ALBERT

Description: Development and field testing of a rapid and ultra-stable atmospheric carbon dioxide spectrometer Atmospheric Measurement Techniques, 7, 4445-4453, 2014 Author(s): B. Xiang, D. D. Nelson, J. B. McManus, M. S. Zahniser, R. A. Wehr, and S. C. Wofsy We present field test results for a new spectroscopic instrument to measure atmospheric carbon dioxide (CO 2 ) with high precision (0.02 μmol mol −1 , or ppm at 1 Hz) and demonstrate high stability (within 0.1 ppm over more than 8 months), without the need for hourly, daily, or even monthly calibration against high-pressure gas cylinders. The technical novelty of this instrument (ABsolute Carbon dioxide, ABC) is the spectral null method using an internal quartz reference cell with known CO 2 column density. Compared to a previously described prototype, the field instrument has better stability and benefits from more precise thermal control of the optics and more accurate pressure measurements in the sample cell (at the mTorr level). The instrument has been deployed at a long-term ecological research site (the Harvard Forest, USA), where it has measured for 8 months without on-site calibration and with minimal maintenance, showing drift bounds of less than 0.1 ppm. Field measurements agree well with those of a commercially available cavity ring-down CO 2 instrument (Picarro G2301) run with a standard calibration protocol. This field test demonstrates that ABC is capable of performing high-accuracy, unattended, continuous field measurements with minimal use of reference gas cylinders.

Description: Investigating uptake of N 2 O in agricultural soils using a high-precision dynamic chamber method Atmospheric Measurement Techniques, 7, 4455-4462, 2014 Author(s): N. J. Cowan, D. Famulari, P. E. Levy, M. Anderson, D. S. Reay, and U. M. Skiba Uptake (or negative flux) of nitrous oxide (N 2 O) in agricultural soils is a controversial issue which has proved difficult to investigate in the past due to constraints such as instrumental precision and methodological uncertainties. Using a recently developed high-precision quantum cascade laser gas analyser combined with a closed dynamic chamber, a well-defined detection limit of 4 μg N 2 O-N m −2 h −1 could be achieved for individual soil flux measurements. 1220 measurements of N 2 O flux were made from a variety of UK soils using this method, of which 115 indicated uptake by the soil (i.e. a negative flux in the micrometeorological sign convention). Only four of these apparently negative fluxes were greater than the detection limit of the method, which suggests that the vast majority of reported negative fluxes from such measurements are actually due to instrument noise. As such, we suggest that the bulk of negative N 2 O fluxes reported for agricultural fields are most likely due to limits in detection of a particular flux measurement methodology and not a result of microbiological activity consuming atmospheric N 2 O.

Description: Rapid, optical measurement of the atmospheric pressure on a fast research aircraft using open-path TDLAS Atmospheric Measurement Techniques, 7, 3653-3666, 2014 Author(s): B. Buchholz, A. Afchine, and V. Ebert Because of the high travel speed, the complex flow dynamics around an aircraft, and the complex dependency of the fluid dynamics on numerous airborne parameters, it is quite difficult to obtain accurate pressure values at a specific instrument location of an aircraft's fuselage. Complex simulations using computational fluid dynamics (CFD) models can in theory computationally "transfer" pressure values from one location to another. However, for long flight patterns, this process is inconvenient and cumbersome. Furthermore, these CFD transfer models require a local experimental validation, which is rarely available. In this paper, we describe an integrated approach for a spectroscopic, calibration-free, in-flight pressure determination in an open-path White cell on an aircraft fuselage using ambient, atmospheric water vapour as the "sensor species". The presented measurements are realised with the HAI (Hygrometer for Atmospheric Investigations) instrument, built for multiphase water detection via calibration-free TDLAS (tunable diode laser absorption spectroscopy). The pressure determination is based on raw data used for H 2 O concentration measurement, but with a different post-flight evaluation method, and can therefore be conducted at deferred time intervals on any desired flight track. The spectroscopic pressure is compared in-flight with the static ambient pressure of the aircraft avionic system and a micro-mechanical pressure sensor, located next to the open-path cell, over a pressure range from 150 to 800 hPa, and a water vapour concentration range of more than 3 orders of magnitude. The correlation between the micro-mechanical pressure sensor measurements and the spectroscopic pressure measurements shows an average deviation from linearity of only 0.14% and a small offset of 9.5 hPa. For the spectroscopic pressure evaluation we derive measurement uncertainties under laboratory conditions of 3.2 and 5.1% during in-flight operation on the HALO airplane. Under certain flight conditions we quantified, for the first time, stalling-induced, dynamic pressure deviations of up to 30% (at 200 hPa) between the avionic sensor and the optical and mechanical pressure sensors integrated in HAI. Such severe local pressure deviations from the typically used avionic pressure are important to take into account for other airborne sensors employed on such fast flying platforms as the HALO aircraft.

Description: Mixing-layer height retrieval with ceilometer and Doppler lidar: from case studies to long-term assessment Atmospheric Measurement Techniques, 7, 3685-3704, 2014 Author(s): J. H. Schween, A. Hirsikko, U. Löhnert, and S. Crewell Aerosol signatures observed by ceilometers are frequently used to derive mixing-layer height (MLH) which is an essential variable for air quality modelling. However, Doppler wind lidar measurements of vertical velocity can provide a more direct estimation of MLH via simple thresholding. A case study reveals difficulties in the aerosol-based MLH retrieval during transition times when the mixing layer builds up in the morning and when turbulence decays in the afternoon. The difficulties can be explained by the fact that the aerosol distribution is related to the history of the mixing process and aerosol characteristics are modified by humidification. The results of the case study are generalized by evaluating one year of joint measurements by a Vaisala CT25K and a HALO Photonics Streamline wind lidar. On average the aerosol-based retrieval gives higher MLH than the wind lidar with an overestimation of MLH by about 300 m (600 m) in the morning (late afternoon). Also, the daily aerosol-based maximum MLH is larger and occurs later during the day and the average morning growth rates are smaller than those derived from the vertical wind. In fair weather conditions classified by less than 4 octa cloud cover the mean diurnal cycle of cloud base height corresponds well to the mixing-layer height showing potential for a simplified MLH estimation.

Description: Intercomparison of stratospheric gravity wave observations with AIRS and IASI Atmospheric Measurement Techniques, 7, 4517-4537, 2014 Author(s): L. Hoffmann, M. J. Alexander, C. Clerbaux, A. W. Grimsdell, C. I. Meyer, T. Rößler, and B. Tournier Gravity waves are an important driver for the atmospheric circulation and have substantial impact on weather and climate. Satellite instruments offer excellent opportunities to study gravity waves on a global scale. This study focuses on observations from the Atmospheric Infrared Sounder (AIRS) onboard the National Aeronautics and Space Administration Aqua satellite and the Infrared Atmospheric Sounding Interferometer (IASI) onboard the European MetOp satellites. The main aim of this study is an intercomparison of stratospheric gravity wave observations of both instruments. In particular, we analyzed AIRS and IASI 4.3 μm brightness temperature measurements, which directly relate to stratospheric temperature. Three case studies showed that AIRS and IASI provide a clear and consistent picture of the temporal development of individual gravity wave events. Statistical comparisons based on a 5-year period of measurements (2008–2012) showed similar spatial and temporal patterns of gravity wave activity. However, the statistical comparisons also revealed systematic differences of variances between AIRS and IASI that we attribute to the different spatial measurement characteristics of both instruments. We also found differences between day- and nighttime data that are partly due to the local time variations of the gravity wave sources. While AIRS has been used successfully in many previous gravity wave studies, IASI data are applied here for the first time for that purpose. Our study shows that gravity wave observations from different hyperspectral infrared sounders such as AIRS and IASI can be directly related to each other, if instrument-specific characteristics such as different noise levels and spatial resolution and sampling are carefully considered. The ability to combine observations from different satellites provides an opportunity to create a long-term record, which is an exciting prospect for future climatological studies of stratospheric gravity wave activity.

Description: Collection efficiency of the soot-particle aerosol mass spectrometer (SP-AMS) for internally mixed particulate black carbon Atmospheric Measurement Techniques, 7, 4507-4516, 2014 Author(s): M. D. Willis, A. K. Y. Lee, T. B. Onasch, E. C. Fortner, L. R. Williams, A. T. Lambe, D. R. Worsnop, and J. P. D. Abbatt The soot-particle aerosol mass spectrometer (SP-AMS) uses an intra-cavity infrared laser to vaporize refractory black carbon (rBC) containing particles, making the particle beam–laser beam overlap critical in determining the collection efficiency (CE) for rBC and associated non-refractory particulate matter (NR-PM). This work evaluates the ability of the SP-AMS to quantify rBC and NR-PM mass in internally mixed particles with different thicknesses of organic coating. Using apparent relative ionization efficiencies for uncoated and thickly coated rBC particles, we report measurements of SP-AMS sensitivity to NR-PM and rBC, for Regal Black, the recommended particulate calibration material. Beam width probe (BWP) measurements are used to illustrate an increase in sensitivity for highly coated particles due to narrowing of the particle beam, which enhances the CE of the SP-AMS by increasing the laser beam–particle beam overlap. Assuming complete overlap for thick coatings, we estimate CE for bare Regal Black particles of 0.6 ± 0.1, which suggests that previously measured SP-AMS sensitivities to Regal Black were underestimated by up to a factor of 2. The efficacy of the BWP measurements is highlighted by studies at a busy road in downtown Toronto and at a non-roadside location, which show particle beam widths similar to, but greater than that of bare Regal Black and coated Regal Black, respectively. Further BWP measurements at field locations will help to constrain the range of CE for fresh and aged rBC-containing particles. The ability of the SP-AMS to quantitatively assess the composition of internally mixed particles is validated through measurements of laboratory-generated organic coated particles, which demonstrate that the SP-AMS can quantify rBC and NR-PM over a wide range of particle compositions and rBC core sizes.

Description: Reference quality upper-air measurements: GRUAN data processing for the Vaisala RS92 radiosonde Atmospheric Measurement Techniques, 7, 4463-4490, 2014 Author(s): R. J. Dirksen, M. Sommer, F. J. Immler, D. F. Hurst, R. Kivi, and H. Vömel The GCOS (Global Climate Observing System) Reference Upper-Air Network (GRUAN) data processing for the Vaisala RS92 radiosonde was developed to meet the criteria for reference measurements. These criteria stipulate the collection of metadata, the use of well-documented correction algorithms, and estimates of the measurement uncertainty. An important and novel aspect of the GRUAN processing is that the uncertainty estimates are vertically resolved. This paper describes the algorithms that are applied in version 2 of the GRUAN processing to correct for systematic errors in radiosonde measurements of pressure, temperature, humidity, and wind, as well as how the uncertainties related to these error sources are derived. Currently, the RS92 is launched on a regular basis at 13 out of 15 GRUAN sites. An additional GRUAN requirement for performing reference measurements with the RS92 is that the manufacturer-prescribed procedure for the radiosonde's preparation, i.e. heated reconditioning of the sensors and recalibration during ground check, is followed. In the GRUAN processing however, the recalibration of the humidity sensors that is applied during ground check is removed. For the dominant error source, solar radiation, laboratory experiments were performed to investigate and model its effect on the RS92's temperature and humidity measurements. GRUAN uncertainty estimates are 0.15 K for night-time temperature measurements and approximately 0.6 K at 25 km during daytime. The other uncertainty estimates are up to 6% relative humidity for humidity, 10–50 m for geopotential height, 0.6 hPa for pressure, 0.4–1 m s −1 for wind speed, and 1° for wind direction. Daytime temperature profiles for GRUAN and Vaisala processing are comparable and consistent within the estimated uncertainty. GRUAN daytime humidity profiles are up to 15% moister than Vaisala processed profiles, of which two-thirds is due to the radiation dry bias correction and one-third is due to an additional calibration correction. Redundant measurements with frost point hygrometers (CFH and NOAA FPH) show that GRUAN-processed RS92 humidity profiles and frost point data agree within 15% in the troposphere. No systematic biases occur, apart from a 5% dry bias for GRUAN data around −40 °C at night.

Description: Deployment of a sequential two-photon laser-induced fluorescence sensor for the detection of gaseous elemental mercury at ambient levels: fast, specific, ultrasensitive detection with parts-per-quadrillion sensitivity Atmospheric Measurement Techniques, 7, 4251-4265, 2014 Author(s): D. Bauer, S. Everhart, J. Remeika, C. Tatum Ernest, and A. J. Hynes The operation of a laser-based sensor for gas-phase elemental mercury, Hg(0), is described. It utilizes sequential two-photon laser excitation with detection of blue-shifted laser-induced fluorescence (LIF) to provide a highly specific detection scheme that precludes detection of anything other than atomic mercury. It has high sensitivity, fast temporal resolution, and can be deployed for in situ measurements in the open atmosphere with essentially no perturbation of the environment. An ambient sample can also be pulled through a fluorescence cell, allowing for standard addition calibrations of the concentration. No type of preconcentration is required and there appears to be no significant interferences from other atmospheric constituents, including gas-phase oxidized mercury species. As a consequence, it is not necessary to remove oxidized mercury, commonly referred to as reactive gaseous mercury (RGM), from the air sample. The instrument has been deployed as part of an instrument intercomparison and compares well with conventional instrumentation that utilizes preconcentration on gold followed by analysis using cold-vapor atomic fluorescence spectroscopy (CVAFS). Currently, the achievable detection sensitivity is ~ 15 pg m −3 (~ 5 × 10 4 atoms cm −3 , ~ 2 ppq) at a sampling rate of 0.1 Hz, i.e., averaging 100 shots with a 10 Hz laser system. Preliminary results are described for a 50 Hz instrument that utilizes a modified excitation sequence and has monitored ambient elemental mercury with an effective sampling rate of 10 Hz. Additional work is required to produce the precision necessary to perform eddy correlation measurements. Addition of a pyrolysis channel should allow for the measurement of total gaseous mercury (TGM) and hence RGM (by difference) with good sensitivity and time resolution.

Description: Prerequisites for application of hyperbolic relaxed eddy accumulation on managed grasslands and alternative net ecosystem exchange flux partitioning Atmospheric Measurement Techniques, 7, 4237-4250, 2014 Author(s): M. Riederer, J. Hübner, J. Ruppert, W. A. Brand, and T. Foken Relaxed eddy accumulation is still applied in ecosystem sciences for measuring trace gas fluxes. On managed grasslands, the length of time between management events and the application of relaxed eddy accumulation has an essential influence on the determination of the proportionality factor b and thus on the resulting flux. In this study this effect is discussed for the first time. Also, scalar similarity between proxy scalars and scalars of interest is affected until the ecosystem has completely recovered. Against this background, CO 2 fluxes were continuously measured and 13 CO 2 isofluxes were determined with a high measurement precision on two representative days in summer 2010. Moreover, a common method for the partitioning of the net ecosystem exchange into assimilation and respiration based on temperature and light response was compared with an isotopic approach directly based on the isotope discrimination of the biosphere. This approach worked well on the grassland site and could enhance flux partitioning results by better reproducing the environmental conditions.

Description: Extending the satellite data record of tropospheric ozone profiles from Aura-TES to MetOp-IASI: characterisation of optimal estimation retrievals Atmospheric Measurement Techniques, 7, 4223-4236, 2014 Author(s): H. Oetjen, V. H. Payne, S. S. Kulawik, A. Eldering, J. Worden, D. P. Edwards, G. L. Francis, H. M. Worden, C. Clerbaux, J. Hadji-Lazaro, and D. Hurtmans We apply the Tropospheric Emission Spectrometer (TES) ozone retrieval algorithm to Infrared Atmospheric Sounding Instrument (IASI) radiances and characterise the uncertainties and information content of the retrieved ozone profiles. This study focuses on mid-latitudes for the year 2008. We validate our results by comparing the IASI ozone profiles to ozone sondes. In the sonde comparisons, we find a negative bias (1–10%) in the IASI profiles in the lower to mid-troposphere and a positive bias (up to 14%) in the upper troposphere/lower stratosphere (UTLS) region. For the described cases, the degrees of freedom for signal are on average 3.2, 0.3, 0.8, and 0.9 for the columns 0 km – top of atmosphere, (0–6), (0–11), and (8–16) km, respectively. We find that our biases with respect to sondes and our degrees of freedom for signal for ozone are comparable to previously published results from other IASI ozone algorithms. In addition to evaluating biases, we validate the retrieval errors by comparing predicted errors to the sample covariance matrix of the IASI observations themselves. For the predicted versus empirical error comparison, we find that these errors are consistent and that the measurement noise and the interference of temperature and water vapour on the retrieval together mostly explain the empirically derived random errors. In general, the precision of the IASI ozone profiles is better than 20%.

Description: Solar irradiances measured using SPN1 radiometers: uncertainties and clues for development Atmospheric Measurement Techniques, 7, 4267-4283, 2014 Author(s): J. Badosa, J. Wood, P. Blanc, C. N. Long, L. Vuilleumier, D. Demengel, and M. Haeffelin The fast development of solar radiation and energy applications, such as photovoltaic and solar thermodynamic systems, has increased the need for solar radiation measurement and monitoring, for not only the global but also the diffuse and direct components. End users look for the best compromise between getting close to state-of-the-art measurements and keeping low capital, maintenance and operating costs. Among the existing commercial options, SPN1 is a relatively low cost solar radiometer that estimates global and diffuse solar irradiances from seven thermopile sensors under a shading mask and without moving parts. This work presents a comprehensive study of SPN1 accuracy and sources of uncertainty, drawing on laboratory experiments, numerical modelling and comparison studies between measurements from this sensor and state-of-the art instruments for six diverse sites. Several clues are provided for improving the SPN1 accuracy and agreement with state-of-the art measurements.

Description: Differences in aerosol absorption Ångström exponents between correction algorithms for a particle soot absorption photometer measured on the South African Highveld Atmospheric Measurement Techniques, 7, 4285-4298, 2014 Author(s): J. Backman, A. Virkkula, V. Vakkari, J. P. Beukes, P. G. Van Zyl, M. Josipovic, S. Piketh, P. Tiitta, K. Chiloane, T. Petäjä, M. Kulmala, and L. Laakso Absorption Ångström exponents (AAEs) calculated from filter-based absorption measurements are often used to give information on the origin of the ambient aerosol, for example, to distinguish between urban pollution and biomass burning aerosol. Filter-based absorption measurements are widely used and are common at aerosol monitoring stations globally. Several correction algorithms are used to account for artefacts associated with filter-based absorption techniques. These algorithms are of profound importance when determining the absolute amount of absorption by the aerosol. However, this study shows that there are substantial differences between the AAEs calculated from these corrections. Depending on the used correction, AAEs can change by as much as 46%. The study also highlights that the difference between AAEs calculated using different corrections can lead to conflicting conclusions on the type of aerosol when using the same data set. The AAE ranged between 1.17 for non-corrected data to 1.96 for the correction that gave the greatest values. Furthermore, the study implies that the AAEs reported for a site depend on at which filter transmittance the filter is changed. In this work, the AAEs were calculated from data measured with a three-wavelength particle soot absorption photometer (PSAP) at Elandsfontein on the South African Highveld for 23 months. The sample air of the PSAP was diluted to prolong filter change intervals, by a factor of 15. The correlation coefficient between the dilution-corrected PSAP and a non-diluted Multi-Angle Absorption Photometer (MAAP) was 0.9. Thus, the study also shows that the applicability of the PSAP can be extended to remote sites that are not often visited or suffer from high levels of pollution.

Description: Looking through the haze: evaluating the CALIPSO level 2 aerosol optical depth using airborne high spectral resolution lidar data Atmospheric Measurement Techniques, 7, 4317-4340, 2014 Author(s): R. R. Rogers, M. A. Vaughan, C. A. Hostetler, S. P. Burton, R. A. Ferrare, S. A. Young, J. W. Hair, M. D. Obland, D. B. Harper, A. L. Cook, and D. M. Winker The Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) instrument onboard the Cloud–Aerosol Lidar and Pathfinder Satellite Observations (CALIPSO) spacecraft has provided over 8 yr of nearly continuous vertical profiling of Earth's atmosphere. In this paper we investigate the V3.01 and V3.02 CALIOP 532 nm aerosol layer optical depth (AOD) product (i.e the AOD of individual layers) and the column AOD product (i.e., the sum AOD of the complete column) using an extensive database of coincident measurements. The CALIOP AOD measurements and AOD uncertainty estimates are compared with collocated AOD measurements collected with the NASA High Spectral Resolution Lidar (HSRL) in the North American and Caribbean regions. In addition, the CALIOP aerosol lidar ratios are investigated using the HSRL measurements. In general, compared with the HSRL values, the CALIOP layer AOD are biased high by less than 50% for AOD 〈 0.3 with higher errors for higher AOD. Less than 60% of the HSRL AOD measurements are encompassed within the CALIOP layer 1 SD uncertainty range (around the CALIOP layer AOD), so an error estimate is created to encompass 68% of the HSRL data. Using this new metric, the CALIOP layer AOD error is estimated using the HSRL layer AOD as ±0.035 ± 0.05 · (HSRL layer AOD) at night and ±0.05 ± 0.05 · (HSRL layer AOD) during the daytime. Furthermore, the CALIOP layer AOD error is found to correlate with aerosol loading as well as aerosol subtype, with the AODs in marine and dust layers agreeing most closely with the HSRL values. The lidar ratios used by CALIOP for polluted dust, polluted continental, and biomass burning layers are larger than the values measured by the HSRL in the CALIOP layers, and therefore the AODs for these types retrieved by CALIOP were generally too large. We estimated the CALIOP column AOD error can be expressed as ±0.05 ± 0.07 · (HSRL column AOD) at night and ±0.08 ± 0.1 · (HSRL column AOD) during the daytime. Multiple sources of error contribute to both positive and negative errors in the CALIOP column AOD, including multiple layers in the column of different aerosol types, lidar ratio errors, cloud misclassification, and undetected aerosol layers. The undetected layers were further investigated and we found that the layer detection algorithm works well at night, although undetected aerosols in the free troposphere introduce a mean underestimate of 0.02 in the column AOD in the data set examined. The decreased signal-to-noise ratio (SNR) during the daytime led to poorer performance of the layer detection. This caused the daytime CALIOP column AOD to be less accurate than during the nighttime, because CALIOP frequently does not detect optically thin aerosol layers with AOD 〈 0.1. Given that the median vertical extent of aerosol detected within any column was 1.6 km during the nighttime and 1.5 km during the daytime, we can estimate the minimum extinction detection threshold to be 0.012 km −1 at night and 0.067 km −1 during the daytime in a layer median sense. This extensive validation of level 2 CALIOP AOD products extends previous validation studies to nighttime lighting conditions and provides independent measurements of the lidar ratio; thus, allowing the assessment of the effect on the CALIOP AOD of using inappropriate lidar ratio values in the extinction retrieval.

Description: The use of NO 2 absorption cross section temperature sensitivity to derive NO 2 profile temperature and stratospheric–tropospheric column partitioning from visible direct-sun DOAS measurements Atmospheric Measurement Techniques, 7, 4299-4316, 2014 Author(s): E. Spinei, A. Cede, W. H. Swartz, J. Herman, and G. H. Mount This paper presents a temperature sensitivity method (TESEM) to accurately calculate total vertical NO 2 column, atmospheric slant NO 2 profile-weighted temperature ( T ), and to separate stratospheric and tropospheric columns from direct-sun (DS), ground-based measurements using the retrieved T . TESEM is based on differential optical absorption spectroscopy (DOAS) fitting of the linear temperature-dependent NO 2 absorption cross section, σ ( T ), regression model (Vandaele et al., 2003). Separation between stratospheric and tropospheric columns is based on the primarily bimodal vertical distribution of NO 2 and an assumption that stratospheric effective temperature can be represented by temperature at 27 km ± 3 K, and tropospheric effective temperature is equal to surface temperature within 3–5 K. These assumptions were derived from the Global Modeling Initiative (GMI) chemistry-transport model (CTM) simulations over two northern midlatitude sites in 2011. TESEM was applied to the Washington State University Multi-Function DOAS instrument (MFDOAS) measurements at four midlatitude locations with low and moderate NO 2 anthropogenic emissions: (1) the Jet Propulsion Laboratory's Table Mountain Facility (JPL-TMF), CA, USA (34.38° N/117.68° W); (2) Pullman, WA, USA (46.73° N/117.17° W); (3) Greenbelt, MD, USA (38.99° N/76.84° W); and (4) Cabauw, the Netherlands (51.97° N/4.93° E) during July 2007, June–July 2009, July–August and October 2011, November 2012–May 2013, respectively. NO 2 T and total, stratospheric, and tropospheric NO 2 vertical columns were determined over each site.

Description: A Fabry–Perot interferometer-based camera for two-dimensional mapping of SO 2 distributions Atmospheric Measurement Techniques, 7, 3705-3715, 2014 Author(s): J. Kuhn, N. Bobrowski, P. Lübcke, L. Vogel, and U. Platt We examine a new imaging method for the remote sensing of volcanic gases, which relies on the regularly spaced narrow-band absorption structures in the UV–VIS of many molecules. A Fabry–Perot interferometer (FPI) is used to compare the scattered sunlight radiance at wavelengths corresponding to absorption bands with the radiance at wavelengths in between the bands, thereby identifying and quantifying the gas. In this first theoretical study, we present sample calculations for the detection of sulfur dioxide (SO 2 ). Optimum values for the FPI setup parameters are proposed. Furthermore, the performance of the FPI method is compared to SO 2 cameras. We show that camera systems using an FPI are far less influenced by changes in atmospheric radiative transfer (e.g., due to aerosol) and have a great potential as a future technique for examining emissions of SO 2 (or other gases) from volcanic sources and other point sources.

Description: Middle-atmospheric zonal and meridional wind profiles from polar, tropical and midlatitudes with the ground-based microwave Doppler wind radiometer WIRA Atmospheric Measurement Techniques, 7, 4491-4505, 2014 Author(s): R. Rüfenacht, A. Murk, N. Kämpfer, P. Eriksson, and S. A. Buehler WIRA is a ground-based microwave Doppler spectroradiometer specifically designed for the measurement of profiles of horizontal wind in the upper stratosphere and lower mesosphere region where no other continuously running measurement technique exists. A proof of principle has been delivered in a previous publication. A technical upgrade including a new high-frequency amplifier and sideband filter has improved the signal to noise ratio by a factor of 2.4. Since this upgrade the full horizontal wind field comprising zonal and meridional wind profiles is continuously measured. A completely new retrieval based on optimal estimation has been set up. Its characteristics are detailed in the present paper. Since the start of the routine operation of the first prototype in September 2010, WIRA has been measuring at four different locations at polar, mid- and tropical latitudes (67°22' N/26°38' E, 46°57' N/7°26' E, 43°56' N/5°43' E and 21°04' S/55°23' E) for time periods between 5.5 and 11 months. The data presented in this paper are daily average wind profiles with typical uncertainties and resolutions of 10 to 20 m s −1 and 10 to 16 km, respectively. A comparison between the data series from WIRA and European Centre for Medium-Range Weather Forecasts (ECMWF) model data revealed agreement within 10% in the stratospheric zonal wind. The meridional wind profiles agree within their error bars over the entire sensitive altitude range of WIRA. However, significant differences in the mesospheric zonal wind speed of up to 50% have been found.

Description: Analysis of internal gravity waves with GPS RO density profiles Atmospheric Measurement Techniques, 7, 4123-4132, 2014 Author(s): P. Šácha, U. Foelsche, and P. Pišoft GPS radio occultation (RO) data have proved to be a great tool for atmospheric monitoring and studies. In the past decade, they were frequently used for analyses of the internal gravity waves in the upper troposphere and lower stratosphere region. Atmospheric density is the first quantity of state gained in the retrieval process and is not burdened by additional assumptions. However, there are no studies elaborating in detail the utilization of GPS RO density profiles for gravity wave analyses. In this paper, we introduce a method for density background separation and a methodology for internal gravity wave analysis using the density profiles. Various background choices are discussed and the correspondence between analytical forms of the density and temperature background profiles is examined. In the stratosphere, a comparison between the power spectrum of normalized density and normalized dry temperature fluctuations confirms the suitability of the density profiles' utilization. In the height range of 8–40 km, results of the continuous wavelet transform are presented and discussed. Finally, the limits of our approach are discussed and the advantages of the density usage are listed.

Description: Characterization of model errors in the calculation of tangent heights for atmospheric infrared limb measurements Atmospheric Measurement Techniques, 7, 4117-4122, 2014 Author(s): M. Ridolfi and L. Sgheri We review the main factors driving the calculation of the tangent height of spaceborne limb measurements: the ray-tracing method, the refractive index model and the assumed atmosphere. We find that commonly used ray tracing and refraction models are very accurate, at least in the mid-infrared. The factor with largest effect in the tangent height calculation is the assumed atmosphere. Using a climatological model in place of the real atmosphere may cause tangent height errors up to ± 200 m. Depending on the adopted retrieval scheme, these errors may have a significant impact on the derived profiles.

Description: Recovering long-term aerosol optical depth series (1976–2012) from an astronomical potassium-based resonance scattering spectrometer Atmospheric Measurement Techniques, 7, 4103-4116, 2014 Author(s): A. Barreto, E. Cuevas, P. Pallé, P. M. Romero, C. Guirado, C. J. Wehrli, and F. Almansa A 37-year long-term series of monochromatic aerosol optical depth (AOD) has been recovered from solar irradiance measurements performed with the solar spectrometer Mark-I, deployed at Izaña mountain since 1976. The instrument operation is based on the method of resonant scattering, which affords wavelength absolute reference and stability (long-term stability and high precision) in comparison to other instruments based purely on interference filters. However, it has been specifically designed as a reference instrument for helioseismology, and its ability to determine AOD from transmitted and scattered monochromatic radiation at 769.9 nm inside a potassium vapour cell in the presence of a permanent magnetic field is evaluated in this paper. Particularly, the use of an exposed mirror arrangement to collect sunlight as well as the Sun–laboratory velocity dependence of the scattered component introduces some important inconveniences to overcome when we perform the instrument's calibration. We have solved this problem using a quasi-continuous Langley calibration technique and a refinement procedure to correct for calibration errors as well as for the fictitious diurnal cycle on AOD data. Our results showed similar calibration errors retrieved by means of this quasi-continuous Langley technique applied in different aerosol load events (from 0.04 to 0.3), provided aerosol concentration remains constant throughout the calibration interval. It assures the validity of this technique when it is applied in those periods with relatively high aerosol content. The comparative analysis between the recovered AOD data set from the Mark-I and collocated quasi-simultaneous data from the Cimel-AErosol RObotic NETwork (AERONET) and Precision Filter Radiometer (PFR) instruments showed an absolute mean bias ≤ 0.01 in the 10- and 12-year comparison, respectively. High correlation coefficients between AERONET and Mark-I and PFR/Mark-I pairs confirmed a very good linear relationship between instruments, proving that recovered AOD data series from Mark-I can be used together with PFR and AERONET AOD data to build a long-term AOD data series at the Izaña site (1976–now), suitable for future analysis of aerosols trends and inter-annual variability. Finally, the AOD preliminary trend analysis in the 29-year period from 1984 to 2012 with Mark-I AOD revealed no significant trends.

Description: Multistation intercomparison of column-averaged methane from NDACC and TCCON: impact of dynamical variability Atmospheric Measurement Techniques, 7, 4081-4101, 2014 Author(s): A. Ostler, R. Sussmann, M. Rettinger, N. M. Deutscher, S. Dohe, F. Hase, N. Jones, M. Palm, and B.-M. Sinnhuber Dry-air column-averaged mole fractions of methane (XCH 4 ) retrieved from ground-based solar Fourier transform infrared (FTIR) measurements provide valuable information for satellite validation, evaluation of chemical-transport models, and source-sink-inversions. In this context, Sussmann et al. (2013) have shown that midinfrared (MIR) soundings from the Network for the Detection of Atmospheric Composition Change (NDACC) can be combined with near-infrared (NIR) soundings from the Total Carbon Column Observing Network (TCCON) without the need to apply an overall intercalibration factor. However, in spite of efforts to reduce a priori impact, some residual seasonal biases were identified, and the reasons behind remained unclear. In extension to this previous work, which was based on multiannual quasi-coincident MIR and NIR measurements from the stations Garmisch (47.48° N, 11.06° E, 743 m a.s.l.) and Wollongong (34.41° S, 150.88° E, 30 m a.s.l.), we now investigate upgraded retrievals with longer temporal coverage and include three additional stations (Ny-Ålesund, 78.92° N, 11.93° E, 20 m a.s.l.; Karlsruhe, 49.08° N, 8.43° E, 110 m a.s.l.; Izaña, 28.31° N, 16.45° W, 2.370 m a.s.l.). Our intercomparison results (except for Ny-Ålesund) confirm that there is no overall bias between MIR and NIR XCH 4 retrievals, and all MIR and NIR time series reveal a quasi-periodic seasonal bias for all stations, except for Izaña. We find that dynamical variability causes MIR–NIR differences of up to ~ 30 ppb (parts per billion) for Ny-Ålesund, ~ 20 ppb for Wollongong, ~ 18 ppb for Garmisch, and ~ 12 ppb for Karlsruhe. The mechanisms behind this variability are elaborated via two case studies, one dealing with stratospheric subsidence induced by the polar vortex at Ny-Ålesund and the other with a deep stratospheric intrusion event at Garmisch. Smoothing effects caused by the dynamical variability during these events are different for MIR and NIR retrievals depending on the altitude of the perturbation area. MIR retrievals appear to be more realistic in the case of stratospheric subsidence, while NIR retrievals are more accurate in the case of stratosphere–troposphere exchange (STE) in the upper troposphere/lower stratosphere (UTLS) region. About 35% of the FTIR measurement days at Garmisch are impacted by STE, and about 23% of the measurement days at Ny-Ålesund are influenced by polar vortex subsidence. The exclusion of data affected by these dynamical situations resulted in improved agreement of MIR and NIR seasonal cycles for Ny-Ålesund and Garmisch. We found that dynamical variability is a key factor in constraining the accuracy of MIR and NIR seasonal cycles. To mitigate this impact it is necessary to use more realistic a priori profiles that take these dynamical events into account (e.g., via improved models), and/or to improve the FTIR retrievals to achieve a more uniform sensitivity at all altitudes (possibly including profile retrievals for the TCCON data).

Description: Open-path, quantum cascade-laser-based sensor for high-resolution atmospheric ammonia measurements Atmospheric Measurement Techniques, 7, 81-93, 2014 Author(s): D. J. Miller, K. Sun, L. Tao, M. A. Khan, and M. A. Zondlo We demonstrate a compact, open-path, quantum cascade-laser-based atmospheric ammonia sensor operating at 9.06 μm for high-sensitivity, high temporal resolution, ground-based measurements. Atmospheric ammonia (NH 3 ) is a gas-phase precursor to fine particulate matter, with implications for air quality and climate change. Currently, NH 3 sensing challenges have led to a lack of widespread in situ measurements. Our open-path sensor configuration minimizes sampling artifacts associated with NH 3 surface adsorption onto inlet tubing and reduced pressure sampling cells, as well as condensed-phase partitioning ambiguities. Multi-harmonic wavelength modulation spectroscopy allows for selective and sensitive detection of atmospheric pressure-broadened absorption features. An in-line ethylene reference cell provides real-time calibration (±20% accuracy) and normalization for instrument drift under rapidly changing field conditions. The sensor has a sensitivity and noise-equivalent limit (1σ) of 0.15 ppbv NH 3 at 10 Hz, a mass of ~ 5 kg and consumes ~ 50 W of electrical power. The total uncertainty in NH 3 measurements is 0.20 ppbv NH 3 ± 10%, based on a spectroscopic calibration method. Field performance of this open-path NH 3 sensor is demonstrated, with 10 Hz time resolution and a large dynamic response for in situ NH 3 measurements. This sensor provides the capabilities for improved in situ gas-phase NH 3 sensing relevant for emission source characterization and flux measurements.

Description: A fast and easy-to-implement inversion algorithm for mobility particle size spectrometers considering particle number size distribution information outside of the detection range Atmospheric Measurement Techniques, 7, 95-105, 2014 Author(s): S. Pfeifer, W. Birmili, A. Schladitz, T. Müller, A. Nowak, and A. Wiedensohler Multiple-charge inversion is an essential procedure to convert the raw mobility distributions recorded by mobility particle size spectrometers, such as the DMPS or SMPS (differential or scanning mobility particle sizers), into true particle number size distributions. In this work, we present a fast and easy-to-implement multiple-charge inversion algorithm with sufficient precision for atmospheric conditions, but extended functionality. The algorithm can incorporate size distribution information from sensors that measure beyond the upper sizing limit of the mobility spectrometer, such as an aerodynamic particle sizer (APS) or an optical particle counter (OPC). This feature can considerably improve the multiple-charge inversion result in the upper size range of the mobility spectrometer, for example, when substantial numbers of coarse particles are present. The program also yields a continuous size distribution from both sensors as an output. The algorithm is able to calculate the propagation of measurement errors, such as those based on counting statistics, into on the final particle number size distribution. As an additional aspect, the algorithm can perform all inversion steps under the assumption of non-spherical particle shape, including constant or size-dependent shape factors.

Description: Freezing nucleation apparatus puts new slant on study of biological ice nucleators in precipitation Atmospheric Measurement Techniques, 7, 129-134, 2014 Author(s): E. Stopelli, F. Conen, L. Zimmermann, C. Alewell, and C. E. Morris For decades, drop-freezing instruments have contributed to a better understanding of biological ice nucleation and its likely implications for cloud and precipitation development. Yet, current instruments have limitations. Drops analysed on a cold stage are subject to evaporation and potential contamination. The use of closed tubes provides a partial solution to these problems, but freezing events are still difficult to be clearly detected. Here, we present a new apparatus where freezing in closed tubes is detected automatically by a change in light transmission upon ice development, caused by the formation of air bubbles and crystal facets that scatter light. Risks of contamination and introduction of biases linked to detecting the freezing temperature of a sample are then minimized. To illustrate the performance of the new apparatus we show initial results of two assays with snow samples. In one, we repeatedly analysed the sample (208 tubes) over the course of a month with storage at +4 °C, during which evidence for biological ice nucleation activity emerged through an increase in the number of ice nucleators active around −4 °C. In the second assay, we indicate the possibility of increasingly isolating a single ice nucleator from a precipitation sample, potentially determining the nature of a particle responsible for a nucleation activity measured directly in the sample. These two seminal approaches highlight the relevance of this handy apparatus for providing new points of view in biological ice nucleation research.

Description: Combining airborne gas and aerosol measurements with HYSPLIT: a visualization tool for simultaneous evaluation of air mass history and back trajectory consistency Atmospheric Measurement Techniques, 7, 107-128, 2014 Author(s): S. Freitag, A. D. Clarke, S. G. Howell, V. N. Kapustin, T. Campos, V. L. Brekhovskikh, and J. Zhou The history of air masses is often investigated using backward trajectories to gain knowledge about processes along the air parcel path as well as possible source regions. Here, we describe a refined approach that incorporates airborne gas, aerosol, and environmental data into back trajectories and show how this technique allows for simultaneous evaluation of air mass history and back trajectory reliability without the need to calculate trajectory errors. We use the HYbrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and add a simple semi-automated computing routine to facilitate high-frequency coverage of back trajectories initiated along free tropospheric (FT) flight tracks and profiles every 10 s. We integrate our in situ physiochemical data by color-coding each of these trajectories with its corresponding in situ tracer values measured at the back trajectory start points along the flight path. The unique color for each trajectory aids assessment of trajectory reliability through the visual clustering of air mass pathways of similar coloration. Moreover, marked changes in trajectories associated with marked changes evident in measured physiochemical or thermodynamic properties of an air mass add credence to trajectories. This is particularly true when these air mass properties are linked to trajectory features characteristic of recognized sources or processes. This visual clustering of air mass pathways is of particular value for large-scale 3-D flight tracks common to aircraft experiments where air mass features of interest are often spatially distributed and temporally separated. The cluster-visualization tool used here reveals that most FT back trajectories with pollution signatures measured in the central equatorial Pacific reach back to sources on the South American continent over 10 000 km away and 12 days back in time, e.g., the Amazonian basin. We also demonstrate the distinctions in air mass properties between these and trajectories that penetrate deep convection in the Inter-Tropical Convergence Zone. Additionally, for the first time we show consistency of modeled precipitation along back trajectories with scavenging signatures in the aerosol measured for these trajectories.

Description: Mobile measurements of ship emissions in two harbour areas in Finland Atmospheric Measurement Techniques, 7, 149-161, 2014 Author(s): L. Pirjola, A. Pajunoja, J. Walden, J.-P. Jalkanen, T. Rönkkö, A. Kousa, and T. Koskentalo Four measurement campaigns were performed in two different environments – inside the harbour areas in the city centre of Helsinki, and along the narrow shipping channel near the city of Turku, Finland – using a mobile laboratory van during winter and summer conditions in 2010–2011. The characteristics of gaseous (CO, CO 2 , SO 2 , NO, NO 2 , NO x ) and particulate (number and volume size distributions as well as PM 2.5 ) emissions for 11 ships regularly operating on the Baltic Sea were studied to determine the emission parameters. The highest particle concentrations were 1.5 × 10 6 and 1.6 × 10 5 cm −3 in Helsinki and Turku, respectively, and the particle number size distributions had two modes. The dominating mode peaked at 20–30 nm, and the accumulation mode at 80–100 nm. The majority of the particle mass was volatile, since after heating the sample to 265 °C, the particle volume of the studied ship decreased by around 70%. The emission factors for NO x varied in the range of 25–100 g (kg fuel) −1 , for SO 2 in the range of 2.5–17.0 g (kg fuel) −1 , for particle number in the range of (0.32–2.26) × 10 16 # (kg fuel) −1 , and for PM 2.5 between 1.0–4.9 g (kg fuel) −1 . The ships equipped with SCR (selective catalytic reduction) had the lowest NO x emissions, whereas the ships with DWI (direct water injection) and HAMs (humid air motors) had the lowest SO 2 emissions but the highest particulate emissions. For all ships, the averaged fuel sulphur contents (FSCs) were less than 1% (by mass) but none of them was below 0.1% which will be the new EU directive starting 1 January 2015 in the SO x emission control areas; this indicates that ships operating on the Baltic Sea will face large challenges.

Description: Characterization of Aura TES carbonyl sulfide retrievals over ocean Atmospheric Measurement Techniques, 7, 163-172, 2014 Author(s): L. Kuai, J. Worden, S. S. Kulawik, S. A. Montzka, and J. Liu We present a description of the NASA Aura Tropospheric Emission Spectrometer (TES) carbonyl sulfide (OCS) retrieval algorithm for oceanic observations, along with evaluation of the biases and uncertainties using aircraft profiles from the HIPPO (HIAPER Pole-to-Pole Observations) campaign and data from the NOAA Mauna Loa site. In general, the OCS retrievals (1) have less than 1.0 degree of freedom for signals (DOFs), (2) are sensitive in the mid-troposphere with a peak sensitivity typically between 300 and 500 hPa, (3) but have much smaller systematic errors from temperature, CO 2 and H 2 O calibrations relative to random errors from measurement noise. We estimate the monthly means from TES measurements averaged over multiple years so that random errors are reduced and useful information about OCS seasonal and latitudinal variability can be derived. With this averaging, TES OCS data are found to be consistent (within the calculated uncertainties) with NOAA ground observations and HIPPO aircraft measurements. TES OCS data also captures the seasonal and latitudinal variations observed by these in situ data.

Description: Lidar-based remote sensing of atmospheric boundary layer height over land and ocean Atmospheric Measurement Techniques, 7, 173-182, 2014 Author(s): T. Luo, R. Yuan, and Z. Wang Atmospheric boundary layer (ABL) processes are important in climate, weather and air quality. A better understanding of the structure and the behavior of the ABL is required for understanding and modeling of the chemistry and dynamics of the atmosphere on all scales. Based on the systematic variations of the ABL structures over different surfaces, different lidar-based methods were developed and evaluated to determine the boundary layer height and mixing layer height over land and ocean. With Atmospheric Radiation Measurement Program (ARM) Climate Research Facility (ACRF) micropulse lidar (MPL) and radiosonde measurements, diurnal and season cycles of atmospheric boundary layer depth and the ABL vertical structure over ocean and land are analyzed. The new methods are then applied to satellite lidar measurements. The aerosol-derived global marine boundary layer heights are evaluated with marine ABL stratiform cloud top heights and results show a good agreement between them.

Description: Aspects of quality control of wind profiler measurements in complex topography Atmospheric Measurement Techniques, 7, 135-148, 2014 Author(s): M. Maruri, J. A. Romo, and L. Gomez It is well known in the scientific community that some remote sensing instruments assume that sample volumes present homogeneous conditions within a defined meteorological profile. At complex topographic sites and under extreme meteorological conditions, this assumption may be fallible depending on the site, and it is more likely to fail in the lower layers of the atmosphere. This piece of work tests the homogeneity of the wind field over a boundary layer wind profiler radar located in complex terrain on the coast under different meteorological conditions. The results reveal the qualitative importance of being aware of deviations in this homogeneity assumption and evaluate its effect on the final product. Patterns of behavior in data have been identified in order to simplify the analysis of the complex signal registered. The quality information obtained from the homogeneity study under different meteorological conditions provides useful indicators for the best alternatives the system can offer to build wind profiles. Finally, the results are also to be considered in order to integrate them in a quality algorithm implemented at the product level.

Description: A new experimental approach to study the hygroscopic and optical properties of aerosols: application to ammonium sulfate particles Atmospheric Measurement Techniques, 7, 183-197, 2014 Author(s): C. Denjean, P. Formenti, B. Picquet-Varrault, Y. Katrib, E. Pangui, P. Zapf, and J. F. Doussin A new methodology for the determination of the changes due to hygroscopic growth with relative humidity of the number size distribution and optical properties of polydispersed aerosols is described. This method uses the simulation chamber CESAM where the hygroscopic properties of polydispersed aerosol particles can be investigated in situ by exposing them to RH ranging from 0 to 100% for approximately 1 h. In situ humidification is used to provide simultaneous information on the RH-dependence of the particle size and the corresponding scattering coefficient (σ scat ), and that for the entire size distribution. Optical closure studies, based on integrated nephelometer and aethalometer measurements, Mie scattering calculations and measured particle size distributions, can therefore be performed to yield derived parameters such as the complex refractive index (CRI) at λ = 525 nm. The CRI can also be retrieved in the visible spectrum by combining differential mobility analyzer (DMA) and white light aerosol spectrometer (Palas Welas®) measurements. We have applied this methodology to ammonium sulfate particles, which have well known optical and hygroscopic properties. The CRI obtained from the two methods (1.54–1.57) compared favourably to each other and are also in reasonable agreement with the literature values. The particle's growth was compared to values obtained for one selected size of particles (150 nm) with a H-TDMA and the effect of the residence time for particles humidification was investigated. When the humidification was performed in the chamber for a few minutes, a continuous increase of the ammonium sulfate particle's size and σ scat was observed from RH values as low as 30% RH. Comparison of the measured and modelled values based on Köhler and Mie theories shows that layers of water are adsorbed on ammonium sulfate particles below the deliquescence point. In contradiction, the particle's growth reported with H-TDMAs showed a prompt deliquescence of ammonium sulfate particles with no continuous growth in size at low RH. These findings highlight the need to allow sufficient time for particle-water vapour equilibrium in investigating the aerosols hygroscopic properties. H-TDMA instruments induce limited residence time for humidification and seem to be insufficient for water adsorption on ammonium sulfate particles.

Description: Validation of FORMOSAT-3/COSMIC level 2 "atmPrf" global temperature data in the stratosphere Atmospheric Measurement Techniques, 7, 731-742, 2014 Author(s): U. Das and C. J. Pan GPS radio occultations by Formosa Satellite mission-3/Constellation Observing System for Meteorology, Ionosphere, and Climate (FORMOSAT-3/COSMIC) provide bending angle profiles, which are further processed to give profiles of temperature and water vapour in the lower atmosphere and electron density in the upper atmosphere. The level 2 "atmPrf" (atmospheric profile) product of version 2010.2640 gives temperature from surface to 0.2 hPa (~ 60 km). This is a dry temperature data product that does not include relative humidity in the inversion process and hence is reliable at altitudes 〈 100 hPa and erroneous at lower altitudes. In the current study we compare the COSMIC "atmPrf" data from December 2010 to November 2011 with other satellite (SABER/TIMED and MLS/Aura) temperatures from 50 to 0.2 hPa, COSMIC "wetPrf" data and reanalysis (NCEP, ERA-Interim and UKMO) outputs at 100, 10, 1 and 0.5 hPa pressure levels. The satellite comparisons show that below 1 hPa the observed median differences are most likely produced due to the biases in the retrievals of SABER and MLS. "atmPrf" and "wetPrf" temperatures compare extremely well in the common altitudes with differences being absolute zero between 200 and 10 hPa. When compared to reanalysis outputs, COSMIC seasonal means match NCEP and ECMWF seasonal mean temperatures very well, especially at 100 and 10 hPa. We conclude from this study that with the COSMIC dry temperature retrievals obtained from radio occultations of GPS, there is a 20 km extension of reliable data in the middle atmosphere. "atmPrf" data are of good quality and provide reliable and unprecedentedly large number of profiles at greater temporal and spatial resolutions for further studies and investigations of the middle atmosphere up to 1 hPa, i.e., approximately up to the stratopause at around 50 km.

Description: Retrieval of aerosol backscatter, extinction, and lidar ratio from Raman lidar with optimal estimation Atmospheric Measurement Techniques, 7, 757-776, 2014 Author(s): A. C. Povey, R. G. Grainger, D. M. Peters, and J. L. Agnew Optimal estimation retrieval is a form of nonlinear regression which determines the most probable circumstances that produced a given observation, weighted against any prior knowledge of the system. This paper applies the technique to the estimation of aerosol backscatter and extinction (or lidar ratio) from two-channel Raman lidar observations. It produces results from simulated and real data consistent with existing Raman lidar analyses and additionally returns a more rigorous estimate of its uncertainties while automatically selecting an appropriate resolution without the imposition of artificial constraints. Backscatter is retrieved at the instrument's native resolution with an uncertainty between 2 and 20%. Extinction is less well constrained, retrieved at a resolution of 0.1–1 km depending on the quality of the data. The uncertainty in extinction is 〉 15%, in part due to the consideration of short 1 min integrations, but is comparable to fair estimates of the error when using the standard Raman lidar technique. The retrieval is then applied to several hours of observation on 19 April 2010 of ash from the Eyjafjallajökull eruption. A depolarising ash layer is found with a lidar ratio of 20–30 sr, much lower values than observed by previous studies. This potentially indicates a growth of the particles after 12–24 h within the planetary boundary layer. A lower concentration of ash within a residual layer exhibited a backscatter of 10 Mm −1 sr −1 and lidar ratio of 40 sr.

Description: Tunable diode laser in-situ CH 4 measurements aboard the CARIBIC passenger aircraft: instrument performance assessment Atmospheric Measurement Techniques, 7, 743-755, 2014 Author(s): C. Dyroff, A. Zahn, S. Sanati, E. Christner, A. Rauthe-Schöch, and T. J. Schuck A laser spectrometer for automated monthly measurements of methane (CH 4 ) mixing ratios aboard the CARIBIC passenger aircraft is presented. The instrument is based on a commercial Fast Greenhouse Gas Analyser (FGGA, Los Gatos Res.), which was adapted to meet the requirements imposed by unattended airborne operation. It was characterised in the laboratory with respect to instrument stability, precision, cross sensitivity to H 2 O, and accuracy. For airborne operation, a calibration strategy is described that utilises CH 4 measurements obtained from flask samples taken during the same flights. The precision of airborne measurements is 2 ppb for 10 s averages. The accuracy at aircraft cruising altitude is 3.85 ppb. During aircraft ascent and descent, where no flask samples were obtained, instrumental drifts can be less accurately determined and the uncertainty is estimated to be 12.4 ppb. A linear humidity bias correction was applied to the CH 4 measurements, which was most important in the lower troposphere. On average, the correction bias was around 6.5 ppb at an altitude of 2 km, and negligible at cruising flight level. Observations from 103 long-distance flights are presented that span a large part of the northern hemispheric upper troposphere and lowermost stratosphere (UT/LMS), with occasional crossing of the tropics on flights to southern Africa. These accurate data mark the largest UT/LMS in-situ CH 4 dataset worldwide. An example of a tracer-tracer correlation study with ozone is given, highlighting the possibility for accurate cross-tropopause transport analyses.

Description: Corrigendum to "Comparison between MODIS and AIRS/AMSU satellite-derived surface skin temperatures" published in Atmos. Meas. Tech., 6, 445–455, 2013 Atmospheric Measurement Techniques, 7, 1151-1152, 2014 Author(s): Y.-R. Lee, J.-M. Yoo, M.-J. Jeong, Y.-I. Won, T. Hearty, and D.-B. Shin No abstract available.

Description: Atmospheric composition and thermodynamic retrievals from the ARIES airborne FTS system – Part 1: Technical aspects and simulated capability Atmospheric Measurement Techniques, 7, 1133-1150, 2014 Author(s): S. M. Illingworth, G. Allen, S. Newman, A. Vance, F. Marenco, R. C. Harlow, J. Taylor, D. P. Moore, and J. J. Remedios In this study we present an assessment of the retrieval capability of the Airborne Research Interferometer Evaluation System (ARIES): an airborne remote-sensing Fourier transform spectrometer (FTS) operated on the UK Facility for Airborne Atmospheric Measurement (FAAM) aircraft. Simulated maximum a posteriori retrievals of partial column trace gas concentrations, and thermodynamic vertical profiles throughout the troposphere and planetary boundary layer have been performed here for simulated infrared spectra representative of the ARIES system operating in the nadir-viewing geometry. We also describe the operational and technical aspects of the pre-processing necessary for routine retrieval from the FAAM platform and the selection and construction of a priori information. As exemplars of the capability of the ARIES retrieval system, simulated retrievals of temperature, water vapour (H 2 O), carbon monoxide (CO), ozone (O 3 ), and methane (CH 4 ), and their corresponding sources of error and potential vertical sensitivity, are discussed for ARIES scenes across typical global environments. The maximum Degrees of Freedom for Signal (DOFS) for the retrievals, assuming a flight altitude of 7 km, were 3.99, 2.97, 0.85, 0.96, and 1.45 for temperature, H 2 O, CO, O 3 , and CH 4 , respectively, for the a priori constraints specified. Retrievals of temperature display significant vertical sensitivity (DOFS in the range 2.6 to 4.0 across the altitude range) as well as excellent simulated accuracy, with the vertical sensitivity for H 2 O also extending to lower altitudes (DOFS ranging from 1.6 to 3.0). It was found that the maximum sensitivity for CO, O 3 , and CH 4 was approximately 1–2 km below the simulated altitudes in all scenarios. Comparisons of retrieved and simulated-truth partial atmospheric columns are used to assess the capability of the ARIES measurement system. Maximum mean biases (and bias standard deviations) in partial columns (i.e. below aircraft total columns) were found to be +0.06 (±0.02 at 1σ)%, +3.95 (±3.11)%, +3.74 (±2.97)%, −8.26 (±4.64)%, and +3.01 (±2.61)% for temperature, H 2 O, CO, O 3 , and CH 4 , respectively, illustrating that the retrieval system performs well compared to an optimal scheme. The maximum total a posteriori retrieval errors across the partial columns were also calculated, and were found to be 0.20, 22.57, 18.22, 17.61, and 16.42% for temperature, H 2 O, CO, O 3 , and CH 4 , respectively.

Description: Field calibrations of a low-cost aerosol sensor at a regulatory monitoring site in California Atmospheric Measurement Techniques, 7, 1121-1131, 2014 Author(s): D. M. Holstius, A. Pillarisetti, K. R. Smith, and E. Seto Health effects attributed to ambient fine particulate matter (PM 2.5 ) now rank it among the risk factors with the highest health burdens in the world, but existing monitoring infrastructure cannot adequately characterize spatial and temporal variability in urban PM 2.5 concentrations, nor in human population exposures. The development and evaluation of more portable and affordable monitoring instruments based on low-cost sensors may offer a means to supplement and extend existing infrastructure, increasing the density and coverage of empirical measurements and thereby improving exposure science and control. Here, we report on field calibrations of a custom-built, battery-operated aerosol monitoring instrument we developed using low-cost, off-the-shelf optical aerosol sensors. We calibrated our instruments using 1 h and 24 h PM 2.5 data from a class III US EPA Federal Equivalent Method (FEM) PM 2.5 β-attenuation monitor in continuous operation at a regulatory monitoring site in Oakland, California. We observed negligible associations with ambient humidity and temperature; linear corrections were sufficient to explain 60% of the variance in 1 h reference PM 2.5 data and 72% of the variance in 24 h data. Performance at 1 h integration times was comparable to commercially available optical instruments costing considerably more. These findings warrant further exploration of the circumstances under which this class of aerosol sensors may profitably be deployed to generate improved PM 2.5 data sets.

Description: Evaluation of gridded scanning ARM cloud radar reflectivity observations and vertical doppler velocity retrievals Atmospheric Measurement Techniques, 7, 1089-1103, 2014 Author(s): K. Lamer, A. Tatarevic, I. Jo, and P. Kollias The scanning Atmospheric Radiation Measurement (ARM) cloud radars (SACRs) provide continuous atmospheric observations aspiring to capture the 3-D cloud-scale structure. Sampling clouds in 3-D is challenging due to their temporal–spatial scales, the need to sample the sky at high elevations and cloud radar limitations. Thus, a suggested scan strategy is to repetitively slice the atmosphere from horizon to horizon as clouds advect over the radar (Cross-Wind Range-Height Indicator – CW-RHI). Here, the processing and gridding of the SACR CW-RHI scans are presented. First, the SACR sample observations from the ARM Southern Great Plains and Cape Cod sites are post-processed (detection mask, gaseous attenuation correction, insect filtering and velocity de-aliasing). The resulting radial Doppler moment fields are then mapped to Cartesian coordinates with time as one of the dimensions. Next the Cartesian-gridded Doppler velocity fields are decomposed into the horizontal wind velocity contribution and the vertical Doppler velocity component. For validation purposes, all gridded and retrieved fields are compared to collocated zenith-pointing ARM cloud radar measurements. We consider that the SACR sensitivity loss with range, the cloud type observed and the research purpose should be considered in determining the gridded domain size. Our results also demonstrate that the gridded SACR observations resolve the main features of low and high stratiform clouds. It is established that the CW-RHI observations complemented with processing techniques could lead to robust 3-D cloud dynamical representations up to 25–30 degrees off zenith. The proposed gridded products are expected to advance our understanding of 3-D cloud morphology, dynamics and anisotropy and lead to more realistic 3-D radiative transfer calculations.

Description: Sub-3 nm particle size and composition dependent response of a nano-CPC battery Atmospheric Measurement Techniques, 7, 689-700, 2014 Author(s): J. Kangasluoma, C. Kuang, D. Wimmer, M. P. Rissanen, K. Lehtipalo, M. Ehn, D. R. Worsnop, J. Wang, M. Kulmala, and T. Petäjä In this study we built a nano-CPC (condensation particle counter) battery, consisting of four ultrafine CPCs optimized for the detection of sub-3 nm particles. Two of the CPCs use diethylene glycol as a working fluid: a laminar type diethlylene glycol CPC and a mixing type Airmodus A09 particle size magnifier. The other two CPCs are a laminar type TSI 3025A and a TSI 3786 with butanol and water as the working fluids, respectively. The nano-CPC battery was calibrated with seven different test aerosols: tetraheptyl ammonium bromide, ammonium sulfate, sodium chloride, tungsten oxide, sucrose, candle flame products and limonene ozonolysis products. The results show that ammonium sulfate and sodium chloride have a higher activation efficiency with the water-based 3786 than with the butanol-based 3025A, whereas the other aerosols were activated better with butanol than with water as the working fluid. It is worthwhile to mention that sub-2 nm limonene ozonolysis products were detected very poorly with all of the CPCs, butanol being the best fluid to activate the oxidation products. To explore how the detection efficiency is affected if the aerosol is an internal mixture of two different chemical substances, we made the first attempt to control the mixing state of sub-3 nm laboratory generated aerosol. We show that we generated an internally mixed aerosol of ammonium sulfate nucleated onto tungsten oxide seed particles, and observed that the activation efficiency of the internally mixed clusters was a function of the internal mixture composition.

Description: The Spectral Aerosol Extinction Monitoring System (SǼMS): setup, observational products, and comparisons Atmospheric Measurement Techniques, 7, 701-712, 2014 Author(s): A. Skupin, A. Ansmann, R. Engelmann, H. Baars, and T. Müller The Spectral Aerosol Extinction Monitoring System (SǼMS) is presented that allows us to continuously measure the spectral extinction coefficient of atmospheric aerosol particles along an approximately 2.7 km long optical path at 30–50 m height above ground in Leipzig (51.3° N, 12.4° E), Germany. The fully automated instrument measures the ambient aerosol extinction coefficients from 300 to 1000 nm. The main goal of SǼMS observations are long-term studies of the relationship between particle extinction and relative humidity from below 40% to almost 100%. The setup is presented and observations (a case study and statistical results for 2009) are discussed in terms of time series of 550 nm particle optical depth, Ångström exponent, and particle size distribution retrieved from the spectrally resolved extinction. The SǼMS measurements are compared with simultaneously performed EARLINET (European Aerosol Research Lidar Network) lidar, AERONET (Aerosol Robotic Network) sun photometer, and in situ aerosol observations of particle size distribution and related extinction coefficients on the roof of our institute. Consistency between the different measurements is found, which corroborates the quality of the SǼMS observations. Statistical results of a period of 1 yr (2009) show mode extinction values of 0.09 km −1 (SǼMS), 0.075 km −1 (AERONET), and 0.03 km −1 (in situ). Ångström exponents for this period are 0.19 (390–880 nm, SǼMS) and 1.55 (440–870 nm, AERONET).

Description: Net ecosystem CO 2 exchange measurements by the closed chamber method and the eddy covariance technique and their dependence on atmospheric conditions Atmospheric Measurement Techniques, 7, 1057-1064, 2014 Author(s): M. Riederer, A. Serafimovich, and T. Foken Carbon dioxide flux measurements in ecosystem sciences are mostly conducted by eddy covariance technique or the closed chamber method. But there is a lack of detailed comparisons that assess present differences and uncertainties. To determine underlying processes, a 10-day, side-by-side measurement of the net ecosystem exchange with both techniques was evaluated with regard to various atmospheric conditions during the diurnal cycle. It was found that, depending on the particular atmospheric condition, the chamber carbon dioxide flux was either (i) equal to the carbon dioxide flux measured by the reference method eddy covariance, by day with well-developed atmospheric turbulence; (ii) higher, in the afternoon in times of oasis effect; (iii) lower, predominantly at night while large coherent structure fluxes or high wind velocities prevailed; or (iv) showed less variation in the flux pattern, at night while stable stratification was present. At night – when respiration forms the net ecosystem exchange – lower chamber carbon dioxide fluxes were found. In the afternoon – when the ecosystem is still a net carbon sink – the carbon dioxide fluxes measured by the chamber prevailed. These two complementary aspects resulted in an overestimation of the ecosystem sink capacity by the chamber of 40% in this study.

Description: A concept of an automated function control for ambient aerosol measurements using mobility particle size spectrometers Atmospheric Measurement Techniques, 7, 1065-1073, 2014 Author(s): A. Schladitz, M. Merkel, S. Bastian, W. Birmili, K. Weinhold, G. Löschau, and A. Wiedensohler An automated function control unit was developed to regularly check the ambient particle number concentration derived from a mobility particle size spectrometer as well as its zero-point behaviour. The function control allows unattended quality assurance experiments at remote air quality monitoring or research stations under field conditions. The automated function control also has the advantage of being able to get a faster system stability response than the recommended on-site comparisons with reference instruments. The method is based on a comparison of the total particle number concentration measured by a mobility particle size spectrometer and a condensation particle counter while removing diffusive particles smaller than 20 nm in diameter. In practice, the small particles are removed by a set of diffusion screens, as traditionally used in a diffusion battery. Another feature of the automated function control is to check the zero-point behaviour of the ambient aerosol passing through a high-efficiency particulate air (HEPA) filter. The performance of the function control is illustrated with the aid of a 1-year data set recorded at Annaberg-Buchholz, a station in the Saxon air quality monitoring network. During the period of concern, the total particle number concentration derived from the mobility particle size spectrometer slightly overestimated the particle number concentration recorded by the condensation particle counter by 2 % (grand average). Based on our first year of experience with the function control, we developed tolerance criteria that allow a performance evaluation of a tested mobility particle size spectrometer with respect to the total particle number concentration. We conclude that the automated function control enhances the quality and reliability of unattended long-term particle number size distribution measurements. This will have beneficial effects for intercomparison studies involving different measurement sites, and help provide a higher data accuracy for cohort health and climate research studies.

Description: Measuring long chain alkanes in diesel engine exhaust by thermal desorption PTR-MS Atmospheric Measurement Techniques, 7, 225-239, 2014 Author(s): M. H. Erickson, M. Gueneron, and B. T. Jobson A method using thermal desorption sampling and analysis by proton transfer reaction mass spectrometry (PTR-MS) to measure long chain alkanes (C 12 –C 18 ) and other larger organics associated with diesel engine exhaust emissions is described. Long chain alkanes undergo dissociative proton transfer reactions forming a series of fragment ions with formula C n H 2 n +1 . The PTR-MS is insensitive to n-alkanes less than C 8 but displays an increasing sensitivity for larger alkanes. Fragment ion distribution and sensitivity is a function of drift conditions. At 80 Td the most abundant ion fragments from C 10 to C 16 n-alkanes were m/z 57, 71 and 85. The mass spectrum of gasoline and diesel fuel at 80 Td displayed ion group patterns that can be related to known fuel constituents, such as alkanes, alkylbenzenes and cycloalkanes, and other compound groups that are inferred from molecular weight distributions such as dihydronapthalenes and naphthenic monoaromatics. It is shown that thermal desorption sampling of gasoline and diesel engine exhausts at 80 Td allows for discrimination against volatile organic compounds, allowing for quantification of long chain alkanes from the abundance of C n H 2 n +1 fragment ions. The total abundance of long chain alkanes in diesel engine exhaust was measured to be similar to the total abundance of C 1 –C 4 alkylbenzene compounds. The abundance patterns of compounds determined by thermal desorption sampling may allow for emission profiles to be developed to better quantify the relative contributions of diesel and gasoline exhaust emissions on organic compounds concentrations in urban air.

Description: Design and characterization of a smog chamber for studying gas-phase chemical mechanisms and aerosol formation Atmospheric Measurement Techniques, 7, 301-313, 2014 Author(s): X. Wang, T. Liu, F. Bernard, X. Ding, S. Wen, Y. Zhang, Z. Zhang, Q. He, S. Lü, J. Chen, S. Saunders, and J. Yu We describe here characterization of a new state-of-the-art smog chamber facility for studying atmospheric gas-phase and aerosol chemistry. The chamber consists of a 30 m 3 fluorinated ethylene propylene (FEP) Teflon film reactor housed in a temperature-controlled enclosure equipped with black lamps as the light source. Temperature can be set in the range from −10 to 40 °C at accuracy of ±1 °C as measured by eight temperature sensors inside the enclosure and one just inside the reactor. Matrix air can be purified with non-methane hydrocarbons (NMHCs) 〈 0.5 ppb, NO x /O 3 /carbonyls 〈 1 ppb and particles 〈 1 cm −3 . The photolysis rate of NO 2 is adjustable between 0 and 0.49 min −1 . At 298 K under dry conditions, the average wall loss rates of NO, NO 2 and O 3 were measured to be 1.41 × 10 −4 min −1 , 1.39 × 10 −4 min −1 and 1.31 × 10 −4 min −1 , respectively, and the particle number wall loss rate was measured to be 0.17 h −1 . Auxiliary mechanisms of this chamber are determined and included in the Master Chemical Mechanism to evaluate and model propene–NO x –air irradiation experiments. The results indicate that this new smog chamber can provide high-quality data for mechanism evaluation. Results of α-pinene dark ozonolysis experiments revealed secondary organic aerosol (SOA) yields comparable to those from other chamber studies, and the two-product model gives a good fit for the yield data obtained in this work. Characterization experiments demonstrate that our Guangzhou Institute of Geochemistry, Chinese Academy Sciences (GIG-CAS), smog chamber facility can be used to provide valuable data for gas-phase chemistry and secondary aerosol formation.

Description: Cavity ring-down spectroscopy sensor for detection of hydrogen chloride Atmospheric Measurement Techniques, 7, 345-357, 2014 Author(s): C. L. Hagen, B. C. Lee, I. S. Franka, J. L. Rath, T. C. VandenBoer, J. M. Roberts, S. S. Brown, and A. P. Yalin A laser-based cavity ring-down spectroscopy (CRDS) sensor for measurement of hydrogen chloride (HCl) has been developed and characterized. The instrument uses light from a distributed-feedback diode laser at 1742 nm coupled to a high finesse optical cavity to make sensitive and quantifiable concentration measurements of HCl based on optical absorption. The instrument has a (1σ) limit of detection of

Description: A smog chamber comparison of a microfluidic derivatisation measurement of gas-phase glyoxal and methylglyoxal with other analytical techniques Atmospheric Measurement Techniques, 7, 373-389, 2014 Author(s): X. Pang, A. C. Lewis, A. R. Rickard, M. T. Baeza-Romero, T. J. Adams, S. M. Ball, M. J. S. Daniels, I. C. A. Goodall, P. S. Monks, S. Peppe, M. Ródenas García, P. Sánchez, and A. Muñoz A microfluidic lab-on-a-chip derivatisation technique has been developed to measure part per billion (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method is compared with other techniques in a smog chamber experiment. The method uses o -(2, 3, 4, 5, 6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatisation reagent and a microfabricated planar glass micro-reactor comprising an inlet, gas and fluid splitting and combining channels, mixing junctions, and a heated capillary reaction microchannel. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the micro-reactor resulted in a fast and highly efficient derivatisation reaction, generating an effluent stream ready for direct introduction to a gas chromatograph-mass spectrometer (GC-MS). A linear response for GLY was observed over a calibration range 0.7 to 400 ppbV, and for MGLY of 1.2 to 300 ppbV, when derivatised under optimal reaction conditions. The analytical performance shows good accuracy (6.6% for GLY and 7.5% for MGLY), suitable precision (

Description: Ground-based all-sky mid-infrared and visible imagery for purposes of characterizing cloud properties Atmospheric Measurement Techniques, 7, 637-645, 2014 Author(s): D. I. Klebe, R. D. Blatherwick, and V. R. Morris This paper describes the All Sky Infrared Visible Analyzer (ASIVA), a multi-purpose visible and infrared sky imaging and analysis instrument whose primary function is to provide radiometrically calibrated imagery in the mid-infrared (mid-IR) atmospheric window. This functionality enables the determination of diurnal fractional sky cover and estimates of sky/cloud temperature from which one can derive estimates of sky/cloud emissivity and cloud height. This paper describes the calibration methods and performance of the ASIVA instrument with particular emphasis on data products being developed for the meteorological community. Data presented here were collected during the Solmirus' ASIVA campaign conducted at the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) Climate Research Facility from 21 May to 27 July 2009. The purpose of this campaign was to determine the efficacy of IR technology in providing reliable nighttime sky cover data. Significant progress has been made in the analysis of the campaign data over the past several years and the ASIVA has proven to be an excellent instrument for determining sky cover as well as the potential for determining sky/cloud temperature, sky/cloud emissivity, precipitable water vapor (PWV), and ultimately cloud height.

Description: High spectral resolution ozone absorption cross-sections – Part 1: Measurements, data analysis and comparison with previous measurements around 293 K Atmospheric Measurement Techniques, 7, 609-624, 2014 Author(s): V. Gorshelev, A. Serdyuchenko, M. Weber, W. Chehade, and J. P. Burrows In this paper we discuss the methodology of taking broadband relative and absolute measurements of ozone cross-sections including uncertainty budget, experimental set-ups, and methods for data analysis. We report on new ozone absorption cross-section measurements in the solar spectral region using a combination of Fourier transform and echelle spectrometers. The new cross-sections cover the spectral range 213–1100 nm at a spectral resolution of 0.02–0.06 nm in the UV–visible and 0.12–0.24 nm in the IR at eleven temperatures from 193 to 293 K in steps of 10 K. The absolute accuracy is better than three percent for most parts of the spectral region and wavelength calibration accuracy is better than 0.005 nm. The new room temperature cross-section data are compared in detail with previously available literature data. The temperature dependence of our cross-sections is described in a companion paper (Serdyuchenko et al., 2014).

Description: High spectral resolution ozone absorption cross-sections – Part 2: Temperature dependence Atmospheric Measurement Techniques, 7, 625-636, 2014 Author(s): A. Serdyuchenko, V. Gorshelev, M. Weber, W. Chehade, and J. P. Burrows We report on the temperature dependence of ozone absorption cross-sections measured in our laboratory in the broad spectral range 213–1100 nm with a spectral resolution of 0.02–0.24 nm (full width at half maximum, FWHM) in the atmospherically relevant temperature range from 193 K to 293 K. The temperature dependence of ozone absorption cross-sections was established using measurements at eleven temperatures. This investigation is superior in terms of spectral range and number of considered temperatures compared to the previous studies. The methodology of the absolute broadband measurements, experimental procedures and spectra processing were described in our companion paper together with the associated uncertainty budget. In this paper, we report in detail on our data below room temperature and compare them with literature data using direct comparisons as well as the standard approach using a quadratic polynomial in temperature fitted to the cross-section data.

Description: Retrieval techniques for airborne imaging of methane concentrations using high spatial and moderate spectral resolution: application to AVIRIS Atmospheric Measurement Techniques, 7, 491-506, 2014 Author(s): A. K. Thorpe, C. Frankenberg, and D. A. Roberts Two quantitative retrieval techniques were evaluated to estimate methane (CH 4 ) enhancement in concentrated plumes using high spatial and moderate spectral resolution data from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS). An iterative maximum a posteriori differential optical absorption spectroscopy (IMAP-DOAS) algorithm performed well for an ocean scene containing natural CH 4 emissions from the Coal Oil Point (COP) seep field near Santa Barbara, California. IMAP-DOAS retrieval precision errors are expected to equal between 0.31 to 0.61 ppm CH 4 over the lowest atmospheric layer (height up to 1.04 km), corresponding to about a 30 to 60 ppm error for a 10 m thick plume. However, IMAP-DOAS results for a terrestrial scene were adversely influenced by the underlying land cover. A hybrid approach using singular value decomposition (SVD) was particularly effective for terrestrial surfaces because it could better account for spectral variability in surface reflectance. Using this approach, a CH 4 plume was observed extending 0.1 km downwind of two hydrocarbon storage tanks at the Inglewood Oil Field in Los Angeles, California (USA) with a maximum near surface enhancement of 8.45 ppm above background. At COP, the distinct plume had a maximum enhancement of 2.85 ppm CH 4 above background, and extended more than 1 km downwind of known seep locations. A sensitivity analysis also indicates CH 4 sensitivity should be more than doubled for the next generation AVIRIS sensor (AVIRISng) due to improved spectral resolution and sampling. AVIRIS-like sensors offer the potential to better constrain emissions on local and regional scales, including sources of increasing concern like industrial point source emissions and fugitive CH 4 from the oil and gas industry.

Description: Fast reconstruction of hyperspectral radiative transfer simulations by using small spectral subsets: application to the oxygen A band Atmospheric Measurement Techniques, 7, 599-607, 2014 Author(s): A. Hollstein and R. Lindstrot Hyperspectral radiative transfer simulations are a versatile tool in remote sensing but can pose a major computational burden. We describe a simple method to construct hyperspectral simulation results by using only a small spectral subsample of the simulated wavelength range, thus leading to major speedups in such simulations. This is achieved by computing principal components for a small number of representative hyperspectral spectra and then deriving a reconstruction matrix for a specific spectral subset of channels to compute the hyperspectral data. The method is applied and discussed in detail using the example of top-of-atmosphere radiances in the oxygen A band, leading to speedups in the range of one to two orders of magnitude when compared to radiative transfer simulations at full spectral resolution.

Description: CO 2 , CO, and CH 4 measurements from tall towers in the NOAA Earth System Research Laboratory's Global Greenhouse Gas Reference Network: instrumentation, uncertainty analysis, and recommendations for future high-accuracy greenhouse gas monitoring efforts Atmospheric Measurement Techniques, 7, 647-687, 2014 Author(s): A. E. Andrews, J. D. Kofler, M. E. Trudeau, J. C. Williams, D. H. Neff, K. A. Masarie, D. Y. Chao, D. R. Kitzis, P. C. Novelli, C. L. Zhao, E. J. Dlugokencky, P. M. Lang, M. J. Crotwell, M. L. Fischer, M. J. Parker, J. T. Lee, D. D. Baumann, A. R. Desai, C. O. Stanier, S. F. J. De Wekker, D. E. Wolfe, J. W. Munger, and P. P. Tans A reliable and precise in situ CO 2 and CO analysis system has been developed and deployed at eight sites in the NOAA Earth System Research Laboratory's (ESRL) Global Greenhouse Gas Reference Network. The network uses very tall (〉 300 m) television and radio transmitter towers that provide a convenient platform for mid-boundary-layer trace-gas sampling. Each analyzer has three sample inlets for profile sampling, and a complete vertical profile is obtained every 15 min. The instrument suite at one site has been augmented with a cavity ring-down spectrometer for measuring CO 2 and CH 4 . The long-term stability of the systems in the field is typically better than 0.1 ppm for CO 2 , 6 ppb for CO, and 0.5 ppb for CH 4 , as determined from repeated standard gas measurements. The instrumentation is fully automated and includes sensors for measuring a variety of status parameters, such as temperatures, pressures, and flow rates, that are inputs for automated alerts and quality control algorithms. Detailed and time-dependent uncertainty estimates have been constructed for all of the gases, and the uncertainty framework could be readily adapted to other species or analysis systems. The design emphasizes use of off-the-shelf parts and modularity to facilitate network operations and ease of maintenance. The systems report high-quality data with 〉 93% uptime. Recurrent problems and limitations of the current system are discussed along with general recommendations for high-accuracy trace-gas monitoring. The network is a key component of the North American Carbon Program and a useful model for future research-grade operational greenhouse gas monitoring efforts.

Description: Odin–OSIRIS detection of the Chelyabinsk meteor Atmospheric Measurement Techniques, 7, 777-780, 2014 Author(s): L. A. Rieger, A. E. Bourassa, and D. A. Degenstein On 15 February 2013 an 11 000 ton meteor entered Earth's atmosphere southeast of Chelyabinsk, creating a large fireball at 23 km altitude. The resulting stratospheric aerosol loading was detected by the Ozone Mapping and Profiler Suite (OMPS) in a high-altitude polar belt. This work confirms the presence and lifetime of the stratospheric debris using the Optical Spectrograph and InfraRed Imaging System (OSIRIS) onboard the Odin satellite. Although OSIRIS coverage begins in mid-March, the measurements show a belt of enhanced scattering near 35 km altitude between 50° N and 70° N. Initially, enhancements show increased scattering of up to 15% over the background conditions, decaying in intensity and dropping in altitude until they are indistinguishable from background conditions by mid-May. An inversion is also attempted using the standard OSIRIS processing algorithm to determine the extinction in the meteoric debris.

Description: Methods for estimating uncertainty in factor analytic solutions Atmospheric Measurement Techniques, 7, 781-797, 2014 Author(s): P. Paatero, S. Eberly, S. G. Brown, and G. A. Norris The EPA PMF (Environmental Protection Agency positive matrix factorization) version 5.0 and the underlying multilinear engine-executable ME-2 contain three methods for estimating uncertainty in factor analytic models: classical bootstrap (BS), displacement of factor elements (DISP), and bootstrap enhanced by displacement of factor elements (BS-DISP). The goal of these methods is to capture the uncertainty of PMF analyses due to random errors and rotational ambiguity. It is shown that the three methods complement each other: depending on characteristics of the data set, one method may provide better results than the other two. Results are presented using synthetic data sets, including interpretation of diagnostics, and recommendations are given for parameters to report when documenting uncertainty estimates from EPA PMF or ME-2 applications.

Description: Probabilistic approach to cloud and snow detection on Advanced Very High Resolution Radiometer (AVHRR) imagery Atmospheric Measurement Techniques, 7, 799-822, 2014 Author(s): J. P. Musial, F. Hüsler, M. Sütterlin, C. Neuhaus, and S. Wunderle Derivation of probability estimates complementary to geophysical data sets has gained special attention over the last years. Information about a confidence level of provided physical quantities is required to construct an error budget of higher-level products and to correctly interpret final results of a particular analysis. Regarding the generation of products based on satellite data a common input consists of a cloud mask which allows discrimination between surface and cloud signals. Further the surface information is divided between snow and snow-free components. At any step of this discrimination process a misclassification in a cloud/snow mask propagates to higher-level products and may alter their usability. Within this scope a novel probabilistic cloud mask (PCM) algorithm suited for the 1 km × 1 km Advanced Very High Resolution Radiometer (AVHRR) data is proposed which provides three types of probability estimates between: cloudy/clear-sky, cloudy/snow and clear-sky/snow conditions. As opposed to the majority of available techniques which are usually based on the decision-tree approach in the PCM algorithm all spectral, angular and ancillary information is used in a single step to retrieve probability estimates from the precomputed look-up tables (LUTs). Moreover, the issue of derivation of a single threshold value for a spectral test was overcome by the concept of multidimensional information space which is divided into small bins by an extensive set of intervals. The discrimination between snow and ice clouds and detection of broken, thin clouds was enhanced by means of the invariant coordinate system (ICS) transformation. The study area covers a wide range of environmental conditions spanning from Iceland through central Europe to northern parts of Africa which exhibit diverse difficulties for cloud/snow masking algorithms. The retrieved PCM cloud classification was compared to the Polar Platform System (PPS) version 2012 and Moderate Resolution Imaging Spectroradiometer (MODIS) collection 6 cloud masks, SYNOP (surface synoptic observations) weather reports, Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) vertical feature mask version 3 and to MODIS collection 5 snow mask. The outcomes of conducted analyses proved fine detection skills of the PCM method with results comparable to or better than the reference PPS algorithm.

Description: Determination of circumsolar radiation from Meteosat Second Generation Atmospheric Measurement Techniques, 7, 823-838, 2014 Author(s): B. Reinhardt, R. Buras, L. Bugliaro, S. Wilbert, and B. Mayer Reliable data on circumsolar radiation, which is caused by scattering of sunlight by cloud or aerosol particles, is becoming more and more important for the resource assessment and design of concentrating solar technologies (CSTs). However, measuring circumsolar radiation is demanding and only very limited data sets are available. As a step to bridge this gap, a method was developed which allows for determination of circumsolar radiation from cirrus cloud properties retrieved by the geostationary satellites of the Meteosat Second Generation (MSG) family. The method takes output from the COCS algorithm to generate a cirrus mask from MSG data and then uses the retrieval algorithm APICS to obtain the optical thickness and the effective radius of the detected cirrus, which in turn are used to determine the circumsolar radiation from a pre-calculated look-up table. The look-up table was generated from extensive calculations using a specifically adjusted version of the Monte Carlo radiative transfer model MYSTIC and by developing a fast yet precise parameterization. APICS was also improved such that it determines the surface albedo, which is needed for the cloud property retrieval, in a self-consistent way instead of using external data. Furthermore, it was extended to consider new ice particle shapes to allow for an uncertainty analysis concerning this parameter. We found that the nescience of the ice particle shape leads to an uncertainty of up to 50%. A validation with 1 yr of ground-based measurements shows, however, that the frequency distribution of the circumsolar radiation can be well characterized with typical ice particle shape mixtures, which feature either smooth or severely roughened particle surfaces. However, when comparing instantaneous values, timing and amplitude errors become evident. For the circumsolar ratio (CSR) this is reflected in a mean absolute deviation (MAD) of 0.11 for both employed particle shape mixtures, and a bias of 4 and 11%, for the mixture with smooth and roughend particles, respectively. If measurements with sub-scale cumulus clouds within the relevant satellite pixels are manually excluded, the instantaneous agreement between satellite and ground measurements improves. For a 2-monthly time series, for which a manual screening of all-sky images was performed, MAD values of 0.08 and 0.07 were obtained for the two employed ice particle mixtures, respectively.

Description: Multi-modal analysis of aerosol robotic network size distributions for remote sensing applications: dominant aerosol type cases Atmospheric Measurement Techniques, 7, 839-858, 2014 Author(s): M. Taylor, S. Kazadzis, and E. Gerasopoulos To date, size distributions obtained from the aerosol robotic network (AERONET) have been fit with bi-lognormals defined by six secondary microphysical parameters: the volume concentration, effective radius, and the variance of fine and coarse particle modes. However, since the total integrated volume concentration is easily calculated and can be used as an accurate constraint, the problem of fitting the size distribution can be reduced to that of deducing a single free parameter – the mode separation point. We present a method for determining the mode separation point for equivalent-volume bi-lognormal distributions based on optimization of the root mean squared error and the coefficient of determination. The extracted secondary parameters are compared with those provided by AERONET's Level 2.0 Version 2 inversion algorithm for a set of benchmark dominant aerosol types, including desert dust, biomass burning aerosol, urban sulphate and sea salt. The total volume concentration constraint is then also lifted by performing multi-modal fits to the size distribution using nested Gaussian mixture models, and a method is presented for automating the selection of the optimal number of modes using a stopping condition based on Fisher statistics and via the application of statistical hypothesis testing. It is found that the method for optimizing the location of the mode separation point is independent of the shape of the aerosol volume size distribution (AVSD), does not require the existence of a local minimum in the size interval 0.439 μm ≤ r ≤ 0.992 μm, and shows some potential for optimizing the bi-lognormal fitting procedure used by AERONET particularly in the case of desert dust aerosol. The AVSD of impure marine aerosol is found to require three modes. In this particular case, bi-lognormals fail to recover key features of the AVSD. Fitting the AVSD more generally with multi-modal models allows automatic detection of a statistically significant number of aerosol modes, is applicable to a very diverse range of aerosol types, and gives access to the secondary microphysical parameters of additional modes currently not available from bi-lognormal fitting methods.

Description: Ozone ProfilE Retrieval Algorithm (OPERA) for nadir-looking satellite instruments in the UV–VIS Atmospheric Measurement Techniques, 7, 859-876, 2014 Author(s): J. C. A. van Peet, R. J. van der A, O. N. E. Tuinder, E. Wolfram, J. Salvador, P. F. Levelt, and H. M. Kelder For the retrieval of the vertical distribution of ozone in the atmosphere the Ozone ProfilE Retrieval Algorithm (OPERA) has been further developed. The new version (1.26) of OPERA is capable of retrieving ozone profiles from UV–VIS observations of most nadir-looking satellite instruments like GOME, SCIAMACHY, OMI and GOME-2. The setup of OPERA is described and results are presented for GOME and GOME-2 observations. The retrieved ozone profiles are globally compared to ozone sondes for the years 1997 and 2008. Relative differences between GOME/GOME-2 and ozone sondes are within the limits as specified by the user requirements from the Climate Change Initiative (CCI) programme of ESA (20% in the troposphere, 15% in the stratosphere). To demonstrate the performance of the algorithm under extreme circumstances, the 2009 Antarctic ozone hole season was investigated in more detail using GOME-2 ozone profiles and lidar data, which showed an unusual persistence of the vortex over the Río Gallegos observing station (51° S, 69.3° W). By applying OPERA to multiple instruments, a time series of ozone profiles from 1996 to 2013 from a single robust algorithm can be created.

Description: Volcanic ash infrared signature: porous non-spherical ash particle shapes compared to homogeneous spherical ash particles Atmospheric Measurement Techniques, 7, 919-929, 2014 Author(s): A. Kylling, M. Kahnert, H. Lindqvist, and T. Nousiainen The reverse absorption technique is often used to detect volcanic ash clouds from thermal infrared satellite measurements. From these measurements effective particle radius and mass loading may be estimated using radiative transfer modelling. The radiative transfer modelling usually assumes that the ash particles are spherical. We calculated thermal infrared optical properties of highly irregular and porous ash particles and compared these with mass- and volume-equivalent spherical models. Furthermore, brightness temperatures pertinent to satellite observing geometry were calculated for the different ash particle shapes. Non-spherical shapes and volume-equivalent spheres were found to produce a detectable ash signal for larger particle sizes than mass-equivalent spheres. The assumption of mass-equivalent spheres for ash mass loading estimates was found to underestimate mass loading compared to morphologically complex inhomogeneous ash particles. The underestimate increases with the mass loading. For an ash cloud recorded during the Eyjafjallajökull 2010 eruption, the mass-equivalent spheres underestimate the total mass of the ash cloud by approximately 30% compared to the morphologically complex inhomogeneous particles.

Description: Role of Coarse and Fine Mode Aerosols in MODIS AOD Retrieval: a case study over southern India Atmospheric Measurement Techniques, 7, 907-917, 2014 Author(s): M. N. Sai Suman, H. Gadhavi, V. Ravi Kiran, A. Jayaraman, and S. V. B. Rao In the present study we compare the MODIS (Moderate Resolution Imaging Spectroradiometer) derived aerosol optical depth (AOD) data with that obtained from operating sky-radiometer at a remote rural location in southern India (Gadanki, 13.45° N, 79.18° E) from April 2008 to March 2011. While the comparison between total (coarse mode + fine mode) AODs shows correlation coefficient ( R ) value of about 0.71 for Terra and 0.77 for Aqua, if one separates the AOD into fine and coarse mode, the comparison becomes very poor, particularly for fine mode with an R value of 0.44 for both Terra and Aqua. The coarse mode AOD derived from MODIS and sky-radiometer compare better with an R value of 0.74 for Terra and 0.66 for Aqua. The seasonal variation is also well captured by both ground-based and satellite measurements. It is shown that both the total AOD and fine mode AOD are significantly underestimated with slope of regression line 0.75 and 0.35 respectively, whereas the coarse mode AOD is overestimated with a slope value of 1.28 for Terra. Similar results are found for Aqua where the slope of the regression line for total AOD and fine mode AOD are 0.72 and 0.27 whereas 0.95 for coarse mode. The fine mode fraction derived from MODIS data is less than one-half of that derived from the sky-radiometer data. Based on these observations and comparison of single scattering albedo observed using sky-radiometer with that of MODIS aerosol models, we argue that the selection of aerosol types used in the MODIS retrieval algorithm may not be appropriate particularly in the case of southern India. Instead of selecting a moderately absorbing aerosol model (as being done currently in the MODIS retrieval) a more absorbing aerosol model could be a better fit for the fine mode aerosols, while reverse is true for the coarse mode aerosols, where instead of using "dust aerosols" which is relatively absorbing type, usage of coarse sea-salt particles which is less absorbing is more appropriate. However, not all the differences could be accounted based on aerosol model, other factors like errors in retrieval of surface reflectance may also be significant in causing underestimation of AOD by MODIS.

Description: Inversion of droplet aerosol analyzer data for long-term aerosol–cloud interaction measurements Atmospheric Measurement Techniques, 7, 877-886, 2014 Author(s): M. I. A. Berghof, G. P. Frank, S. Sjogren, and B. G. Martinsson The droplet aerosol analyzer (DAA) was developed to study the influence of aerosol properties on clouds. It measures the ambient particle size of individual droplets and interstitial particles, the size of the dry (residual) particles after the evaporation of water vapor and the number concentration of the dry (residual) particles. A method was developed for the evaluation of DAA data to obtain the three-parameter data set: ambient particle diameter, dry (residual) particle diameter and number concentration. First results from in-cloud measurements performed on the summit of Mt. Brocken in Germany are presented. Various aspects of the cloud–aerosol data set are presented, such as the number concentration of interstitial particles and cloud droplets, the dry residue particle size distribution, droplet size distributions, scavenging ratios due to cloud droplet formation and size-dependent solute concentrations. This data set makes it possible to study clouds and the influence of the aerosol population on clouds.

Description: Characteristics of cloud liquid water path from SEVIRI onboard the Meteosat Second Generation 2 satellite for several cloud types Atmospheric Measurement Techniques, 7, 887-905, 2014 Author(s): A. Kniffka, M. Stengel, M. Lockhoff, R. Bennartz, and R. Hollmann In this study the temporal and spatial characteristics of the liquid water path (LWP) of low, middle and high level clouds are analysed using space-based observations from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) instrument onboard the Meteosat Second Generation 2 (MSG 2) satellite. Both geophysical quantities are part of the CLAAS (CLoud property dAtAset using SEVIRI) data set and are generated by EUMETSAT's Satellite Application Facility on Climate Monitoring (CM SAF). In this article we focus on the statistical properties of LWP, retrieved during daylight conditions, associated with individual cloud types. We analysed the intrinsic variability of LWP, that is, the variability in only cloudy regions and the variations driven by cloud amount. The relative amplitude of the intrinsic diurnal cycle exceeded the cloud amount driven amplitude in our analysed cases. Our results reveal that each cloud type possesses a characteristic intrinsic LWP distribution. These frequency distributions are constant with time in the entire SEVIRI field of view, but vary for smaller regions like Central Europe. Generally the average LWP is higher over land than over sea; in the case of low clouds this amounts to 15–27% in 2009. The variance of the frequency distributions is enhanced as well. Also, the average diurnal cycle of LWP is related to cloud type with the most pronounced relative diurnal variations being detected for low and middle level clouds. Maps of the relative amplitude and the local time of maximum LWP show the variation throughout the SEVIRI field of view.

Description: Overview: Tropospheric profiling: state of the art and future challenges – introduction to the AMT special issue Atmospheric Measurement Techniques, 7, 2981-2986, 2014 Author(s): D. Cimini, V. Rizi, P. Di Girolamo, F. S. Marzano, A. Macke, G. Pappalardo, and A. Richter This paper introduces the Atmospheric Measurement Techniques special issue on tropospheric profiling, which was conceived to host full papers presenting the results shown at the 9th International Symposium on Tropospheric Profiling (ISTP9). ISTP9 was held in L'Aquila (Italy) from 3 to 7 September 2012, bringing together 150 scientists representing of 28 countries and 3 continents. The tropospheric profiling special issue collects the highlights of ISTP9, reporting recent advances and future challenges in research and technology development.

Description: Measuring the atmospheric organic aerosol volatility distribution: a theoretical analysis Atmospheric Measurement Techniques, 7, 2953-2965, 2014 Author(s): E. Karnezi, I. Riipinen, and S. N. Pandis Organic compounds represent a significant fraction of submicrometer atmospheric aerosol mass. Even if most of these compounds are semi-volatile in atmospheric concentrations, the ambient organic aerosol volatility is quite uncertain. The most common volatility measurement method relies on the use of a thermodenuder (TD). The aerosol passes through a heated tube where its more volatile components evaporate, leaving the less volatile components behind in the particulate phase. The typical result of a thermodenuder measurement is the mass fraction remaining (MFR), which depends, among other factors, on the organic aerosol (OA) vaporization enthalpy and the accommodation coefficient. We use a new method combining forward modeling, introduction of "experimental" error, and inverse modeling with error minimization for the interpretation of TD measurements. The OA volatility distribution, its effective vaporization enthalpy, the mass accommodation coefficient and the corresponding uncertainty ranges are calculated. Our results indicate that existing TD-based approaches quite often cannot estimate reliably the OA volatility distribution, leading to large uncertainties, since there are many different combinations of the three properties that can lead to similar thermograms. We propose an improved experimental approach combining TD and isothermal dilution measurements. We evaluate this experimental approach using the same model, and show that it is suitable for studies of OA volatility in the lab and the field.

Description: A horizontal mobile measuring system for atmospheric quantities Atmospheric Measurement Techniques, 7, 2967-2980, 2014 Author(s): J. Hübner, J. Olesch, H. Falke, F. X. Meixner, and T. Foken A fully automatic horizontal mobile measuring system (HMMS) for atmospheric quantities has been developed. The HMMS is based on the drive mechanism of a garden railway system and can be installed at any location and along any measuring track. In addition to meteorological quantities (temperature, humidity and short-/long-wave down/upwelling radiation), HMMS also measures trace gas concentrations (carbon dioxide and ozone). While sufficient spatial resolution is a problem even for measurements on distributed towers, this could be easily achieved with the HMMS, which has been specifically developed to obtain higher information density about horizontal gradients in a heterogeneous forest ecosystem. There, horizontal gradients of meteorological quantities and trace gases could be immense, particularly at the transition from a dense forest to an open clearing, with large impact on meteorological parameters and exchange processes. Consequently, HMMS was firstly applied during the EGER IOP3 project (ExchanGE processes in mountainous Regions – Intense Observation Period 3) in the Fichtelgebirge Mountains (SE Germany) during summer 2011. At a constant 1 m above ground, the measuring track of the HMMS consisted of a straight line perpendicular to the forest edge, starting in the dense spruce forest and leading 75 m into an open clearing. Tags with bar codes, mounted every metre on the wooden substructure, allowed (a) keeping the speed of the HMMS constant (approx. 0.5 m s −1 ) and (b) operation of the HMMS in a continuous back and forth running mode. During EGER IOP3, HMMS was operational for almost 250 h. Results show that – due to considerably long response times (between 4 and 20 s) of commercial temperature, humidity and the radiation sensors – true spatial variations of the meteorological quantities could not be adequately captured (mainly at the forest edge). Corresponding dynamical (spatial) errors of the measurement values were corrected on the basis of well-defined individual response times of the sensors and application of a linear correction algorithm. Due to the very short response times (≤ 1 s) of the applied commercial CO 2 and O 3 analysers, dynamical errors for the trace gas data were negligible and no corrections were done.

Description: Constraining regional greenhouse gas emissions using geostationary concentration measurements: a theoretical study Atmospheric Measurement Techniques, 7, 3285-3293, 2014 Author(s): P. J. Rayner, S. R. Utembe, and S. Crowell We investigate the ability of column-integrated trace gas measurements from a geostationary satellite to constrain surface fluxes at regional scale. The proposed GEOCARB instrument measures CO 2 , CO and CH 4 at a maximum resolution of 3 km east–west × 2.7 km north–south. Precisions are 3 ppm for CO 2 , 10 ppb for CO and 18 ppb for CH 4 . Sampling frequency is flexible. Here we sample a region at the location of Shanghai every 2 daylight hours for 6 days in June. We test the observing system by calculating the posterior uncertainty covariance of fluxes. We are able to constrain urban emissions at 3 km resolution including an isolated power plant. The CO measurement plays the strongest role; without it our effective resolution falls to 5 km. Methane fluxes are similarly well estimated at 5 km resolution. Estimating the errors for a full year suggests such an instrument would be a useful tool for both science and policy applications.

Description: Construction of merged satellite total O 3 and NO 2 time series in the tropics for trend studies and evaluation by comparison to NDACC SAOZ measurements Atmospheric Measurement Techniques, 7, 3337-3354, 2014 Author(s): M. Pastel, J.-P. Pommereau, F. Goutail, A. Richter, A. Pazmiño, D. Ionov, and T. Portafaix Long time series of ozone and NO 2 total column measurements in the southern tropics are available from two ground-based SAOZ (Système d'Analyse par Observation Zénithale) UV-visible spectrometers operated within the Network for the Detection of Atmospheric Composition Change (NDACC) in Bauru (22° S, 49° W) in S-E Brazil since 1995 and Reunion Island (21° S, 55° E) in the S-W Indian Ocean since 1993. Although the stations are located at the same latitude, significant differences are observed in the columns of both species, attributed to differences in tropospheric content and equivalent latitude in the lower stratosphere. These data are used to identify which satellites operating during the same period, are capturing the same features and are thus best suited for building reliable merged time series for trend studies. For ozone, the satellites series best matching SAOZ observations are EP-TOMS (1995–2004) and OMI-TOMS (2005–2011), whereas for NO 2 , best results are obtained by combining GOME version GDP5 (1996–2003) and SCIAMACHY – IUP (2003–2011), displaying lower noise and seasonality in reference to SAOZ. Both merged data sets are fully consistent with the larger columns of the two species above South America and the seasonality of the differences between the two stations, reported by SAOZ, providing reliable time series for further trend analyses and identification of sources of interannual variability in the future analysis.

Description: Improving the bias characteristics of the ROPP refractivity and bending angle operators Atmospheric Measurement Techniques, 7, 3445-3458, 2014 Author(s): C. P. Burrows, S. B. Healy, and I. D. Culverwell The bending angle observation operator (forward model) currently used to assimilate radio occultation (RO) data at the Met Office, the European Centre for Medium-Range Weather Forecasts (ECMWF) and other centres is the same as is included in the Radio Occultation Processing Package (ROPP), along with the corresponding tangent-linear and adjoint code. The functionality of this package will be described in another paper in this issue. The mean bending angle innovations produced with this operator using Met Office background fields show a bias that oscillates with height and whose magnitude peaks between the model levels. These oscillations have been attributed to shortcomings in the assumption of exponentially varying refractivity between model levels. This is used directly in the refractivity operator, and indirectly to produce forward-modelled bending angles via the Abel transform. When the spacing between the model levels is small, this assumption is acceptable, but at stratospheric heights where the model level spacing is large, these biases can be significant, and can potentially degrade analyses. This paper provides physically based improvements to the functional form of refractivity with height. These new assumptions considerably improve the oscillatory bias, and a number of approaches for practical implementation of the bending angle operator are provided.

Description: Retrieval of tropospheric column-averaged CH 4 mole fraction by solar absorption FTIR-spectrometry using N 2 O as a proxy Atmospheric Measurement Techniques, 7, 3295-3305, 2014 Author(s): Z. Wang, N. M. Deutscher, T. Warneke, J. Notholt, B. Dils, D. W. T. Griffith, M. Schmidt, M. Ramonet, and C. Gerbig Tropospheric column-averaged CH 4 mole fractions were derived from ground-based column absorption measurements. The method uses stratospheric N 2 O columns to correct for the stratospheric contribution to the CH 4 total column. The method was applied to four Total Carbon Column Observing Network (TCCON) sites covering locations from the Northern Arctic to the tropics. It performs well for all sites. The derived tropospheric CH 4 concentrations were compared with profiles measured by aircraft at three sites. The results indicate an inter-site consistency within 6 ppb (~0.3%). With aircraft profiles up to 3 km, the seasonal behavior of the derived tropospheric CH 4 concentration was also checked, revealing a difference of around 20 ppb. The mean relative uncertainty of the four sites, as estimated from the daily standard deviations, is 0.23%.

Description: Characterisation of an inlet pre-injector laser-induced fluorescence instrument for the measurement of atmospheric hydroxyl radicals Atmospheric Measurement Techniques, 7, 3413-3430, 2014 Author(s): A. Novelli, K. Hens, C. Tatum Ernest, D. Kubistin, E. Regelin, T. Elste, C. Plass-Dülmer, M. Martinez, J. Lelieveld, and H. Harder Atmospheric measurements of hydroxyl radicals (OH) are challenging due to a high reactivity and consequently low concentration. The importance of OH as an atmospheric oxidant has motivated a sustained effort leading to the development of a number of highly sensitive analytical techniques. Recent work has indicated that the laser-induced fluorescence of the OH molecules method based on the fluorescence assay by gas expansion technique (LIF-FAGE) for the measurement of atmospheric OH in some environments may be influenced by artificial OH generated within the instrument, and a chemical method to remove this interference was implemented in a LIF-FAGE system by Mao et al. (2012). While it is not clear whether other LIF-FAGE instruments suffer from the same interference, we have applied this method to our LIF-FAGE HORUS (Hydroxyl Radical Measurement Unit based on fluorescence Spectroscopy) system, and developed and deployed an inlet pre-injector (IPI) to determine the chemical zero level in the instrument via scavenging the ambient OH radical. We describe and characterise this technique in addition to its application at field sites in forested locations in Finland, Spain and Germany. Ambient measurements show that OH generated within the HORUS instrument is a non-negligible fraction of the total OH signal, which can comprise 30 to 80% during daytime and 60 to 100% during the night. The contribution of the background OH varied greatly between measurement sites and was likely related to the type and concentration of volatile organic compounds (VOCs) present at each particular location. Two inter-comparisons in contrasting environments between the HORUS instrument and two different chemical ionisation mass spectrometers (CIMS) are described to demonstrate the efficacy of IPI and the necessity of the chemical zeroing method for our LIF-FAGE instrument in such environments.

Description: Mirror contamination in space I: mirror modelling Atmospheric Measurement Techniques, 7, 3387-3398, 2014 Author(s): J. M. Krijger, R. Snel, G. van Harten, J. H. H. Rietjens, and I. Aben We present a comprehensive model that can be employed to describe and correct for degradation of (scan) mirrors and diffusers in satellite instruments that suffer from changing optical Ultraviolet to visible (UV–VIS) properties during their operational lifetime. As trend studies become more important, so does the importance of understanding and correcting for this degradation. This is the case not only with respect to the transmission of the optical components, but also with respect to wavelength, polarisation, or scan-angle effects. Our hypothesis is that mirrors in flight suffer from the deposition of a thin absorbing layer of contaminant, which slowly builds up over time. We describe this with the Mueller matrix formalism and Fresnel equations for thin multi-layer contamination films. Special care is taken to avoid the confusion often present in earlier publications concerning the Mueller matrix calculus with out-of-plane reflections. The method can be applied to any UV–VIS satellite instrument. We illustrate and verify our approach to the optical behaviour of the multiple scan mirrors of SCIAMACHY (onboard ENVISAT).

Description: Long-path averaged mixing ratios of O 3 and NO 2 in the free troposphere from mountain MAX-DOAS Atmospheric Measurement Techniques, 7, 3373-3386, 2014 Author(s): L. Gomez, M. Navarro-Comas, O. Puentedura, Y. Gonzalez, E. Cuevas, and M. Gil-Ojeda A new approximation is proposed to estimate O 3 and NO 2 mixing ratios in the northern subtropical free troposphere (FT). The proposed method uses O 4 slant column densities (SCDs) at horizontal and near-zenith geometries to estimate a station-level differential path. The modified geometrical approach (MGA) is a simple method that takes advantage of a very long horizontal path to retrieve mixing ratios in the range of a few pptv. The methodology is presented, and the possible limitations are discussed. Multi-axis differential optical absorption spectroscopy (MAX-DOAS) high-mountain measurements recorded at the Izaña observatory (28° 18' N, 16° 29' W) are used in this study. The results show that under low aerosol loading, O 3 and NO 2 mixing ratios can be retrieved even at very low concentrations. The obtained mixing ratios are compared with those provided by in situ instrumentation at the observatory. The MGA reproduces the O 3 mixing ratio measured by the in situ instrumentation with a difference of 28%. The different air masses scanned by each instrument are identified as a cause of the discrepancy between the O 3 observed by MAX-DOAS and the in situ measurements. The NO 2 is in the range of 20–40 ppt, which is below the detection limit of the in situ instrumentation, but it is in agreement with measurements from previous studies for similar conditions.

Description: Cloud mask via cumulative discriminant analysis applied to satellite infrared observations: scientific basis and initial evaluation Atmospheric Measurement Techniques, 7, 3355-3372, 2014 Author(s): U. Amato, L. Lavanant, G. Liuzzi, G. Masiello, C. Serio, R. Stuhlmann, and S. A. Tjemkes We introduce a classification method (cumulative discriminant analysis) of the discriminant analysis type to discriminate between cloudy and clear-sky satellite observations in the thermal infrared. The tool is intended for the high-spectral-resolution infrared sounder (IRS) planned for the geostationary METEOSAT (Meteorological Satellite) Third Generation platform and uses IASI (Infrared Atmospheric Sounding Interferometer) data as a proxy. The cumulative discriminant analysis does not introduce biases intrinsic with the approximation of the probability density functions and is flexible enough to adapt to different strategies to optimize the cloud mask. The methodology is based on nine statistics computed from IASI spectral radiances, which exploit the high spectral resolution of the instrument and which effectively summarize information contained within the IASI spectrum. A principal component analysis prior step is also introduced, which makes the problem more consistent with the statistical assumptions of the methodology. An initial assessment of the scheme is performed based on global and regional IASI real data sets and cloud masks obtained from AVHRR (Advanced Very High Resolution Radiometer) and SEVIRI (Spinning Enhanced Visible and Infrared Imager) imagers. The agreement with these independent cloud masks is generally well above 80 %, except at high latitudes in the winter seasons.

Description: Refractory black carbon mass concentrations in snow and ice: method evaluation and inter-comparison with elemental carbon measurement Atmospheric Measurement Techniques, 7, 3307-3324, 2014 Author(s): S. Lim, X. Faïn, M. Zanatta, J. Cozic, J.-L. Jaffrezo, P. Ginot, and P. Laj Accurate measurement of black carbon (BC) mass concentrations in snow and ice is crucial for the assessment of climatic impacts. However, it is difficult to compare methods used to assess BC levels in the literature as they are not the same. The single particle soot photometer (SP2) method appears to be one of the most suitable to measure low concentrations of BC in snow and ice. In this paper, we evaluated a method for the quantification of refractory BC (rBC) in snow and ice samples coupling the SP2 with the APEX-Q nebulizer. The paper reviews all the steps of rBC determination, including SP2 calibration, correction for rBC particle aerosolization efficiency (75 ± 7% using the APEX-Q nebulizer), and treatment of the samples. In addition, we compare the SP2 method and the thermal–optical method – Sunset organic carbon (OC) / elemental carbon (EC) aerosol analyzer with EUSAAR2 protocol – using snow and firn samples with different characteristics from the Greenland Summit, the French Alps, the Caucasus, and the Himalayas. Careful investigation was undertaken of analytical artifacts that potentially affect both methods. The SP2-based rBC quantification may be underestimated when the SP2 detection range does not cover correctly the existing size distribution of the sample. Thermal–optical EC measurements can be underestimated by low filtration efficiency of quartz fiber filter before analysis or dust properties (concentration and type), and overestimated by pyrolyzed OC artifacts during EC analysis. These results underline the need for careful assessment of the analytical technique and procedure for correct data interpretation.

Description: The next generation of low-cost personal air quality sensors for quantitative exposure monitoring Atmospheric Measurement Techniques, 7, 3325-3336, 2014 Author(s): R. Piedrahita, Y. Xiang, N. Masson, J. Ortega, A. Collier, Y. Jiang, K. Li, R. P. Dick, Q. Lv, M. Hannigan, and L. Shang Advances in embedded systems and low-cost gas sensors are enabling a new wave of low-cost air quality monitoring tools. Our team has been engaged in the development of low-cost, wearable, air quality monitors (M-Pods) using the Arduino platform. These M-Pods house two types of sensors – commercially available metal oxide semiconductor (MOx) sensors used to measure CO, O 3 , NO 2 , and total VOCs, and NDIR sensors used to measure CO 2 . The MOx sensors are low in cost and show high sensitivity near ambient levels; however they display non-linear output signals and have cross-sensitivity effects. Thus, a quantification system was developed to convert the MOx sensor signals into concentrations. We conducted two types of validation studies – first, deployments at a regulatory monitoring station in Denver, Colorado, and second, a user study. In the two deployments (at the regulatory monitoring station), M-Pod concentrations were determined using collocation calibrations and laboratory calibration techniques. M-Pods were placed near regulatory monitors to derive calibration function coefficients using the regulatory monitors as the standard. The form of the calibration function was derived based on laboratory experiments. We discuss various techniques used to estimate measurement uncertainties. The deployments revealed that collocation calibrations provide more accurate concentration estimates than laboratory calibrations. During collocation calibrations, median standard errors ranged between 4.0–6.1 ppb for O 3 , 6.4–8.4 ppb for NO 2 , 0.28–0.44 ppm for CO, and 16.8 ppm for CO 2 . Median signal to noise (S / N) ratios for the M-Pod sensors were higher than the regulatory instruments: for NO 2 , 3.6 compared to 23.4; for O 3 , 1.4 compared to 1.6; for CO, 1.1 compared to 10.0; and for CO 2 , 42.2 compared to 300–500. By contrast, lab calibrations added bias and made it difficult to cover the necessary range of environmental conditions to obtain a good calibration. A separate user study was also conducted to assess uncertainty estimates and sensor variability. In this study, 9 M-Pods were calibrated via collocation multiple times over 4 weeks, and sensor drift was analyzed, with the result being a calibration function that included baseline drift. Three pairs of M-Pods were deployed, while users individually carried the other three. The user study suggested that inter-M-Pod variability between paired units was on the same order as calibration uncertainty; however, it is difficult to make conclusions about the actual personal exposure levels due to the level of user engagement. The user study provided real-world sensor drift data, showing limited CO drift (under −0.05 ppm day −1 ), and higher for O 3 (−2.6 to 2.0 ppb day −1 ), NO 2 (−1.56 to 0.51 ppb day −1 ), and CO 2 (−4.2 to 3.1 ppm day −1 ). Overall, the user study confirmed the utility of the M-Pod as a low-cost tool to assess personal exposure.

Description: Space-based retrieval of NO 2 over biomass burning regions: quantifying and reducing uncertainties Atmospheric Measurement Techniques, 7, 3431-3444, 2014 Author(s): N. Bousserez The accuracy of space-based nitrogen dioxide (NO 2 ) retrievals from solar backscatter radiances critically depends on a priori knowledge of the vertical profiles of NO 2 and aerosol optical properties. This information is used to calculate an air mass factor (AMF), which accounts for atmospheric scattering and is used to convert the measured line-of-sight "slant" columns into vertical columns. In this study we investigate the impact of biomass burning emissions on the AMF in order to quantify NO 2 retrieval errors in the Ozone Monitoring Instrument (OMI) products over these sources. Sensitivity analyses are conducted using the Linearized Discrete Ordinate Radiative Transfer (LIDORT) model. The NO 2 and aerosol profiles are obtained from a 3-D chemistry-transport model (GEOS-Chem), which uses the Fire Locating and Monitoring of Burning Emissions (FLAMBE) daily biomass burning emission inventory. Aircraft in situ data collected during two field campaigns, the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) and the Dust and Biomass-burning Experiment (DABEX), are used to evaluate the modeled aerosol optical properties and NO 2 profiles over Canadian boreal fires and West African savanna fires, respectively. Over both domains, the effect of biomass burning emissions on the AMF through the modified NO 2 shape factor can be as high as −60%. A sensitivity analysis also revealed that the effect of aerosol and shape factor perturbations on the AMF is very sensitive to surface reflectance and clouds. As an illustration, the aerosol correction can range from −20 to +100% for different surface reflectances, while the shape factor correction varies from −70 to −20%. Although previous studies have shown that in clear-sky conditions the effect of aerosols on the AMF was in part implicitly accounted for by the modified cloud parameters, here it is suggested that when clouds are present above a surface layer of scattering aerosols, an explicit aerosol correction would be beneficial to the NO 2 retrieval. Finally, a new method that uses slant column information to correct for shape-factor-related AMF error over NO x emission sources is proposed, with possible application to near-real-time OMI retrievals.

Description: Verification and application of the extended spectral deconvolution algorithm (SDA+) methodology to estimate aerosol fine and coarse mode extinction coefficients in the marine boundary layer Atmospheric Measurement Techniques, 7, 3399-3412, 2014 Author(s): K. C. Kaku, J. S. Reid, N. T. O'Neill, P. K. Quinn, D. J. Coffman, and T. F. Eck The spectral deconvolution algorithm (SDA) and SDA+ (extended SDA) methodologies can be employed to separate the fine and coarse mode extinction coefficients from measured total aerosol extinction coefficients, but their common use is currently limited to AERONET (AErosol RObotic NETwork) aerosol optical depth (AOD). Here we provide the verification of the SDA+ methodology on a non-AERONET aerosol product, by applying it to fine and coarse mode nephelometer and particle soot absorption photometer (PSAP) data sets collected in the marine boundary layer. Using data sets collected on research vessels by NOAA-PMEL(National Oceanic and Atmospheric Administration – Pacific Marine Environmental Laboratory), we demonstrate that with accurate input, SDA+ is able to predict the fine and coarse mode scattering and extinction coefficient partition in global data sets representing a range of aerosol regimes. However, in low-extinction regimes commonly found in the clean marine boundary layer, SDA+ output accuracy is sensitive to instrumental calibration errors. This work was extended to the calculation of coarse and fine mode scattering coefficients with similar success. This effort not only verifies the application of the SDA+ method to in situ data, but by inference verifies the method as a whole for a host of applications, including AERONET. Study results open the door to much more extensive use of nephelometers and PSAPs, with the ability to calculate fine and coarse mode scattering and extinction coefficients in field campaigns that do not have the resources to explicitly measure these values.

Description: The Heidelberg Airborne Imaging DOAS Instrument (HAIDI) – a novel imaging DOAS device for 2-D and 3-D imaging of trace gases and aerosols Atmospheric Measurement Techniques, 7, 3459-3485, 2014 Author(s): S. General, D. Pöhler, H. Sihler, N. Bobrowski, U. Frieß, J. Zielcke, M. Horbanski, P. B. Shepson, B. H. Stirm, W. R. Simpson, K. Weber, C. Fischer, and U. Platt Many relevant processes in tropospheric chemistry take place on rather small scales (e.g., tens to hundreds of meters) but often influence areas of several square kilometer. Thus, measurements of the involved trace gases with high spatial resolution are of great scientific interest. In order to identify individual sources and sinks and ultimately to improve chemical transport models, we developed a new airborne instrument, which is based on the well established Differential Optical Absorption Spectroscopy (DOAS) method. The Heidelberg Airborne Imaging DOAS Instrument (HAIDI) is a passive imaging DOAS spectrometer, which is capable of recording horizontal and vertical trace gas distributions with a resolution of better than 100 m. Observable species include NO 2 , HCHO, C 2 H 2 O 2 , H 2 O, O 3 , O 4 , SO 2 , IO, OClO and BrO. Here we give a technical description of the instrument including its custom-built spectrographs and CCD detectors. Also first results from measurements with the new instrument are presented. These comprise spatial resolved SO 2 and BrO in volcanic plumes, mapped at Mt. Etna (Sicily, Italy), NO 2 emissions in the metropolitan area of Indianapolis (Indiana, USA) as well as BrO and NO 2 distributions measured during arctic springtime in context of the BRomine, Ozone, and Mercury EXperiment (BROMEX) campaign, which was performed 2012 in Barrow (Alaska, USA).

Description: Variable anisotropy of small-scale stratospheric irregularities retrieved from stellar scintillation measurements by GOMOS/Envisat Atmospheric Measurement Techniques, 7, 1861-1872, 2014 Author(s): V. Kan, V. F. Sofieva, and F. Dalaudier In this paper, we consider possibilities for studying the anisotropy of small-scale air density irregularities using satellite observations of bi-chromatic stellar scintillations during tangential occultations. Estimation of the anisotropy coefficient (the ratio of the characteristic horizontal to vertical scales) and other atmospheric parameters is based on the comparison of simulated/theoretical and experimental auto-spectra and coherency spectra of scintillation. Our analyses exploit a 3-D model of the spectrum of atmospheric inhomogeneities, which consists of anisotropic and isotropic components. For the anisotropic component, a spectral model with variable anisotropy is used. Using stellar scintillation measurements by GOMOS (Global Ozone Monitoring by Occultation of Stars) fast photometers, estimates of the anisotropy coefficient are obtained for atmospheric irregularities with vertical scales of 8–55 m at altitudes of 43–30 km. It is shown that the anisotropy increases from about 10 to 50 with increasing vertical scales.

Description: Performance of a mobile car platform for mean wind and turbulence measurements Atmospheric Measurement Techniques, 7, 1825-1837, 2014 Author(s): D. Belušić, D. H Lenschow, and N. J. Tapper The lack of adequate near-surface observations of the stable atmospheric boundary layer spatial structure motivated the development of an instrumented car for mobile turbulence measurements. The calibration and validation of the car measurements are performed using controlled field experiments and a comparison with an instrumented tower. The corrections required to remove the effects of the car motion are shown to be smaller and simpler than the corrections for research aircraft measurements. A car can therefore satisfactorily measure near-surface turbulence using relatively low-cost equipment. Other natural advantages of a car, such as the ability to drive on any road at any time of day or night and follow the terrain slope, as well as its low cost of operation, make it applicable to observations of a variety of flow regimes that cannot be achieved with the usual platforms, such as research aircraft or networks of flux towers.

Description: An introduction to the FY3 GNOS instrument and mountain-top tests Atmospheric Measurement Techniques, 7, 1817-1823, 2014 Author(s): W. H. Bai, Y. Q. Sun, Q. F. Du, G. L. Yang, Z. D. Yang, P. Zhang, Y. M. Bi, X. Y. Wang, C. Cheng, and Y. Han The FY3 (Feng-Yun-3) GNOS (GNSS Occultation Sounder) mission is a GNSS (Global Navigation Satellite System) radio occultation mission of China for remote sensing of Earth's neutral atmosphere and the ionosphere. GNOS will use both the global positioning system (GPS) and the Beidou navigation satellite systems on the China Feng-Yun-3 (FY3) series satellites. The first FY3-C was launched at 03:07 UTC on 23 September 2013. GNOS was developed by the Center for Space Science and Applied Research, Chinese Academy of Sciences (CSSAR). It will provide vertical profiles of atmospheric temperature, pressure, and humidity, as well as ionospheric electron density profiles on a global basis. These data will be used for numerical weather prediction, climate research, and ionospheric research and space weather. This paper describes the FY3 GNOS mission and the GNOS instrument characteristics. It presents simulation results of the number and distribution of GNOS occultation events with the regional Beidou constellation and the full GPS constellation, under the limitation of the GNOS instrument occultation channel number. This paper presents the instrument performance as derived from analysis of measurement data in laboratory and mountain-based occultation validation experiments at Mt. Wuling in Hebei Province. The mountain-based GNSS occultation validation tests show that GNOS can acquire or track low-elevation radio signal for rising or setting occultation events. The refractivity profiles of GNOS obtained during the mountain-based experiment were compared with those from radiosondes. The results show that the refractivity profiles obtained by GNOS are consistent with those from the radiosonde. The rms of the differences between the GNOS and radiosonde refractivities is less than 3%.

Description: A simple and versatile cloud-screening method for MAX-DOAS retrievals Atmospheric Measurement Techniques, 7, 3509-3527, 2014 Author(s): C. Gielen, M. Van Roozendael, F. Hendrick, G. Pinardi, T. Vlemmix, V. De Bock, H. De Backer, C. Fayt, C. Hermans, D. Gillotay, and P. Wang We present a cloud-screening method based on differential optical absorption spectroscopy (DOAS) measurements, more specifically using intensity measurements and O 4 differential slant-column densities (DSCDs). Using the colour index (CI), i.e. the ratio of the radiance at two wavelengths, we define different sky conditions including clear, thin clouds/polluted, fully-cloudy, and heavily polluted. We also flag the presence of broken and scattered clouds. The O 4 absorption is a good tracer for cloud-induced light-path changes and is used to detect clouds and discriminate between instances of high aerosol optical depth (AOD) and high cloud optical depth (COD). We apply our cloud screening to MAX-DOAS (multi-axis DOAS) retrievals at three different sites with different typical meteorological conditions, more specifically suburban Beijing (39.75° N, 116.96° E), Brussels (50.78° N, 4.35° E) and Jungfraujoch (46.55° N, 7.98° E). We find that our cloud screening performs well characterizing the different sky conditions. The flags based on the colour index are able to detect changes in visibility due to aerosols and/or (scattered) clouds. The O 4 -based multiple-scattering flag is able to detect optically thick clouds, and is needed to correctly identify clouds for sites with extreme aerosol pollution. Removing data taken under cloudy conditions results in a better agreement, in both correlation and slope, between the MAX-DOAS AOD retrievals and measurements from other co-located instruments.

Description: Measurements of diurnal variations and eddy covariance (EC) fluxes of glyoxal in the tropical marine boundary layer: description of the Fast LED-CE-DOAS instrument Atmospheric Measurement Techniques, 7, 3579-3595, 2014 Author(s): S. Coburn, I. Ortega, R. Thalman, B. Blomquist, C. W. Fairall, and R. Volkamer Here we present first eddy covariance (EC) measurements of fluxes of glyoxal, the smallest α-dicarbonyl product of hydrocarbon oxidation, and a precursor for secondary organic aerosol (SOA). The unique physical and chemical properties of glyoxal – i.e., high solubility in water (effective Henry's law constant, K H = 4.2 × 10 5 M atm −1 ) and short atmospheric lifetime (~2 h at solar noon) – make it a unique indicator species for organic carbon oxidation in the marine atmosphere. Previous reports of elevated glyoxal over oceans remain unexplained by atmospheric models. Here we describe a Fast Light-Emitting Diode Cavity-Enhanced Differential Optical Absorption Spectroscopy (Fast LED-CE-DOAS) instrument to measure diurnal variations and EC fluxes of glyoxal and inform about its unknown sources. The fast in situ sensor is described, and first results are presented from a cruise deployment over the eastern tropical Pacific Ocean (20° N to 10° S; 133 to 85° W) as part of the Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated VOCs (TORERO) field experiment (January to March 2012). The Fast LED-CE-DOAS is a multispectral sensor that selectively and simultaneously measures glyoxal (CHOCHO), nitrogen dioxide (NO 2 ), oxygen dimers (O 4 ), and water vapor (H 2 O) with ~2 Hz time resolution (Nyquist frequency ~1 Hz) and a precision of ~40 pptv Hz −0.5 for glyoxal. The instrument is demonstrated to be a "white-noise" sensor suitable for EC flux measurements. Fluxes of glyoxal are calculated, along with fluxes of NO 2 , H 2 O, and O 4 , which are used to aid the interpretation of the glyoxal fluxes. Further, highly sensitive and inherently calibrated glyoxal measurements are obtained from temporal averaging of data (e.g., detection limit smaller than 2.5 pptv in an hour). The campaign average mixing ratio in the Southern Hemisphere (SH) is found to be 43 ± 9 pptv glyoxal, which is higher than the Northern Hemisphere (NH) average of 32 ± 6 pptv (error reflects variability over multiple days). The diurnal variation of glyoxal in the marine boundary layer (MBL) is measured for the first time, and mixing ratios vary by ~8 pptv (NH) and ~12 pptv (SH) over the course of 24 h. Consistently, maxima are observed at sunrise (NH: 35 ± 5 pptv; SH: 47 ± 7 pptv), and minima at dusk (NH: 27 ± 5 pptv; SH: 35 ± 8 pptv). In both hemispheres, the daytime flux was directed from the atmosphere into the ocean, indicating that the ocean is a net sink for glyoxal during the day. After sunset the ocean was a source for glyoxal to the atmosphere (positive flux) in the SH; this primary ocean source was operative throughout the night. In the NH, the nighttime flux was positive only shortly after sunset and negative during most of the night. Positive EC fluxes of soluble glyoxal over oceans indicate the presence of an ocean surface organic microlayer (SML) and locate a glyoxal source within the SML. The origin of most atmospheric glyoxal, and possibly other oxygenated hydrocarbons over tropical oceans, remains unexplained and warrants further investigation.

Description: Measurements of hydrogen sulfide (H 2 S) using PTR-MS: calibration, humidity dependence, inter-comparison and results from field studies in an oil and gas production region Atmospheric Measurement Techniques, 7, 3597-3610, 2014 Author(s): R. Li, C. Warneke, M. Graus, R. Field, F. Geiger, P. R. Veres, J. Soltis, S.-M. Li, S. M. Murphy, C. Sweeney, G. Pétron, J. M. Roberts, and J. de Gouw Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H 2 S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H 2 S using proton-transfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H 2 S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H 2 S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H 2 S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H 2 S is only slightly higher than that of water. The H 2 S sensitivity of PTR-MS ranged between 0.6–1.4 ncps ppbv −1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H 2 S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H 2 S measurements using a PTR time-of-flight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H 2 S / CH 4 . On average 0.6 ± 0.3 ppbv H 2 S was present at Horse Pool during UBWOS 2013. The correlation between H 2 S and methane enhancements suggests that the source of H 2 S is associated with oil and gas extraction in the basin. Significant H 2 S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H 2 S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of H 2 S at levels below 1 ppbv.

Description: Amine permeation sources characterized with acid neutralization and sensitivities of an amine mass spectrometer Atmospheric Measurement Techniques, 7, 3611-3621, 2014 Author(s): N. A. Freshour, K. K. Carlson, Y. A. Melka, S. Hinz, B. Panta, and D. R. Hanson An acid titration method for quantifying amine permeation rates was used to calibrate an Ambient pressure Proton transfer Mass Spectrometer (AmPMS) that monitors ambient amine compounds. The method involves capturing amines entrained in a N 2 flow by bubbling it through an acidified solution (~10 −5 M HCl), and the amines are quantified via changes in solution pH with time. Home-made permeation tubes had permeation rates (typically tens of pmol s −1 ) that depended on the type of amine and tubing and on temperature. Calibrations of AmPMS yielded sensitivities for ammonia, methylamine, dimethylamine, and trimethylamine that are close to the sensitivity assuming a gas-kinetic, ion-molecule rate coefficient. The permeation tubes were also designed to deliver a reproducible amount of amine to a flow reactor where nucleation with sulfuric acid was studied. The high proton affinity compound dimethyl sulfoxide (DMSO), linked to oceanic environments, was also studied and AmPMS is highly sensitive to it. AmPMS was deployed recently in two field campaigns and, using these sensitivities, mixing ratios for ammonia and the alkyl amines are derived from the signals. Correlations between these species and with particle formation events are discussed.

Description: MIPAS temperature from the stratosphere to the lower thermosphere: Comparison of vM21 with ACE-FTS, MLS, OSIRIS, SABER, SOFIE and lidar measurements Atmospheric Measurement Techniques, 7, 3633-3651, 2014 Author(s): M. García-Comas, B. Funke, A. Gardini, M. López-Puertas, A. Jurado-Navarro, T. von Clarmann, G. Stiller, M. Kiefer, C. D. Boone, T. Leblanc, B. T. Marshall, M. J. Schwartz, and P. E. Sheese We present vM21 MIPAS temperatures from the lower stratosphere to the lower thermosphere, which cover all optimized resolution measurements performed by MIPAS in the middle-atmosphere, upper-atmosphere and noctilucent-cloud modes during its lifetime, i.e., from January 2005 to April 2012. The main upgrades with respect to the previous version of MIPAS temperatures (vM11) are the update of the spectroscopic database, the use of a different climatology of atomic oxygen and carbon dioxide, and the improvement in important technical aspects of the retrieval setup (temperature gradient along the line of sight and offset regularizations, apodization accuracy). Additionally, an updated version of ESA-calibrated L1b spectra (5.02/5.06) is used. The vM21 temperatures correct the main systematic errors of the previous version because they provide on average a 1–2 K warmer stratopause and middle mesosphere, and a 6–10 K colder mesopause (except in high-latitude summers) and lower thermosphere. These lead to a remarkable improvement in MIPAS comparisons with ACE-FTS, MLS, OSIRIS, SABER, SOFIE and the two Rayleigh lidars at Mauna Loa and Table Mountain, which, with a few specific exceptions, typically exhibit differences smaller than 1 K below 50 km and than 2 K at 50–80 km in spring, autumn and winter at all latitudes, and summer at low to midlatitudes. Differences in the high-latitude summers are typically smaller than 1 K below 50 km, smaller than 2 K at 50–65 km and 5 K at 65–80 km. Differences between MIPAS and the other instruments in the mid-mesosphere are generally negative. MIPAS mesopause is within 4 K of the other instruments measurements, except in the high-latitude summers, when it is within 5–10 K, being warmer there than SABER, MLS and OSIRIS and colder than ACE-FTS and SOFIE. The agreement in the lower thermosphere is typically better than 5 K, except for high latitudes during spring and summer, when MIPAS usually exhibits larger vertical gradients.

Description: Direct aerosol chemical composition measurements to evaluate the physicochemical differences between controlled sea spray aerosol generation schemes Atmospheric Measurement Techniques, 7, 3667-3683, 2014 Author(s): D. B. Collins, D. F. Zhao, M. J. Ruppel, O. Laskina, J. R. Grandquist, R. L. Modini, M. D. Stokes, L. M. Russell, T. H. Bertram, V. H. Grassian, G. B. Deane, and K. A. Prather Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be under-pinned by a physically and chemically accurate representation of the bubble-mediated production of nascent SSA particles. Bubble bursting is sensitive to the physico-chemical properties of seawater. For a sample of seawater, any important differences in the SSA production mechanism are projected into the composition of the aerosol particles produced. Using direct chemical measurements of SSA at the single-particle level, this study presents an intercomparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging-waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than those produced by sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic-enriched particles and a different size-resolved elemental composition, especially in the 0.8–2 μm dry diameter range. Interestingly, chemical differences between the methods only emerged when the particles were chemically analyzed at the single-particle level as a function of size; averaging the elemental composition of all particles across all sizes masked the differences between the SSA samples. When dried, SSA generated by the sintered glass filters had the highest fraction of particles with spherical morphology compared to the more cubic structure expected for pure NaCl particles produced when the particle contains relatively little organic carbon. In addition to an intercomparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method on SSA composition was under-taken. In organic-enriched seawater, the continuous operation of the plunging waterfall resulted in the accumulation of surface foam and an over-expression of organic matter in SSA particles compared to those produced by a pulsed plunging waterfall. Throughout this set of experiments, comparative differences in the SSA number size distribution were coincident with differences in aerosol particle composition, indicating that the production mechanism of SSA exerts important controls on both the physical and chemical properties of the resulting aerosol with respect to both the internal and external mixing state of particles. This study provides insight into the inextricable physicochemical differences between each of the bubble-mediated SSA generation mechanisms tested and the aerosol particles that they produce, and also serves as a guideline for future laboratory studies of SSA particles.

Description: Potential of airborne lidar measurements for cirrus cloud studies Atmospheric Measurement Techniques, 7, 2745-2755, 2014 Author(s): S. Groß, M. Wirth, A. Schäfler, A. Fix, S. Kaufmann, and C. Voigt Aerosol and water vapour measurements were performed with the lidar system WALES of Deutsches Zentrum für Luft- und Raumfahrt (DLR) in October and November 2010 during the first mission with the new German research aircraft G55-HALO. Curtains composed of lidar profiles beneath the aircraft show the vertical and horizontal distribution and variability of water vapour mixing ratio and backscatter ratio above Germany. Two missions on 3 and 4 November 2010 were selected to derive the water vapour mixing ratio inside cirrus clouds from the lidar instrument. A good agreement was found with in situ observations performed on a second research aircraft flying below HALO. ECMWF analysis temperature data are used to derive relative humidity fields with respect to ice (RHi) inside and outside of cirrus clouds from the lidar water vapour observations. The RHi variability is dominated by small-scale fluctuations in the water vapour fields while the temperature variation has a minor impact. The most frequent in-cloud RHi value from lidar observations is 98%. The RHi variance is smaller inside the cirrus than outside of the cloud. 2-D histograms of relative humidity and backscatter ratio show significant differences for in-cloud and out-of-cloud situations for two different cirrus cloud regimes. Combined with accurate temperature measurements, the lidar observations have a great potential for detailed statistical cirrus cloud and related humidity studies.

Description: Measurement of gas-phase ammonia and amines in air by collection onto an ion exchange resin and analysis by ion chromatography Atmospheric Measurement Techniques, 7, 2733-2744, 2014 Author(s): M. L. Dawson, V. Perraud, A. Gomez, K. D. Arquero, M. J. Ezell, and B. J. Finlayson-Pitts Ammonia and amines are common trace gases in the atmosphere and have a variety of both biogenic and anthropogenic sources, with a major contribution coming from agricultural sites. In addition to their malodorous nature, both ammonia and amines have been shown to enhance particle formation from acids such as nitric, sulfuric and methanesulfonic acids, which has implications for visibility, human health and climate. A key component of quantifying the effects of these species on particle formation is accurate gas-phase measurements in both laboratory and field studies. However, these species are notoriously difficult to measure as they are readily taken up on surfaces, including onto glass surfaces from aqueous solution as established in the present studies. We describe here a novel technique for measuring gas-phase ammonia and amines that involves uptake onto a weak cation exchange resin followed by extraction and analysis using ion chromatography. Two variants – one for parts per billion concentrations in air and the second with lower (parts per trillion) detection limits – are described. The latter involves the use of a custom-designed high-pressure cartridge to hold the resin for in-line extraction. These methods avoid the use of sampling lines, which can lead to significant inlet losses of these compounds. They also have the advantages of being relatively simple and inexpensive. The applicability of this technique to ambient air is demonstrated in measurements made near a cattle farm in Chino, CA.

Description: The performance of Aeolus in heterogeneous atmospheric conditions using high-resolution radiosonde data Atmospheric Measurement Techniques, 7, 2695-2717, 2014 Author(s): X. J. Sun, R. W. Zhang, G. J. Marseille, A. Stoffelen, D. Donovan, L. Liu, and J. Zhao The European Space Agency Aeolus mission aims to measure wind profiles from space. A major challenge is to retrieve high quality winds in heterogeneous atmospheric conditions, i.e. where both the atmospheric dynamics and optical properties vary strongly within the sampling volume. In preparation for launch we aim to quantify the expected error of retrieved winds from atmospheric heterogeneity, particularly in the vertical, and develop algorithms for wind error correction, as part of the level-2B processor (L2Bp). We demonstrate that high-resolution data from radiosondes provide valuable input to establish a database of collocated wind and atmospheric optics at 10 m vertical resolution to simulate atmospheric conditions along Aeolus' lines of sight. The database is used to simulate errors of Aeolus winds retrieved from the Mie and Rayleigh channel signals. The non-uniform distribution of molecules in the measurement bin introduces height assignment errors in Rayleigh channel winds up to 2.5% of the measurement bin size in the stratosphere which translates to 0.5 m s −1 bias for typical atmospheric conditions, if not corrected. The presence of cloud or aerosol layers in the measurement bin yields biases in Mie channel winds which cannot be easily corrected and mostly exceed the mission requirement of 0.4 m s −1 . The collocated Rayleigh channel wind solution is generally preferred because of smaller biases, in particular for transparent cloud and aerosol layers with one-way transmission above 0.8. The results show that Aeolus L2Bp, under development, can be improved by the estimation of atmosphere optical properties to correct for height assignment errors and to identify wind solutions potentially detrimental when used in Numerical Weather Prediction.

Description: The MUSICA MetOp/IASI H 2 O and δD products: characterisation and long-term comparison to NDACC/FTIR data Atmospheric Measurement Techniques, 7, 2719-2732, 2014 Author(s): A. Wiegele, M. Schneider, F. Hase, S. Barthlott, O. E. García, E. Sepúlveda, Y. González, T. Blumenstock, U. Raffalski, M. Gisi, and R. Kohlhepp Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) ground- and space-based remote sensing as well as in situ data sets of tropospheric water vapour isotopologues are provided. The space-based remote-sensing data set is produced from spectra measured by the IASI (Infrared Atmospheric Sounding Interferometer) sensor and is potentially available on a global scale. Here, we present the MUSICA IASI data for three different geophysical locations (subtropics, midlatitudes, and Arctic), and we provide a comprehensive characterisation of the complex nature of such space-based isotopologue remote-sensing products. The quality assessment study is complemented by a comparison to MUSICA's ground-based FTIR (Fourier Transform InfraRed) remote-sensing data retrieved from the spectra recorded at three different locations within the framework of NDACC (Network for the Detection of Atmospheric Composition Change). We confirm that IASI is able to measure tropospheric H 2 O profiles with a vertical resolution of about 4 km and a random error of about 10%. In addition IASI can observe middle tropospheric δD that adds complementary value to IASI's middle tropospheric H 2 O observations. Our study presents theoretical and empirical proof that IASI has the capability for a global observation of middle tropospheric water vapour isotopologues on a daily timescale and at a quality that is sufficiently high for water cycle research purposes.

Description: Comparing the cloud vertical structure derived from several methods based on radiosonde profiles and ground-based remote sensing measurements Atmospheric Measurement Techniques, 7, 2757-2773, 2014 Author(s): M. Costa-Surós, J. Calbó, J. A. González, and C. N. Long The cloud vertical distribution and especially the cloud base height, which is linked to cloud type, are important characteristics in order to describe the impact of clouds on climate. In this work, several methods for estimating the cloud vertical structure (CVS) based on atmospheric sounding profiles are compared, considering the number and position of cloud layers, with a ground-based system that is taken as a reference: the Active Remote Sensing of Clouds (ARSCL). All methods establish some conditions on the relative humidity, and differ in the use of other variables, the thresholds applied, or the vertical resolution of the profile. In this study, these methods are applied to 193 radiosonde profiles acquired at the Atmospheric Radiation Measurement (ARM) Southern Great Plains site during all seasons of the year 2009 and endorsed by Geostationary Operational Environmental Satellite (GOES) images, to confirm that the cloudiness conditions are homogeneous enough across their trajectory. The perfect agreement (i.e., when the whole CVS is estimated correctly) for the methods ranges between 26 and 64%; the methods show additional approximate agreement (i.e., when at least one cloud layer is assessed correctly) from 15 to 41%. Further tests and improvements are applied to one of these methods. In addition, we attempt to make this method suitable for low-resolution vertical profiles, like those from the outputs of reanalysis methods or from the World Meteorological Organization's (WMO) Global Telecommunication System. The perfect agreement, even when using low-resolution profiles, can be improved by up to 67% (plus 25% of the approximate agreement) if the thresholds for a moist layer to become a cloud layer are modified to minimize false negatives with the current data set, thus improving overall agreement.

Description: Tropospheric CO vertical profiles deduced from total columns using data assimilation: methodology and validation Atmospheric Measurement Techniques, 7, 3035-3057, 2014 Author(s): L. El Amraoui, J.-L. Attié, P. Ricaud, W. A. Lahoz, A. Piacentini, V.-H. Peuch, J. X. Warner, R. Abida, J. Barré, and R. Zbinden This paper presents a validation of a method to derive the vertical profile of carbon monoxide (CO) from its total column using data assimilation. We choose version 3 of MOPITT CO total columns to validate the proposed method. MOPITT products have the advantage of providing both the vertical profiles and the total columns of CO. Furthermore, this version has been extensively validated by comparison with many independent data sets, and has been used in many scientific studies. The first step of the paper consists in the specification of the observation errors based on the chi-square (χ 2 ) test. The observations have been binned according to three types: over land during daytime, over land during night-time, and over sea. Their respective errors using the χ 2 metric have been found to be 8, 11 and 7%. In the second step, the CO total columns, with their specified errors, are used within the assimilation system to estimate the vertical profiles. These are compared to the retrieved profiles of MOPITT V3 at global and regional scales. Generally, the two data sets show similar patterns and good agreement at both scales. Nevertheless, total column analyses slightly overestimate CO concentrations compared to MOPITT observations. The mean bias between both data sets is +15 and +12% at 700 and 250 hPa, respectively. In the third step, the assimilation of total column has been compared to the assimilation of MOPITT vertical profiles. The differences between both analyses are very small. In terms longitude–latitude maps, the mean bias between the two data sets is +6 and +8% at the pressure levels 700 and 200 hPa, respectively. In terms of zonal means, the CO distribution is similar for both analyses, with a mean bias which does not exceed 12%. Finally, the two analyses have been validated using independent observations from the aircraft-based MOZAIC program in terms of vertical profiles over eight airports. Over most airports, both analyses agree well with aircraft profiles. For more than 50% of recorded measurements, the difference between the analyses and MOZAIC does not exceed 5 ppbv (parts per billion by volume).

Description: Smoothing error pitfalls Atmospheric Measurement Techniques, 7, 3023-3034, 2014 Author(s): T. von Clarmann The difference due to the content of a priori information between a constrained retrieval and the true atmospheric state is usually represented by a diagnostic quantity called smoothing error. In this paper it is shown that, regardless of the usefulness of the smoothing error as a diagnostic tool in its own right, the concept of the smoothing error as a component of the retrieval error budget is questionable because it is not compliant with Gaussian error propagation. The reason for this is that the smoothing error does not represent the expected deviation of the retrieval from the true state but the expected deviation of the retrieval from the atmospheric state sampled on an arbitrary grid, which is itself a smoothed representation of the true state; in other words, to characterize the full loss of information with respect to the true atmosphere, the effect of the representation of the atmospheric state on a finite grid also needs to be considered. The idea of a sufficiently fine sampling of this reference atmospheric state is problematic because atmospheric variability occurs on all scales, implying that there is no limit beyond which the sampling is fine enough. Even the idealization of infinitesimally fine sampling of the reference state does not help, because the smoothing error is applied to quantities which are only defined in a statistical sense, which implies that a finite volume of sufficient spatial extent is needed to meaningfully discuss temperature or concentration. Smoothing differences, however, which play a role when measurements are compared, are still a useful quantity if the covariance matrix involved has been evaluated on the comparison grid rather than resulting from interpolation and if the averaging kernel matrices have been evaluated on a grid fine enough to capture all atmospheric variations that the instruments are sensitive to. This is, under the assumptions stated, because the undefined component of the smoothing error, which is the effect of smoothing implied by the finite grid on which the measurements are compared, cancels out when the difference is calculated. If the effect of a retrieval constraint is to be diagnosed on a grid finer than the native grid of the retrieval by means of the smoothing error, the latter must be evaluated directly on the fine grid, using an ensemble covariance matrix which includes all variability on the fine grid. Ideally, the averaging kernels needed should be calculated directly on the finer grid, but if the grid of the original averaging kernels allows for representation of all the structures the instrument is sensitive to, then their interpolation can be an adequate approximation.

Description: Validation of the Aura High Resolution Dynamics Limb Sounder geopotential heights Atmospheric Measurement Techniques, 7, 2775-2785, 2014 Author(s): L. L. Smith and J. C. Gille The geopotential height (GPH) product created from global observations by the High Resolution Dynamics Limb Sounder (HIRDLS) instrument on NASA's Earth Observing System (EOS) Aura spacecraft is discussed. The accuracy, resolution and precision of the HIRDLS version 7 algorithms are assessed and data screening recommendations are made. Comparisons with GPH from observations, reanalyses and models including European Centre for Medium-Range Weather Forecasts Interim Reanalysis (ERA-Interim), and National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) Reanalysis illustrate the HIRDLS GPHs have a precision ranging from 2 to 30 m and an accuracy of ±100 m up to 1 hPa. Comparisons indicate HIRDLS GPH may have a slight low bias in the tropics and a slight high bias at high latitudes. Geostrophic winds computed with HIRDLS GPH qualitatively agree with winds from other data sources including ERA-Interim.

Description: The AquaVIT-1 intercomparison of atmospheric water vapor measurement techniques Atmospheric Measurement Techniques, 7, 3177-3213, 2014 Author(s): D. W. Fahey, R.-S. Gao, O. Möhler, H. Saathoff, C. Schiller, V. Ebert, M. Krämer, T. Peter, N. Amarouche, L. M. Avallone, R. Bauer, Z. Bozóki, L. E. Christensen, S. M. Davis, G. Durry, C. Dyroff, R. L. Herman, S. Hunsmann, S. M. Khaykin, P. Mackrodt, J. Meyer, J. B. Smith, N. Spelten, R. F. Troy, H. Vömel, S. Wagner, and F. G. Wienhold The AquaVIT-1 intercomparison of atmospheric water vapor measurement techniques was conducted at the aerosol and cloud simulation chamber AIDA (Aerosol Interaction and Dynamics in the Atmosphere) at the Karlsruhe Institute of Technology, Germany, in October 2007. The overall objective was to intercompare state-of-the-art and prototype atmospheric hygrometers with each other and with independent humidity standards under controlled conditions. This activity was conducted as a blind intercomparison with coordination by selected referees. The effort was motivated by persistent discrepancies found in atmospheric measurements involving multiple instruments operating on research aircraft and balloon platforms, particularly in the upper troposphere and lower stratosphere, where water vapor reaches its lowest atmospheric values (less than 10 ppm). With the AIDA chamber volume of 84 m 3 , multiple instruments analyzed air with a common water vapor mixing ratio, by extracting air into instrument flow systems, by locating instruments inside the chamber, or by sampling the chamber volume optically. The intercomparison was successfully conducted over 10 days during which pressure, temperature, and mixing ratio were systematically varied (50 to 500 hPa, 185 to 243 K, and 0.3 to 152 ppm). In the absence of an accepted reference instrument, the absolute accuracy of the instruments was not established. To evaluate the intercomparison, the reference value was taken to be the ensemble mean of a core subset of the measurements. For these core instruments, the agreement between 10 and 150 ppm of water vapor is considered good with variation about the reference value of about ±10% (±1σ). In the region of most interest between 1 and 10 ppm, the core subset agreement is fair with variation about the reference value of ±20% (±1σ). The upper limit of precision was also derived for each instrument from the reported data. The implication for atmospheric measurements is that the substantially larger differences observed during in-flight intercomparisons stem from other factors associated with the moving platforms or the non-laboratory environment. The success of AquaVIT-1 provides a template for future intercomparison efforts with water vapor or other species that are focused on improving the analytical quality of atmospheric measurements on moving platforms.

Description: Satellite retrieval of aerosol microphysical and optical parameters using neural networks: a new methodology applied to the Sahara desert dust peak Atmospheric Measurement Techniques, 7, 3151-3175, 2014 Author(s): M. Taylor, S. Kazadzis, A. Tsekeri, A. Gkikas, and V. Amiridis In order to exploit the full-earth viewing potential of satellite instruments to globally characterise aerosols, new algorithms are required to deduce key microphysical parameters like the particle size distribution and optical parameters associated with scattering and absorption from space remote sensing data. Here, a methodology based on neural networks is developed to retrieve such parameters from satellite inputs and to validate them with ground-based remote sensing data. For key combinations of input variables available from the MODerate resolution Imaging Spectro-radiometer (MODIS) and the Ozone Measuring Instrument (OMI) Level 3 data sets, a grid of 100 feed-forward neural network architectures is produced, each having a different number of neurons and training proportion. The networks are trained with principal components accounting for 98% of the variance of the inputs together with principal components formed from 38 AErosol RObotic NETwork (AERONET) Level 2.0 (Version 2) retrieved parameters as outputs. Daily averaged, co-located and synchronous data drawn from a cluster of AERONET sites centred on the peak of dust extinction in Northern Africa is used for network training and validation, and the optimal network architecture for each input parameter combination is identified with reference to the lowest mean squared error. The trained networks are then fed with unseen data at the coastal dust site Dakar to test their simulation performance. A neural network (NN), trained with co-located and synchronous satellite inputs comprising three aerosol optical depth measurements at 470, 550 and 660 nm, plus the columnar water vapour (from MODIS) and the modelled absorption aerosol optical depth at 500 nm (from OMI), was able to simultaneously retrieve the daily averaged size distribution, the coarse mode volume, the imaginary part of the complex refractive index, and the spectral single scattering albedo – with moderate precision: correlation coefficients in the range 0.368 ≤ R ≤ 0.514. The network failed to recover the spectral behaviour of the real part of the complex refractive index. This new methodological approach appears to offer some potential for moderately accurate daily retrieval of the total volume concentration of the coarse mode of aerosol at the Saharan dust peak in the area of Northern Africa.

Description: Simultaneous retrieval of effective refractive index and density from size distribution and light-scattering data: weakly absorbing aerosol Atmospheric Measurement Techniques, 7, 3247-3261, 2014 Author(s): E. Kassianov, J. Barnard, M. Pekour, L. K. Berg, J. Shilling, C. Flynn, F. Mei, and A. Jefferson We propose here a novel approach for retrieving in parallel the effective density and real refractive index of weakly absorbing aerosol from optical and size distribution measurements. Here we define "weakly absorbing" as aerosol single-scattering albedos that exceed 0.95 at 0.5 μm. The required optical measurements are the scattering coefficient and the hemispheric backscatter fraction, obtained in this work from an integrating nephelometer. The required size spectra come from mobility and aerodynamic particle size spectrometers commonly referred to as a scanning mobility particle sizer and an aerodynamic particle sizer. The performance of this approach is first evaluated using a sensitivity study with synthetically generated but measurement-related inputs. The sensitivity study reveals that the proposed approach is robust to random noise; additionally the uncertainties of the retrieval are almost linearly proportional to the measurement errors, and these uncertainties are smaller for the real refractive index than for the effective density. Next, actual measurements are used to evaluate our approach. These measurements include the optical, microphysical, and chemical properties of weakly absorbing aerosol which are representative of a variety of coastal summertime conditions observed during the Two-Column Aerosol Project (TCAP; http://campaign.arm.gov/tcap/ ). The evaluation includes calculating the root mean square error (RMSE) between the aerosol characteristics retrieved by our approach, and the same quantities calculated using the conventional volume mixing rule for chemical constituents. For dry conditions (defined in this work as relative humidity less than 55%) and sub-micron particles, a very good (RMSE ~ 3%) and reasonable (RMSE ~ 28%) agreement is obtained for the retrieved real refractive index (1.49 ± 0.02) and effective density (1.68 ± 0.21), respectively. Our approach permits discrimination between the retrieved aerosol characteristics of sub-micron and sub-10-micron particles. The evaluation results also reveal that the retrieved density and refractive index tend to decrease with an increase of the relative humidity.

Description: A gas chromatograph for quantification of peroxycarboxylic nitric anhydrides calibrated by thermal dissociation cavity ring-down spectroscopy Atmospheric Measurement Techniques, 7, 3263-3283, 2014 Author(s): T. W. Tokarek, J. A. Huo, C. A. Odame-Ankrah, D. Hammoud, Y. M. Taha, and H. D. Osthoff The peroxycarboxylic nitric anhydrides (PANs, molecular formula: RC(O)O 2 NO 2 ) can readily be observed by gas chromatography (PAN-GC) coupled to electron capture detection. Calibration of a PAN-GC remains a challenge, because the response factors differ for each of the PANs, and because their synthesis in sufficiently high purity is non-trivial, in particular for PANs containing unsaturated side chains. In this manuscript, a PAN-GC and its calibration using diffusion standards, whose output was quantified by blue diode laser thermal dissociation cavity ring-down spectroscopy (TD-CRDS), are described. The PAN-GC peak areas correlated linearly with total peroxy nitrate (ΣPN) mixing ratios measured by TD-CRDS ( r 〉 0.96). Accurate determination of response factors required the concentrations of PAN impurities in the synthetic standards to be subtracted from ΣPN. The PAN-GC and its TD-CRDS calibration method were deployed during ambient air measurement campaigns in Abbotsford, BC, from 20 July to 5 August 2012, and during the Fort McMurray Oil Sands Strategic Investigation of Local Sources (FOSSILS) campaign at the AMS13 ground site in Fort McKay, AB, from 10 August to 5 September 2013. The PAN-GC limits of detection for PAN, PPN, and MPAN during FOSSILS were 1, 2, and 3 pptv, respectively. For the Abbotsford data set, the PAN-GC mixing ratios were compared, and agreed with those determined in parallel by thermal dissociation chemical ionization mass spectrometry (TD-CIMS). Advantages and disadvantages of the PAN measurement techniques used in this work and the utility of TD-CRDS as a PAN-GC calibration method are discussed.

Description: Aircraft validation of Aura Tropospheric Emission Spectrometer retrievals of HDO / H 2 O Atmospheric Measurement Techniques, 7, 3127-3138, 2014 Author(s): R. L. Herman, J. E. Cherry, J. Young, J. M. Welker, D. Noone, S. S. Kulawik, and J. Worden The EOS (Earth Observing System) Aura Tropospheric Emission Spectrometer (TES) retrieves the atmospheric HDO / H 2 O ratio in the mid-to-lower troposphere as well as the planetary boundary layer. TES observations of water vapor and the HDO isotopologue have been compared with nearly coincident in situ airborne measurements for direct validation of the TES products. The field measurements were made with a commercially available Picarro L1115-i isotopic water analyzer on aircraft over the Alaskan interior boreal forest during the three summers of 2011 to 2013. TES special observations were utilized in these comparisons. The TES averaging kernels and a priori constraints have been applied to the in situ data, using version 5 (V005) of the TES data. TES calculated errors are compared with the standard deviation (1σ) of scan-to-scan variability to check consistency with the TES observation error. Spatial and temporal variations are assessed from the in situ aircraft measurements. It is found that the standard deviation of scan-to-scan variability of TES δD is ±34.1‰ in the boundary layer and ± 26.5‰ in the free troposphere. This scan-to-scan variability is consistent with the TES estimated error (observation error) of 10–18‰ after accounting for the atmospheric variations along the TES track of ±16‰ in the boundary layer, increasing to ±30‰ in the free troposphere observed by the aircraft in situ measurements. We estimate that TES V005 δD is biased high by an amount that decreases with pressure: approximately +123‰ at 1000 hPa, +98‰ in the boundary layer and +37‰ in the free troposphere. The uncertainty in this bias estimate is ±20‰. A correction for this bias has been applied to the TES HDO Lite Product data set. After bias correction, we show that TES has accurate sensitivity to water vapor isotopologues in the boundary layer.

Description: Reconstruction of global solar radiation time series from 1933 to 2013 at the Izaña Atmospheric Observatory Atmospheric Measurement Techniques, 7, 3139-3150, 2014 Author(s): R. D. García, E. Cuevas, O. E. García, V. E. Cachorro, P. Pallé, J. J. Bustos, P. M. Romero-Campos, and A. M. de Frutos This paper presents the reconstruction of the 80-year time series of daily global solar radiation (GSR) at the subtropical high-mountain Izaña Atmospheric Observatory (IZO) located in Tenerife (The Canary Islands, Spain). For this purpose, we combine GSR estimates from sunshine duration (SD) data using the Ångström–Prescott method over the 1933/1991 period, and GSR observations directly performed by pyranometers between 1992 and 2013. Since GSR measurements have been used as a reference, a strict quality control has been applied based on principles of physical limits and comparison with LibRadtran model. By comparing with high quality GSR measurements, the precision and consistency over time of GSR estimations from SD data have been successfully documented. We obtain an overall root mean square error (RMSE) of 9.2% and an agreement between the variances of GSR estimations and GSR measurements within 92%. Nonetheless, this agreement significantly increases when the GSR estimation is done considering different daily fractions of clear sky (FCS). In that case, RMSE is reduced by half, to about 4.5%, when considering percentages of FCS 〉 40% (~ 90% of days in the testing period). Furthermore, we prove that the GSR estimations can monitor the GSR anomalies in consistency with GSR measurements and, then, can be suitable for reconstructing solar radiation time series. The reconstructed IZO GSR time series between 1933 and 2013 confirms change points and periods of increases/decreases of solar radiation at Earth's surface observed at a global scale, such as the early brightening, dimming and brightening. This fact supports the consistency of the IZO GSR time series presented in this work, which may be a reference for solar radiation studies in the subtropical North Atlantic region.

Description: Retrieval of cirrus cloud optical thickness and top altitude from geostationary remote sensing Atmospheric Measurement Techniques, 7, 3233-3246, 2014 Author(s): S. Kox, L. Bugliaro, and A. Ostler A novel approach for the detection of cirrus clouds and the retrieval of optical thickness and top altitude based on the measurements of the Spinning Enhanced Visible and Infrared Imager (SEVIRI) aboard the geostationary Meteosat Second Generation (MSG) satellite is presented. Trained with 8 000 000 co-incident measurements of the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) aboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) mission the new "cirrus optical properties derived from CALIOP and SEVIRI algorithm during day and night" (COCS) algorithm utilizes a backpropagation neural network to provide accurate measurements of cirrus optical depth τ at λ = 532 nm and top altitude z every 15 min covering almost one-third of the Earth's atmosphere. The retrieved values are validated with independent measurements of CALIOP and the optical thickness derived by an airborne high spectral resolution lidar.