Showing papers in "Atmospheric Measurement Techniques in 2009"

Particle Loss Calculator – a new software tool for the assessment of the performance of aerosol inlet systems

Abstract: . Most aerosol measurements require an inlet system to transport aerosols from a select sampling location to a suitable measurement device through some length of tubing. Such inlet systems must be optimized to minimize aerosol sampling artifacts and maximize sampling efficiency. In this study we introduce a new multifunctional software tool (Particle Loss Calculator, PLC) that can be used to quickly determine aerosol sampling efficiency and particle transport losses due to passage through arbitrary tubing systems. The software employs relevant empirical and theoretical relationships found in established literature and accounts for the most important sampling and transport effects that might be encountered during deployment of typical, ground-based ambient aerosol measurements through a constant-diameter sampling probe. The software treats non-isoaxial and non-isokinetic aerosol sampling, aerosol diffusion and sedimentation as well as turbulent inertial deposition and inertial deposition in bends and contractions of tubing. This software was validated through comparison with experimentally determined particle losses for several tubing systems bent to create various diffusion, sedimentation and inertial deposition properties. As long as the tube geometries are not "too extreme", agreement is satisfactory. We discuss the conclusions of these experiments, the limitations of the software and present three examples of the use of the Particle Loss Calculator in the field.

Retrieval of temperature, H 2 O, O 3 , HNO 3 , CH 4 , N 2 O, ClONO 2 and ClO from MIPAS reduced resolution nominal mode limb emission measurements

Abstract: . Retrievals of temperature, H2O, O3, HNO3, CH4, N2O, ClONO2 and ClO from MIPAS reduced spectral resolution nominal mode limb emission measurements outperform retrievals from respective full spectral resolution measurements both in terms of altitude resolution and precision. The estimated precision (including measurement noise and propagation of uncertain parameters randomly varying in the time domain) and altitude resolution are typically 0.5–1.4 K and 2–3.5 km for temperature between 10 and 50 km altitude, and 5–6%, 2–4 km for H2O below 30 km altitude, 4–5%, 2.5–4.5 km for O3 between 15 and 40 km altitude, 3–8%, 3–5 km for HNO3 between 10 and 35 km altitude, 5–8%, 2–3 km for CH4 between 15 and 35 km altitude, 5–10%, 3 km for N2O between 15 and 35 km altitude, 8–14%, 2.5–9 km for ClONO2 below 40 km, and larger than 35%, 3–7 km for ClO in the lower stratosphere. As for the full spectral resolution measurements, the reduced spectral resolution nominal mode horizontal sampling (410 km) is coarser than the horizontal smoothing (often below 400 km), depending on species, altitude and number of tangent altitudes actually used for the retrieval. Thus, aliasing might be an issue even in the along-track domain. In order to prevent failure of convergence, it was found to be essential to consider horizontal temperature gradients during the retrieval.

Chlorine activation by N 2 O 5 : simultaneous, in situ detection of ClNO 2 and N 2 O 5 by chemical ionization mass spectrometry

Abstract: . We report a new method for the simultaneous in situ detection of nitryl chloride (ClNO2) and dinitrogen pentoxide (N2O5) using chemical ionization mass spectrometry (CIMS). The technique relies on the formation and detection of iodide ion-molecule clusters, I(ClNO2)− and I(N2O5)−. The novel N2O5 detection scheme is direct. It does not suffer from high and variable chemical interferences, which are associated with the typical method of nitrate anion detection. We address the role of water vapor, CDC electric field strength, and instrument zero determinations, which influence the overall sensitivity and detection limit of this method. For both species, the method demonstrates high sensitivity (>1 Hz/pptv), precision (~10% for 100 pptv in 1 s), and accuracy (~20%), the latter ultimately determined by the nitrogen dioxide (NO2) cylinder calibration standard and characterization of inlet effects. For the typically low background signals (

Intercomparison study of six HTDMAs: results and recommendations

Abstract: . We report on an intercomparison of six different hygroscopicity tandem differential mobility analysers HTDMAs). These HTDMAs are used worldwide in laboratory experiments and field campaigns to measure the water uptake of aerosol particles and have never been intercompared. After an investigation of the different design of the instruments with their advantages and inconveniencies, the methods for calibration, validation and data analysis are presented. Measurements of nebulised ammonium sulphate as well as of secondary organic aerosol generated from a smog chamber were performed. Agreement and discrepancies between the instruments and to the theory are discussed, and final recommendations for a standard instrument are given, as a benchmark for laboratory or field experiments to ensure a high quality of HTDMA data.

Measurement of atmospheric sesquiterpenes by proton transfer reaction-mass spectrometry (PTR-MS)

Abstract: The ability to measure sesquiterpenes (SQT; C15H24) by a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS) was investigated. SQT calibration standards were prepared by a capillary diffusion method and the PTR-MS- estimated mixing ratios were derived from the counts of product ions and proton transfer reaction constants. These values were compared with mixing ratios determined by a calibrated Gas Chromatograph (GC) coupled to a Flame Ion- ization Detector (GC-FID). Product ion distributions from soft-ionization occurring in a selected ion drift tube via pro- ton transfer were measured as a function of collision ener- gies. Results after the consideration of the mass discrimina- tion of the PTR-MS system suggest that quantitative SQT measurements within 20% accuracy can be achieved with PTR-MS if two major product ions (m/z 149 + and 205 + ), out of seven major product ions (m/z 81 + , 95 + , 109 + , 123 + , 135 + , 149 + and 205 + ), are accounted for. Con- siderable fragmentation of bicyclic sesquiterpenes, i.e. - caryophyllene and -humulene, cause the accuracy to be reduced to 50% if only the parent ion (m/z 205 + ) is con- sidered. These findings were applied to a field dataset collected above a deciduous forest at the PROPHET (Pro- gram for Research on Oxidants: Photochemistry, Emissions, and Transport) research station in 2005. Inferred aver- age daytime ecosystem scale mixing ratios (fluxes) of iso- prene, sum of monoterpenes (MT), and sum of SQT ex- hibited values of 15µg m 3 (4.5 mg m 2 h 1 ), 1.2µg m 3 (0.21 mg m 2 h 1 ), and 0.0016µg m 3 (0.10 mg m 2 h 1 ), respectively. A range of MT and SQT reactivities with re- spect to the OH radical was calculated and compared to an earlier study inferring significantly underestimated OH reac- tivities due to unknown terpenes above this deciduous forest. The results indicate that incorporating these MT and SQT re- sults can resolve 30% of missing OH reactivity reported for this site.

Design and performance of an automatic regenerating adsorption aerosol dryer for continuous operation at monitoring sites

Abstract: . Sizes of aerosol particles depend on the relative humidity of their carrier gas. Most monitoring networks require therefore that the aerosol is dried to a relative humidity below 50% r.H. to ensure comparability of measurements at different sites. Commercially available aerosol dryers are often not suitable for this purpose at remote monitoring sites. Adsorption dryers need to be regenerated frequently and maintenance-free single column Nafion dryers are not designed for high aerosol flow rates. We therefore developed an automatic regenerating adsorption aerosol dryer with a design flow rate of 1 m3/h. Particle transmission efficiency of this dryer has been determined during a 3 week experiment. The lower 50% cut-off was found to be smaller than 3 nm at the design flow rate of the instrument. Measured transmission efficiencies are in good agreement with theoretical calculations. One dryer has been successfully deployed in the Amazon river basin. We present data from this monitoring site for the first 6 months of measurements (February 2008–August 2008). Apart from one unscheduled service, this dryer did not require any maintenance during this time period. The average relative humidity of the dried aerosol was 27.1+/−7.5% r.H. compared to an average ambient relative humidity of nearly 80% and temperatures around 30°C. This initial deployment demonstrated that these dryers are well suitable for continuous operation at remote monitoring sites under adverse ambient conditions.

Validation of CALIPSO space-borne-derived attenuated backscatter coefficient profiles using a ground-based lidar in Athens, Greece

Abstract: . We present initial aerosol validation results of the space-borne lidar CALIOP -onboard the CALIPSO satellite- Level 1 attenuated backscatter coefficient profiles, using coincident observations performed with a ground-based lidar in Athens, Greece (37.9° N, 23.6° E). A multi-wavelength ground-based backscatter/Raman lidar system is operating since 2000 at the National Technical University of Athens (NTUA) in the framework of the European Aerosol Research LIdar NETwork (EARLINET), the first lidar network for tropospheric aerosol studies on a continental scale. Since July 2006, a total of 40 coincidental aerosol ground-based lidar measurements were performed over Athens during CALIPSO overpasses. The ground-based measurements were performed each time CALIPSO overpasses the station location within a maximum distance of 100 km. The duration of the ground–based lidar measurements was approximately two hours, centred on the satellite overpass time. From the analysis of the ground-based/satellite correlative lidar measurements, a mean bias of the order of 22% for daytime measurements and of 8% for nighttime measurements with respect to the CALIPSO profiles was found for altitudes between 3 and 10 km. The mean bias becomes much larger for altitudes lower that 3 km (of the order of 60%) which is attributed to the increase of aerosol horizontal inhomogeneity within the Planetary Boundary Layer, resulting to the observation of possibly different air masses by the two instruments. In cases of aerosol layers underlying Cirrus clouds, comparison results for aerosol tropospheric profiles become worse. This is attributed to the significant multiple scattering effects in Cirrus clouds experienced by CALIPSO which result in an attenuation which is less than that measured by the ground-based lidar.

Characterization of a thermodenuder-particle beam mass spectrometer system for the study of organic aerosol volatility and composition

Abstract: . This paper describes the development and evaluation of a method for measuring the vapor pressure distribution and volatility-dependent mass spectrum of organic aerosol particles using a thermodenuder-particle beam mass spectrometer. The method is well suited for use with the widely used Aerodyne Aerosol Mass Spectrometer (AMS) and other quantitative aerosol mass spectrometers. The data that can be obtained are valuable for modeling organic gas-particle partitioning and for gaining improved composition information from aerosol mass spectra. The method is based on an empirically determined relationship between the thermodenuder temperature at which 50% of the organic aerosol mass evaporates (T50) and the organic component vapor pressure at 25°C (P25). This approach avoids the need for complex modeling of aerosol evaporation, which normally requires detailed information on aerosol composition and physical properties. T50 was measured for a variety of monodisperse, single-component organic aerosols with known P25 values and the results used to create a logP25 vs. T50 calibration curve. Experiments and simulations were used to estimate the uncertainties in P25 introduced by variations in particle size and mass concentration as well as mixing with other components. A vapor pressure distribution and volatility-dependent mass spectrum were then measured for laboratory-generated secondary organic aerosol particles. Vaporization profiles from this method can easily be converted to a volatility basis set representation, which shows the distribution of mass vs. saturation concentration and the gas-particle partitioning of aerosol material. The experiments and simulations indicate that this method can be used to estimate organic aerosol component vapor pressures to within approximately an order of magnitude and that useful mass-spectral separation based on volatility can be achieved.

Cloud particle size distributions measured with an airborne digital in-line holographic instrument

Abstract: . Holographic data from the prototype airborne digital holographic instrument HOLODEC (Holographic Detector for Clouds), taken during test flights are digitally reconstructed to obtain the size (equivalent diameters in the range 23 to 1000 μm), three-dimensional position, and two-dimensional image of ice particles and then ice particle size distributions and number densities are calculated using an automated algorithm with minimal user intervention. The holographic method offers the advantages of a well-defined sample volume size that is not dependent on particle size or airspeed, and offers a unique method of detecting shattered particles. The holographic method also allows the volume sample rate to be increased beyond that of the prototype HOLODEC instrument, limited solely by camera technology. HOLODEC size distributions taken in mixed-phase regions of cloud compare well to size distributions from a PMS FSSP probe also onboard the aircraft during the test flights. A conservative algorithm for detecting shattered particles utilizing their depth-position along the optical axis eliminates the obvious ice particle shattering events from the data set. In this particular case, the size distributions of non-shattered particles are reduced by approximately a factor of two for particles 15 to 70 μm in equivalent diameter, compared to size distributions of all particles.

Greenhouse gas analysis of air samples collected onboard the CARIBIC passenger aircraft

Abstract: . CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) is a long-term atmospheric measurement program based on the use of a comprehensive scientific instrument package aboard a commercial passenger aircraft. In addition to real-time measurements, whole air sampling is performed regularly at cruising altitudes in the tropical middle troposphere and the extra-tropical UT/LS region. Air samples are analyzed for greenhouse gases, NMHCs, halocarbons, and trace gas isotopic composition. The routinely performed greenhouse gas analysis comprises gas chromatography measurements of CO2, CH4, N2O and SF6. The air sampling procedure, the GC system and its performance are described. Comparisons with similar systems employed in other laboratories and a comparison with results from a CO2 in-situ analyzer that is also part of the CARIBIC instrumentation are shown. In addition, the time series of CO2, obtained from the collection of 684 samples at latitudes between 30° N and 56° N on 21 round trips out of Germany to different destinations in Asia between November 2005 and October 2008, is presented. A time shift in the seasonal cycle of about one month was observed between the upper troposphere and the tropopause region. For two sets of return flights from Germany to the Philippines the relationship between the four greenhouse gases is briefly discussed.

An improved tropospheric NO 2 retrieval for OMI observations in the vicinity of mountainous terrain

Abstract: . We present an approach to reduce topography-related errors of vertical tropospheric columns (VTC) of NO2 retrieved from the Ozone Monitoring Instrument (OMI) in the vicinity of mountainous terrain. This is crucial for reliable estimates of air pollution levels over our particular area of interest, the Alpine region and the adjacent planes, where the Dutch OMI NO2 product (DOMINO) exhibits significant biases due to the coarse resolution of surface parameters used in the retrieval. Our approach replaces the coarse-gridded surface pressures by accurate pixel-average values using a high-resolution topography data set, and scales the a priori NO2 profiles accordingly. NO2 VTC reprocessed in this way for the period 2006–2007 suggest that NO2 over the Po Valley in Italy and over the Swiss plateau is underestimated by DOMINO by about 15–20% in winter and 5% in summer under clear-sky conditions (cloud radiance fraction

Determination of aerosol properties from MAX-DOAS observations of the Ring effect

Abstract: . The first quantitative comparison of MAX-DOAS observations of the Ring effect with model simulations is presented. It is performed for a large variety of viewing geometries (solar zenith angles: 45° to 90°, elevation angles: 3°, 6°, 10°, 18°, 90°; three different azimuth angles), which allows a comprehensive test of our capabilities to measure and simulate the Ring effect. In addition to the Ring effect, also the observed O4 absorptions (optical densities) and radiances are compared with model simulations. In general good agreement is found for all measured quantities. From several sensitivity studies it is found that for most measurement situations, the aerosol optical depth has usually the strongest influence on the observed quantities, but also other aerosol properties like e.g. the vertical distribution have a significant effect. In some aspects, the qualitative dependence of the Ring effect on aerosol properties is similar to that of the O4 absorption. This can be understood, since both quantities depend strongly on the light path length in the lower atmosphere. However, since the Ring effect depends also on the properties of the scattering processes, in specific cases observation of the Ring effect can provide complementary information to that retrieved from the O4 observations. This is e.g. possible for measurements at small relative azimuth angles, from which information on the aerosol phase function can be derived. Observations at large solar zenith angle might allow the retrieval of stratospheric aerosol properties, even in cases with very low aerosol optical depths. In addition, Ring effect observations in zenith direction are rather sensitive to the aerosol optical depth (in contrast to O4 observations), which might allow to retrieve information on aerosol properties from existing zenith UV data sets prior to the MAX-DOAS era.

Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) – applicability and corrections

Abstract: . 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.

Relationship between the NO2 photolysis frequency and the solar global irradiance

Abstract: . 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

Retrieval of SO 2 from thermal infrared satellite measurements: correction procedures for the effects of volcanic ash

Abstract: . The simultaneous presence of SO2 and ash in a volcanic plume can lead to a significant error in the SO2 column abundance retrieval when multispectral Thermal InfraRed (TIR) data are used. The ash particles within the plume with effective radii from 1 to 10 μm reduce the Top Of Atmosphere (TOA) radiance in the entire TIR spectral range, including the channels used for SO2 retrieval. The net effect is a significant SO2 overestimation. In this work the interference of ash is discussed and two correction procedures for satellite SO2 volcanic plume retrieval in the TIR spectral range are developed to achieve an higher computational speed and a better accuracy. The ash correction can be applied when the sensor spectral range includes the 7.3 and/or 8.7 μm SO2 absorption bands, and the split window bands centered around 11 and 12 μm required for ash retrieval. This allows the possibility of simultaneous estimation of both volcanic SO2 and ash in the same data set. The proposed ash correction procedures have been applied to the Moderate Resolution Imaging Spectroradiometer (MODIS) and the Spin Enhanced Visible and Infrared Imager (SEVIRI) measurements. Data collected during the 24 November 2006 Mt. Etna eruption have been used to illustrate the technique. The SO2 and ash estimation is carried out by using a best weighted least squares fit method and the Brightness Temperature Difference (BTD) procedures, respectively. The simulated TOA radiance Look-Up Table (LUT) needed for the SO2 column abundance and the ash retrievals have been computed using the MODTRAN 4 Radiative Transfer Model. The results show the importance of the ash correction on SO2 retrievals at 8.7 μm, where the corrected SO2 column abundance values are less than 50% of the uncorrected values. The ash correction on SO2 retrieval at 7.3 μm is much less important and only significant for low SO2 column abundances. Results also show that the simplified and faster correction procedure underestimates the ash correction compared with the more time consuming but more accurate correction procedure. Such underestimation is greater for instruments having better ground pixel resolution, i.e. greater for MODIS than for SEVIRI.

Three-dimensional simulation of the Ring effect in observations of scattered sun light using Monte Carlo radiative transfer models

Abstract: . We present a new technique for the quantitative simulation of the "Ring effect" for scattered light observations from various platforms and under different atmospheric situations. The method is based on radiative transfer calculations at only one wavelength λ0 in the wavelength range under consideration, and is thus computationally fast. The strength of the Ring effect is calculated from statistical properties of the photon paths for a given situation, which makes Monte Carlo radiative transfer models in particular appropriate. We quantify the Ring effect by the so called rotational Raman scattering probability, the probability that an observed photon has undergone a rotational Raman scattering event. The Raman scattering probability is independent from the spectral resolution of the instrument and can easily be converted into various definitions used to characterise the strength of the Ring effect. We compare the results of our method to the results of previous studies and in general good quantitative agreement is found. In addition to the simulation of the Ring effect, we developed a detailed retrieval strategy for the analysis of the Ring effect based on DOAS retrievals, which allows the precise determination of the strength of the Ring effect for a specific wavelength while using the spectral information within a larger spectral interval around the selected wavelength. Using our technique, we simulated synthetic satellite observation of an atmospheric scenario with a finite cloud illuminated from different sun positions. The strength of the Ring effect depends systematically on the measurement geometry, and is strongest if the satellite points to the side of the cloud which lies in the shadow of the sun.

The GRAPE aerosol retrieval algorithm

Abstract: . The aerosol component of the Oxford-Rutherford Aerosol and Cloud (ORAC) combined cloud and aerosol retrieval scheme is described and the theoretical performance of the algorithm is analysed. ORAC is an optimal estimation retrieval scheme for deriving cloud and aerosol properties from measurements made by imaging satellite radiometers and, when applied to cloud free radiances, provides estimates of aerosol optical depth at a wavelength of 550 nm, aerosol effective radius and surface reflectance at 550 nm. The aerosol retrieval component of ORAC has several incarnations – this paper addresses the version which operates in conjunction with the cloud retrieval component of ORAC (described by Watts et al., 1998), as applied in producing the Global Retrieval of ATSR Cloud Parameters and Evaluation (GRAPE) data-set. The algorithm is described in detail and its performance examined. This includes a discussion of errors resulting from the formulation of the forward model, sensitivity of the retrieval to the measurements and a priori constraints, and errors resulting from assumptions made about the atmospheric/surface state.

In-situ measurements of oxygen, carbon monoxide and greenhouse gases from Ochsenkopf tall tower in Germany

Abstract: . We present 2.5 years (from June 2006 to December 2008) of in-situ measurements of CO2, O2, CH4, CO, N2O and SF6 mixing ratios sampled from 23, 90 and 163 m above ground on the Ochsenkopf tower in the Fichtelgebirge range, Germany (50°01'49" N, 11°48'30" E, 1022 m a.s.l.). In addition to the in-situ measurements, flask samples are taken at Ochsenkopf at approximately weekly intervals and are subsequently analysed for the mixing ratios of the same species, as well as H2, and the stable isotopes, δ13C, δ18O in CO2. The in-situ measurements of CO2 and O2 from 23 m show substantial diurnal variations that are modulated by biospheric fluxes, combustion of fossil fuels, and by diurnal changes in the planetary boundary layer height. Measurements from 163 m exhibit only very weak diurnal variability, as this height (1185 m a.s.l.) is generally above the nocturnal boundary layer. CH4, CO, N2O and SF6 show little diurnal variation even at 23 m owing to the absence of any significant diurnal change in the fluxes and the absence of any strong local sources or sinks. From the in-situ record, the seasonal cycles of the gas species have been characterized and the multi-annual trends determined. Because the record is short, the calculation of the trend is sensitive to inter-annual variations in the amplitudes of the seasonal cycles. However, for CH4 a significant change in the growth-rate was detected for 2006.5–2008.5 as compared with the global mean from 1999 to 2006 and is consistent with other recent observations of a renewed increasing global growth rate in CH4 since the beginning of 2007.

Aerosol quantification with the Aerodyne Aerosol Mass Spectrometer: Detection limits and ionizer background effects

Abstract: . Systematic laboratory experiments were performed to investigate quantification of various species with two versions of the Aerodyne Aerosol Mass Spectrometer, a Quadrupole Aerosol Mass Spectrometer (Q-AMS) and a compact Time-of-Flight Aerosol Mass Spectrometer (c-ToF-AMS). Here we present a new method to continuously determine the detection limits of the AMS analyzers during regular measurements, yielding detection limit (DL) information under various measurement conditions. Minimum detection limits range from 0.03 μg m−3 (nitrate, sulfate, and chloride) up to 0.5 μg m−3 (organics) for the Q-AMS. Those of the c-ToF-AMS are found between 0.003 μg m−3 (nitrate, sulfate) and 0.03 μg m−3 (ammonium, organics). The DL values found for the c-ToF-AMS were ~10 times lower than those of the Q-AMS, mainly due to differences in ion duty cycle. Effects causing an increase of the detection limits include long-term instrument contamination, measurement of high aerosol mass concentrations and short-term instrument history. The self-cleaning processes which reduce the instrument background after measurement of large aerosol concentrations as well as the influences of increased instrument background on mass concentration measurements are discussed. Finally, improvement of detection limits by extension of averaging time intervals, selected or reduced ion monitoring, and variation of particle-to-background measurement ratio are investigated.

New perspectives on gravity wave remote sensing by spaceborne infrared limb imaging

Abstract: . Gravity wave (GW) remote sensing from space now has reached a stage of maturity that some first confinements for GW modeling can be deduced. This is in particular due to global distributions of absolute values of GW momentum flux from infrared limb sounders and due to 2-D maps of the horizontal wave field provided by nadir viewing instruments. The logical step forward is an infrared limb imager (ILI) which combines the good vertical resolution of limb sounding with horizontal mapping capabilities and provides 3-D images of the GW temperature structures. In this paper we investigate 1) how an ILI advances measurements of GW momentum flux, 2) which additional benefits are achieved by limb imaging of GWs, and 3) how an ILI compares to other GW momentum flux measurements, in-situ, ground-based, and from space. In particular, the large advance made by gaining regular 3-D sampling is demonstrated.

A flow-tube based laser-induced fluorescence instrument to measure OH reactivity in the troposphere

Abstract: . A field instrument utilising the artificial generation of OH radicals in a sliding injector flow-tube reactor with detection by laser-induced fluorescence spectroscopy has been developed to measure the rate of decay of OH by reaction with its atmospheric sinks. The OH reactivity instrument has been calibrated using known concentrations of CO, NO2 and single hydrocarbons in a flow of zero air, and the impact of recycling of OH via the reaction HO2+NO→OH+NO2 on the measured OH reactivity has been quantified. As well as a detailed description of the apparatus, the capabilities of the new instrument are illustrated using representative results from deployment in the semi-polluted marine boundary layer at the Weybourne Atmospheric Observatory, UK, and in a tropical rainforest at the Bukit Atur Global Atmospheric Watch station, Danum Valley, Borneo.

Airborne lidar reflectance measurements at 1.57 μm in support of the A-SCOPE mission for atmospheric CO 2

Abstract: . 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.

A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO2, CH4, N2O, SF6 and CO

Abstract: . We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured with only one device, making it a very cost-efficient system. No time lags are introduced between the measured mixing ratios. The system is designed to operate fully autonomously which makes it ideal for measurements at remote and unmanned stations. Only a small amount of sample air is needed, which makes this system also highly suitable for flask air measurements. In principle, only two reference cylinders are needed for daily operation and only one calibration per year against international WMO standards is sufficient to obtain high measurement precision and accuracy. The system described in this paper is in use since May 2006 at our atmospheric measurement site Lutjewad near Groningen, The Netherlands at 6°21´ E, 53°24´N, 1 m a.s.l. Results show the long-term stability of the system. Observed measurement precisions at our remote research station Lutjewad were: ±0.04 ppm for CO2, ±0.8 ppb for CH4, ±0.8 ppb for CO, ±0.3 ppb for N2O, and ±0.1 ppt for SF6. The ambient mixing ratios of all measured species as observed at station Lutjewad for the period of May 2007 to August 2008 are presented as well.

An experimental technique for the direct measurement of N 2 O 5 reactivity on ambient particles

Abstract: . An experimental approach for the direct measurement of trace gas reactivity on ambient aerosol particles has been developed. The method utilizes a newly designed entrained aerosol flow reactor coupled to a custom-built chemical ionization mass spectrometer. The experimental method is described via application to the measurement of the N2O5 reaction probability, γ (N2O5). Laboratory investigations on well characterized aerosol particles show that measurements of γ (N2O5) observed with this technique are in agreement with previous observations, using conventional flow tube methods, to within ±20% at atmospherically relevant particle surface area concentrations (0–1000 μm2 cm−3). Uncertainty in the measured γ (N2O5) is discussed in the context of fluctuations in potential ambient biases (e.g., temperature, relative humidity and trace gas loadings). Under ambient operating conditions we estimate a single-point uncertainty in γ (N2O5) that ranges between ± (1.3×10-2 + 0.2×γ (N2O5)), and ± (1.3×10-3 + 0.2×γ (N2O5)) for particle surface area concentrations of 100 to 1000 μm2 cm−3, respectively. Examples from both laboratory investigations and field observations are included alongside discussion of future applications for the reactivity measurement and optimal deployment locations and conditions.

A cavity ring down / cavity enhanced absorption device for measurement of ambient NO3 and N2O5

Abstract: . An inexpensive, compact instrument for the sensitive measurement of NO3 and N2O5 in ambient air at high time resolution is described. Light from a red-emitting laser diode (≈662 nm) is coupled off-axis into an optical resonator defined by two highly reflective mirrors to achieve effective absorption paths exceeding 20 km. Light leaking from the cavity is detected either as single ring-down events (time constant of ≈100 μs) following rapid switching of the laser intensity at 200 Hz (Cavity Ring Down mode), or as an integrated intensity (Cavity Enhanced Absorption mode). The operational conditions, detection limits (2 pptv in 5 s) and total uncertainty (

The horizontal resolution of MIPAS

Abstract: . Limb remote sensing from space provides atmospheric composition measurements at high vertical resolution while the information is smeared in the horizontal domain. The horizontal components of two-dimensional (altitude and along-track coordinate) averaging kernels of a limb retrieval constrained to horizontal homogeneity can be used to estimate the horizontal resolution of limb retrievals. This is useful for comparisons of measured data with modeled data, to construct horizontal observation operators in data assimilation applications or when measurements of different horizontal resolution are intercompared. We present these averaging kernels for retrievals of temperature, H2O, O3, CH4, N2O, HNO3 and NO2 from MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) high-resolution limb emission spectra. The horizontal smearing of a MIPAS retrieval in terms of full width at half maximum of the rows of the horizontal averaging kernel matrix varies typically between about 200 and 350 km for most species, altitudes and atmospheric conditions. The range where 95% of the information originates from varies from about 260 to 440 km for these cases. This information spread is smaller than the MIPAS horizontal sampling, i.e. MIPAS data are horizontally undersampled, and the effective horizontal resolution is driven by the sampling rather than the smearing. The point where the majority of the information originates from is displaced from the tangent point towards the satellite by typically less than 10 km for trace gas profiles and about 50 to 100 km for temperature, with a few exceptions for uppermost altitudes. The geolocation of a MIPAS profile is defined as the tangent point of the middle line of sight in a MIPAS limb scan. The majority of the information displacement with respect to this nominal geolocation of the measurement is caused by the satellite movement and the geometrical displacement of the actual tangent point as a function of the elevation angle.

Design and construction of a simple Knudsen Effusion Mass Spectrometer (KEMS) system for vapour pressure measurements of low volatility organics

Abstract: . A design of and initial results from a Knudsen Effusion Mass Spectrometer (KEMS) are presented. The design was adapted from high temperature alloy studies with a view to using it to measure vapour pressures for low volatility organics. The system uses a temperature controlled cell with an effusive orifice. This produces a molecular beam which is sampled by a quadropole mass spectrometer with electron impact ionization calibrated to a known vapour pressure. We have determined P(298 K) and ΔHsub of the first 5 saturated straight chain dicarboxylic acids: 2.15±1.19×10-2 Pa and 75±19 KJ mol−1 respectively for oxalic acid, 5.73±1.14×10-4 Pa and 91±4 KJ mol−1 for Malonic acid, 1.13±0.47×10-4 Pa and 93±6 KJ mol−1 for Succinic acid, 4.21±1.66×10-4 Pa and 123±22 KJ mol−1 for Glutaric acid and 6.09±3.85×10-6 Pa and 125±40 KJ mol−1 for Adipic acid.

Experimental characterization of the COndensation PArticle counting System for high altitude aircraft-borne application

Abstract: . A characterization of the ultra-fine aerosol particle counter COPAS (COndensation PArticle counting System) for operation on board the Russian high altitude research aircraft M-55 Geophysika is presented. The COPAS instrument consists of an aerosol inlet and two dual-channel continuous flow Condensation Particle Counters (CPCs) operated with the chlorofluorocarbon FC-43. It operates at pressures between 400 and 50 hPa for aerosol detection in the particle diameter (dp) range from 6 nm up to 1 μm. The aerosol inlet, designed for the M-55, is characterized with respect to aspiration, transmission, and transport losses. The experimental characterization of counting efficiencies of three CPCs yields dp50 (50% detection particle diameter) of 6 nm, 11 nm, and 15 nm at temperature differences (ΔT) between saturator and condenser of 17°C, 30°C, and 33°C, respectively. Non-volatile particles are quantified with a fourth CPC, with dp50=11 nm. It includes an aerosol heating line (250°C) to evaporate H2SO4-H2O particles of 11 nm

Uncertainty analysis of computational methods for deriving sensible heat flux values from scintillometer measurements

Abstract: . 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 (

Cloud sensitivity studies for stratospheric and lower mesospheric ozone profile retrievals from measurements of limb-scattered solar radiation

Abstract: . Clouds in the atmosphere play an important role in reflection, absorption and transmission of solar radiation and thus affect trace gas retrievals. The main goal of this paper is to examine the sensitivity of stratospheric and lower mesospheric ozone retrievals from limb-scattered radiance measurements to clouds using the SCIATRAN radiative transfer model and retrieval package. The retrieval approach employed is optimal estimation, and the considered clouds are vertically and horizontally homogeneous. Assuming an aerosol-free atmosphere and Mie phase functions for cloud particles, we compute the relative error of ozone profile retrievals in a cloudy atmosphere if clouds are neglected in the retrieval. To access altitudes from the lower stratosphere up to the lower mesosphere, we combine the retrievals in the Chappuis and Hartley ozone absorption bands. We find significant cloud sensitivity of the limb ozone retrievals in the Chappuis bands at lower stratospheric altitudes. The relative error in the retrieved ozone concentrations gradually decreases with increasing altitude and becomes negligible above approximately 40 km. The parameters with the largest impact on the ozone retrievals are cloud optical thickness, ground albedo and solar zenith angle. Clouds with different geometrical thicknesses or different cloud altitudes have a similar impact on the ozone retrievals for a given cloud optical thickness value, if the clouds are outside the field of view of the instrument. The effective radius of water droplets has a small influence on the error, i.e., less than 0.5% at altitudes above the cloud top height. Furthermore, the impact of clouds on the ozone profile retrievals was found to have a rather small dependence on the solar azimuth angle (less than 1% for all possible azimuth angles). For the most frequent cloud types, the total error is below 6% above 15 km altitude, if clouds are completely neglected in the retrieval. Neglecting clouds in the ozone profile retrievals generally leads to a low bias for a low ground albedo and to a high bias for a high ground albedo, assuming that the ground albedo is well known.