Commentary on 'Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification' by Knopf et al.

In a recent published paper Knopf et a1. (2002) have suggested that the homogeneous freezing behavior of stratospheric aerosols, under polar winter conditions, can be simulated experimentally in large bulk phase-sized droplet samples (0.12-0.27 cm in diameter). Their hypothesis is based on the fact that a nucleus, which freezes the supercooled phase, forms within the bulk volume of a given sample, and therefore, if large bulk volumes don't freeze in the laboratory, then small volumes in particles most certainly remain unfrozen in the stratosphere. The important question to ask here is whether their initial hypothesis, which they have used to analyze their data, is even correct to begin with. For example, does a nucleus, which turns over the phase, forms within the bulk volume or on the surface of the supercooled phase? Some recent studies provide both experimental (Tabazadeh et al., 2002a, b) and theoretical (Djikaev et al., 2002, 2003) support for the formation of the nucleus at the surface of a supercooled droplet. If the homogeneous nucleation process initiates at the droplet surface, then the approach taken by Knopf. et al. to study this crystallization process may not be directly applicable to the stratospheric situation

Nitric acid scavenging by mineral and biomass burning aerosols

The abundance of gas phase nitric acid in the upper troposphere is overestimated by global chemistry-transport models, especially during the spring and summer seasons. Recent aircraft data obtained over the central US show that mineral aerosols were abundant in the upper troposphere during spring. Chemical reactions on mineral dust may provide an important sink for nitric acid. In regions where the mineral dust abundance is low in the upper troposphere similar HNO3 removal processes may occur on biomass burning aerosols. We propose that mineral and biomass burning aerosols may provide an important global sink for gas phase nitric acid, particularly during spring and summer when aerosol composition in the upper troposphere may be greatly affected by dust storms from east Asia or tropical biomass burning plumes

Heterogeneous Chemistry Involving Methanol in Tropospheric Clouds

In this report we analyze airborne measurements to suggest that methanol in biomass burning smoke is lost heterogeneously in clouds. When a smoke plume intersected a cumulus cloud during the SAFARI 2000 field project, the observed methanol gas phase concentration rapidly declined. Current understanding of gas and aqueous phase chemistry cannot explain the loss of methanol documented by these measurements. Two plausible heterogeneous reactions are proposed to explain the observed simultaneous loss and production of methanol and formaldehyde, respectively. If the rapid heterogeneous processing of methanol, seen in a cloud impacted by smoke, occurs in more pristine clouds, it could affect the oxidizing capacity of the troposphere on a global scale

CALIPSO observations of wave-induced PSCs with near-unity optical depth over Antarctica in 2006-2007

International audienceGround-based and satellite observations have hinted at the existence of polar stratospheric clouds (PSCs) with relatively high optical depths, even if optical depth values are hard to come by. This study documents a type II PSC observed from spaceborne lidar, with visible optical depths up to 0.8. Comparisons with multiple temperature fields, including reanalyses and results from mesoscale simulations, suggest that intense small-scale temperature fluctuations due to gravity waves play an important role in its formation, while nearby observations show the presence of a potentially related type Ia PSC farther downstream inside the polar vortex. Following this first case, the geographic distribution and microphysical properties of PSCs with optical depths above 0.3 are explored over Antarctica during the 2006 and 2007 austral winters. These clouds are rare (less than 1% of profiles) and concentrated over areas where strong winds hit steep ground slopes in the Western Hemisphere, especially over the peninsula. Such PSCs are colder than the general PSC population, and their detection is correlated with daily temperature minima across Antarctica. Lidar and depolarization ratios within these clouds suggest they are most likely ice-based (type II). Similarities between the case study and other PSCs suggest they might share the same formation mechanisms

Ice nucleation processes in upper tropospheric wave-clouds observed during SUCCESS

We have compared in situ measurements near the leading-edges of wave-clouds observed during the SUCCESS experiment with numerical simulations. Observations of high supersaturations with respect to ice (> 50%) near the leading edge of a very cold wave cloud (T < -60°C) are approximately consistent with recent theoretical and laboratory studies suggesting that large supersaturations are required to homogeneously freeze sulfate aerosols. Also, the peak ice crystal number densities observed in this cloud (about 4 cm¯³) are consistent with the number densities calculated in our model. In the warmer wave-cloud (T ~ -37°C) relatively large ice number densities were observed (20-40 cm¯³). Our model calculations suggest that these large number densities are probably caused by activation of sulfate aerosols into liquid droplets followed by subsequent homogeneous freezing. If moderate numbers of effective heterogeneous freezing nuclei (0.5-1cm¯³) had been present in either of these clouds, then the number densities of ice crystals and the peak relative humidities should have been lower than the observed values

Multimodel projections of stratospheric ozone in the 21st century

Simulations from eleven coupled chemistry-climate models (CCMs) employing nearly identical forcings have been used to project the evolution of stratospheric ozone throughout the 21st century. The model-to-model agreement in projected temperature trends is good, and all CCMs predict continued, global mean cooling of the stratosphere over the next 5 decades, increasing from around 0.25 K/decade at 50 hPa to around 1 K/ decade at 1 hPa under the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenarios (SRES) A1B scenario. In general, the simulated ozone evolution is mainly determined by decreases in halogen concentrations and continued cooling of the global stratosphere due to increases in greenhouse gases (GHGs). Column ozone is projected to increase as stratospheric halogen concentrations return to 1980s levels. Because of ozone increases in the middle and upper stratosphere due to GHGinduced cooling, total ozone averaged over midlatitudes, outside the polar regions, and globally, is projected to increase to 1980 values between 2035 and 2050 and before lower stratospheric halogen amounts decrease to 1980 values. In the polar regions the CCMs simulate small temperature trends in the first and second half of the 21st century in midwinter. Differences in stratospheric inorganic chlorine (Cly) among the CCMs are key to diagnosing the intermodel differences in simulated ozone recovery, in particular in the Antarctic. It is found that there are substantial quantitative differences in the simulated Cly, with the October mean Antarctic Cly peak value varying from less than 2 ppb to over 3.5 ppb in the CCMs, and the date at which the Cly returns to 1980 values varying from before 2030 to after 2050. There is a similar variation in the timing of recovery of Antarctic springtime column ozone back to 1980 values. As most models underestimate peak Cly near 2000, ozone recovery in the Antarctic could occur even later, between 2060 and 2070. In the Arctic the column ozone increase in spring does not follow halogen decreases as closely as in the Antarctic, reaching 1980 values before Arctic halogen amounts decrease to 1980 values and before the Antarctic. None of the CCMs predict future large decreases in the Arctic column ozone. By 2100, total column ozone is projected to be substantially above 1980 values in all regions except in the tropics