Showing papers in "Atmospheric Measurement Techniques in 2011"

An improved tropospheric NO 2 column retrieval algorithm for the Ozone Monitoring Instrument

Abstract: . We present an improved tropospheric nitrogen dioxide column retrieval algorithm (DOMINO v2.0) for OMI based on better air mass factors (AMFs) and a correction for across-track stripes resulting from calibration errors in the OMI backscattered reflectances. Since October 2004, NO2 retrievals from the Ozone Monitoring Instrument (OMI), a UV/Vis nadir spectrometer onboard NASA's EOS-Aura satellite, have been used with success in several scientific studies focusing on air quality monitoring, detection of trends, and NOx emission estimates. Dedicated evaluations of previous DOMINO tropospheric NO2 retrievals indicated their good quality, but also suggested that the tropospheric columns were susceptible to high biases (by 0–40%), probably because of errors in the air mass factor calculations. Here we update the DOMINO air mass factor approach. We calculate a new look-up table (LUT) for altitude-dependent AMFs based on more realistic atmospheric profile parameters, and include more surface albedo and surface pressure reference points than before. We improve the sampling of the TM4 model, resulting in a priori NO2 profiles that are better mixed throughout the boundary layer. We evaluate the NO2 profiles simulated with the improved TM4 sampling as used in the AMF calculations and show that they are highly consistent with in situ NO2 measurements from aircraft during the INTEX-A and INTEX-B campaigns in 2004 and 2006. Our air mass factor calculations are further updated by the implementation of a high-resolution terrain height and a high-resolution surface albedo climatology based on OMI measurements. Together with a correction for across-track stripes, the overall impact of the improved terrain height and albedo descriptions is modest (

Statistically optimized inversion algorithm for enhanced retrieval of aerosol properties from spectral multi-angle polarimetric satellite observations

Abstract: . The proposed development is an attempt to enhance aerosol retrieval by emphasizing statistical optimization in inversion of advanced satellite observations. This optimization concept improves retrieval accuracy relying on the knowledge of measurement error distribution. Efficient application of such optimization requires pronounced data redundancy (excess of the measurements number over number of unknowns) that is not common in satellite observations. The POLDER imager on board the PARASOL micro-satellite registers spectral polarimetric characteristics of the reflected atmospheric radiation at up to 16 viewing directions over each observed pixel. The completeness of such observations is notably higher than for most currently operating passive satellite aerosol sensors. This provides an opportunity for profound utilization of statistical optimization principles in satellite data inversion. The proposed retrieval scheme is designed as statistically optimized multi-variable fitting of all available angular observations obtained by the POLDER sensor in the window spectral channels where absorption by gas is minimal. The total number of such observations by PARASOL always exceeds a hundred over each pixel and the statistical optimization concept promises to be efficient even if the algorithm retrieves several tens of aerosol parameters. Based on this idea, the proposed algorithm uses a large number of unknowns and is aimed at retrieval of extended set of parameters affecting measured radiation. The algorithm is designed to retrieve complete aerosol properties globally. Over land, the algorithm retrieves the parameters of underlying surface simultaneously with aerosol. In all situations, the approach is anticipated to achieve a robust retrieval of complete aerosol properties including information about aerosol particle sizes, shape, absorption and composition (refractive index). In order to achieve reliable retrieval from PARASOL observations even over very reflective desert surfaces, the algorithm was designed as simultaneous inversion of a large group of pixels within one or several images. Such multi-pixel retrieval regime takes advantage of known limitations on spatial and temporal variability in both aerosol and surface properties. Specifically the variations of the retrieved parameters horizontally from pixel-to-pixel and/or temporary from day-to-day are enforced to be smooth by additional a priori constraints. This concept is expected to provide satellite retrieval of higher consistency, because the retrieval over each single pixel will be benefiting from coincident aerosol information from neighboring pixels, as well, from the information about surface reflectance (over land) obtained in preceding and consequent observations over the same pixel. The paper provides in depth description of the proposed inversion concept, illustrates the algorithm performance by a series of numerical tests and presents the examples of preliminary retrieval results obtained from actual PARASOL observations. It should be noted that many aspects of the described algorithm design considerably benefited from experience accumulated in the preceding effort on developments of currently operating AERONET and PARASOL retrievals, as well as several core software components were inherited from those earlier algorithms.

Retrieval algorithm for CO 2 and CH 4 column abundances from short-wavelength infrared spectral observations by the Greenhouse gases observing satellite

Abstract: . The Greenhouse gases Observing SATellite (GOSAT) was launched on 23 January 2009 to monitor the global distributions of carbon dioxide and methane from space. It has operated continuously since then. Here, we describe a retrieval algorithm for column abundances of these gases from the short-wavelength infrared spectra obtained by the Thermal And Near infrared Sensor for carbon Observation-Fourier Transform Spectrometer (TANSO-FTS). The algorithm consists of three steps. First, cloud-free observational scenes are selected by several cloud-detection methods. Then, column abundances of carbon dioxide and methane are retrieved based on the optimal estimation method. Finally, the retrieval quality is examined to exclude low-quality and/or aerosol-contaminated results. Most of the retrieval random errors come from instrumental noise. The interferences due to auxiliary parameters retrieved simultaneously with gas abundances are small. The evaluated precisions of the retrieved column abundances for single observations are less than 1% in most cases. The interhemispherical differences and temporal variation patterns of the retrieved column abundances show features similar to those of an atmospheric transport model.

Characterization of aerosol photooxidation flow reactors: heterogeneous oxidation, secondary organic aerosol formation and cloud condensation nuclei activity measurements

Abstract: . Motivated by the need to develop instrumental techniques for characterizing organic aerosol aging, we report on the performance of the Toronto Photo-Oxidation Tube (TPOT) and Potential Aerosol Mass (PAM) flow tube reactors under a variety of experimental conditions. The PAM system was designed with lower surface-area-to-volume (SA/V) ratio to minimize wall effects; the TPOT reactor was designed to study heterogeneous aerosol chemistry where wall loss can be independently measured. The following studies were performed: (1) transmission efficiency measurements for CO2, SO2, and bis(2-ethylhexyl) sebacate (BES) particles, (2) H2SO4 yield measurements from the oxidation of SO2, (3) residence time distribution (RTD) measurements for CO2, SO2, and BES particles, (4) aerosol mass spectra, O/C and H/C ratios, and cloud condensation nuclei (CCN) activity measurements of BES particles exposed to OH radicals, and (5) aerosol mass spectra, O/C and H/C ratios, CCN activity, and yield measurements of secondary organic aerosol (SOA) generated from gas-phase OH oxidation of m-xylene and α-pinene. OH exposures ranged from (2.0 ± 1.0) × 1010 to (1.8 ± 0.3) × 1012 molec cm−3 s. Where applicable, data from the flow tube reactors are compared with published results from the Caltech smog chamber. The TPOT yielded narrower RTDs. However, its transmission efficiency for SO2 was lower than that for the PAM. Transmission efficiency for BES and H2SO4 particles was size-dependent and was similar for the two flow tube designs. Oxidized BES particles had similar O/C and H/C ratios and CCN activity at OH exposures greater than 1011 molec cm−3 s, but different CCN activity at lower OH exposures. The O/C ratio, H/C ratio, and yield of m-xylene and α-pinene SOA was strongly affected by reactor design and operating conditions, with wall interactions seemingly having the strongest influence on SOA yield. At comparable OH exposures, flow tube SOA was more oxidized than smog chamber SOA, possibly because of faster gas-phase oxidation relative to particle nucleation. SOA yields were lower in the TPOT than in the PAM, but CCN activity of flow-tube-generated SOA particles was similar. For comparable OH exposures, α-pinene SOA yields were similar in the PAM and Caltech chambers, but m-xylene SOA yields were much lower in the PAM compared to the Caltech chamber.

Remote sensing of aerosols by using polarized, directional and spectral measurements within the A-Train: the PARASOL mission

Abstract: . Instruments dedicated to aerosol monitoring are recently available and the POLDER (POLarization and Directionality of the Earth's Reflectances) instrument on board the PARASOL (Polarization & Anisotropy of Reflectances for Atmospheric Sciences coupled with Observations from a Lidar) mission is one of them. By measuring the spectral, angular and polarization properties of the radiance at the top of the atmosphere, in coordination with the other A-Train instruments, PARASOL provides the aerosol optical depths (AOD) as well as several optical and microphysical aerosol properties. The instrument, the inversion schemes and the list of aerosol parameters are described. Examples of retrieved aerosol parameters are provided as well as innovative approaches and further inversion techniques.

Characterization and intercomparison of aerosol absorption photometers: result of two intercomparison workshops

Abstract: . Absorption photometers for real time application have been available since the 1980s, but the use of filter-based instruments to derive information on aerosol properties (absorption coefficient and black carbon, BC) is still a matter of debate. Several workshops have been conducted to investigate the performance of individual instruments over the intervening years. Two workshops with large sets of aerosol absorption photometers were conducted in 2005 and 2007. The data from these instruments were corrected using existing methods before further analysis. The inter-comparison shows a large variation between the responses to absorbing aerosol particles for different types of instruments. The unit to unit variability between instruments can be up to 30% for Particle Soot Absorption Photometers (PSAPs) and Aethalometers. Multi Angle Absorption Photometers (MAAPs) showed a variability of less than 5%. Reasons for the high variability were identified to be variations in sample flow and spot size. It was observed that different flow rates influence system performance with respect to response to absorption and instrumental noise. Measurements with non absorbing particles showed that the current corrections of a cross sensitivity to particle scattering are not sufficient. Remaining cross sensitivities were found to be a function of the total particle load on the filter. The large variation between the response to absorbing aerosol particles for different types of instruments indicates that current correction functions for absorption photometers are not adequate.

An over-land aerosol optical depth data set for data assimilation by filtering, correction, and aggregation of MODIS Collection 5 optical depth retrievals

Abstract: . MODIS Collection 5 retrieved aerosol optical depth (AOD) over land (MOD04/MYD04) was evaluated using 4 years of matching AERONET observations, to assess its suitability for aerosol data assimilation in numerical weather prediction models. Examination of errors revealed important sources of variation in random errors (e.g., atmospheric path length, scattering angle "hot spot"), and systematic biases (e.g., snow and cloud contamination, surface albedo bias). A set of quality assurance (QA) filters was developed to avoid conditions with potential for significant AOD error. An empirical correction for surface boundary condition using the MODIS 16-day albedo product captured 25% of the variability in the site mean bias at low AOD. A correction for regional microphysical bias using the AERONET fine/coarse partitioning information increased the global correlation between MODIS and AERONET from r2 = 0.62–0.65 to r2 = 0.71–0.73. Application of these filters and corrections improved the global fraction of MODIS AOD within (0.05 ± 20%) of AERONET to 77%, up from 67% using only built-in MODIS QA. The compliant fraction in individual regions was improved by as much as 20% (South America). An aggregated Level 3 product for use in a data assimilation system is described, along with a prognostic error model to estimate uncertainties on a per-observation basis. The new filtered and corrected Level 3 product has improved performance over built-in MODIS QA with less than a 15% reduction in overall data available for data assimilation.

Exploring earth's atmosphere with radio occultation: contributions to weather, climate and space weather

Abstract: . The launch of the proof-of-concept mission GPS/MET (Global Positioning System/Meteorology) in 1995 began a revolution in profiling Earth's atmosphere through radio occultation (RO). GPS/MET; subsequent single-satellite missions CHAMP (CHAllenging Minisatellite Payload), SAC-C (Satellite de Aplicaciones Cientificas-C), GRACE (Gravity Recovery and Climate Experiment), METOP-A, and TerraSAR-X (Beyerle et al., 2010); and the six-satellite constellation, FORMOSAT-3/COSMIC (Formosa Satellite mission {#}3/Constellation Observing System for Meteorology, Ionosphere, and Climate) have proven the theoretical capabilities of RO to provide accurate and precise profiles of electron density in the ionosphere and refractivity, containing information on temperature and water vapor, in the stratosphere and troposphere. This paper summarizes results from these RO missions and the applications of RO observations to atmospheric research and operational weather analysis and prediction.

Preliminary validation of column-averaged volume mixing ratios of carbon dioxide and methane retrieved from GOSAT short-wavelength infrared spectra

Abstract: . Column-averaged volume mixing ratios of carbon dioxide and methane retrieved from the Greenhouse gases Observing SATellite (GOSAT) Short-Wavelength InfraRed observation (GOSAT SWIR XCO2 and XCH4) were compared with the reference calibrated data obtained by ground-based high-resolution Fourier Transform Spectrometers (g-b FTSs) participating in the Total Carbon Column Observing Network (TCCON). Preliminary results are as follows: the GOSAT SWIR XCO2 and XCH4 (Version 01.xx) are biased low by 8.85 ± 4.75 ppm (2.3 ± 1.2 %) and 20.4 ± 18.9 ppb (1.2 ± 1.1 %), respectively. The standard deviation of the GOSAT SWIR XCO2 and XCH4 is about 1 % (1 σ) after correcting the negative biases of XCO2 and XCH4 by 8.85 ppm and 20.4 ppb, respectively. The latitudinal distributions of zonal means of the GOSAT SWIR XCO2 and XCH4 show similar features to those of the g-b FTS data except for the negative biases in the GOSAT data.

A field-deployable, chemical ionization time-of-flight mass spectrometer

Abstract: . We constructed a new chemical ionization time-of-flight mass spectrometer (CI-TOFMS) that measures atmospheric trace gases in real time with high sensitivity. We apply the technique to the measurement of formic acid via negative-ion proton transfer, using acetate as the reagent ion. A novel high pressure interface, incorporating two RF-only quadrupoles is used to efficiently focus ions through four stages of differential pumping before analysis with a compact TOFMS. The high ion-duty cycle (>20 %) of the TOFMS combined with the efficient production and transmission of ions in the high pressure interface results in a highly sensitive (>300 ions s−1 pptv−1 formic acid) instrument capable of measuring and saving complete mass spectra at rates faster than 10 Hz. We demonstrate the efficient transfer and detection of both bare ions and ion-molecule clusters, and characterize the instrument during field measurements aboard the R/V Atlantis as part of the CalNex campaign during the spring of 2010. The in-field short-term precision is better than 5 % at 1 pptv (pL/L), for 1-s averages. The detection limit (3 σ, 1-s averages) of the current version of the CI-TOFMS, as applied to the in situ detection of formic acid, is limited by the magnitude and variability in the background determination and was determined to be 4 pptv. Application of the CI-TOFMS to the detection of other inorganic and organic acids, as well as the use of different reagent ion molecules (e.g. I−, CF3O−, CO3−) is promising, as we have demonstrated efficient transmission and detection of both bare ions and their associated ion-molecule clusters.

A 2.5 year's source apportionment study of black carbon from wood burning and fossil fuel combustion at urban and rural sites in Switzerland

Abstract: . The contributions of fossil fuel (FF) and wood burning (WB) emissions to black carbon (BC) have been investigated in the recent past by analysis of multi-wavelength aethalometer data. This approach utilizes the stronger light absorption of WB aerosols in the near ultraviolet compared to the light absorption of aerosols from FF combustion. Here we present 2.5 years of seven-wavelength aethalometer data from one urban and two rural background sites in Switzerland measured from 2008–2010. The contribution of WB and FF to BC was directly determined from the aerosol absorption coefficients of FF and WB aerosols which were calculated by using confirmed Angstrom exponents and aerosol light absorption cross-sections that were determined for all sites. Reasonable separation of total BC into contributions from FF and WB was achieved for all sites and seasons. The obtained WB contributions to BC are well correlated with measured concentrations of levoglucosan and potassium while FF contributions to BC correlate nicely with NOx. These findings support our approach and show that the applied source apportionment of BC is well applicable for long-term data sets. During winter, we found that BC from WB contributes on average 24–33 % to total BC at the considered measurement sites. This is a noticeable high fraction as the contribution of wood burning to the total final energy consumption is in Switzerland less than 4 %.

Design and performance of a three-wavelength LED-based total scatter and backscatter integrating nephelometer

Abstract: . Integrating nephelometers are instruments that directly measure a value close to the light scattering coefficient of airborne particles. Different models of nephelometers have been used for decades for monitoring and research applications. Now, a series of nephelometers (Ecotech models M9003, Aurora 1000 and Aurora 3000) with newly designed light sources based on light emitting diodes are available. This article reports on the design of these integrating nephelometers and a comparison of the Aurora 3000 to another commercial instrument (TSI model 3563) that uses an incandescent lamp. Both instruments are three-wavelength, total and backscatter integrating nephelometers. We present a characterization of the new light source design of the Aurora 3000 and provide parameterizations for its angular sensitivity functions. These parameterizations facilitate to correct for measurement artefacts using Mie-theory. Furthermore, correction factors are provided as a function of the Angstrom exponent. Comparison measurements against the TSI 3563 with laboratory generated white particles and ambient air are also shown and discussed. Both instruments agree well within the calibration uncertainties and detection limit for total scattering with differences less than 5 %. Differences for backscattering are higher by up to 11 %. Highest differences were found for the longest wavelengths, where the signal to noise ratio is lowest. Differences at the blue and green wavelengths are less than 4 % and 3 %, respectively, for both total and backscattering.

Detection of HO 2 by laser-induced fluorescence: calibration and interferences from RO 2 radicals

Abstract: . HO2 concentration measurements are widely accomplished by chemical conversion of HO2 to OH including reaction with NO and subsequent detection of OH by laser-induced fluorescence. RO2 radicals can be converted to OH via a similar radical reaction sequence including reaction with NO, so that they are potential interferences for HO2 measurements. Here, the conversion efficiency of various RO2 species to HO2 is investigated. Experiments were conducted with a radical source that produces OH and HO2 by water photolysis at 185 nm, which is frequently used for calibration of LIF instruments. The ratio of HO2 and the sum of OH and HO2 concentrations provided by the radical source was investigated and was found to be 0.50 ± 0.02. RO2 radicals are produced by the reaction of various organic compounds with OH in the radical source. Interferences via chemical conversion from RO2 radicals produced by the reaction of OH with methane and ethane (H-atom abstraction) are negligible consistent with measurements in the past. However, RO2 radicals from OH plus alkene- and aromatic-precursors including isoprene (mainly OH-addition) are detected with a relative sensitivity larger than 80 % with respect to that for HO2 for the configuration of the instrument with which it was operated during field campaigns. Also RO2 from OH plus methyl vinyl ketone and methacrolein exhibit a relative detection sensitivity of 60 %. Thus, previous measurements of HO2 radical concentrations with this instrument were biased in the presence of high RO2 radical concentrations from isoprene, alkenes or aromatics, but were not affected by interferences in remote clean environment with no significant emissions of biogenic VOCs, when the OH reactivity was dominated by small alkanes. By reducing the NO concentration and/or the transport time between NO addition and OH detection, interference from these RO2 species are suppressed to values below 20 % relative to the HO2 detection sensitivity. The HO2 conversion efficiency is also smaller by a factor of four, but this is still sufficient for atmospheric HO2 concentration measurements for a wide range of conditions.

Assessment of BSRN radiation records for the computation of monthly means

Abstract: . The integrity of the Baseline Surface Radiation Network (BSRN) radiation monthly averages are assessed by investigating the impact on monthly means due to the frequency of data gaps caused by missing or discarded high time resolution data. The monthly statistics, especially means, are considered to be important and useful values for climate research, model performance evaluations and for assessing the quality of satellite (time- and space-averaged) data products. The study investigates the spread in different algorithms that have been applied for the computation of monthly means from 1-min values. The paper reveals that the computation of monthly means from 1-min observations distinctly depends on the method utilized to account for the missing data. The intra-method difference generally increases with an increasing fraction of missing data. We found that a substantial fraction of the radiation fluxes observed at BSRN sites is either missing or flagged as questionable. The percentage of missing data is 4.4%, 13.0%, and 6.5% for global radiation, direct shortwave radiation, and downwelling longwave radiation, respectively. Most flagged data in the shortwave are due to nighttime instrumental noise and can reasonably be set to zero after correcting for thermal offsets in the daytime data. The study demonstrates that the handling of flagged data clearly impacts on monthly mean estimates obtained with different methods. We showed that the spread of monthly shortwave fluxes is generally clearly higher than for downwelling longwave radiation. Overall, BSRN observations provide sufficient accuracy and completeness for reliable estimates of monthly mean values. However, the value of future data could be further increased by reducing the frequency of data gaps and the number of outliers. It is shown that two independent methods for accounting for the diurnal and seasonal variations in the missing data permit consistent monthly means to within less than 1 W m−2 in most cases. The authors suggest using a standardized method for the computation of monthly means which addresses diurnal variations in the missing data in order to avoid a mismatch of future published monthly mean radiation fluxes from BSRN. The application of robust statistics would probably lead to less biased results for data records with frequent gaps and/or flagged data and outliers. The currently applied empirical methods should, therefore, be completed by the development of robust methods.

Maritime aerosol network as a component of AERONET - first results and comparison with global aerosol models and satellite retrievals

Abstract: . The Maritime Aerosol Network (MAN) has been collecting data over the oceans since November 2006. Over 80 cruises were completed through early 2010 with deployments continuing. Measurement areas included various parts of the Atlantic Ocean, the Northern and Southern Pacific Ocean, the South Indian Ocean, the Southern Ocean, the Arctic Ocean and inland seas. MAN deploys Microtops hand-held sunphotometers and utilizes a calibration procedure and data processing traceable to AERONET. Data collection included areas that previously had no aerosol optical depth (AOD) coverage at all, particularly vast areas of the Southern Ocean. The MAN data archive provides a valuable resource for aerosol studies in maritime environments. In the current paper we present results of AOD measurements over the oceans, and make a comparison with satellite AOD retrievals and model simulations.

Effective density of Aquadag and fullerene soot black carbon reference materials used for SP2 calibration

Abstract: . The mass and effective density of black carbon (BC) particles generated from aqueous suspensions of Aquadag and fullerene soot was measured and parametrized as a function of their mobility diameter. The measurements were made by two independent research groups by operating a differential mobility analyser (DMA) in series with an aerosol particle mass analyser (APM) or a Couette centrifugal particle mass analyser (CPMA). Consistent and reproducible results were found in this study for different production lots of Aquadag, indicating that the effective density of these particles is a stable quantity and largely unaffected by differences in aerosol generation procedures and suspension treatments. The effective density of fullerene soot particles from one production lot was also found to be stable and independent of suspension treatments. Some differences to previous literature data were observed for both Aquadag and fullerene soot at larger particle diameters. Knowledge of the exact relationship between mobility diameter and particle mass is of great importance, as DMAs are commonly used to size-select particles from BC reference materials for calibration of single particle soot photometers (SP2), which quantitatively detect the BC mass in single particles.

Inversion of tropospheric profiles of aerosol extinction and HCHO and NO 2 mixing ratios from MAX-DOAS observations in Milano during the summer of 2003 and comparison with independent data sets

Abstract: . We present aerosol and trace gas profiles derived from MAX-DOAS observations. Our inversion scheme is based on simple profile parameterisations used as input for an atmospheric radiative transfer model (forward model). From a least squares fit of the forward model to the MAX-DOAS measurements, two profile parameters are retrieved including integrated quantities (aerosol optical depth or trace gas vertical column density), and parameters describing the height and shape of the respective profiles. From these results, the aerosol extinction and trace gas mixing ratios can also be calculated. We apply the profile inversion to MAX-DOAS observations during a measurement campaign in Milano, Italy, September 2003, which allowed simultaneous observations from three telescopes (directed to north, west, south). Profile inversions for aerosols and trace gases were possible on 23 days. Especially in the middle of the campaign (17–20 September 2003), enhanced values of aerosol optical depth and NO2 and HCHO mixing ratios were found. The retrieved layer heights were typically similar for HCHO and aerosols. For NO2, lower layer heights were found, which increased during the day. The MAX-DOAS inversion results are compared to independent measurements: (1) aerosol optical depth measured at an AERONET station at Ispra; (2) near-surface NO2 and HCHO (formaldehyde) mixing ratios measured by long path DOAS and Hantzsch instruments at Bresso; (3) vertical profiles of HCHO and aerosols measured by an ultra light aircraft. Depending on the viewing direction, the aerosol optical depths from MAX-DOAS are either smaller or larger than those from AERONET observations. Similar comparison results are found for the MAX-DOAS NO2 mixing ratios versus long path DOAS measurements. In contrast, the MAX-DOAS HCHO mixing ratios are generally higher than those from long path DOAS or Hantzsch instruments. The comparison of the HCHO and aerosol profiles from the aircraft showed reasonable agreement with the respective MAX-DOAS layer heights. From the comparison of the results for the different telescopes, it was possible to investigate the internal consistency of the MAX-DOAS observations. As part of our study, a cloud classification algorithm was developed (based on the MAX-DOAS zenith viewing directions), and the effects of clouds on the profile inversion were investigated. Different effects of clouds on aerosols and trace gas retrievals were found: while the aerosol optical depth is systematically underestimated and the HCHO mixing ratio is systematically overestimated under cloudy conditions, the NO2 mixing ratios are only slightly affected. These findings are in basic agreement with radiative transfer simulations.

Eight-component retrievals from ground-based MAX-DOAS observations

Abstract: . We attempt for the first time to retrieve lower-tropospheric vertical profile information for 8 quantities from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. The components retrieved are the aerosol extinction coefficients at two wavelengths, 357 and 476 nm, and NO2, HCHO, CHOCHO, H2O, SO2, and O3 volume mixing ratios. A Japanese MAX-DOAS profile retrieval algorithm, version 1 (JM1), is applied to observations performed at Cabauw, the Netherlands (51.97° N, 4.93° E), in June–July 2009 during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI). Of the retrieved profiles, we focus here on the lowest-layer data (mean values at altitudes 0–1 km), where the sensitivity is usually highest owing to the longest light path. In support of the capability of the multi-component retrievals, we find reasonable overall agreement with independent data sets, including a regional chemical transport model (CHIMERE) and in situ observations performed near the surface (2–3 m) and at the 200-m height level of the tall tower in Cabauw. Plumes of enhanced HCHO and SO2 were likely affected by biogenic and ship emissions, respectively, and an improvement in their emission strengths is suggested for better agreement between CHIMERE simulations and MAX-DOAS observations. Analysis of air mass factors indicates that the horizontal spatial representativeness of MAX-DOAS observations is about 3–15 km (depending mainly on aerosol extinction), comparable to or better than the spatial resolution of current UV-visible satellite observations and model calculations. These demonstrate that MAX-DOAS provides multi-component data useful for the evaluation of satellite observations and model calculations and can play an important role in bridging different data sets having different spatial resolutions.

An improved NO 2 retrieval for the GOME-2 satellite instrument

Abstract: . Satellite observations of nitrogen dioxide (NO2) provide valuable information on both stratospheric and tropospheric composition. Nadir measurements from GOME, SCIAMACHY, OMI, and GOME-2 have been used in many studies on tropospheric NO2 burdens, the importance of different NOx emissions sources and their change over time. The observations made by the three GOME-2 instruments will extend the existing data set by more than a decade, and a high quality of the data as well as their good consistency with existing time series is of particular importance. In this paper, an improved GOME-2 NO2 retrieval is described which reduces the scatter of the individual NO2 columns globally but in particular in the region of the Southern Atlantic Anomaly. This is achieved by using a larger fitting window including more spectral points, and by applying a two step spike removal algorithm in the fit. The new GOME-2 data set is shown to have good consistency with SCIAMACHY NO2 columns. Remaining small differences are shown to be linked to changes in the daily solar irradiance measurements used in both GOME-2 and SCIAMACHY retrievals. In the large retrieval window, a not previously identified spectral signature was found which is linked to deserts and other regions with bare soil. Inclusion of this empirically derived pseudo cross-section significantly improves the retrievals and potentially provides information on surface properties and desert aerosols. Using the new GOME-2 NO2 data set, a long-term average of tropospheric columns was computed and high-pass filtered. The resulting map shows evidence for pollution from several additional shipping lanes, not previously identified in satellite observations. This illustrates the excellent signal to noise ratio achievable with the improved GOME-2 retrievals.

Intercomparison of column aerosol optical depths from CALIPSO and MODIS-Aqua

Abstract: . The Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) is carried on the CALIPSO satellite and has acquired global aerosol profiles since June 2006. CALIPSO is flown in formation with the Aqua satellite as part of the A-train satellite constellation, so that a large number of coincident aerosol observations are available from CALIOP and the MODIS-Aqua instrument. This study compares column aerosol optical depth at 0.532 μm derived from CALIOP aerosol profiles with MODIS-Aqua 0.55 μm aerosol optical depth over the period June 2006 through August 2008. The study is based on the CALIOP Version 2 Aerosol Layer Product and MODIS Collection 5. While CALIOP is first and foremost a profiling instrument, this comparison of column aerosol optical depth provides insight into quality of CALIOP aerosol data. It is found that daytime aerosol optical depth from the CALIOP Version 2 product has only a small global mean bias relative to MODIS Collection 5. Regional biases, of both signs, are larger and biases are seen to vary somewhat with season. Good agreement between the two sensors in ocean regions with low cloudiness suggests that the selection of lidar ratios used in the CALIOP aerosol retrieval is sufficient to provide a regional mean AOD consistent with that retrieved from MODIS. Although differences over land are observed to be larger than over ocean, the bias between CALIOP and MODIS AOD on a regional-seasonal basis is found to be roughly within the envelope of the MODIS expected uncertainty over land and ocean. This work forms a basis for further comparisons using the recently released CALIOP Version 3 data.

Design of a new multi-phase experimental simulation chamber for atmospheric photosmog, aerosol and cloud chemistry research

Abstract: . A new simulation chamber has been built at the Interuniversitary Laboratory of Atmospheric Systems (LISA). The CESAM chamber (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber) is designed to allow research in multiphase atmospheric (photo-) chemistry which involves both gas phase and condensed phase processes including aerosol and cloud chemistry. CESAM has the potential to carry out variable temperature and pressure experiments under a very realistic artificial solar irradiation. It consists of a 4.2 m3 stainless steel vessel equipped with three high pressure xenon arc lamps which provides a controlled and steady environment. Initial characterization results, all carried out at 290–297 K under dry conditions, concerning lighting homogeneity, mixing efficiency, ozone lifetime, radical sources, NOy wall reactivity, particle loss rates, background PM, aerosol formation and cloud generation are given. Photolysis frequencies of NO2 and O3 related to chamber radiation system were found equal to (4.2 × 10−3 s−1) for JNO2 and (1.4 × 10−5 s−1) for JO1D which is comparable to the solar radiation in the boundary layer. An auxiliary mechanism describing NOy wall reactions has been developed. Its inclusion in the Master Chemical Mechanism allowed us to adequately model the results of experiments on the photo-oxidation of propene-NOx-Air mixtures. Aerosol yields for the α-pinene + O3 system chosen as a reference were determined and found in good agreement with previous studies. Particle lifetime in the chamber ranges from 10 h to 4 days depending on particle size distribution which indicates that the chamber can provide high quality data on aerosol aging processes and their effects. Being evacuable, it is possible to generate in this new chamber clouds by fast expansion or saturation with or without the presence of pre-existing particles, which will provide a multiphase environment for aerosol-droplet interaction.

Operational total and tropospheric NO 2 column retrieval for GOME-2

Abstract: . This paper presents the algorithm for the operational near real time retrieval of total and tropospheric NO2 columns from the Global Ozone Monitoring Experiment (GOME-2). The retrieval is performed with the GOME Data Processor (GDP) version 4.4 as used by the EUMETSAT Satellite Application Facility on Ozone and Atmospheric Chemistry Monitoring (O3M-SAF). The differential optical absorption spectroscopy (DOAS) method is used to determine NO2 slant columns from GOME-2 (ir)radiance data in the 425–450 nm range. Initial total NO2 columns are computed using stratospheric air mass factors, and GOME-2 derived cloud properties are used to calculate the air mass factors for scenarios in the presence of clouds. To obtain the stratospheric NO2 component, a spatial filtering approach is used, which is shown to be an improvement on the Pacific reference sector method. Tropospheric air mass factors are computed using monthly averaged NO2 profiles from the MOZART-2 chemistry transport model. An error analysis shows that the random error in the GOME-2 NO2 slant columns is approximately 0.45 × 1015 molec cm−2. As a result of the improved quartz diffuser plate used in the GOME-2 instrument, the systematic error in the slant columns is strongly reduced compared to GOME/ERS-2. The estimated uncertainty in the GOME-2 tropospheric NO2 column for polluted conditions ranges from 40 to 80 %. An end-to-end ground-based validation approach for the GOME-2 NO2 columns is illustrated based on multi-axis MAXDOAS measurements at the Observatoire de Haute Provence (OHP). The GOME-2 stratospheric NO2 columns are found to be in good overall agreement with coincident ground-based measurements at OHP. A time series of the MAXDOAS and the GOME-2 tropospheric NO2 columns shows that pollution episodes at OHP are well captured by GOME-2. Monthly mean tropospheric columns are in very good agreement, with differences generally within 0.5 × 1015 molec cm−2.

Effects of ice particles shattering on the 2D-S probe

Abstract: . Recently, considerable attention has been focused on the issue of large ice particles shattering on the inlets and tips of cloud particle probes, which produces copious ice particles that can be mistakenly measured as real ice particles. Currently two approaches are being used to mitigate the problem: (1) Based on recent high-speed video in icing tunnels, probe tips have been designed that reduce the number of shattered particles that reach the probe sample volume, and (2) Post processing techniques such as image processing and using the arrival time of each individual particle. This paper focuses on exposing suspected errors in measurements of ice particle size distributions due to shattering, and evaluation of the two techniques used to reduce the errors. Data from 2D-S probes constitute the primary source of the investigation, however, when available comparisons with 2D-C and CIP measurements are also included. Korolev et al. (2010b) report results from a recent field campaign (AIIE) and conclude that modified probe tips are more effective than an arrival time algorithm when applied to 2D-C and CIP measurements. Analysis of 2D-S data from the AIIE and SPARTICUS field campaigns shows that modified probe tips significantly reduce the number of shattered particles, but that a particle arrival time algorithm is more effective than the probe tips designed to reduce shattering. A large dataset of 2D-S measurements with and without modified probe tips was not available from the AIEE and SPARTICUS field campaigns. Instead, measurements in regions with large ice particles are presented to show that shattering on the 2D-S with modified probe tips produces large quantities of small particles that are likely produced by shattering. Also, when an arrival time algorithm is applied to the 2D-S data, the results show that it is more effective than the modified probe tips in reducing the number of small (shattered) particles. Recent results from SPARTICUS and MACPEX show that 2D-S ice particle concentration measurements are more consistent with physical arguments and numerical simulations than measurements with older cloud probes from previous field campaigns. The analysis techniques in this paper can also be used to estimate an upper bound for the effects of shattering. For example, the additional spurious concentration of small ice particles can be measured as a function of the mass concentration of large ice particles. The analysis provides estimates of upper bounds on the concentration of natural ice, and on the remaining concentration of shattered ice particles after application of the post-processing techniques. However, a comprehensive investigation of shattering is required to quantify effects that arise from the multiple degrees of freedom associated with this process, including different cloud environments, probe geometries, airspeed, angle of attack, particle size and type.

Diode laser-based cavity ring-down instrument for NO 3 , N 2 O 5 , NO, NO 2 and O 3 from aircraft

Abstract: . This article presents a diode laser-based, cavity ring-down spectrometer for simultaneous in situ measurements of four nitrogen oxide species, NO3, N2O5, NO, NO2, as well as O3, designed for deployment on aircraft. The instrument measures NO3 and NO2 by optical extinction at 662 nm and 405 nm, respectively; N2O5 is measured by thermal conversion to NO3, while NO and O3 are measured by chemical conversion to NO2. The instrument has several advantages over previous instruments developed by our group for measurement of NO2, NO3 and N2O5 alone, based on a pulsed Nd:YAG and dye laser. First, the use of continuous wave diode lasers reduces the requirements for power and weight and eliminates hazardous materials. Second, detection of NO2 at 405 nm is more sensitive than our previously reported 532 nm instrument, and does not have a measurable interference from O3. Third, the instrument includes chemical conversion of NO and O3 to NO2 to provide measurements of total NOx (= NO + NO2) and Ox (= NO2 + O3) on two separate channels; mixing ratios of NO and O3 are determined by subtraction of NO2. Finally, all five species are calibrated against a single standard based on 254 nm O3 absorption to provide high accuracy. Disadvantages include an increased sensitivity to water vapor on the 662 nm NO3 and N2O5 channels and a modest reduction in sensitivity for these species compared to the pulsed laser instrument. The in-flight detection limit for both NO3 and N2O5 is 3 pptv (2 σ, 1 s) and for NO, NO2 and O3 is 140, 90, and 120 pptv (2 σ, 1 s) respectively. Demonstrated performance of the instrument in a laboratory/ground based environment is better by approximately a factor of 2–3. The NO and NO2 measurements are less precise than research-grade chemiluminescence instruments. However, the combination of these five species in a single instrument, calibrated to a single analytical standard, provides a complete and accurate picture of nighttime nitrogen oxide chemistry. The instrument performance is demonstrated using data acquired during a recent field campaign in California.

Meteorological profiling of the lower troposphere using the research UAV "M 2 AV Carolo"

Abstract: . Vertical profiles of temperature, humidity and wind up to a height of 1500 m a.g.l. (above ground level) were measured with the automatically operating small unmanned research aircraft M2AV (Meteorological Mini Aerial Vehicle) during the LITFASS-2009 LI ndenberg- T o- F alkenberg: A ircraft, S cintillometer and large-eddy S imulation) experiment. The campaign took place in July 2009 over the heterogeneous landscape around the Meteorological Observatory Lindenberg – Richard-Asmann-Observatory in the eastern part of Germany. Due to a high vertical resolution of about 10 cm the M2AV data show details of the turbulent structure of the atmospheric boundary layer (ABL). One profile took about 10–15 min allowing for a continuous monitoring of certain phases of ABL development by successive ascents and descents during one flight (50–60 min duration). Two case studies of measurements performed during the morning and evening ABL transition periods are discussed in detail. Comparison of the aircraft-based temperature, humidity and wind profiles with tower, sodar/RASS, wind profiler/RASS, radiosoundings and microwave radiometer profiler measurements show good agreement taking into account the different sampling strategies of these measurement systems.

Nitrous oxide emissions from managed grassland: a comparison of eddy covariance and static chamber measurements

Abstract: . Managed grasslands are known to be an important source of N2O with estimated global losses of 2.5 Tg N2O-N yr−1. Chambers are to date the most widely used method to measure N2O fluxes, but also micrometeorological methods are successfully applied. In this paper we present a comparison of N2O fluxes measured by non-steady state chambers and eddy covariance (EC) (using an ultra-sonic anemometer coupled with a tunable diode laser) from an intensively grazed and fertilised grassland site in South East Scotland. The measurements were taken after fertilisation events in 2003, 2007 and 2008. In four out of six comparison periods, a short-lived increase of N2O emissions was observed after mineral N application, returning to background level within 2–6 days. Highest fluxes were measured by both methods in July 2007 with maximum values of 1438 ng N2O-N m−2 s−1 (EC) and 651 ng N2O-N m−2 s−1 (chamber method). Negative fluxes above the detection limit were observed in all comparison periods by EC, while with chambers, the recorded negative fluxes were always below detection limit. Median and average fluxes over each period were always positive. Over all 6 comparison periods, 69% of N2O fluxes measured by EC at the time of chamber closure were within the range of the chamber measurements. N2O fluxes measured by EC during the time of chamber closure were not consistently smaller, neither larger, compared to those measured by chambers: this reflects the fact that the different techniques integrate fluxes over different spatial and temporal scales. Large fluxes measured by chambers may be representing local hotspots providing a small contribution to the flux measured by the EC method which integrates over a larger area. The spatial variability from chamber measurements was high, as shown by a coefficient of variation of up to 139%. No diurnal pattern of N2O fluxes was observed, possibly due to the small diurnal variations of soil temperature. The calculation of cumulative fluxes using different integration methods showed EC data provide generally lower estimates of N2O emissions than chambers.

Inter-comparison of lidar and ceilometer retrievals for aerosol and Planetary Boundary Layer profiling over Athens, Greece

Abstract: . This study presents an inter-comparison of two active remote sensors (lidar and ceilometer) to determine the mixing layer height and structure of the Planetary Boundary Layer (PBL) and to retrieve tropospheric aerosol vertical profiles over Athens, Greece. This inter-comparison was performed under various strongly different aerosol loads/types (urban air pollution, biomass burning and Saharan dust event), implementing two different lidar systems (one portable Raymetrics S.A. lidar system running at 355 nm and one multi-wavelength Raman lidar system running at 355 nm, 532 nm and 1064 nm) and one CL31 Vaisala S.A. ceilometer (running at 910 nm). Spectral conversions of the ceilometer's data were performed using the Angstrom exponent estimated by ultraviolet multi-filter radiometer (UV-MFR) measurements. The inter-comparison was based on two parameters: the mixing layer height determined by the presence of the suspended aerosols and the attenuated backscatter coefficient. Additionally, radiosonde data were used to derive the PBL height. In general, a good agreement was found between the ceilometer and the lidar techniques in both inter-compared parameters in the height range from 500 m to 5000 m, while the limitations of each instrument are also examined.

Sensitivity studies for a space-based methane lidar mission

Abstract: . Methane is the third most important greenhouse gas in the atmosphere after water vapour and carbon dioxide. A major handicap to quantify the emissions at the Earth's surface in order to better understand biosphere-atmosphere exchange processes and potential climate feedbacks is the lack of accurate and global observations of methane. Space-based integrated path differential absorption (IPDA) lidar has potential to fill this gap, and a Methane Remote Lidar Mission (MERLIN) on a small satellite in polar orbit was proposed by DLR and CNES in the frame of a German-French climate monitoring initiative. System simulations are used to identify key performance parameters and to find an advantageous instrument configuration, given the environmental, technological, and budget constraints. The sensitivity studies use representative averages of the atmospheric and surface state to estimate the measurement precision, i.e. the random uncertainty due to instrument noise. Key performance parameters for MERLIN are average laser power, telescope size, orbit height, surface reflectance, and detector noise. A modest-size lidar instrument with 0.45 W average laser power and 0.55 m telescope diameter on a 506 km orbit could provide 50-km averaged methane column measurement along the sub-satellite track with a precision of about 1% over vegetation. The use of a methane absorption trough at 1.65 μm improves the near-surface measurement sensitivity and vastly relaxes the wavelength stability requirement that was identified as one of the major technological risks in the pre-phase A studies for A-SCOPE, a space-based IPDA lidar for carbon dioxide at the European Space Agency. Minimal humidity and temperature sensitivity at this wavelength position will enable accurate measurements in tropical wetlands, key regions with largely uncertain methane emissions. In contrast to actual passive remote sensors, measurements in Polar Regions will be possible and biases due to aerosol layers and thin ice clouds will be minimised.

Greenhouse gas observations from Cabauw Tall Tower (1992–2010)

Abstract: . Since 1992 semi-continuous in-situ observations of greenhouse gas concentrations have been performed at the tall tower of Cabauw (4.927° E, 51.971° N, −0.7 m a.s.l.). Through 1992 up to now, the measurement system has been gradually extended and improved in precision, starting with CO2 and CH4 concentrations from 200 m a.g.l. in 1992 to vertical gradients at 4 levels of the gases CO2, CH4, SF6, N2O, H2, CO and gradients at 2 levels for 222Rn. In this paper the measurement systems and measurement results are described for the main greenhouse gases and CO, for the whole period. The automatic measurement system now provides half-hourly concentration gradients with a precision better than or close to the WMO recommendations. The observations at Cabauw show a complex pattern caused by the influence of sources and sinks from a large area around the tower with significant contributions of sources and sinks at distances up to 500–700 km. The concentration footprint area of Cabauw is one the most intensive and complex source areas of greenhouse gases in the world. Despite this, annual mean trends for the most important greenhouse gases, compatible with the values derived using the global network, can be reproduced from the measured concentrations at Cabauw over the entire measurement period, with a measured increase in the period 2000–2009 for CO2 of 1.90 ± 0.1 ppm yr−1, for CH4 of 4.4 ± 0.6 ppb yr−1, for N2O of 0.86 ± 0.04 ppb yr−1, and for SF6 of 0.27 ± 0.01 ppt yr−1; for CO no significant trend could be detected. The influences of strong local sources and sinks are reflected in the amplitude of the mean seasonal cycles observed at Cabauw, that are larger than the mean Northern Hemisphere average; Cabauw mean seasonal amplitude for CO2 is 25–30 ppm (higher value for lower sampling levels). The observed CH4 seasonal amplitude is 50–110 ppb. All gases except N2O show highest concentrations in winter and lower concentrations in summer, N2O observations show two additional concentration maxima in early summer and in autumn. Seasonal cycles of the day-time mean concentrations show that surface concentrations or high elevation concentrations alone do not give a representative value for the boundary layer concentrations, especially in winter time, but that the vertical profile data along the mast can be used to construct a useful boundary layer mean value. The variability at Cabauw in the atmospheric concentrations of CO2 on time scales of minutes to hours is several ppm and is much larger than the precision of the measurements (0.1 ppm). The diurnal and synoptical variability of the concentrations at Cabauw carry information on the sources and sinks in the footprint area of the mast, that will be useful in combination with inverse atmospheric transport model to verify emission estimates and improve ecosystem models. For this purpose a network of tall tower stations like Cabauw forms a very useful addition to the existing global observing network for greenhouse gases.

A critical examination of spatial biases between MODIS and MISR aerosol products – application for potential AERONET deployment

Abstract: . AErosol RObotic NETwork (AERONET) data are the primary benchmark for evaluating satellite-retrieved aerosol properties. However, despite its extensive coverage, the representativeness of the AERONET data is rarely discussed. Indeed, many studies have shown that satellite retrieval biases have a significant degree of spatial correlation that may be problematic for higher-level processes or inverse-emissions-modeling studies. To consider these issues and evaluate relative performance in regions of few surface observations, cross-comparisons between the Aerosol Optical Depth (AOD) products of operational MODIS Collection 5.1 Dark Target (DT) and operational MODIS Collection 5.1 Deep Blue (DB) with MISR version 22 were conducted. Through such comparisons, we can observe coherent spatial features of the AOD bias while sidestepping the full analysis required for determining when or where either retrieval is more correct. We identify regions where MODIS to MISR AOD ratios were found to be above 1.4 and below 0.7. Regions where lower boundary condition uncertainty is likely to be a dominant factor include portions of Western North America, the Andes mountains, Saharan Africa, the Arabian Peninsula, and Central Asia. Similarly, microphysical biases may be an issue in South America, and specific parts of Southern Africa, India Asia, East Asia, and Indonesia. These results help identify high-priority locations for possible future deployments of both in situ and ground based remote sensing measurements. The Supplement includes a kml file.