ALBERT

Description: A system to study the gas and particle phase products from gas phase hydrocarbon oxidation is described. It consists of a gas phase photochemical flow reactor followed by a diffusion membrane denuder to remove gases from the reacted products, or a filter to remove the particles. Chemical analysis is performed by an atmospheric pressure chemical ionization (APCI) triple quadrupole mass spectrometer. A diffusion membrane denuder is shown to remove trace gases to below detectable limits so the particle phase can be studied. The system was tested by examining the products of the oxidation of m-xylene initiated by HO radicals. Dimethylphenol was observed in both the gas and particle phases although individual isomers could not be identified. Two furanone isomers, 5-methyl-2(3H)furanone and 3-methyl-2(5H)furanone were identified in the particulate phase, but the isobaric product 2,5 furandione was not observed. One isomer of dimethyl-nitrophenol was identified in the particle phase but not in the gas phase.

Description: Accurate knowledge about the distribution of atomic oxygen is crucial for many studies of the mesosphere and lower thermosphere. Direct measurements of atomic oxygen by the resonance fluorescence technique at 130 nm have been made from many sounding rocket payloads in the past. This measurement technique yields atomic oxygen profiles with good sensitivity and altitude resolution. However, accuracy is a problem as calibration and aerodynamics make the quantitative analysis challenging. Most often, accuracies better than a factor 2 are not to be expected from direct atomic oxygen measurements. As an example, we present results from the NLTE (Non Local Thermodynamic Equilibrium) sounding rocket campaign at Esrange, Sweden, in 1998, with simultaneous O2 airglow and O resonance fluorescence measurements. O number densities are found to be consistent with the nightglow analysis, but only within the uncertainty limits of the resonance fluorescence technique. Based on these results, we here describe how better atomic oxygen number densities can be obtained by calibrating direct techniques with complementary airglow photometer measurements and detailed aerodynamic analysis. Night-time direct O measurements can be complemented by photometric detection of the O2 (b1∑g+−X3∑g-) Atmospheric Band at 762 nm, while during daytime the O2 (a1Δg−X3∑g-) Infrared Atmospheric Band at 1.27 μm can be used. The combination of a photometer and a rather simple resonance fluorescence probe can provide atomic oxygen profiles with both good accuracy and good height resolution.

Description: A breadboard demonstrator of a novel UV/VIS grating spectrometer has been developed based upon a concentric arrangement of a spherical meniscus lens, concave spherical mirror and curved diffraction grating suitable for a range of atmospheric remote sensing applications from the ground or space. The spectrometer is compact and provides high optical efficiency and performance benefits over traditional instruments. The concentric design is capable of handling high relative apertures, owing to spherical aberration and comma being near zero at all surfaces. The design also provides correction for transverse chromatic aberration and distortion, in addition to correcting for the distortion called "smile", the curvature of the slit image formed at each wavelength. These properties render this design capable of superior spectral and spatial performance with size and weight budgets significantly lower than standard configurations. This form of spectrometer design offers the potential for exceptionally compact instrument for differential optical absorption spectroscopy (DOAS) applications from LEO, GEO, HAP or ground-based platforms. The breadboard demonstrator has been shown to offer high throughput and a stable Gaussian line shape with a spectral range from 300 to 450 nm at 0.5 nm resolution, suitable for a number of typical DOAS applications.

Description: During the airborne research mission ASTAR 2004 (Arctic Study of Tropospheric Aerosols, Clouds and Radiation) performed over the island of Svalbard in the Arctic a constant-temperature hot-wire Nevzorov Probe designed for aircraft measurements, has been used onboard the aircraft POLAR 2. The Nevzorov probe measured liquid water (LWC) and total condensed water content (TWC) in supercooled liquid and partly mixed phase clouds, respectively. As for other hotwire probes the calculation of LWC and/or TWC (and thus the ice water content IWC) has to take into account the collection efficiencies of the two separate sensors for LWC and TWC which both react differently with respect to cloud phase and what is even more difficult to quantify with respect to the size of ice and liquid cloud particles. The study demonstrates that during pure liquid cloud sequences the ASTAR data set of the Nevzorov probe allowed to improve the quantification of the collection efficiency, particularly of the LWC probe part with respect to water. The improved quantification of liquid water content should lead to improved retrievals of IWC content. Simultaneous retrievals of LWC and IWC are correlated with the asymmetry factor derived from the Polar Nephelometer instrument.

Description: A method for real-time profiling of volatile organic compounds (VOCs) was developed combining the advantages of a tethered balloon as a research platform and of proton transfer reaction mass spectrometry (PTR-MS) as an analytical technique for fast and highly sensitive VOC measurements. A 200 m Teflon tube was used to draw sampling air from a tethered aerodynamic balloon to the PTR-MS instrument. Positive and negative artefacts (i.e. formation and loss of VOCs in the tube) were characterised in the laboratory and in the field by a set of 11 atmospherically relevant VOCs including both pure and oxygenated hydrocarbons. The only two compounds that increased or decreased when sampled through the tube were acetone (+7%) and xylene (-6%). The method was successfully deployed during a winter field campaign to determine the small scale spatial and temporal patterns of air pollutants under winter inversion conditions.

Description: The characteristics of the lidar reflectance of the Earth's surface is an important issue for the IPDA lidar technique (integrated path differential absorption lidar) which is the proposed method for the spaceborne measurement of atmospheric carbon dioxide within the framework of ESA's A-SCOPE project. Both, the absolute reflectance of the ground and its variations have an impact on the measurement sensitivity. The first aspect influences the instrument's signal to noise ratio, the second one can lead to retrieval errors, if the ground reflectance changes are strong on small scales. The investigation of the latter is the main purpose of this study. Airborne measurements of the lidar ground reflectance at 1.57 μm wavelength were performed in Central and Western Europe, including many typical land surface coverages as well as the open sea. The analyses of the data show, that the lidar ground reflectance is highly variable on a wide range of spatial scales. However, by means of the assumption of laser footprints in the order of several tens of meters, as planned for spaceborne systems, and by means of an averaging of the data it was shown, that this specific retrieval error is well below 1 ppm (CO2 column mixing ratio), and so compatible with the sensitivity requirements of spaceborne CO2 measurements. Several approaches for upscaling the data in terms of the consideration of larger laser footprints, compared to the one used here, are shown and discussed. Furthermore, the collected data are compared to MODIS ground reflectance data.

Description: The use of scintillometers to determine sensible heat fluxes is now common in studies of land-atmosphere interactions. The main interest in these instruments is due to their ability to quantify energy distributions at the landscape scale, as they can calculate sensible heat flux values over long distances, in contrast to Eddy Covariance systems. However, scintillometer data do not provide a direct measure of sensible heat flux, but require additional data, such as the Bowen ratio (β), to provide flux values. The Bowen ratio can either be measured using Eddy Covariance systems or derived from the energy balance closure. In this work, specific requirements for estimating energy fluxes using a scintillometer were analyzed, as well as the accuracy of two flux calculation methods. We first focused on the classical method (used in standard softwares) and we analysed the impact of the Bowen ratio on flux value and uncertainty. For instance, an averaged Bowen ratio (β) of less than 1 proved to be a significant source of measurement uncertainty. An alternative method, called the "β-closure method", for which the Bowen ratio measurement is not necessary, was also tested. In this case, it was observed that even for low β values, flux uncertainties were reduced and scintillometer data were well correlated with the Eddy Covariance results. Besides, both methods should tend to the same results, but the second one slightly underestimates H while β decreases (

Description: Representative values of the atmospheric NO2 photolysis frequency j(NO2) are required for the adequate calculation and interpretation of NO and NO2 concentrations and exchange fluxes near the surface. Direct measurements of j(NO2) at ground level are often not available in field studies. In most cases, modeling approaches involving complex radiative transfer calculations are used to estimate j(NO2) and other photolysis frequencies for air chemistry studies. However, important input parameters for accurate modeling are often missing, most importantly with regard to the radiative effects of clouds. On the other hand, solar global irradiance ("global radiation", G) is nowadays measured as a standard parameter in most field experiments and in many meteorological observation networks around the world. Previous studies mainly reported linear relationships between j(NO2) and G. We have measured j(NO2) using spectro- or filter radiometers and G using pyranometers side-by-side at several field sites. Our results cover a solar zenith angle range of 0–90°, and are based on nine field campaigns in temperate, subtropical and tropical environments during the period 1994–2008. We show that a second-order polynomial function (intercept = 0): j(NO2)=(1+α)× (B1×G+B2×G2), with α defined as the site-dependent UV-A surface albedo and the polynomial coefficients: B1=(1.47± 0.03)×10-5 W−1 m2 s−1 and B2=(-4.84±0.31)×10-9 W−2 m4 s−1 can be used to estimate ground-level j(NO2) directly from G, independent of solar zenith angle under all atmospheric conditions. The absolute j(NO2) residual of the empirical function is ±6×10-4 s−1(2σ). The relationship is valid for sites below 800 m a.s.l. and with low surface albedo (α

Description: Atmospheric trace gas measurements by cavity assisted long-path absorption spectroscopy are an emerging technology. An interesting approach is the combination of CEAS with broadband light sources, the broadband CEAS (BB-CEAS). BB-CEAS lends itself to the application of the DOAS technique to analyse the derived absorption spectra. While the DOAS approach has enormous advantages in terms of sensitivity and specificity of the measurement, an important implication is the reduction of the light path by the trace gas absorption, since cavity losses due to absorption by gases reduce the quality (Q) of the cavity. In fact, at wavelength, where the quality of the BB-CEAS cavity is dominated by the trace gas absorption (especially at very high mirror reflectivity), the average light path will vary nearly inversely with the trace gas concentration and the strength of the band will become only weakly dependent on the trace gas concentration c in the cavity, (the differential optical density being proportional to the logarithm of the trace gas concentration). Only in the limiting case where the mirror reflectivity determines Q at all wavelength, the strength of the band as seen by the CE-DOAS instrument becomes directly proportional to the concentration c. We investigate these relationships in detail and present methods to correct for the cases between the two above extremes, which are of course the important ones in practice.

Description: We performed MS/MS investigations of biogenic volatile organic compounds (BVOC) using a triple quadrupole tandem mass spectrometer (QqQ-MS) equipped with a Townsend Discharge ion source and a Proton Transfer Reaction Linear Ion Trap (PTR-LIT) mass spectrometer. Both instruments use H2O chemical ionization to produce protonated molecules. Here we report a study of the application of these instruments to determine methyl vinyl ketone (MVK) and methacrolein (MACR) and a series of monoterpenes (α-pinene, β-pinene, 3-carene, limonene, myrcene, ocimene) and sesquiterpenes (humulene and farnesene). Both instruments achieved sub-ppb detection limits in the single MS mode and in the MS/MS mode for differentiating MVK and MACR. Collision induced dissociation (CID) of protonated monoterpenes and sesquiterpenes was studied under the relatively high-energy, single-to-few collision conditions of the QqQ-MS instrument and under the low-energy, multiple collision conditions of the PTR-LIT. Differences and similarities in the breakdown curves obtained are discussed. In addition, we performed MS4 of protonated limonene to illustrate the analytical power of the PTR-LIT. In spite of the progress we have made, the selective on-line mass-spectrometric detection of individual monoterpenes or sesquiterpenes in complex mixtures currently does not yet seem to be possible.