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Atmospheric sulphuric acid and aerosol formation: implications from atmospheric measurements for nucleation and early growth mechanisms

We have investigated the formation and early growth of atmospheric secondary aerosol particles building on atmospheric measurements. The measurements were part of the QUEST 2 campaign which took place in spring 2003 in Hyytiälä (Finland). During the campaign numerous aerosol particle formation events occurred of which 15 were accompanied by gaseous sulphuric acid measurements. Our detailed analysis of these 15 events is focussed on nucleation and early growth (to a diameter of 3 nm) of fresh particles. It revealed that new particle formation seems to be a function of the gaseous sulphuric acid concentration to the power from one to two when the time delay between the sulphuric acid and particle number concentration is taken into account. From the time delay the growth rates of freshly nucleated particles from 1 nm to 3 nm were determined. The mean growth rate was 1.2 nm/h and it was clearly correlated with the gaseous sulphuric acid concentration. We tested two nucleation mechanisms – recently proposed cluster activation and kinetic type nucleation – as possible candidates to explain the observed dependences, and determined experimental nucleation coefficients. We found that some events are dominated by the activation mechanism and some by the kinetic mechanism. Inferred coefficients for the two nucleation mechanisms are the same order of magnitude as chemical reaction coefficients in the gas phase and they correlate with the product of gaseous sulphuric acid and ammonia concentrations. This indicates that besides gaseous sulphuric acid also ammonia has a role in nucleation.
A scaling analysis of ozone photochemistry

A scaling analysis has been used to capture the integrated behaviour of several photochemical mechanisms for a wide range of precursor concentrations and a variety of environmental conditions. The Buckingham Pi method of dimensional analysis was used to express the relevant variables in terms of dimensionless groups. These grouping show maximum ozone, initial NOx and initial VOC concentrations are made non-dimensional by the average NO2 photolysis rate (jav) and the rate constant for the NO–O3 titration reaction (kNO); temperature by the NO–O3 activation energy (ENO) and Boltzmann constant (k) and total irradiation time by the cumulative javΔt photolysis rate. The analysis shows dimensionless maximum ozone concentration can be described by a product of powers of dimensionless initial NOx concentration, dimensionless temperature, and a similarity curve directly dependent on the ratio of initial VOC to NOx concentration and implicitly dependent on the cumulative NO2 photolysis rate. When Weibull transformed, the similarity relationship shows a scaling break with dimensionless model output clustering onto two straight line segments, parameterized using four variables: two describing the slopes of the line segments and two giving the location of their intersection. A fifth parameter is used to normalize the model output. The scaling analysis, similarity curve and parameterization appear to be independent of the details of the chemical mechanism, hold for a variety of VOC species and mixtures and a wide range of temperatures and actinic fluxes.
Long-memory processes in ozone and temperature variations at the region 60° S–60° N

Global column ozone and tropospheric temperature observations made by ground-based (1964–2004) and satellite-borne (1978–2004) instrumentation are analyzed. Ozone and temperature fluctuations in small time-intervals are found to be positively correlated to those in larger time-intervals in a power-law fashion. For temperature, the exponent of this dependence is larger in the mid-latitudes than in the tropics at long time scales, while for ozone, the exponent is larger in tropics than in the mid-latitudes. In general, greater persistence could be a result of either stronger positive feedbacks or larger inertia. Therefore, the increased slope of the power distribution of temperature in mid-latitudes at long time scales compared to the slope in the tropics could be connected to the poleward increase in climate sensitivity predicted by the global climate models. The detrended fluctuation analysis of model and observed time series provides a helpful tool for visualizing errors in the treatment of long-range correlations, whose correct modeling would greatly enhance confidence in long-term climate and atmospheric chemistry modeling.
Observations of lunar tides in the mesosphere and lower thermosphere at Arctic and middle latitudes

Meteor radars have been used to measure the horizontal winds in the mesosphere and lower thermosphere over Castle Eaton (52° N) in the UK and over Esrange (68° N) in Arctic Sweden. We consider a 16-year data set covering the interval 1988–2004 for the UK and a 6-year data set covering the interval 1999–2005 for the Arctic. The signature of the 12.42-h (M2) lunar tide has been identified at both locations. The lunar tide is observed to reach amplitudes as large as 11 ms−1. The Arctic radar has an interferometer and so allows investigation of the vertical structure of the lunar tide. At both locations the tide has maximum amplitudes in winter with a second autumnal maximum. The amplitude is found to increase with height over the 80–100 km height range observed. Vertical wavelengths are very variable, ranging from about 15 km in summer to more than 60 km in winter. Comparisons with the Vial and Forbes (1994) model reveals generally good agreement, except in the case of the summer vertical wavelengths which are observed to be significantly shorter than predicted.
Organics in the Northeastern Pacific and their impacts on aerosol hygroscopicity in the subsaturated and supersaturated regimes

Aerosol samples were collected by aircraft during the summer of 2004 in the Northeastern Pacific and compared to measurements of aerosol hygroscopicity. Chemical speciation analyses of the samples revealed that a significant portion of the marine aerosols was organic, and on average 8% of the total aerosol mass was insoluble organic material, tentatively attributed to natural marine emissions. Two chemical models were explored in an attempt to achieve closure between the marine aerosol chemical and physical properties through reproduction of the observed aerosol growth, both in the subsaturated and supersaturated regimes. Results suggest that at subsaturated relative humidities, the nonideal behavior of water activity with respect to aerosol chemistry has an important effect on aerosol growth. At supersaturations, the underprediction of critical supersaturations by all models suggests the hypothesis that formation of a complete monolayer by the insoluble organics may inhibit the activation of aerosols to form cloud droplets.
COMET: a Lagrangian transport model for greenhouse gas emission estimation – forward model technique and performance for methane

The Lagrangian transport model COMET has been developed to evaluate emission estimates based on atmospheric concentration observations. This paper describes the model and its application in modelling the methane concentrations at the European stations Cabauw and Macehead. The COMET model captures in most cases both synoptic and diurnal variations of the concentrations as a function of time and in absolute size quite well. The explained variability by COMET of the mixed layer concentration for Cabauw varies from 50% to 84%; for all hourly observations in 2002 the explained variability is 71% with a RMSE of 112 ppb. The explained variability for Macehead is 48%. The most important model parameters were tested for their influence on model performance, but in general the model is not very sensitive to variations within acceptable limits. For a regionally and locally polluted continental site the COMET model shows only a small bias and a moderate random error, and therefore is considered to capture the influence of the sources on the concentration variations quite well. It is therefore concluded that inverse methods and more specifically the COMET model is suitable to be applied in deriving independent estimates of greenhouse gas emissions using Source-Receptor relationships.
The semianalytical cloud retrieval algorithm for SCIAMACHY II. The application to MERIS and SCIAMACHY data

The SemiAnalytical CloUd Retrieval Algorithm (SACURA) is applied to the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) data. In particular, we derive simultaneously cloud optical thickness (COT) and cloud top height (CTH), using SCIAMACHY measurements in the visible (442 nm, COT) and in the oxygen A-band (755–775 nm, CTH). Some of the results obtained are compared with those derived from the Medium Resolution Imaging Spectrometer (MERIS), which has better spatial resolution and observes almost the same scene as SCIAMACHY. The same cloud algorithm is applied to both MERIS and SCIAMACHY data. In addition, we perform the vicarious calibration of SCIAMACHY at the wavelength 442 nm, using MERIS measurements at the same wavelength. Differences in the retrieved COT for the same cloud field obtained using MERIS and SCIAMACHY measurements are discussed.
Source and origin of atmospheric trace elements entrapped in winter snow of the Italian Eastern Alps

Trace elements concentrations were determined in shallow snow samples from 21 sites in the Italian Eastern Alps in order to identify the sources of the contaminants present in the tropospheric winter boundary layer. The collection of superficial snow layers was carried out weekly at altitudes between 1000 and 3000 m next to meteorological stations, far away from villages, roads and ski slopes. Ultra clean procedures were adopted in order to avoid contamination of the snow during the different experimental phases. Trace elements (Ag, Ba, Bi, Cd, Co, Cr, Cu, Fe, Mo, Mn, Pb, Sb, Ti, U, V and Zn) were determined by Inductively Coupled Plasma Sector Field Mass Spectrometer (ICP-SFMS). Ancillary parameters such as major ions (SO42−, NO3−, Ca2+;, Mg2+, K<sup+, Na+, Cl−) were measured by Ion Chromatography (IC) and were useful in identifying the trace elements sources. The structure of the data was studied by using Principal Component Analysis (PCA) applied on the ranked data set matrix in order to minimize the weight of the outliers. Although concentrations were low at high altitudes in the heart of the Alps, and higher at lower altitudes (Pre-Alps), the structure of the chemical content deposited by wet/dry mechanisms, resulted as rather uniform over the territory studied during the time considered. PCA shows that the chemical content of the snow is characterised by an anthropogenic component (V, Sb, Zn, Cd, Mo, Pb, Ag, Bi, SO42−, NO3−), mainly originating from the traffic in the adjacent Alpine valleys and the nearby heavily industrialised area of the Po Valley, a crustal component (Ca2+, Mg2+, Mn, U, Ti, Fe, Cr, Co, Cu and Ba) mainly from the geological carbonate background (Dolomites) of the Eastern Alps, and a marine component (Na+, Cl−) from the Mediterranean Sea. It is likely that transport and mixing of trace elements in the winter boundary layer occurred at a local (~10 km) and regional (~100 km) scale, and was due not only to the weak convection within the winter boundary layer but also to orographically induced winds and turbulences arising in the Alpine valleys due to the action of the synoptic wind.
A modified band approach for the accurate calculation of online photolysis rates in stratospheric-tropospheric Chemical Transport Models

Here we present an efficient and accurate method for the online calculation of photolysis rates relevant to both the stratosphere and troposphere for use in global Chemistry Transport Models and General Circulation Models. The method is a modified version of the band model introduced by Landgraf and Crutzen (1998) which has been updated to improve the performance of the approach for solar zenith angles >72° without the use of any implicit parameterisations. For this purpose, additional sets of band parameters have been defined for instances where the incident angle of the light beam is between 72–93°, in conjunction with a scaling component for the far UV region of the spectrum (λ=178.6–202.0 nm). For incident angles between 85–93° we introduce a modification for pseudo-sphericity that improves the accuracy of the 2-stream approximation. We show that this modified version of the Practical Improved Flux Method (PIFM) is accurate for angles <93° by comparing the resulting height resolved actinic fluxes with a recently developed full spherical reference model. We also show that the modified band method is more accurate than the original, with errors generally being less than ±10% throughout the atmospheric column for a diverse range of chemical species. Moreover, we perform certain sensitivity studies that indicate it is robust and performs well over a wide range of conditions relevant to the atmosphere.
Columnar modelling of nucleation burst evolution in the convective boundary layer – first results from a feasibility study Part IV: A compilation of previous observations for valuation of simulation results from a columnar modelling study

In the preceding Papers I, II and III a revised columnar high-order modelling approach to model gas-aerosol-turbulence interactions in the convective boundary layer (CBL) was proposed, and simulation results of two synthetic nucleation scenarios (binary vs. ternary) on new particle formation (NPF) in the anthropogenically influenced CBL were presented and discussed. The purpose of the present finishing Paper IV is twofold: Firstly, an attempt is made to compile previous observational findings on NPF bursts in the CBL, obtained from a number of field experiments. Secondly, the scenario simulations discussed in Paper III will be evaluated with respect to the role of CBL turbulence in NPF burst evolution. It was demonstrated, that completely different nucleation mechanisms can lead to the occurrence of NPF bursts in the surface layer, but the corresponding evolution patterns strongly differ with respect to the origin, amplitude and phase of the NPF burst as well as with respect to the time-height evolution of turbulent vertical fluxes and double correlation terms of physicochemical and aerosoldynamical variables. The large differences between the binary and ternary case scenario indicate, that ammonia (NH3) can not be considered as a time-independent tuning parameter in nucleation modelling. Its contribution to the evolution of the NPF burst pattern is much more complicated and reflects the influence of CBL turbulence as well as the strong non-linearity of the ternary nucleation rate. The impact of water (H2O) vapour on the nucleation rate is quite varying depending on the considered nucleation mechanism. According to the classical theory of binary nucleation involving H2O and sulphuric acid (H2SO4), H2O vapour favours NPF, according to the classical theory of ternary nuncleation involving H2O, H2SO4 and NH3 and according to organic nucleation via chemical reactions involving stabilised Criegee intermediates (SCIs), H2O vapour disfavours nucleation, and according to the parameterisation of the collision-controlled binary nucleation rate proposed by Weber et al. (1996), H2O vapour does not explicitly affect the particle formation. Since the H2SO4 concentration is overpredicted in the simulations presented in Paper III, the nucleation rates are too high compared to previous estimations. Therefore, the results are not directly comparable to measurements. Especially NPF events, where organics are suspected to play a key role, such as those observed at the boreal forest station in Hyytiälä (Southern Finland) or at Hohenpeissenberg (mountain site in Southern Germany), can not be explained by employing simple sulphur/ammonia chemistry. However, some valuable hints regarding the role of CBL turbulence in NPF can be obtained. In the literature a number of observations on the link between turbulence and NPF can be found, whose burst patterns support a strong contribution of CBL turbulence to the NPF burst evolution simulated here. Observations, that do not correspond to the scenarios are discussed with respect to possible reasons for the differences between model and observation. The model simulations support some state-of-the-art hypotheses on the contribution of CBL turbulence to NPF. Considering the application of box models, the present study shows, that CBL turbulence, not explicitly considered in such models, can strongly affect the spatio-temporal NPF burst evolution. The columnar high-order model presented here is a helpful tool to elucidate gas-aerosol-turbulence interactions, especially the genesis of NPF bursts in the CBL. An advanced description of the cluster formation and condensation growth is required as well as a comprehensive verification/validation study using observed high-order moments. Further scenario simulations remain to be performed.