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Iodine-mediated coastal particle formation: an overview of the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) Roscoff coastal study

This paper presents a summary of the measurements made during the heavily-instrumented Reactive Halogens in the Marine Boundary Layer (RHaMBLe) coastal study in Roscoff on the North West coast of France throughout September 2006. It was clearly demonstrated that iodine-mediated coastal particle formation occurs, driven by daytime low tide emission of molecular iodine, I2, by macroalgal species fully or partially exposed by the receding waterline. Ultrafine particle concentrations strongly correlate with the rapidly recycled reactive iodine species, IO, produced at high concentrations following photolysis of I2. The heterogeneous macroalgal I2 sources lead to variable relative concentrations of iodine species observed by path-integrated and in situ measurement techniques. Apparent particle emission fluxes were associated with an enhanced apparent depositional flux of ozone, consistent with both a direct O3 deposition to macroalgae and involvement of O3 in iodine photochemistry and subsequent particle formation below the measurement height. The magnitude of the particle formation events was observed to be greatest at the lowest tides with the highest concentrations of ultrafine particles growing to the largest sizes, probably by the condensation of anthropogenically-formed condensable material. At such sizes the particles should be able to act as cloud condensation nuclei at reasonable atmospheric supersaturations.
The role of sulphates and organic vapours in growth of newly formed particles in a eucalypt forest

The influence of biogenic particle formation on climate is a well recognised phenomenon. To understand the mechanisms underlying the biogenic particle formation, determining the chemical composition of the new particles and therefore the species that drive the particle production is of utmost importance. Due to the very small amount of mass involved, indirect approaches are frequently used to infer the composition. We present here the results of such an indirect approach by simultaneously measuring volatile and hygroscopic properties of newly formed particles in a forest environment. It is shown that the particles are composed of both sulphates and organics, with the amount of sulphate component strongly depending on the available gas-phase sulphuric acid, and the organic components having the same volatility and hygroscopicity as photo-oxidation products of a monoterpene such as α-pinene. Our findings agree with a two-step process through nucleation and cluster formation followed by simultaneous growth by condensation of sulphates and organics that take the particles to climatically relevant sizes.
Scanning electron microscopy and molecular dynamics of surfaces of growing and ablating hexagonal ice crystals

We present the first clearly resolved observations of surfaces of growing and ablating hexagonal ice crystals using variable-pressure scanning electron microscopy. The ice surface develops trans-prismatic strands, separated from one another by distances of 5–10 μm. The strands are present at a wide range of supersaturations, but are most pronounced at temperatures near the frost point. Pyramidal facets consistent with Miller-Bravais indices of 1011, and possibly also 2021, are associated with ice growth under these conditions. A molecular-dynamics model of a free-standing ice Ih nanocolumn containing 8400 water molecules does not develop trans-prismatic strands, suggesting these features originate at larger spatial or temporal scales. The possible relevance of these surface features to cirrus ice is discussed.
Uncertainties in estimating mercury emissions from coal-fired power plants in China

A detailed multiple-year inventory of mercury emissions from anthropogenic activities in China has been developed. Coal combustion and nonferrous metals production continue to be the two leading mercury sources in China, together contributing ~80% of total mercury emissions. However, many uncertainties still remain in our knowledge of primary anthropogenic releases of mercury to the atmosphere in China. In situations involving large uncertainties, our previous mercury emission inventory that used a deterministic approach could produce results that might not be a true reflection of reality; and in such cases stochastic simulations incorporating uncertainties need to be performed. Within our inventory, a new comprehensive sub-module for estimation of mercury emissions from coal-fired power plants in China is constructed as an uncertainty case study. The new sub-module integrates up-to-date information regarding mercury content in coal by province, coal washing and cleaning, coal consumption by province, mercury removal efficiencies by control technology or technology combinations, etc. Based on these detailed data, probability-based distribution functions are built into the sub-module to address the uncertainties of these key parameters. The sub-module incorporates Monte Carlo simulations to take into account the probability distributions of key input parameters and produce the mercury emission results in the form of a statistical distribution. For example, the best estimate for total mercury emissions from coal-fired power plants in China in 2003 is 90.5 Mg, with the uncertainty range from 57.1 Mg (P10) to 154.6 Mg (P90); and the best estimate for elemental mercury emissions is 43.0 Mg, with the uncertainty range from 25.6 Mg (P10) to 75.7 Mg (P90). The results further indicate that the majority of the uncertainty in mercury emission estimation comes from two factors: mercury content of coal and mercury removal efficiency.
Uptake of NO3 and N2O5 to Saharan dust, ambient urban aerosol and soot: a relative rate study

The uptake of NO3 and N2O5 to Saharan dust, ambient aerosols and soot was investigated using a novel and simple relative rate method with simultaneous detection of both NO3 and N2O5. The use of cavity ring down spectroscopy to detect both trace gases enabled the measurements to be carried out at low mixing ratios (<500 pptv or 1×1010 molecule cm−3). The uptake coefficient ratio, γ(NO3)/γ(N2O5), was determined to be 0.9±0.4 for Saharan dust, independent of relative humidity, NO3 or N2O5 mixing ratio and exposure time. Ambient (urban) aerosols showed a very limited capacity to take up N2O5 but were reactive towards NO3 with γ(NO3)/γ(N2O5)>15. A value of γ(NO3)/γ(N2O5)~1.5–3 was obtained when using candle generated soot. The relative rate obtained for Saharan dust can be placed on an absolute basis using our recently determined value of γ(N2O5)=1×10−2 to give γ(NO3)=9×10−3, which is significantly smaller than the single previous value. With the present uptake coefficient, reaction of NO3 with mineral dust will generally not contribute significantly to its NO3 loss in the boundary atmosphere or to the nitration of mineral dust.
Distribution of gaseous and particulate organic composition during dark α-pinene ozonolysis

Secondary Organic Aerosol (SOA) affects atmospheric composition, air quality and radiative transfer, however major difficulties are encountered in the development of reliable models for SOA formation. Constraints on processes involved in SOA formation can be obtained by interpreting the speciation and evolution of organics in the gaseous and condensed phase simultaneously. In this study we investigate SOA formation from dark α-pinene ozonolysis with particular emphasis upon the mass distribution of gaseous and particulate organic species. A detailed model for SOA formation is compared with the results from experiments performed in the EUropean PHOtoREactor (EUPHORE) simulation chamber, including on-line gas-phase composition obtained from Chemical-Ionization-Reaction Time-Of-Flight Mass-Spectrometry measurements, and off-line analysis of SOA samples performed by Ion Trap Mass Spectrometry and Liquid Chromatography. The temporal profile of SOA mass concentration is relatively well reproduced by the model. Sensitivity analysis highlights the importance of the choice of vapour pressure estimation method, and the potential influence of condensed phase chemistry. Comparisons of the simulated gaseous- and condensed-phase mass distributions with those observed show a generally good agreement. The simulated speciation has been used to (i) propose a chemical structure for the principal gaseous semi-volatile organic compounds and condensed monomer organic species, (ii) provide evidence for the occurrence of recently suggested radical isomerisation channels not included in the basic model, and (iii) explore the possible contribution of a range of accretion reactions occurring in the condensed phase. We find that oligomer formation through esterification reactions gives the best agreement between the observed and simulated mass spectra.
Technical Note: Characterisation of a DUALER instrument for the airborne measurement of peroxy radicals during AMMA 2006

A DUALER (dual-channel airborne peroxy radical chemical amplifier) instrument has been developed and optimised for the airborne measurement of the total sum of peroxy radicals during the AMMA (African Monsoon Multidisciplinary Analyses) measurement campaign which took place in Burkina Faso in August 2006. The innovative feature of the instrument is that both reactors are sampling simultaneously from a common pre-reactor nozzle while the whole system is kept at a constant pressure to ensure more signal stability and accuracy. Laboratory experiments were conducted to characterise the stability of the NO2 detector signal and the chain length with the pressure. The results show that airborne measurements using chemical amplification require constant pressure at the luminol detector. Wall losses of main peroxy radicals HO2 and CH3O2 were investigated. The chain length was experimentally determined for different ambient mixtures and compared with simulations performed by a chemical box model. The DUALER instrument was successfully mounted within the German DLR-Falcon. The analysis of AMMA data utilises a validation procedure based on the O3 mixing ratios simultaneously measured onboard. The validation and analysis procedure is illustrated by means of the data measured during the AMMA campaign. The detection limit and the accuracy of the ambient measurements are also discussed.
Cross-hemispheric transport of central African biomass burning pollutants: implications for downwind ozone production

Pollutant plumes with enhanced concentrations of trace gases and aerosols were observed over the southern coast of West Africa during August 2006 as part of the AMMA wet season field campaign. Plumes were observed both in the mid and upper troposphere. In this study we examined the origin of these pollutant plumes, and their potential to photochemically produce ozone (O3) downwind over the Atlantic Ocean. Their possible contribution to the Atlantic O3 maximum is also discussed. Runs using the BOLAM mesoscale model including biomass burning carbon monoxide (CO) tracers were used to confirm an origin from central African biomass burning fires. The plumes measured in the mid troposphere (MT) had significantly higher pollutant concentrations over West Africa compared to the upper tropospheric (UT) plume. The mesoscale model reproduces these differences and the two different pathways for the plumes at different altitudes: transport to the north-east of the fire region, moist convective uplift and transport to West Africa for the upper tropospheric plume versus north-west transport over the Gulf of Guinea for the mid-tropospheric plume. Lower concentrations in the upper troposphere are mainly due to enhanced mixing during upward transport. Model simulations suggest that MT and UT plumes are 16 and 14 days old respectively when measured over West Africa. The ratio of tracer concentrations at 600 hPa and 250 hPa was estimated for 14–15 August in the region of the observed plumes and compares well with the same ratio derived from observed carbon dioxide (CO2) enhancements in both plumes. It is estimated that, for the period 1–15 August, the ratio of Biomass Burning (BB) tracer concentration transported in the UT to the ones transported in the MT is 0.6 over West Africa and the equatorial South Atlantic. Runs using a photochemical trajectory model, CiTTyCAT, initialized with the observations, were used to estimate in-situ net photochemical O3 production rates in these plumes during transport downwind of West Africa. The mid-troposphere plume spreads over altitude between 1.5 and 6 km over the Atlantic Ocean. Even though the plume was old, it was still very photochemically active (mean net O3 production rates over 10 days of 2.6 ppbv/day and up to 7 ppbv/day during the first days) above 3 km especially during the first few days of transport westward. It is also shown that the impact of high aerosol loads in the MT plume on photolysis rates serves to delay the peak in modelled O3 concentrations. These results suggest that a significant fraction of enhanced O3 in mid-troposphere over the Atlantic comes from BB sources during the summer monsoon period. According to simulated occurrence of such transport, BB may be the main source for O3 enhancement in the equatorial south Atlantic MT, at least in August 2006. The upper tropospheric plume was also still photochemically active, although mean net O3 production rates were slower (1.3 ppbv/day). The results suggest that, whilst the transport of BB pollutants to the UT is variable (as shown by the mesoscale model simulations), pollution from biomass burning can make an important contribution to additional photochemical production of O3 in addition to other important sources such as nitrogen oxides (NOx) from lightning.
What can we learn from European continuous atmospheric CO2 measurements to quantify regional fluxes – Part 1: Potential of the 2001 network

An inverse model using atmospheric CO2 observations from a European network of stations to reconstruct daily CO2 fluxes and their uncertainties over Europe at 40 km resolution has been developed within a Bayesian framework. In this first part, a pseudo-data experiment is performed to assess the potential of continuous measurements over Europe using a network of 10 stations of the AEROCARB project such as in 2001 (<a href="http://www.aerocarb.cnrs-gif.fr/"target="_blank">http://www.aerocarb.cnrs-gif.fr/</a>). Under the assumptions of a small observation noise and a perfect atmospheric transport model, the reconstruction of daily CO2 fluxes and in particular of their synoptic variability is best over Western Europe where the network is the densest. At least a 10 days temporal and a 1000 km spatial averaging of the inverted daily/40 km fluxes is required in order to obtain a good agreement between the estimated and the "true" fluxes in terms of correlation and variability. The performance of the inversion system rapidly degrades when fluxes are sought for a smaller temporal or spatial averaging.
Technical Note: Variance-covariance matrix and averaging kernels for the Levenberg-Marquardt solution of the retrieval of atmospheric vertical profiles

The variance-covariance matrix (VCM) and the averaging kernel matrix (AKM) are widely used tools to characterize atmospheric vertical profiles retrieved from remote sensing measurements. Accurate estimation of these quantities is essential for both the evaluation of the quality of the retrieved profiles and for the correct use of the profiles themselves in subsequent applications such as data comparison, data assimilation and data fusion. We propose a new method to estimate the VCM and AKM of vertical profiles retrieved using the Levenberg-Marquardt iterative technique. We apply the new method to the inversion of simulated limb emission measurements. Then we compare the obtained VCM and AKM with those resulting from other methods already published in the literature and with accurate estimates derived using statistical and numerical estimators. The proposed method accounts for all the iterations done in the inversion and provides the most accurate VCM and AKM. Furthermore, it correctly estimates the VCM and the AKM also if the retrieval iterations are stopped when a physically meaningful convergence criterion is fulfilled, i.e. before achievement of the numerical convergence at machine precision. The method can be easily implemented in any Levenberg-Marquardt iterative retrieval scheme, either constrained or unconstrained, without significant computational overhead.