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.

Abstract. NO 2 concentrations were measured by various instruments during the NO3Comp campaign at the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich, Germany, in June 2007. Analytical methods included photolytic conversion with chemiluminescence (PC-CLD), broadband cavity ring-down spectroscopy (BBCRDS), pulsed cavity ring-down spectroscopy (CRDS), incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS), and laser-induced fluorescence (LIF). All broadband absorption spectrometers were optimized for the detection of the main target species of the campaign, NO 3 , but were also capable of detecting NO 2 simultaneously with reduced sensitivity. NO 2 mixing ratios in the chamber were within a range characteristic of polluted, urban conditions, with a maximum mixing ratio of approximately 75 ppbv. The overall agreement between measurements of all instruments was excellent. Linear fits of the combined data sets resulted in slopes that differ from unity only within the Correspondence to: S. S. Brown (steven.s.brown@noaa.gov) stated uncertainty of each instrument. Possible interferences from species such as water vapor and ozone were negligible under the experimental conditions.

Abstract. Broadband optical cavity spectrometers are maturing as a technology for trace-gas detection, but only recently have they been used to retrieve the extinction coefficient of aerosols. Sensitive broadband extinction measurements allow explicit separation of gas and particle phase spectral contributions, as well as continuous spectral measurements of aerosol extinction in favourable cases. In this work, we report an intercomparison study of the aerosol extinction coefficients measured by three such instruments: a broadband cavity ring-down spectrometer (BBCRDS), a cavity-enhanced differential optical absorption spectrometer (CE-DOAS), and an incoherent broadband cavity-enhanced absorption spectrometer (IBBCEAS). Experiments were carried out in the SAPHIR atmospheric simulation chamber as part of the NO3Comp campaign to compare the measurement capabilities of NO 3 and N 2 O 5 instrumentation. Aerosol extinction coefficients between 655 and 690 nm are reported for secondary organic aerosols (SOA) formed by the NO 3 oxidation of β-pinene under dry and humid conditions. Despite different measurement approaches and spectral analysis procedures, the three instruments retrieved aerosol extinction coefficients that were in close agreement. The refractive index of SOA formed from the β-pinene + NO 3 reaction was 1.61, and was not measurably affected by the chamber humidity or by aging of the aerosol over several hours. This refractive index is significantly larger than SOA refractive indices observed in other studies of OH and ozone-initiated terpene oxidations, and may be caused by the large proportion of organic nitrates in the particle phase. In an experiment involving ammonium sulfate particles, the aerosol extinction coefficients as measured by IBBCEAS were found to be in reasonable agreement with those calculated using the Mie theory. The results of the study demonstrate the potential of broadband cavity spectrometers for determining the optical properties of aerosols.

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