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Impact of land convection on temperature diurnal variation in the tropical lower stratosphere inferred from COSMIC GPS radio occultations

Following recent studies evidencing the influence of deep convection on the chemical composition and thermal structure of the tropical lower stratosphere, we explore its impact on the temperature diurnal variation in the upper troposphere and lower stratosphere using the high-resolution COSMIC GPS radio-occultation temperature measurements spanning from 2006 through 2011. The temperature in the lowermost stratosphere over land during summer displays a marked diurnal cycle characterized by an afternoon cooling. This diurnal cycle is shown collocated with most intense land convective areas observed by the Tropical Rainfall Measurement Mission (TRMM) precipitation radar and in phase with the maximum overshooting occurrence frequency in late afternoon. Two processes potentially responsible for that are identified: (i) non-migrating tides, whose physical nature is internal gravity waves, and (ii) local cross-tropopause mass transport of adiabatically cooled air by overshooting turrets. Although both processes can contribute, only the lofting of adiabatically cooled air is well captured by models, making it difficult to characterize the contribution of non-migrating tides. The impact of deep convection on the temperature diurnal cycle is found larger in the southern tropics, suggesting more vigorous convection over clean rain forest continents than desert areas and polluted continents in the northern tropics.
Could aerosol emissions be used for regional heat wave mitigation?

Geoengineering applications by injection of sulfate aerosols into the stratosphere are under consideration as a measure of last resort to counter global warming. Here a potential regional-scale application to offset the impacts of heat waves is critically examined. Using the Weather Research and Forecasting model with fully coupled chemistry (WRF-Chem), the effect of regional-scale sulfate aerosol emission over California in each of two days of the July 2006 heat wave is used to quantify potential reductions in surface temperature as a function of emission rates in a layer at 12 km altitude. Local meteorological factors yield geographical differences in surface air temperature sensitivity. For emission rates of approximately 30 μg m−2 s−1 of sulfate aerosols (with standard WRF-Chem size distribution) over the region, temperature decreases of around 7 °C result during the middle part of the day over the Central Valley, one of the areas hardest hit by the heat wave. Regions more ventilated with oceanic air such as Los Angeles have slightly smaller reductions. The length of the hottest part of the day is also reduced. Advection effects on the aerosol cloud must be more carefully forecast for smaller injection regions. Verification of the impacts could be done via measurements of differences in reflected and surface downward shortwave. Such regional geoengineering applications with specific near-term target effects but smaller cost and side effects could potentially provide a means of testing larger scale applications. However, design considerations for regional applications, such as a preference for injection at a level of relatively low wind speed, differ from those for global applications. The size of the required injections and the necessity of injection close to the target region raise substantial concerns. The evaluation of this regional-scale application is thus consistent with global model evaluations, emphasizing that mitigation via reduction of fossil fuels remains preferable to considering geoengineering with sulfate aerosols.
222Rn-calibrated mercury fluxes from terrestrial surface of southern Africa

Gaseous elemental mercury (GEM) and 222Rn, a radioactive gas of primarily terrestrial origin with a half-life of 3.8 days, have been measured simultaneously at Cape Point, South Africa, since March 2007. Between March 2007 and December 2011, altogether 191 events with high 222Rn concentrations were identified. GEM correlated with 222Rn in 94 of the events and was constant during almost all the remaining events without significant correlation. The average GEM / 222Rn flux ratio of all events including the non-significant ones was −0.0001 with a standard error of ±0.0030 pg mBq−1. Weighted with the event duration, the average GEM / 222Rn flux ratio was −0.0048 ± 0.0011 pg mBq−1. With an emission rate of 1.1 222Rn atoms cm−2 s−1 and a correction for the transport time, this flux ratio corresponds to a radon-calibrated flux of about −0.54 ng GEM m−2 h−1 with a standard error of ±0.13 ng GEM m−2 h−1 (n = 191). With wet deposition, which is not included in this estimate, the terrestrial surface of southern Africa seems to be a net mercury sink of about −1.55 ng m−2 h−1. The additional contribution of an unknown but presumably significant deposition of reactive gaseous mercury would further increase this sink.
Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen

It is now accepted that one of the important pathways of secondary organic aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the chemical mechanisms leading to macromolecules are still not well understood. It was recently shown that oligomer production by OH radical oxidation in the aerosol aqueous phase from α-dicarbonyl precursors, such as methylglyoxal and glyoxal, is irreversible and fast. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α,β-unsaturated carbonyl that can undergo radical oligomerization in the aerosol aqueous phase. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under various conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights in our experiments the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the dominance of oligomerization reactions after several minutes of reaction. These processes, together with the large range of initial concentrations investigated show the fundamental role that radical oligomerization processes likely play in polluted fogs and atmospheric aerosol.
Uptake of HO2 radicals on Arizona Test Dust

The interaction of HO2 radicals with solid films of Arizona Test Dust (ATD) was studied using a low-pressure flow reactor (1–9 Torr) combined with a modulated molecular beam mass spectrometer for monitoring of the gaseous species involved. The reactive uptake coefficient of HO2 was measured from the kinetics of HO2 consumption on Pyrex rods coated with ATD as a function of HO2 concentration ((0.35–3.30) × 1012 molecule cm−3), relative humidity (RH = 0.02–94%), temperature (T = 275–320 K) and UV irradiance intensity (JNO2 = 0–0.012 s−1). The initial uptake coefficient was found to be independent of concentration of HO2, temperature and irradiation conditions, and to decrease with increasing relative humidity: γ0 = 1.2/(18.7 + RH1.1) (with 30% estimated conservative uncertainty). The uptake coefficient was calculated using geometric surface area and should be considered as an upper limit of γ0. An upper limit of 5% was found for the gaseous H2O2-forming pathway of the HO2 reaction with ATD surface. The results of the measurements indicate that HO2 loss on dust aerosol may be a non-negligible sink for HOx species in the troposphere with the effect depending on specific local conditions.
Corrigendum to "Aerosol indirect effects from shipping emissions: sensitivity studies with the global aerosol-climate model ECHAM-HAM" published in Atmos. Chem. Phys., 12, 5985–6007, 2012

An error in the calculation of the emitted number of primary sulfate particles for a given mass of emitted elementary sulfur has recently been identified in HAM, i.e. the aerosol module utilised in the ECHAM-HAM aerosol climate model. Correcting for this error substantially alters the estimates of top-of-atmosphere radiative forcing due to aerosol indirect effects from global shipping emissions (year 2000) as presented in Peters et al. (2012). Here, we shortly present these new results.
Photosensitised heterogeneous oxidation kinetics of biomass burning aerosol surrogates by ozone using an irradiated rectangular channel flow reactor

Heterogeneous reaction kinetics involving organic aerosol and atmospheric oxidants such as ozone can be enhanced under visible or UV irradiation in the presence of a photosensitiser, with subsequent implications for the climate, cloud radiative properties, air quality, and source appointment. In this study we report the steady-state reactive uptake coefficient, γ, of O3 by levoglucosan and 5-nitroguaiacol acting as surrogates for biomass burning aerosol particles, with and without the presence of Pahokee peat acting as a photosensitiser. The reactive uptake has been determined in the dark and as a function of visible and UV-A irradiation and ozone concentration. In addition, γ was determined for 1 : 1, 1 : 10, and 1 : 100 by mass mixtures of Pahokee peat and 5-nitroguaiacol, and for a 10 : 1 : 3 mixture of levoglucosan, Pahokee peat, and 5-nitroguaiacol. We developed a novel irradiated rectangular channel flow reactor (I-RCFR) that was operated under low pressures of about 2–4 hPa, and allowed for uniform irradiation of the organic substrates. The I-RCFR was coupled to a chemical ionisation mass spectrometer and has been successfully validated by measuring the kinetics between various organic species and oxidants. γ of O3 and levoglucosan in the dark and under visible and UV-A irradiation was determined to be in the range of (2–11) × 10−6 and did not change in the presence of Pahokee peat. The determined γ of O3 and 5-nitroguaiacol in the dark was 5.7 × 10−6 and was only enhanced under UV-A irradiation, yielding a value of 3.6 × 10−5. γ of the 1 : 1 Pahokee peat/5-nitroguaiacol substrate was enhanced under visible and UV-A irradiation to 2.4 × 10−5 and 2.8 × 10−5, respectively. Decreasing the amount of Pahokee peat in the 5-nitroguaiacol/Pahokee peat substrate resulted in lower values of γ under visible irradiation, however, γ was consistent under UV-A irradiation regardless of the amount of Pahokee peat. The 10 : 1 : 3 mixture by mass of levoglucosan, Pahokee peat, and 5-nitroguaiacol, under both visible and UV-A irradiation yielded γ values of 2.8 × 10−5 and 1.4 × 10−5, respectively. γ was determined as a function of photon flux for O3 with the 1 : 1 Pahokee peat/5-nitroguaiacol substrate, yielding a linear relationship under both visible and UV-A irradiation. γ of O3 with the 1 : 1 Pahokee peat/5-nitroguaiacol substrate was determined as a function of ozone concentration and exhibited an inverse dependence of γ on ozone concentration, commonly interpreted as a Langmuir–Hinshelwood mechanism. The reactive uptake data have been represented by a Langmuir-type isotherm. From the O3 uptake data under visible irradiation, the following fit parameters have been derived: ks = (5.5 ± 2.7) × 10−19 cm2 s−1 molecule−1 and KO3 = (2.3 ± 2.0) × 10−12 cm3 molecule−1; and under UV-A irradiation: ks = (8.1 ± 2.0) × 10−19 cm2 s−1 molecule−1 and KO3 = (1.7 ± 0.7) × 10−12 cm3 molecule−1. The oxidative power, or the product of γ and [O3], was determined for O3 with the 1 : 1 Pahokee peat/5-nitroguaiacol substrate and was in the range of (1.2–26) × 106 molecule cm−3. Atmospheric particle lifetimes were estimated for a 0.4 μm 5-nitroguaiacol particle as a function of visible and UV-A irradiation and ozone concentration.
Growth of atmospheric nano-particles by heterogeneous nucleation of organic vapor

Atmospheric aerosols play critical roles in air quality, public health, and visibility. In addition, they strongly influence climate by scattering solar radiation and by changing the reflectivity and lifetime of clouds. One major but still poorly understood source of atmospheric aerosols is new particle formation, which consists of the formation of thermodynamically stable clusters from trace gas molecules (homogeneous nucleation) followed by growth of these clusters to a detectable size (~3 nm). Because freshly nucleated clusters are most susceptible to loss due to high rate of coagulation with pre-existing aerosol population, the initial growth rate strongly influences the rate of new particle formation and ambient aerosol population. Whereas many field observations and modeling studies indicate that organics enhance the initial growth of the clusters and therefore new particle formation, thermodynamic considerations would suggest that the strong increase of equilibrium vapor concentration due to cluster surface curvature (Kelvin effect) may prevent ambient organics from condensing on these small clusters. Here, the contribution of organics to the initial cluster growth is described as heterogeneous nucleation of organic molecules onto these clusters. We find that the strong gradient in cluster population with respect to its size leads to positive cluster number flux. This positive flux drives the growth of clusters substantially smaller than the Kelvin diameter, conventionally considered the minimum particle size that can be grown through condensation. The conventional approach neglects the contribution from the cluster concentration gradient, and underestimates the cluster survival probabilities by a factor of up to 60 if early growth of clusters is due to both condensation of sulfuric acid and heterogeneous nucleation of organic vapors.
Ten-year trends in atmospheric mercury concentrations, meteorological effects and climate variables at Zeppelin, Ny-Ålesund

Results from ten years of gaseous elemental mercury (GEM) measurements at Zeppelin station, Ny-Ålesund, Svalbard, show no overall annual trend between 2000 and 2009. Seasonal trend analysis showed significantly decreasing trends in January, February, March and June (−4.5 to −14.9 pg m−3 yr−1) and significantly increasing trends in May and July through December (1.5 to 28.7 pg m−3 yr −1). Results showed that atmospheric mercury depletion events (AMDEs) were equally distributed between April and May with only a few having been observed in March and June. A negative correlation between AMDEs and temperature is reported and supports earlier observations that AMDEs tend to occur at low temperatures. Lower concentrations of GEM were seen at lower temperatures below a threshold of 0 °C. The occurrence of AMDEs and wind direction were well correlated with the lowest GEM measured when the wind direction was from the Arctic Ocean region. Wind speed was found to not correlate with AMDEs, but the lowest GEM concentrations were observed at low wind speeds between 4 and 11 m s−1. AMDEs and relative humidity did not correlate well, but the lowest GEM levels appeared when the relative humidity was between 80 and 90%. Diurnal variation was observed especially during the month of March and is probably due to daytime snow surface emission induced by solar radiation. Relationships between GEM concentration and the Northern Hemisphere climate indices were investigated to assess if these climate parameters might reflect different atmospheric conditions that enhance or reduce spring AMDE activity. No consistent pattern was observed.
Corrigendum to "Evaluation of preindustrial to present-day black carbon and its albedo forcing from Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)" published in Atmos. Chem. Phys., 13, 2607–2634, 2013