Abstract. Particle formation in the binary H2SO4-H20 vapor system was studied at 295 K in a series of experiments employing a flow reactor. The concentration of H2SO4 was detected by chemical ionization mass spectrometry, and an ultrafine particle condensation nucleus counter was used to count the newly nucleated particles. Results yield a particle formation rate that is approximately proportional to [H2SO4] raised to the eighth power and to [H20] raised to the fifth power. The power dependencies measured here are significantly different from those determined in previous experimental work, and furthermore, the water dependence is markedly different from that predicted from current theories. The effect of adding ammonia vapor to the binary system was investigated; concentrations of NH3 in the many tens of parts per trillion by volume range were observed to promote dramatically the rate of particle nucleation.

The <b>RE</b>gents <b>PAR</b>k and <b>T</b>ower <b>E</b>nvironmental <b>E</b>xperiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types

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A broadband absorption spectrometer has been developed for highly sensitive and target-selective in situ trace gas measurements. The instrument employs two distinct modes of operation: (i) broadband cavity enhanced absorption spectroscopy (BBCEAS) is used to quantify the concentration of gases in sample mixtures from their characteristic absorption features, and (ii) periodic measurements of the cavity mirrors' reflectivity are made using step-scan phase shift cavity ringdown spectroscopy (PSCRDS). The latter PSCRDS method provides a stand-alone alternative to the more usual method of determining mirror reflectivities by measuring BBCEAS absorption spectra for calibration samples of known composition. Moreover, the instrument's two modes of operation use light from the same light emitting diode transmitted through the cavity in the same optical alignment, hence minimizing the potential for systematic errors between mirror reflectivity determinations and concentration measurements. The ability of the instrument to quantify absorber concentrations is tested in instrument intercomparison exercises for NO(2) (versus a laser broadband cavity ringdown spectrometer) and for H(2)O (versus a commercial hygrometer). A method is also proposed for calculating effective absorption cross sections for fitting the differential structure in BBCEAS spectra due to strong, narrow absorption lines that are under-resolved and hence exhibit non-Beer-Lambert law behavior at the resolution of the BBCEAS measurements. This approach is tested on BBCEAS spectra of water vapor's 4v+delta absorption bands around 650 nm. The most immediate analytical application of the present instrument is in quantifying the concentration of reactive trace gases in the ambient atmosphere. The instrument's detection limits for NO(3) as a function of integration time are considered in detail using an Allan variance analysis. Experiments under laboratory conditions produce a 1sigma detection limit of 0.25 pptv for a 10 s acquisition time, which improves with further signal averaging to 0.09 pptv in 400 s. Finally, an example of the instrument's performance under field work conditions is presented, in this case of measurements of the sum of NO(3)+N(2)O(5) concentrations in the marine boundary layer acquired during the Reactive Halogens in the Marine Boundary Layer field campaign.

Abstract. 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 iodinemediated coastal particle formation occurs, driven by daytime low tide emission of molecular iodine, I 2 , 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 I 2 . The heterogeneous macroalgal I 2 sources lead to variable relative concentrations of iodine species observed by path-integrated and in situ measurement techniques.

A compact and low power detector has been developed for the in situ measurement of atmospheric NO(2) using broadband cavity enhanced absorption spectroscopy. Absorption by the O(2)-O(2) collisional pair was used to determine the cavity mirror reflectivity, thus enabling the retrieval of absolute absorber concentrations by differential spectral fitting techniques. Quantitative amounts of ambient NO(2) (between 3 and 32 parts per billion) were retrieved from spectra recorded in the presence of ambient aerosol with statistical uncertainties approaching 100 ppt for a 60 s averaging period. The instrument's response was compared to that of a commercial chemiluminescence detector and was found to agree to within 6%.

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Abstract. This paper describes a broadband cavity ringdown spectrometer and its deployment during the 2002 North Atlantic Marine Boundary Layer Experiment (NAMBLEX) to measure ambient concentrations of NO 3 , N 2 O 5 , I 2 and OIO at the Mace Head Atmospheric Research Station, Co. Galway, Ireland. The effective absorption path lengths accessible with the spectrometer generally exceeded 10 km, enabling sensitive localised "point" measurements of atmospheric absorbers to be made adjacent to the other instruments monitoring chemically related species at the same site. For the majority of observations, the spectrometer was used in an open path configuration thereby avoiding surface losses of reactive species. A subset of observations targeted the N 2 O 5 molecule by detecting the additional NO 3 formed by the thermal dissociation of N 2 O 5 . In all cases the concentrations of the atmospheric absorbers were retrieved by fitting the differential structure in the broadband cavity ringdown spectra using a methodology adapted from long path differential optical absorption spectroscopy. The uncertainty of the retrieval depends crucially on the correct treatment and fitting of the absorption bands due to water vapour, a topic that is discussed in the context of analysing broadband cavity ringdown spectra. The quality of the measurements and the retrieval method are illustrated with representative spectra acquired during NAMBLEX in spectral regions around 660 nm (NO 3 and N 2 O 5 ) and 570 nm (I 2 and OIO). Typical detection limits were 1 pptv for NO 3 in an integration time of 100 s, 4 pptv for OIO and 20 pptv for I 2 in an integration time of 10 min. Additionally, the concentrations of atmospheric water vapour and the aerosol optical extinction were retrieved in both spectral regions. A companion paper in this issue presents the time series of the measurements and discusses their significance for understanding the variability of short lived nitrogen and iodine compounds in the marine boundary layer.