new methodology allows for larger reductions in volatility with each oxidation step than previous volatility basis set models, which is more consistent with the addition of common functional groups and similar to those used by traditional SOA models. The methodology is illustrated using data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. In those experiments, photo-oxidation formed a significant amount of SOA, much of which could not be explained based on the emissions of traditional speciated precursors; we refer to the unexplained SOA as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of unspeciated low-volatility organics measured using sorbents. We show that the parameterization proposed by Robinson et al. (2007) is unable to explain the timing of the NT-SOA formation in the aircraft experiments because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast the new method better reproduces the NT-SOA formation. The NT-SOA yields estimated for the unspeciated low-volatility organic emissions in aircraft exhaust are similar to literature data for large n-alkanes and other low-volatility organics. The estimated yields vary with fuel composition (Jet Propellent-8 versus Fischer-Tropsch) and engine load (ground idle versus non-ground idle). The framework developed here is suitable for modeling SOA formation from emissions from other combustion systems.
Radiative impacts of cloud heterogeneity and overlap in an atmospheric General Circulation Model

The radiative impacts of horizontal heterogeneity of layer cloud condensate, and vertical overlap of both condensate and cloud fraction are examined with the aid of a new radiation package operating in the GEOS-5 Atmospheric General Circulation Model. The impacts are examined in terms of diagnostic top-of-the atmosphere shortwave (SW) and longwave (LW) cloud radiative effect (CRE) calculations for a range of assumptions and overlap parameter specifications. The investigation is conducted for two distinct cloud schemes, one that comes with the standard GEOS-5 distribution, and another used experimentally for its enhanced cloud microphysical capabilities. Both schemes are coupled to a cloud generator allowing arbitrary cloud overlap specification. Results show that cloud overlap radiative impacts are significantly stronger in the operational cloud scheme where a change of cloud fraction overlap from maximum-random to generalized results in global changes of SW and LW CRE of ~4 Wm−2, and zonal changes of up to ~10 Wm−2. This is an outcome of fewer occurrences (compared to the other scheme) of large layer cloud fractions and fewer multi-layer situations where large numbers of atmospheric layers are simultaneously cloudy, both conditions that make overlap details more important. The impact of the specifics of condensate distribution overlap on CRE is much weaker. Once generalized overlap is adopted, both cloud schemes are only modestly sensitive to the exact values of the overlap parameters. When one of the CRE components is overestimated and the other underestimated, both cannot be driven simoultaneously towards observed values by adjustments to cloud condensate heterogeneity and overlap specifications alone.