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Formation of large NAT particles and denitrification in polar stratosphere: possible role of cosmic rays and effect of solar activity

The formation of large nitric acid trihydrate (NAT) particles has important implications for denitrification and ozone depletion. Existing theories have difficulty in explaining the formation of large NAT particles at temperatures above the ice frost point, which has been observed recently over wide Arctic regions. Our analyses reveal that high-energy comic ray particles might induce the freezing of supercooled HNO3-H2O-H2SO4 droplets when they penetrate these thermodynamically unstable droplets. The cosmic ray-induced freezing (CRIF) appears to be consistent with the observed, highly selective formation of NAT particles. We suggest a possible physical process behind the CRIF mechanism: the reorientation of polar solution molecules into the crystalline configuration in the strong electrical fields of moving secondary ions generated by passing cosmic rays. A simple formula connecting the CRIF rate to cosmic ray flux is derived with an undefined parameter constrained by observed NAT formation rates. Our simulations indicate that strong solar proton events (SPEs) may significantly enhance the formation of large NAT particles and denitrification. The CRIF mechanism offers a possible explanation for the observed high correlations between the thin nitrate-rich layers in polar ice cores and major SPEs, and the observed enhancement in the aerosol backscattering ratio at PSC layers shortly after an SPE and the significant precipitation velocity of the enhanced PSC layers. The key uncertainty in the CRIF mechanism is the probability (P) of freezing when a CR particle hits a thermodynamically, unstable STS droplet. Further studies are needed to either confirm or reject the CRIF hypothesis.
The origin of sea salt in snow on Arctic sea ice and in coastal regions

Snow, through its trace constituents, can have a major impact on lower tropospheric chemistry, as evidenced by ozone depletion events (ODEs) in oceanic polar areas. These ODEs are caused by the chemistry of bromine compounds that originate from sea salt bromide. Bromide may be supplied to the snow surface by upward migration from sea ice, by frost flowers being wind-blown to the snow surface, or by wind-transported aerosol generated by sea spray. We investigate here the relative importance of these processes by analyzing ions in snow near Alert and Ny-Ålesund (Canadian and European high Arctic) in winter and spring. Vertical ionic profiles in the snowpack on sea ice are measured to test upward migration of sea salt ions and to seek evidence for ion fractionation processes. Time series of the ionic composition of surface snow layers are investigated to quantify wind-transported ions. Upward migration of unfractionated sea salt to heights of at least 17cm was observed in winter snow, leading to Cl- concentration of several hundred µM. Upward migration thus has the potential to supply ions to surface snow layers. Time series show that wind can deposit aerosols to the top few cm of the snow, leading also to Cl- concentrations of several hundred µM, so that both diffusion from sea ice and wind transport can significantly contribute ions to snow. At Ny-Ålesund, sea salt transported by wind was unfractionated, implying that it comes from sea spray rather than frost flowers. Estimations based on our results suggest that the marine snowpack contains about 10 times more Na+ than the frost flowers, so that both the marine snowpack and frost flowers need to be considered as sea salt sources. Our data suggest that ozone depletion chemistry can significantly enhance the Br- content of snow. We speculate that this can also take place in coastal regions and contribute to propagate ODEs inland. Finally, we stress the need to measure snow physical parameters such as permeability and specific surface area to understand quantitatively changes in snow chemistry.
Alpha-pinene oxidation by OH: simulations of laboratory experiments

This paper presents a state-of-the-art gas-phase mechanism for the degradation of α-pinene by OH and its validation by box model simulations of laboratory measurements. It is based on the near-explicit mechanisms for the oxidation of α-pinene and pinonaldehyde by OH proposed by Peeters and co-workers. The extensive set of α-pinene photooxidation experiments performed in presence as well as in absence of NO by Nozière et al. (1999a) is used to test the mechanism. The comparison of the calculated vs measured concentrations as a function of time shows that the levels of OH, NO, NO2 and light are well reproduced in the model. Noting the large scatter in the experimental results as well as the difficulty to retrieve true product yields from concentrations data, a methodology is proposed for comparing the model and the data. The model succeeds in reproducing the average apparent yields of pinonaldehyde, acetone, total nitrates and total PANs in the experiments performed in presence of NO. In absence of NO, pinonaldehyde is fairly well reproduced, but acetone is largely underestimated. The dependence of the product yields on the concentration of NO and α-pinene is investigated, with a special attention on the influence of the multiple competitions of reactions affecting the peroxy radicals in the mechanism. We show that the main oxidation channels differ largely according to photochemical conditions. E.g. the pinonaldehyde yield is estimated to be about 10% in the remote atmosphere and up to 60% in very polluted areas. We stress the need for additional theoretical/laboratory work to unravel the chemistry of the primary products as well as the ozonolysis and nitrate-initiated oxidation of α-pinene.
Evaluation of archived and off-line diagnosed vertical diffusion coefficients from ERA-40 with 222Rn simulations

Boundary layer turbulence has a profound influence on the distribution of tracers with sources or sinks at the surface. The 40-year ERA-40 meteorological data set of the European Centre for Medium-range Weather Forecasts contains archived vertical diffusion coefficients. We evaluated the use of these archived diffusion coefficients versus off-line diagnosed coefficients based on other meteorological parameters archived during ERA-40 by examining the influence on the distribution of the radionuclide 222Rn in the chemistry transport model TM3. In total four different sets of vertical diffusion coefficients are compared: (i) 3-hourly vertical diffusion coefficients archived during the ERA-40 project, (ii) 3-hourly off-line diagnosed coefficients from a non-local scheme based on Holtslag and Boville (1993), Vogelezang and Holtslag (1996), and Beljaars and Viterbo (1999), (iii) 6-hourly coefficients archived during the ERA-40 project, and (iv) 6-hourly off-line diagnosed coefficients based on a local scheme described in Louis (1979) and Louis et al. (1982). The diffusion scheme to diagnose the coefficients off-line in (ii) is similar to the diffusion scheme used during the ERA-40 project (i and iii).
A pseudo-Lagrangian model study of the size distribution properties over Scandinavia: transport from Aspvreten to Värriö

The evolution of the aerosol size distribution during transport between Aspvreten (58.8° N, 17.4° E) and Värriö (67.46° N, 29.35° E) was studied using a pseudo-Lagrangian approach. Aerosol dynamic processes were studied and interpreted utilizing a state-of-the-art aerosol dynamic box model UHMA (University of Helsinki Multicomponent Aerosol model) complemented with OH, NO3, O3 and terpene chemistry. In the model simulations, the growth and formation of aerosol particles was controlled by sulphuric acid, ammonia, water and an unidentified low volatile organic compound. This organic compound was assumed to be a product of terpene oxidation with a yield of 13% in the base case conditions. Changes of aerosol size distribution properties during transport between the stations were examined in twelve clear sky cases. On average, the modelled number agreed fairly well with observations. Mass concentration was overestimated by 10%. Apart from dilution, the only removal mechanism for aerosol mass is dry deposition. A series of sensitivity tests performed revealed that the absolute magnitude of dry deposition effects on the aerosol size distribution is slow overall. Furthermore, nucleation does not leave a significant contribution to aerosol number in the selected cases. The sensitivity of the modelled size distribution to concentration of precursor gases and oxidants is, however, obvious. In order to explain observed mass increase during transport we conclude that a yield of low volatile products from oxidation of terpenes of 10–15% is required to explain observed growth rates. Coagulation is acknowledged to be highly important in modelled cases.
Hemispheric average Cl atom concentration from 13C/12C ratios in atmospheric methane

Methane is a significant atmospheric trace gas in the context of greenhouse warming and climate change. The dominant sink of atmospheric methane is the hydroxyl radical (OH). Recently, a mechanism for production of chlorine radicals (Cl) in the marine boundary layer (MBL) via bromine autocatalysis has been proposed. The importance of this mechanism in producing a methane sink is not clear at present because of the difficulty of in-situ direct measurement of Cl. However, the large kinetic isotope effect of Cl compared with OH produces a large fractionation of 13C compared with 12C in atmospheric methane. This property can be used to estimate the likely minimum size of the methane sink attributable to MBL Cl. By taking account of the mixing of MBL air into the free troposphere, we estimate that the global methane sink due to reaction with Cl atoms in the MBL could be as large as 19Tgyr-1, or about 3.3% of the total CH4 sink. However, its impact on the methane stable carbon isotope budget is large and warrants further attention.
Kinetic nucleation and ions in boreal forest particle formation events

In order to gain a more comprehensive picture on different mechanisms behind atmospheric particle formation, measurement results from QUEST 2-campaign are analyzed with an aid of an aerosol dynamic model. A special emphasis is laid on air ion and charged aerosol dynamics. Model simulations indicate that kinetic nucleation of ammonia and sulphuric acid together with condensation of sulphuric acid and low-volatile organic vapours onto clusters and particles explain basic features of particle formation events as well as ion characteristics. However, an observed excess of negative ions in the diameter range 1.5-3nm and overcharge of 3-5nm particles demonstrate that ions are also involved in particle formation. These observations can be explained by preferential condensation of sulphuric acid onto negatively charged clusters and particles and/or contribution of ion-induced nucleation on particle formation. According to model simulations, which assume that the nucleation rate is equal to the sulfuric acid collision rate, the relative contribution of ion-based particle formation seems to be smaller than kinetic nucleation of neutral clusters. Conducted model simulations also corroborate the recently-presented hypothesis according to which a large number of so-called thermodynamically stable clusters (TSCs) having a diameter between 1-3nm exist in the atmosphere. TSCs were found to grow to observable sizes only under favorable conditions, e.g. when the pre-existing particle concentration was low.
Aerosol seasonal variability over the Mediterranean region and relative impact of maritime, continental and Saharan dust particles over the basin from MODIS data in the year 2001

The one-year (2001) record of aerosol data from the space borne Moderate Resolution Imaging Spectroradiometer (MODIS) is analyzed focusing on the Mediterranean region. The MODIS aerosol optical thickness standard product (AOT at 550nm) provided over both land and ocean is employed to evaluate the seasonal and spatial variability of the atmospheric particulate over the region. Expected accuracy of the MODIS AOT is (±0.05±0.2xAOT) over land and (±0.03±0.05xAOT) over ocean. The seasonal analysis reveals a significant AOT variability all over the region, with minimum values in Winter (AOT<0.15) and maximum in Summer (AOT>0.2). The spatial variability is also found to be considerable, particularly over land. The impact of some major urban sites and industrialized areas is detectable. For the sole Mediterranean basin, a method (aerosol mask) was implemented to separate the contribution of maritime, continental and desert dust aerosol to the total AOT. Input of both continental and desert dust particles is well captured, showing North-to-South and South-to-North AOT gradients, respectively. A quantitative summary of the AOT seasonal and regional variability is given for different sectors of the Mediterranean basin. Results of this summary were also used to test the aerosol mask assumptions and indicate the method adopted to be suitable for the aerosol type selection. Estimates of the atmospheric aerosol mass load were performed employing specifically-derived mass-to-extinction efficiencies (α). For each aerosol type, a reliable mean α value was determined on the basis of both lidar measurements of extinction and aerosol models. These estimates indicate a total of 43Mtons of desert dust suspended over the basin during 2001. A comparable value is derived for maritime aerosol. Opposite to the dust case, a minor seasonal variability (within 15%) of maritime aerosol mass is found. This latter result is considered a further check of the suitability of the methodology adopted to separate, on the basis of MODIS data, the three aerosol types which dominate the Mediterranean region.
NOGAPS-ALPHA model simulations of stratospheric ozone during the SOLVE2 campaign

This paper presents three-dimensional prognostic O3 simulations with parameterized gas-phase photochemistry from the new NOGAPS-ALPHA middle atmosphere forecast model. We compare 5-day NOGAPS-ALPHA hindcasts of stratospheric O3 with satellite and DC-8 aircraft measurements for two cases during the SOLVE II campaign: (1) the cold, isolated vortex during 11-16 January 2003; and (2) the rapidly developing stratospheric warming of 17-22 January 2003. In the first case we test three different photochemistry parameterizations. NOGAPS-ALPHA O3 simulations using the NRL-CHEM2D parameterization give the best agreement with SAGE III and POAM III profile measurements. 5-day NOGAPS-ALPHA hindcasts of polar O3 initialized with the NASA GEOS4 analyses produce better agreement with observations than do the operational ECMWF O3 forecasts of case 1. For case 2, both NOGAPS-ALPHA and ECMWF 114-h forecasts of the split vortex structure in lower stratospheric O3 on 21 January 2003 show comparable skill. Updated ECMWF O3 forecasts of this event at hour 42 display marked improvement from the 114-h forecast; corresponding updated 42-hour NOGAPS-ALPHA prognostic O3 fields initialized with the GEOS4 analyses do not improve significantly. When NOGAPS-ALPHA prognostic O3 is initialized with the higher resolution ECMWF O3 analyses, the NOGAPS-ALPHA 42-hour lower stratospheric O3 fields closely match the operational 42-hour ECMWF O3 forecast of the 21 January event. We find that stratospheric O3 forecasts at high latitudes in winter can depend on both model initial conditions and the treatment of photochemistry over periods of 1-5 days. Overall, these results show that the new O3 initialization, photochemistry parameterization, and spectral transport in the NOGAPS-ALPHA NWP model can provide reliable short-range stratospheric O3 forecasts during Arctic winter.
Corrigendum to "Formation of solid particles in synoptic-scale Arctic PSCs in early winter 2002/2003" published in Atmos. Chem. Phys., 4, 2001--2013, 2004