Showing papers in "Atmospheric Measurement Techniques in 2012"

Mobility particle size spectrometers: harmonization of technical standards and data structure to facilitate high quality long-term observations of atmospheric particle number size distributions

Abstract: Mobility particle size spectrometers often referred to as DMPS (Differential Mobility Particle Sizers) or SMPS (Scanning Mobility Particle Sizers) have found a wide range of applications in atmospheric aerosol research. However, comparability of measurements conducted world-wide is hampered by lack of generally accepted technical standards and guidelines with respect to the instrumental set-up, measurement mode, data evaluation as well as quality control. Technical standards were developed for a minimum requirement of mobility size spectrometry to perform long-term atmospheric aerosol measurements. Technical recommendations include continuous monitoring of flow rates, temperature, pressure, and relative humidity for the sheath and sample air in the differential mobility analyzer. We compared commercial and custom-made inversion routines to calculate the particle number size distributions from the measured electrical mobility distribution. All inversion routines are comparable within few per cent uncertainty for a given set of raw data. Furthermore, this work summarizes the results from several instrument intercomparison workshops conducted within the European infrastructure project EUSAAR (European Supersites for Atmospheric Aerosol Research) and ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) to determine present uncertainties especially of custom-built mobility particle size spectrometers. Under controlled laboratory conditions, the particle number size distributions from 20 to 200 nm determined by mobility particle size spectrometers of different design are within an uncertainty range of around ±10% after correcting internal particle losses, while below and above this size range the discrepancies increased. For particles larger than 200 nm, the uncertainty range increased to 30%, which could not be explained. The network reference mobility spectrometers with identical design agreed within ±4% in the peak particle number concentration when all settings were done carefully. The consistency of these reference instruments to the total particle number concentration was demonstrated to be less than 5%. Additionally, a new data structure for particle number size distributions was introduced to store and disseminate the data at EMEP (European Monitoring and Evaluation Program). This structure contains three levels: raw data, processed data, and final particle size distributions. Importantly, we recommend reporting raw measurements including all relevant instrument parameters as well as a complete documentation on all data transformation and correction steps. These technical and data structure standards aim to enhance the quality of long-term size distribution measurements, their comparability between different networks and sites, and their transparency and traceability back to raw data. © Author(s) 2012.

The ACOS CO 2 retrieval algorithm – Part 1: Description and validation against synthetic observations

Abstract: . This work describes the NASA Atmospheric CO2 Observations from Space (ACOS) XCO2 retrieval algorithm, and its performance on highly realistic, simulated observations. These tests, restricted to observations over land, are used to evaluate retrieval errors in the face of realistic clouds and aerosols, polarized non-Lambertian surfaces, imperfect meteorology, and uncorrelated instrument noise. We find that post-retrieval filters are essential to eliminate the poorest retrievals, which arise primarily due to imperfect cloud screening. The remaining retrievals have RMS errors of approximately 1 ppm. Modeled instrument noise, based on the Greenhouse Gases Observing SATellite (GOSAT) in-flight performance, accounts for less than half the total error in these retrievals. A small fraction of unfiltered clouds, particularly thin cirrus, lead to a small positive bias of ~0.3 ppm. Overall, systematic errors due to imperfect characterization of clouds and aerosols dominate the error budget, while errors due to other simplifying assumptions, in particular those related to the prior meteorological fields, appear small.

Aerosol classification using airborne High Spectral Resolution Lidar measurements – methodology and examples

Abstract: . The NASA Langley Research Center (LaRC) airborne High Spectral Resolution Lidar (HSRL) on the NASA B200 aircraft has acquired extensive datasets of aerosol extinction (532 nm), aerosol optical depth (AOD) (532 nm), backscatter (532 and 1064 nm), and depolarization (532 and 1064 nm) profiles during 18 field missions that have been conducted over North America since 2006. The lidar measurements of aerosol intensive parameters (lidar ratio, depolarization, backscatter color ratio, and spectral depolarization ratio) are shown to vary with location and aerosol type. A methodology based on observations of known aerosol types is used to qualitatively classify the extensive set of HSRL aerosol measurements into eight separate types. Several examples are presented showing how the aerosol intensive parameters vary with aerosol type and how these aerosols are classified according to this new methodology. The HSRL-based classification reveals vertical variability of aerosol types during the NASA ARCTAS field experiment conducted over Alaska and northwest Canada during 2008. In two examples derived from flights conducted during ARCTAS, the HSRL classification of biomass burning smoke is shown to be consistent with aerosol types derived from coincident airborne in situ measurements of particle size and composition. The HSRL retrievals of AOD and inferences of aerosol types are used to apportion AOD to aerosol type; results of this analysis are shown for several experiments.

Autofluorescence of atmospheric bioaerosols – fluorescent biomolecules and potential interferences

Abstract: . Primary biological aerosol particles (PBAP) are an important subset of air particulate matter with a substantial contribution to the organic aerosol fraction and potentially strong effects on public health and climate. Recent progress has been made in PBAP quantification by utilizing real-time bioaerosol detectors based on the principle that specific organic molecules of biological origin such as proteins, coenzymes, cell wall compounds and pigments exhibit intrinsic fluorescence. The properties of many fluorophores have been well documented, but it is unclear which are most relevant for detection of atmospheric PBAP. The present study provides a systematic synthesis of literature data on potentially relevant biological fluorophores. We analyze and discuss their relative importance for the detection of fluorescent biological aerosol particles (FBAP) by online instrumentation for atmospheric measurements such as the ultraviolet aerodynamic particle sizer (UV-APS) or the wide issue bioaerosol sensor (WIBS). In addition, we provide new laboratory measurement data for selected compounds using bench-top fluorescence spectroscopy. Relevant biological materials were chosen for comparison with existing literature data and to fill in gaps of understanding. The excitation-emission matrices (EEM) exhibit pronounced peaks at excitation wavelengths of ~280 nm and ~360 nm, confirming the suitability of light sources used for online detection of FBAP. They also show, however, that valuable information is missed by instruments that do not record full emission spectra at multiple wavelengths of excitation, and co-occurrence of multiple fluorophores within a detected sample will likely confound detailed molecular analysis. Selected non-biological materials were also analyzed to assess their possible influence on FBAP detection and generally exhibit only low levels of background-corrected fluorescent emission. This study strengthens the hypothesis that ambient supermicron particle fluorescence in wavelength ranges used for most FBAP instruments is likely to be dominated by biological material and that such instrumentation is able to discriminate between FBAP and non-biological material in many situations. More detailed follow-up studies on single particle fluorescence are still required to reduce these uncertainties further, however.

The ACOS CO 2 retrieval algorithm – Part II: Global X CO 2 data characterization

Abstract: . Here, we report preliminary estimates of the column averaged carbon dioxide (CO2) dry air mole fraction, XCO2, retrieved from spectra recorded over land by the Greenhouse gases Observing Satellite, GOSAT (nicknamed "Ibuki"), using retrieval methods originally developed for the NASA Orbiting Carbon Observatory (OCO) mission. After screening for clouds and other known error sources, these retrievals reproduce much of the expected structure in the global XCO2 field, including its variation with latitude and season. However, low yields of retrieved XCO2 over persistently cloudy areas and ice covered surfaces at high latitudes limit the coverage of some geographic regions, even on seasonal time scales. Comparisons of early GOSAT XCO2 retrievals with XCO2 estimates from the Total Carbon Column Observing Network (TCCON) revealed a global, −2% (7–8 parts per million, ppm, with respect to dry air) XCO2 bias and 2 to 3 times more variance in the GOSAT retrievals. About half of the global XCO2 bias is associated with a systematic, 1% overestimate in the retrieved air mass, first identified as a global +10 hPa bias in the retrieved surface pressure. This error has been attributed to errors in the O2 A-band absorption cross sections. Much of the remaining bias and spurious variance in the GOSAT XCO2 retrievals has been traced to uncertainties in the instrument's calibration, oversimplified methods for generating O2 and CO2 absorption cross sections, and other subtle errors in the implementation of the retrieval algorithm. Many of these deficiencies have been addressed in the most recent version (Build 2.9) of the retrieval algorithm, which produces negligible bias in XCO2 on global scales as well as a ~30% reduction in variance. Comparisons with TCCON measurements indicate that regional scale biases remain, but these could be reduced by applying empirical corrections like those described by Wunch et al. (2011b). We recommend that such corrections be applied before these data are used in source sink inversion studies to minimize spurious fluxes associated with known biases. These and other lessons learned from the analysis of GOSAT data are expected to accelerate the delivery of high quality data products from the Orbiting Carbon Observatory-2 (OCO-2), once that satellite is successfully launched and inserted into orbit.

Soot Reference Materials for instrument calibration and intercomparisons: a workshop summary with recommendations

Abstract: . Soot, which is produced from biomass burning and the incomplete combustion of fossil and biomass fuels, has been linked to regional and global climate change and to negative health problems. Scientists measure the properties of soot using a variety of methods in order to quantify source emissions and understand its atmospheric chemistry, reactivity under emission conditions, interaction with solar radiation, influence on clouds, and health impacts. A major obstacle currently limiting progress is the absence of established standards or reference materials for calibrating the many instruments used to measure the various properties of soot. The current state of availability and practicability of soot standard reference materials (SRMs) was reviewed by a group of 50 international experts during a workshop in June of 2011. The workshop was convened to summarize the current knowledge on soot measurement techniques, identify the measurement uncertainties and limitations related to the lack of soot SRMs, and identify attributes of SRMs that, if developed, would reduce measurement uncertainties. The workshop established that suitable SRMs are available for calibrating some, but not all, measurement methods. The community of users of the single-particle soot-photometer (SP2), an instrument using laser-induced incandescence, identified a suitable SRM, fullerene soot, but users of instruments that measure light absorption by soot collected on filters did not. Similarly, those who use thermal optical analysis (TOA) to analyze the organic and elemental carbon components of soot were not satisfied with current SRMs. The workshop, and subsequent, interactive discussions, produced a number of recommendations for the development of new SRMs, and their implementation, that would be suitable for the different soot measurement methods.

Sensitivity of the Single Particle Soot Photometer to different black carbon types

Abstract: . Black carbon (BC) is now mainly of anthropogenic origin. It is the dominant light absorbing component of atmospheric aerosols, playing an important role in the earth's radiative balance and therefore relevant to climate change studies. In addition, BC is known to be harmful to human beings making it relevant to policy makers. Nevertheless, the measurement of BC remains biased by the instrument-based definition of BC. The Single Particle Soot Photometer (SP2), allows the measurement of the refractory BC (rBC) mass of individual particles using laser-induced incandescence. However, the SP2 needs an empirical calibration to retrieve the rBC mass from the incandescence signal and the sensitivity of the SP2 differs between different BC types. Ideally, for atmospheric studies, the SP2 should be calibrated using ambient particles containing a known mass of ambient rBC. However, such "ambient BC" calibration particles cannot easily be obtained and thus commercially available BC particles are commonly used for SP2 calibration instead. In this study we tested the sensitivity of the SP2 to different BC types in order to characterize the potential error introduced by using non-ambient BC for calibration. The sensitivity of the SP2 was determined, using an aerosol particle mass analyzer, for rBC from thermodenuded diesel exhaust, wood burning exhaust and ambient particles as well as for commercially available products: Aquadag® and fullerene soot. Thermodenuded, fresh diesel exhaust has been found to be ideal for SP2 calibration for two reasons. First, the small amount of non-BC matter upon emission reduces the risk of bias due to incomplete removal of non-BC matter and second, it is considered to represent atmospheric rBC in urban locations where diesel exhaust is the main source of BC. The SP2 was found to be up to 16% less sensitive to rBC from thermodenuded ambient particles (≤15 fg) than rBC from diesel exhaust, however, at least part of this difference can be explained by incomplete removal of non-refractory components in the thermodenuder. The amount of remaining non-refractory matter was estimated to be below 30% by mass, according to a comparison of the scattering cross sections of the whole particles with that of the pure BC cores. The SP2 sensitivity to rBC from wood burning exhaust agrees with the SP2 sensitivity to rBC from diesel exhaust within an error of less than 14% (≤40 fg). If, due to experimental restrictions, diesel exhaust cannot be used, untreated fullerene soot was found to give an SP2 calibration curve similar to diesel exhaust and ambient rBC (within ±10% for a rBC mass ≤15 fg) and is therefore recommended although two different batches differed by ~14% between themselves. In addition, the SP2 was found to be up to 40% more sensitive to Aquadag® than to diesel exhaust rBC. Therefore Aquadag® cannot be recommended for atmospheric application without accounting for the sensitivity difference. These findings for fullerene soot and Aquadag® confirm results from previous literature.

Filling-in of near-infrared solar lines by terrestrial fluorescence and other geophysical effects: simulations and space-based observations from SCIAMACHY and GOSAT

Abstract: . Global mapping of terrestrial vegetation fluorescence from space has recently been accomplished with high spectral resolution (ν/Δν > 35 000) measurements from the Japanese Greenhouse gases Observing SATellite (GOSAT). These data are of interest because they can potentially provide global information on the functional status of vegetation including light-use efficiency and global primary productivity that can be used for global carbon cycle modeling. Quantifying the impact of fluorescence on the O2-A band is important as this band is used for photon pathlength characterization in cloud- and aerosol-contaminated pixels for trace-gas retrievals including CO2. Here, we examine whether fluorescence information can be derived from space using potentially lower-cost hyperspectral instrumentation, i.e., more than an order of magnitude less spectral resolution (ν/Δν ~ 1600) than GOSAT, with a relatively simple algorithm. We discuss laboratory measurements of fluorescence near one of the few wide and deep solar Fraunhofer lines in the long-wave tail of the fluorescence emission region, the calcium (Ca) II line at 866 nm that is observable with a spectral resolution of ~0.5 nm. The filling-in of the Ca II line due to additive signals from various atmospheric and terrestrial effects, including fluorescence, is simulated. We then examine filling-in of this line using the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) satellite instrument. In order to interpret the satellite measurements, we developed a general approach to correct for various instrumental artifacts that produce false filling-in of solar lines in satellite measurements. The approach is applied to SCIAMACHY at the 866 nm Ca II line and to GOSAT at 758 and 770 nm on the shoulders of the O2-A feature where there are several strong solar Fraunhofer lines that are filled in primarily by vegetation fluorescence. Finally, we compare temporal and spatial variations of SCIAMACHY additive signals with those of GOSAT and the Enhanced Vegetation Index (EVI) from the MODerate-resolution Imaging Spectroradiometer (MODIS). Although the derived additive signals from SCIAMACHY are extremely weak at 866 nm, their spatial and temporal variations are consistent with chlorophyll a fluorescence or another vegetation-related source. We also show that filling-in occurs at 866 nm over some barren areas, possibly originating from luminescent minerals in rock and soil.

A Fourier transform infrared trace gas and isotope analyser for atmospheric applications

Abstract: . Concern in recent decades about human impacts on Earth's climate has led to the need for improved and expanded measurement capabilities of greenhouse gases in the atmosphere. In this paper we describe in detail an in situ trace gas analyser based on Fourier Transform Infrared (FTIR) spectroscopy that is capable of simultaneous and continuous measurements of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrous oxide (N2O) and 13C in CO2 in air with high precision. High accuracy is established by reference to measurements of standard reference gases. Stable water isotopes can also be measured in undried airstreams. The analyser is automated and allows unattended operation with minimal operator intervention. Precision and accuracy meet and exceed the compatibility targets set by the World Meteorological Organisation – Global Atmosphere Watch for baseline measurements in the unpolluted troposphere for all species except 13C in CO2. The analyser is mobile and well suited to fixed sites, tower measurements, mobile platforms and campaign-based measurements. The isotopic specificity of the optically-based technique and analysis allows its application in isotopic tracer experiments, for example in tracing variations of 13C in CO2 and 15N in N2O. We review a number of applications illustrating use of the analyser in clean air monitoring, micrometeorological flux and tower measurements, mobile measurements on a train, and soil flux chamber measurements.

Single Particle Soot Photometer intercomparison at the AIDA chamber

Abstract: . Soot particles, consisting of black carbon (BC), organic carbon (OC), inorganic salts, and trace elements, are emitted into the atmosphere during incomplete combustion. Accurate measurements of atmospheric BC are important as BC particles cause adverse health effects and impact the climate. Unfortunately, the accurate measurement of the properties and mass concentrations of BC particles remains difficult. The Single Particle Soot Photometer (SP2) can contribute to improving this situation by measuring the mass of refractory BC in individual particles as well as its mixing state. Here, the results of the first detailed SP2 intercomparison, involving 6 SP2s from 6 different research groups, are presented, including the most evolved data products that can presently be calculated from SP2 measurements. It was shown that a detection efficiency of almost 100% down to 1 fg BC per particle can readily be achieved, and that this limit can be pushed down to ∼0.2 fg BC with optimal SP2 setup. Number and mass size distributions of BC cores agreed within ±5% and ±10%, respectively, in between the SP2s, with larger deviations in the range below 1 fg BC. The accuracy of the SP2's mass concentration measurement depends on the calibration material chosen. The SP2 has previously been shown to be equally sensitive to fullerene soot and ambient BC from sources where fossil fuel was dominant and less sensitive to fullerene soot than to Aquadag. Fullerene soot was therefore chosen as the standard calibration material by the SP2 user community; however, many data sets rely solely on Aquadag calibration measurements. The difference in SP2 sensitivity was found to be almost equal (fullerene soot to Aquadag response ratio of ∼0.75 at 8.9 fg BC) for all SP2s. This allows the calculation of a fullerene soot equivalent calibration curve from a measured Aquadag calibration, when no fullerene soot calibration is available. It could be shown that this approach works well for all SP2s over the mass range of 1–10 fg. This range is suitable for typical BC mass size distributions in the ambient air far from sources. The number size distribution of purely scattering particles optically measured by the 6 SP2s also agreed within 15%. Measurements of the thickness of non-refractory coatings (i.e. product from α-pinene ozonolysis) on the BC particles, relying on BC mass optical size and on an additional particle position measurement, also compared well (within ±17%). The estimated coating thickness values were consistent with thermo-optical analysis of OC and elemental carbon (EC) content, though absolutely accurate values cannot be expected given all the assumptions that have to be made regarding refractive index, particle morphology, etc. This study showed that the SP2 provides accurate and reproducible data, but also that high data quality is only achieved if the SP2 is carefully tuned and calibrated. It has to be noted that the agreement observed here does not account for additional variability in output data that could result from the differences in the potentially subjective assumptions made by different SP2 users in the data processing.

Improved Micro Rain Radar snow measurements using Doppler spectra post-processing

Abstract: . The Micro Rain Radar 2 (MRR) is a compact Frequency Modulated Continuous Wave (FMCW) system that operates at 24 GHz. The MRR is a low-cost, portable radar system that requires minimum supervision in the field. As such, the MRR is a frequently used radar system for conducting precipitation research. Current MRR drawbacks are the lack of a sophisticated post-processing algorithm to improve its sensitivity (currently at +3 dBz), spurious artefacts concerning radar receiver noise and the lack of high quality Doppler radar moments. Here we propose an improved processing method which is especially suited for snow observations and provides reliable values of effective reflectivity, Doppler velocity and spectral width. The proposed method is freely available on the web and features a noise removal based on recognition of the most significant peak. A dynamic dealiasing routine allows observations even if the Nyquist velocity range is exceeded. Collocated observations over 115 days of a MRR and a pulsed 35.2 GHz MIRA35 cloud radar show a very high agreement for the proposed method for snow, if reflectivities are larger than −5 dBz. The overall sensitivity is increased to −14 and −8 dBz, depending on range. The proposed method exploits the full potential of MRR's hardware and substantially enhances the use of Micro Rain Radar for studies of solid precipitation.

Retrieval of sulphur dioxide from the infrared atmospheric sounding interferometer (IASI)

Abstract: . Thermal infrared sounding of sulphur dioxide (SO2) from space has gained appreciation as a valuable complement to ultraviolet sounding. There are several strong absorption bands of SO2 in the infrared, and atmospheric sounders, such as AIRS (Atmospheric Infrared Sounder), TES (Tropospheric Emission Spectrometer) and IASI (Infrared Atmospheric Sounding Interferometer) have the ability to globally monitor SO2 abundances. Most of the observed SO2 is found in volcanic plumes. In this paper we outline a novel algorithm for the sounding of SO2 above ~5 km altitude using high resolution infrared sounders and apply it to measurements of IASI. The main features of the algorithm are a wide applicable total column range (over 4 orders of magnitude, from 0.5 to 5000 dobson units), a low theoretical uncertainty (3–5%) and near real time applicability. We make an error analysis and demonstrate the algorithm on the recent eruptions of Sarychev, Kasatochi, Grimsvotn, Puyehue-Cordon Caulle and Nabro.

A method for cloud detection and opacity classification based on ground based sky imagery

Abstract: . Digital images of the sky obtained using a total sky imager (TSI) are classified pixel by pixel into clear sky, optically thin and optically thick clouds. A new classification algorithm was developed that compares the pixel red-blue ratio (RBR) to the RBR of a clear sky library (CSL) generated from images captured on clear days. The difference, rather than the ratio, between pixel RBR and CSL RBR resulted in more accurate cloud classification. High correlation between TSI image RBR and aerosol optical depth (AOD) measured by an AERONET photometer was observed and motivated the addition of a haze correction factor (HCF) to the classification model to account for variations in AOD. Thresholds for clear and thick clouds were chosen based on a training image set and validated with set of manually annotated images. Misclassifications of clear and thick clouds into the opposite category were less than 1%. Thin clouds were classified with an accuracy of 60%. Accurate cloud detection and opacity classification techniques will improve the accuracy of short-term solar power forecasting.

Fall speed measurement and high-resolution multi-angle photography of hydrometeors in free fall

Abstract: . We describe here a new instrument for imaging hydrometeors in free fall. The Multi-Angle Snowflake Camera (MASC) captures high-resolution photographs of hydrometeors from three angles while simultaneously measuring their fall speed. Based on the stereoscopic photographs captured over the two months of continuous measurements obtained at a high altitude location within the Wasatch Front in Utah, we derive statistics for fall speed, hydrometeor size, shape, orientation and aspect ratio. From a selection of the photographed hydrometeors, an illustration is provided for how the instrument might be used for making improved microwave scattering calculations. Complex, aggregated snowflake shapes appear to be more strongly forward scattering, at the expense of reduced back-scatter, than heavily rimed graupel particles of similar size.

Profiles of CH 4 , HDO, H 2 O, and N 2 O with improved lower tropospheric vertical resolution from Aura TES radiances

Abstract: . Thermal infrared (IR) radiances measured near 8 microns contain information about the vertical distribution of water vapor (H2O), the water isotopologue HDO, and methane (CH4), key gases in the water and carbon cycles. Previous versions (Version 4 or less) of the TES profile retrieval algorithm used a "spectral-window" approach to minimize uncertainty from interfering species at the expense of reduced vertical resolution and sensitivity. In this manuscript we document changes to the vertical resolution and uncertainties of the TES version 5 retrieval algorithm. In this version (Version 5), joint estimates of H2O, HDO, CH4 and nitrous oxide (N2O) are made using radiances from almost the entire spectral region between 1100 cm−1 and 1330 cm−1. The TES retrieval constraints are also modified in order to better use this information. The new H2O estimates show improved vertical resolution in the lower troposphere and boundary layer, while the new HDO/H2O estimates can now profile the HDO/H2O ratio between 925 hPa and 450 hPa in the tropics and during summertime at high latitudes. The new retrievals are now sensitive to methane in the free troposphere between 800 and 150 mb with peak sensitivity near 500 hPa; whereas in previous versions the sensitivity peaked at 200 hPa. However, the upper troposphere methane concentrations are biased high relative to the lower troposphere by approximately 4% on average. This bias is likely related to temperature, calibration, and/or methane spectroscopy errors. This bias can be mitigated by normalizing the CH4 estimate by the ratio of the N2O estimate relative to the N2O prior, under the assumption that the same systematic error affects both the N2O and CH4 estimates. We demonstrate that applying this ratio theoretically reduces the CH4 estimate for non-retrieved parameters that jointly affect both the N2O and CH4 estimates. The relative upper troposphere to lower troposphere bias is approximately 2.8% after this bias correction. Quality flags based upon the vertical variability of the methane and N2O estimates can be used to reduce this bias further. While these new CH4, HDO/H2O, and H2O estimates are consistent with previous TES retrievals in the altitude regions where the sensitivities overlap, future comparisons with independent profile measurement will be required to characterize the biases of these new retrievals and determine if the calculated uncertainties using the new constraints are consistent with actual uncertainties.

Remote sensing of near-infrared chlorophyll fluorescence from space in scattering atmospheres: implications for its retrieval and interferences with atmospheric CO 2 retrievals

Abstract: . With the advent of dedicated greenhouse gas space-borne spectrometers sporting high resolution spectra in the O2 A-band spectral region (755–774 nm), the retrieval of chlorophyll fluorescence has become feasible on a global scale. If unaccounted for, however, fluorescence can indirectly perturb the greenhouse gas retrievals as it perturbs the oxygen absorption features. As atmospheric CO2 measurements are used to invert net fluxes at the land–atmosphere interface, a bias caused by fluorescence can be crucial as it will spatially correlate with the fluxes to be inverted. Avoiding a bias and retrieving fluorescence accurately will provide additional constraints on both the net and gross fluxes in the global carbon cycle. We show that chlorophyll fluorescence, if neglected, systematically interferes with full-physics multi-band XCO2 retrievals using the O2 A-band. Systematic biases in XCO2 can amount to +1 ppm if fluorescence constitutes 1% to the continuum level radiance. We show that this bias can be largely eliminated by simultaneously fitting fluorescence in a full-physics based retrieval. If fluorescence is the primary target, a dedicated but very simple retrieval based purely on Fraunhofer lines is shown to be more accurate and very robust even in the presence of large scattering optical depths. We find that about 80% of the surface fluorescence is retained at the top-of-atmosphere, even for cloud optical thicknesses around 2–5. We further show that small instrument modifications to future O2 A-band spectrometer spectral ranges can result in largely reduced random errors in chlorophyll fluorescence, paving the way towards a more dedicated instrument exploiting solar absorption features only.

Global and regional evaluation of over-land spectral aerosol optical depth retrievals from SeaWiFS

Abstract: . This study evaluates a new spectral aerosol optical depth (AOD) dataset derived from Sea-viewing Wide Field-of-view Sensor (SeaWiFS) measurements over land. First, the data are validated against Aerosol Robotic Network (AERONET) direct-sun AOD measurements and found to compare well on a global basis. If only data with the highest quality flag are used, the correlation is 0.86 and 72% of matchups fall within an expected absolute uncertainty of 0.05 + 20% (for the wavelength of 550 nm). The quality is similar at other wavelengths and stable over the 13-yr (1997–2010) mission length. Performance tends to be better over vegetated, low-lying terrain with typical AOD of 0.3 or less, such as found over much of North America and Eurasia. Performance tends to be poorer for low-AOD conditions near backscattering geometries, where SeaWiFS overestimates AOD, or optically-thick cases of absorbing aerosol, where SeaWiFS tends to underestimate AOD. Second, the SeaWiFS data are compared with midvisible AOD derived from the Moderate Resolution Imaging Spectrometer (MODIS) and Multiangle Imaging Spectroradiometer (MISR). All instruments show similar spatial and seasonal distributions of AOD, although there are regional and seasonal offsets between them. At locations where AERONET data are available, these offsets are largely consistent with the known validation characteristics of each dataset. With the results of this study in mind, the SeaWiFS over-land AOD record is suitable for quantitative scientific use.

Interferences of commercial NO 2 instruments in the urban atmosphere and in a smog chamber

Abstract: . Reliable measurements of atmospheric trace gases are necessary for both, a better understanding of the chemical processes occurring in the atmosphere, and for the validation of model predictions. Nitrogen dioxide (NO2) is a toxic gas and is thus a regulated air pollutant. Besides, it is of major importance for the oxidation capacity of the atmosphere and plays a pivotal role in the formation of ozone and acid precipitation. Detection of NO2 is a difficult task since many of the different commercial techniques used are affected by interferences. The chemiluminescence instruments that are used for indirect NO2 detection in monitoring networks and smog chambers use either molybdenum or photolytic converters and are affected by either positive (NOy) or negative interferences (radical formation in the photolytic converter). Erroneous conclusions on NO2 can be drawn if these interferences are not taken into consideration. In the present study, NO2 measurements in the urban atmosphere, in a road traffic tunnel and in a smog-chamber using different commercial techniques, i.e. chemiluminescence instruments with molybdenum or photolytic converters, a Luminol based instrument and a new NO2-LOPAP, were compared with spectroscopic techniques, i.e. DOAS and FTIR. Interferences of the different instruments observed during atmospheric measurements were partly characterised in more detail in the smog chamber experiments. Whereas all the commercial instruments showed strong interferences, excellent agreement was obtained between a new NO2-LOPAP instrument and the FTIR technique for the measurements performed in the smog chamber.

Improved retrieval of global tropospheric formaldehyde columns from GOME-2/MetOp-A addressing noise reduction and instrumental degradation issues

Abstract: . We present a new dataset of formaldehyde vertical columns retrieved from observations of GOME-2 on board the EUMETSAT MetOp-A platform between 2007 and 2011. The new retrieval scheme, which has been optimised for GOME-2, includes a two-step fitting procedure that strongly reduces the impact of spectral interferences between H2CO and BrO, and a modified DOAS approach that better handles ozone absorption effects at moderately low sun elevations. Owing to these new features, the noise in the H2CO slant columns is reduced by up to 40% in comparison to baseline retrieval settings used operationally. Also, the previously reported underestimation of the H2CO columns in tropical and mid-latitude regions has been largely eliminated, improving the agreement with coincident SCIAMACHY observations. To compensate for the drift of the GOME-2 slit function and to mitigate the instrumental degradation effects on H2CO retrievals, an asymmetric Gaussian line-shape is fitted during the irradiance calibration. Additionally, external parameters used in the tropospheric air mass factor computation (surface reflectances, cloud parameters and a priori profile shapes of H2CO) have been updated using most recent databases. Similar updates were also applied to the historical datasets of GOME and SCIAMACHY, leading to the generation of a consistent multi-mission H2CO data record covering the time period from 1997 until 2011. Comparing the resulting time series of monthly averaged H2CO vertical columns in 12 large regions worldwide, the correlation coefficient between SCIAMACHY and GOME-2 columns is generally higher than 0.8 in the overlap period, and linear regression slopes differ by less than 10% from unity in most of the regions. In comparison to SCIAMACHY, the largely improved spatial sampling of GOME-2 allows for a better characterisation of formaldehyde distribution at the regional scale and/or at shorter timescales, leading to a better identification of the emission sources of non-methane volatile organic compounds.

Measuring variations of δ 18 O and δ 2 H in atmospheric water vapour using two commercial laser-based spectrometers: an instrument characterisation study

Abstract: Variations of stable water isotopes in water vapour have become measurable at a measurement frequency of about 1 Hz in recent years using novel laser spectroscopic techniques This enables us to perform continuous measurements for process-based investigations of the atmospheric water cycle at the time scales relevant for synoptic and mesoscale meteorology An important prerequisite for the interpretation of data from automated field measurements lasting for several weeks or months is a detailed knowledge about instrument properties and the sources of measurement uncertainty We present here a comprehensive characterisation and comparison study of two commercial laser spectroscopic systems based on cavity ring-down spectroscopy (Picarro) and off-axis integrated cavity output spectroscopy (Los Gatos Research) The uncertainty components of the measurements were first assessed in laboratory experiments, focussing on the effects of (i) water vapour mixing ratio, (ii) measurement stability, (iii) uncertainties due to calibration and (iv) response times of the isotope measurements due to adsorption-desorption processes on the tubing and measurement cavity walls Based on the experience from our laboratory experiments, we set up a one-week field campaign for comparing measurements of the ambient isotope signals from the two laser spectroscopic systems The optimal calibration strategy determined for both instruments was applied as well as the correction functions for water vapour mixing ratio effects The root mean square difference between the isotope signals from the two instruments during the field deployment was 23‰ for δ2H, 05‰ for δ18O and 31‰ for deuterium excess These uncertainty estimates from field measurements compare well to those found in the laboratory experiments The present quality of measurements from laser spectroscopic instruments combined with a calibration system opens new possibilities for investigating the atmospheric water cycle and the land-atmosphere moisture fluxes

Robust extraction of baseline signal of atmospheric trace species using local regression

Abstract: . The identification of atmospheric trace species measurements that are representative of well-mixed background air masses is required for monitoring atmospheric composition change at background sites. We present a statistical method based on robust local regression that is well suited for the selection of background measurements and the estimation of associated baseline curves. The bootstrap technique is applied to calculate the uncertainty in the resulting baseline curve. The non-parametric nature of the proposed approach makes it a very flexible data filtering method. Application to carbon monoxide (CO) measured from 1996 to 2009 at the high-alpine site Jungfraujoch (Switzerland, 3580 m a.s.l.), and to measurements of 1,1-difluoroethane (HFC-152a) from Jungfraujoch (2000 to 2009) and Mace Head (Ireland, 1995 to 2009) demonstrates the feasibility and usefulness of the proposed approach. The determined average annual change of CO at Jungfraujoch for the 1996 to 2009 period as estimated from filtered annual mean CO concentrations is −2.2 ± 1.1 ppb yr−1. For comparison, the linear trend of unfiltered CO measurements at Jungfraujoch for this time period is −2.9 ± 1.3 ppb yr−1.

Particle sizing calibration with refractive index correction for light scattering optical particle counters and impacts upon PCASP and CDP data collected during the Fennec campaign

Abstract: . Optical particle counters (OPCs) are used regularly for atmospheric research, measuring particle scattering cross sections to generate particle size distribution histograms. This manuscript presents two methods for calibrating OPCs with case studies based on a Passive Cavity Aerosol Spectrometer Probe (PCASP) and a Cloud Droplet Probe (CDP), both of which are operated on the Facility for Airborne Atmospheric Measurements BAe-146 research aircraft. A probability density function based method is provided for modification of the OPC bin boundaries when the scattering properties of measured particles are different to those of the calibration particles due to differences in refractive index or shape. This method provides mean diameters and widths for OPC bins based upon Mie-Lorenz theory or any other particle scattering theory, without the need for smoothing, despite the highly nonlinear and non-monotonic relationship between particle size and scattering cross section. By calibrating an OPC in terms of its scattering cross section the optical properties correction can be applied with minimal information loss, and performing correction in this manner provides traceable and transparent uncertainty propagation throughout the whole process. Analysis of multiple calibrations has shown that for the PCASP the bin centres differ by up to 30% from the manufacturer's nominal values and can change by up to approximately 20% when routine maintenance is performed. The CDP has been found to be less sensitive than the manufacturer's specification with differences in sizing of between 1.6 ± 0.8 μm and 4.7 ± 1.8 μm for one flight. Over the course of the Fennec project in the Sahara the variability of calibration was less than the calibration uncertainty in 6 out of 7 calibrations performed. As would be expected from Mie-Lorenz theory, the impact of the refractive index corrections has been found to be largest for absorbing materials and the impact on Saharan dust measurements made as part of the Fennec project has been found to be up to a factor of 3 for the largest particles measured by CDP with diameters of approximately 120 μm. In an example case, using the calibration and refractive index corrections presented in this work allowed Saharan dust measurement from the PCASP, CDP and a Cloud Imaging Probe to agree within the uncertainty of the calibration. The agreement when using only the manufacturer's specification was poor. Software tools have been developed to perform these calibrations and corrections and are now available as open source resources for the community via the SourceForge repository.

A fast and precise chemiluminescence ozone detector for eddy flux and airborne application

Abstract: . A commercially available dry chemiluminescence (CI) instrument for fast and precise measurement of ozone (O3) is specified. The sensitivity is ~9000 counts s−1 per ppbv of ozone. Its precision is entirely determined by the number of photons reaching the detector (being a photomultiplier), i.e. is quantum-noise limited. The relative precision (ΔO3/O3 in %) thus follows Poisson statistics and scales with the square root of the measurement frequency f and with the inverse O3 mixing ratio: ΔO3/O3 ∝ f0.5 · O3−0.5. At typical O3 mixing ratios between 10 and 100 ppbv (and 1 bar), the precision is 0.3–1.0% at f = 10 Hz. The maximum measurement frequency is 50 Hz. The mechanical and electronic set-up as well as the instrument performance is described. Recommendations on the adequate inlet tube configuration (inlet tube length, sampling flow) and on the way of calibration at stationary ground-based platforms and onboard aircraft are given.

Operational profiling of temperature using ground-based microwave radiometry at Payerne: prospects and challenges

Abstract: . The motivation of this study is to verify theoretical expectations placed on ground-based microwave radiometer (MWR) techniques and to confirm whether they are suitable for supporting key missions of national weather services, such as timely and accurate weather advisories and warnings. We evaluate reliability and accuracy of atmospheric temperature profiles retrieved continuously by the microwave profiler system HATPRO (Humidity And Temperature PROfiler) operated at the aerological station of Payerne (MeteoSwiss) in the time period August 2006–December 2009. Assessment is performed by comparing temperatures from the radiometer against temperature measurements from a radiosonde accounting for a total of 2107 quality-controlled all-season cases. In the evaluated time period, the MWR delivered reliable temperature profiles in 86% of all-weather conditions on a temporal resolution of 12–13 min. Random differences between MWR and radiosonde are down to 0.5 K in the lower boundary layer and increase to 1.7 K at 4 km height. The differences observed between MWR and radiosonde in the lower boundary layer are similar to the differences observed between the radiosonde and another in-situ sensor located on a close-by 30 m tower. Temperature retrievals from above 4 km contain less than 5% of the total information content of the measurements, which makes clear that this technique is mainly suited for continuous observations in the boundary layer. Systematic temperature differences are also observed throughout the retrieved profile and can account for up to ±0.5 K. These errors are due to offsets in the measurements of the microwave radiances that have been corrected for in data post-processing and lead to nearly bias-free overall temperature retrievals. Different reasons for the radiance offsets are discussed, but cannot be unambiguously determined retrospectively. Monitoring and, if necessary, corrections for radiance offsets as well as a real-time rigorous automated data quality control are mandatory for microwave profiler systems that are designated for operational temperature profiling. In the analysis of a subset of different atmospheric situations, it is shown that lifted inversions and data quality during precipitation present the largest challenges for operational MWR temperature profiling.

Smoke aerosol and its radiative effects during extreme fire event over Central Russia in summer 2010

Abstract: . Different microphysical, optical and radiative properties of aerosol were analyzed during the severe fires in summer 2010 over Central Russia using ground measurements at two AERONET sites in Moscow (Meteorological Observatory of Moscow State University – MSU MO) and Zvenigorod (Moscow Region) and radiative measurements at the MSU MO. Volume aerosol size distribution in smoke conditions had a bimodal character with the significant prevalence of fine mode particles, for which effective radius was shifted to higher values (r eff-fine = 0.24 μm against approximately 0.15 μm in typical conditions). For smoke aerosol, the imaginary part of refractive index (REFI) in the visible spectral region was lower than that for typical aerosol (REFIλ =675 nm = 0.006 against REFIλ =675 nm = 0.01), while single scattering albedo (SSA) was significantly higher (SSAλ =675 nm = 0.95 against SSAλ =675 nm ~ 0.9). Extremely high aerosol optical thickness at 500 nm (AOT500) was observed on 6–8 August reaching the absolute maximum on 7 August in Moscow (AOT500 = 6.4) and at Zvenigorod (AOT500 = 5.9). A dramatic attenuation of solar irradiance at ground was also recorded. Maximum irradiance loss had reached 64% for global shortwave irradiance, 91% for UV radiation 300–380 nm, and 97% for erythemally-weighted UV irradiance at relatively high solar elevation 47°. Significant spectral dependence in attenuation of solar irradiance in smoky conditions was mainly explained by higher AOT and smaller SSA in UV (0.8–0.9) compared with SSA in the visible region of spectrum. The assessments of radiative forcing effect (RFE) at the TOA indicated a significant cooling of the smoky atmosphere. Instant RFE reached −167 Wm−2 at AOT500 = 6.4, climatological RFE calculated with August 2010 monthly mean AOT was about −65 Wm−2, compared with −20 Wm−2 for typical aerosol according to the 10 yr period of measurements in Moscow.

XCO 2 -measurements with a tabletop FTS using solar absorption spectroscopy

Abstract: . A commercial low-resolution (0.5 cm−1) Fourier Transform Spectrometer (FTS) has been modified and is used for determining the total column XCO2 of the atmosphere by analysing direct solar radiation. The spectrometer has a small home-built solar tracker attached, so that it is a ready-to-use instrument. The results are validated with temporally coinciding on-site measurements taken with a high-resolution Total Carbon Column Observing Network (TCCON) FTIR spectrometer. For the whole comparison period of 5 months (26 measurement days) an agreement with TCCON results of (0.12 ± 0.08)% is achieved. This makes the spectrometer a promising candidate for a low-cost addition to the TCCON core FTIR sites, especially suitable for locations with limited infrastructure. An impressive mechanical and thermal stability is proved, enabling the spectrometer for use in field campaigns and for the monitoring of local sources.

Assessing Single Particle Soot Photometer and Integrating Sphere/Integrating Sandwich Spectrophotometer measurement techniques for quantifying black carbon concentration in snow

Abstract: . We evaluate the performance of the Single Particle Soot Photometer (SP2) and the Integrating Sphere/Integrating Sandwich Spectrophotometer (ISSW) in quantifying the concentration of refractory black carbon (BC) in snow samples. We find that the SP2 can be used to measure BC mass concentration in snow with substantially larger uncertainty (60%) than for atmospheric sampling (

OH clock determination by proton transfer reaction mass spectrometry at an environmental chamber

Abstract: . The hydroxyl free radical (OH) is the major oxidizing species in the lower atmosphere. Measuring the OH concentration is generally difficult and involves elaborate, expensive, custom-made experimental setups. Thus other more economical techniques, capable of determining OH concentrations at environmental chambers, would be valuable. This work is based on an indirect method of OH concentration measurement, by monitoring an appropriate OH tracer by proton transfer reaction mass spectrometry (PTR-MS). 3-pentanol, 3-pentanone and pinonaldehyde (PA) were used as OH tracers in α-pinene (AP) secondary organic aerosol (SOA) aging studies. In addition we tested butanol-d9 as a potential "universal" OH tracer and determined its reaction rate constant with OH: kbutanol-d9 = 3.4(±0.88) × 10−12 cm3 molecule−1 s−1. In order to make the chamber studies more comparable among each other as well as to atmospheric measurements we suggest the use of a chemical (time) dimension: the OH clock, which corresponds to the integrated OH concentration over time.

Ship emissions of SO2 and NO2: DOAS measurements from airborne platforms

Abstract: . A unique methodology to measure gas fluxes of SO2 and NO2 from ships using optical remote sensing is described and demonstrated in a feasibility study. The measurement system is based on Differential Optical Absorption Spectroscopy using reflected skylight from the water surface as light source. A grating spectrometer records spectra around 311 nm and 440 nm, respectively, with the telescope pointed downward at a 30° angle from the horizon. The mass column values of SO2 and NO2 are retrieved from each spectrum and integrated across the plume. A simple geometric approximation is used to calculate the optical path. To obtain the total emission in kg h−1 the resulting total mass across the plume is multiplied with the apparent wind, i.e. a dilution factor corresponding to the vector between the wind and the ship speed. The system was tested in two feasibility studies in the Baltic Sea and Kattegat, from a CASA-212 airplane in 2008 and in the North Sea outside Rotterdam from a Dauphin helicopter in an EU campaign in 2009. In the Baltic Sea the average SO2 emission out of 22 ships was (54 ± 13) kg h−1, and the average NO2 emission was (33 ± 8) kg h−1, out of 13 ships. In the North Sea the average SO2 emission out of 21 ships was (42 ± 11) kg h−1, NO2 was not measured here. The detection limit of the system made it possible to detect SO2 in the ship plumes in 60% of the measurements when the described method was used. A comparison exercise was carried out by conducting airborne optical measurements on a passenger ferry in parallel with onboard measurements. The comparison shows agreement of (−30 ± 14)% and (−41 ± 11)%, respectively, for two days, with equal measurement precision of about 20%. This gives an idea of the measurement uncertainty caused by errors in the simple geometric approximation for the optical light path neglecting scattering of the light in ocean waves and direct and multiple scattering in the exhaust plume under various conditions. A tentative error budget indicates uncertainties within 30–45% but for a reliable error analysis the optical light path needs to be modelled. A ship emission model, FMI-STEAM, has been compared to the optical measurements showing an 18% overestimation and a correlation coefficient (R2) of 0.6. It is shown that a combination of the optical method with modelled power consumption can estimate the sulphur fuel content within 40%, which would be sufficient to detect the difference between ships running at 1% and at 0.1%, limits applicable within the IMO regulated areas.

Aerosol profiling with the Jenoptik ceilometer CHM15kx

Abstract: . Since a few years, the number of active remote sensing systems has been rapidly increasing as national weather services started to build up networks of ceilometers. As ceilometers can be considered as "simple" backscatter lidars, it is obvious to investigate to which extent they can provide quantitative aerosol information. In this context, the calibration of the ceilometer is the most crucial point: whereas previous studies primarily have relied on the comparisons with co-incident sun photometer measurements and the Rayleigh calibration, we provide an absolute calibration of the ceilometer. The advantage of this approach is that backscatter profiles can be derived during daytime and nighttime, and even in cases when the signal-to-noise ratio of signals from the free troposphere is very low. Moreover, the retrieval can easily be automated. In this paper, we consider the Jenoptik CHM15kx-ceilometer. We discuss the methodology and the achievable accuracy and present a set of examples to highlight the wide range of applications, and the limitations. The achievable temporal resolution is of the order of a few minutes; the relative error of the particle backscatter coefficient is less than 10%. It is emphasized that the accuracy of extinction coefficients and – as a consequence – of the aerosol optical depth is limited due to the unknown lidar ratio. This is, however, an inherent problem of any backscatter lidar and not a special feature of the ceilometer.