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Sample records for absorption spectroscopy max-doas

  1. Multi axis differential optical absorption spectroscopy (MAX-DOAS) of gas and aerosol distributions.

    PubMed

    Sinreich, R; Friess, U; Wagner, T; Platt, U

    2005-01-01

    We present and demonstrate a relatively simple algorithm, which converts a set of slant column density measurements of oxygen dimers (O4) and NO2 at several different elevation angles to determine the atmospheric aerosol extinction and the absolute concentration and mixing ratio of NO2 within the atmospheric boundary layer. In addition the height of the atmospheric boundary layer can usually be derived, also the technique can be readily extended to determine the concentration of several other trace gases including SO2, CH2O, or glyoxal. The algorithm is based on precise radiation transport modelling determination, taking into account the actual aerosol scenario as determined from the O4 measurements. The required hardware is simple encompassing essentially a miniature spectrometer, a small telescope, a pointing mechanism, and a Personal Computer (PC). Effectively the technique combines the simplicity of a passive MAX-DOAS observation with the capability of a much more complex active DOAS instrument to determine path-averaged, absolutely calibrated mixing ratios of atmospheric trace gases at relatively high accuracy.

  2. Multi axis differential optical absorption spectroscopy (MAX-DOAS) of gas and aerosol distributions.

    PubMed

    Sinreich, R; Friess, U; Wagner, T; Platt, U

    2005-01-01

    We present and demonstrate a relatively simple algorithm, which converts a set of slant column density measurements of oxygen dimers (O4) and NO2 at several different elevation angles to determine the atmospheric aerosol extinction and the absolute concentration and mixing ratio of NO2 within the atmospheric boundary layer. In addition the height of the atmospheric boundary layer can usually be derived, also the technique can be readily extended to determine the concentration of several other trace gases including SO2, CH2O, or glyoxal. The algorithm is based on precise radiation transport modelling determination, taking into account the actual aerosol scenario as determined from the O4 measurements. The required hardware is simple encompassing essentially a miniature spectrometer, a small telescope, a pointing mechanism, and a Personal Computer (PC). Effectively the technique combines the simplicity of a passive MAX-DOAS observation with the capability of a much more complex active DOAS instrument to determine path-averaged, absolutely calibrated mixing ratios of atmospheric trace gases at relatively high accuracy. PMID:16161782

  3. Observation of the volcanic plume of Eyjafjallajökull over continental Europe by Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS)

    NASA Astrophysics Data System (ADS)

    Yilmaz, S.; Friess, U.; Kern, C.; Vogel, L.; Hoermann, C.; Wagner, T.; Platt, U.

    2010-12-01

    The recent eruption of Eyjafjallajökull Volcano (Iceland) and the emitted ash plume which disrupted commercial air traffic over Europe for an extended period of time has led to an exhaustive debate on how to improve our ability to quantitatively determine the ash load in the atmosphere as a function of time and geographical location in the aftermath of future eruptions. A combination of satellite remote sensing instruments detecting ash and SO2 and ground-based LIDAR stations can help constrain atmospheric transport and meteorology models used to predict ash dispersion. However, multi-axis Differential Optical Absorption Spectroscopy (MAX-DOAS) represents an additional and often neglected tool with considerable potential for the quantitative detection of elevated volcanic ash and SO2 plumes. It performs especially well during weather conditions in which satellites and LIDARs are impeded in their effectiveness, e.g. in the case of dense clouds above or below the plume, respectively. Here, the advantages and disadvantages of the DOAS technique are discussed, and its potential for monitoring of volcanic ash hazards explored. Results of ash and SO2 measurements of the Eyjafjallajökull plume as it passed over the city of Heidelberg, Germany are presented as an example of a positive detection of a highly diluted volcanic plume. SO2 was detected on several days with differential slant column densities (dSCD) of up to (3.33 ± 0.35) × 1017 molec/cm2. The occurrence of these high dSCDs is in good agreement with model predictions (FLEXPART), in-situ background (Schauinsland, Germany) and remote sensing measurements (GOME-2). For cloud free conditions, also the aerosol optical depth at 350 nm was retrieved from the MAX-DOAS measurements. The retrieved values of up to 1.31 ± 0.02 are in good agreement with Sun photometer measurements. Their relatively low cost and complementary nature in respect to other SO2/ash detection techniques makes multi-axis DOAS a promising

  4. Comparison of ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) and satellite DOAS measurements of NO2 distribution over Ulaanbaatar (Mongolia) during summer 2013

    NASA Astrophysics Data System (ADS)

    Böhnke, Sebastian; Behrendt, Thomas; Bruse, Michael; Meixner, Franz X.; Mamtimin, Buhalqem

    2014-05-01

    Cities are immense sources of air pollutants; however, emission inventories in many of them still are highly uncertain, particularly in developing countries. Ulaanbaatar is the most populous and polluted area in Mongolia. Tropospheric NO2 is proved to be harmful to both, the atmospheric environment and human health. It might be meaningful and important to observe pollutant concentrations in an area-integrated form (satellite observations) to create a sound data basis for air quality control measures. In our study, we preliminary present the results of both satellite and ground-based Differential Optical Absorption Spectroscopy (DOAS) measurements of vertical column densities (VCDs) of NO2 in Ulaanbaatar (urban area). As a ground validation tool, the MAX-DOAS measurements carried out in Ulaanbaatar (Mongolia) summer 2013 and are applied at 3 different sites in the west of Ulaanbaatar (106.73° E / 47.83° N), the city center (106.92° E / 47.92° N) and in the east (107.12° E / 47.87° N). Additionally, Automatic Weather Stations (AWS) have been set up and ozone was measured by UV absorption technique also at the 3 sites. Preliminary results show that the NO2 column densities increase during sunset and decrease after sunrise, which is most likely caused by a longer light path resulting from high solar zenith angles (SZA). The maximum DSCDs (Differential Slant Column Densities) are observed around sunset and sunrise (up to 10^17 molec cm-², mainly a measurement effect as stated above). The daily minima of the vertical column densities (VCD) appear in the morning and in the afternoon (DSCD ~2×10^15 molec cm-²) while, around noon, a second maximum can be observed (DSCD ~4×10^16 molec cm-²). Satellite data show mean VCDs of about 3×10^15 molec cm-² in July and a varying agreement with MAX-DOAS measurements.

  5. Elevated aerosol layers modify the O2-O2 absorption measured by ground-based MAX-DOAS

    NASA Astrophysics Data System (ADS)

    Ortega, Ivan; Berg, Larry K.; Ferrare, Richard A.; Hair, Johnathan W.; Hostetler, Chris A.; Volkamer, Rainer

    2016-06-01

    The oxygen collisional complex (O2-O2, or O4) is a greenhouse gas, and a calibration trace gas used to infer aerosol and cloud properties by Differential Optical Absorption Spectroscopy (DOAS). Recent reports suggest the need for an O4 correction factor (CFO4) when comparing simulated and measured O4 differential slant column densities (dSCD) by passive DOAS. We investigate the sensitivity of O4 dSCD simulations at ultraviolet (360 nm) and visible (477 nm) wavelengths towards separately measured aerosol extinction profiles. Measurements were conducted by the University of Colorado 2D-MAX-DOAS instrument and NASA's multispectral High Spectral Resolution Lidar (HSRL-2) during the Two Column Aerosol Project (TCAP) at Cape Cod, MA in July 2012. During two case study days with (1) high aerosol load (17 July, AOD~0.35 at 477 nm), and (2) near molecular scattering conditions (22 July, AOD<0.10 at 477 nm) the measured and calculated O4 dSCDs agreed within 6.4±0.4% (360 nm) and 4.7±0.6% (477 nm) if the HSRL-2 profiles were used as input to the calculations. However, if in the calculations the aerosol is confined to the surface layer (while keeping AOD constant) we find 0.53MAX-DOAS. Opportunities to identify and better characterize these elevated layers are also discussed.

  6. Absolute calibration of the colour index and O4 absorption derived from Multi AXis (MAX-)DOAS measurements and their application to a standardised cloud classification algorithm

    NASA Astrophysics Data System (ADS)

    Wagner, Thomas; Beirle, Steffen; Remmers, Julia; Shaiganfar, Reza; Wang, Yang

    2016-09-01

    A method is developed for the calibration of the colour index (CI) and the O4 absorption derived from differential optical absorption spectroscopy (DOAS) measurements of scattered sunlight. The method is based on the comparison of measurements and radiative transfer simulations for well-defined atmospheric conditions and viewing geometries. Calibrated measurements of the CI and the O4 absorption are important for the detection and classification of clouds from MAX-DOAS observations. Such information is needed for the identification and correction of the cloud influence on Multi AXis (MAX-)DOAS profile inversion results, but might be also be of interest on their own, e.g. for meteorological applications. The calibration algorithm was successfully applied to measurements at two locations: Cabauw in the Netherlands and Wuxi in China. We used CI and O4 observations calibrated by the new method as input for our recently developed cloud classification scheme and also adapted the corresponding threshold values accordingly. For the observations at Cabauw, good agreement is found with the results of the original algorithm. Together with the calibration procedure of the CI and O4 absorption, the cloud classification scheme, which has been tuned to specific locations/conditions so far, can now be applied consistently to MAX-DOAS measurements at different locations. In addition to the new threshold values, further improvements were introduced to the cloud classification algorithm, namely a better description of the SZA (solar zenith angle) dependence of the threshold values and a new set of wavelengths for the determination of the CI. We also indicate specific areas for future research to further improve the cloud classification scheme.

  7. Multiple Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of Bromine Monoxide (BrO) and ozone over the ice in Arctic and Sub Arctic in the winter, spring and summer of 2008 and 2009

    NASA Astrophysics Data System (ADS)

    Netcheva, Stoyka; Bottenheim, Jan; Bobrowski, Nicole; Staebler, Ralf; Chang, Rachel

    2010-05-01

    Ozone is frequently nearly completely removed from the marine boundary layer in the Polar Regions during the spring time every year. Those spring-time boundary layer ozone depletion events (ODE) are driven by reactive bromine liberated from saline surfaces. ODEs are usually found to be associated with enhanced BrO in the troposphere. ODEs and elevated BrO values over Polar Regions were recorded at ground coastal observation stations, through satellite observations and during a limited number of intensive measurements conducted on board research marine based and aircraft platforms. Improvements of the measurements, retrieval precision and spatial and temporal coverage have been made over the years. However, many questions about the processes remain unanswered including initiation and recycling mechanisms, the role of different surfaces and meteorological conditions for bromine release and recycling, and their vertical extent. Out On The Ice (OOTI) is a fully automated observatory designed to measure BrO, ozone and gaseous elemental mercury along with meteorological parameters in the cold remote Arctic environment. It was developed under OASIS-Canada ("Ocean Atmosphere Sea Ice and Snow interactions in Polar regions") framework to study air-surface interactions right above the sea ice surface. An overview of this work will be presented of the MAX-DOAS BrO and in-situ ozone measurements from four field campaigns selected for recurring elevated BrO values and frequent ozone depletion episodes. The characteristics of the surrounding surface and environmental variables such as temperature, solar radiation, winds speed and direction are combined with back trajectory analysis to improve our understanding on the factors affecting the presence and origin of BrO at specific locations.

  8. MAX-DOAS measurements of tropospheric NO2 over San Salvador: preliminary results

    NASA Astrophysics Data System (ADS)

    Alberti, Carlos; Wagner, Thomas

    2015-04-01

    We present the first Multi-AXis-Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements at San Salvador. MAX-DOAS observes spectra of scattered sun light taken at different elevation angles. From the spectra the so called slant column density (SCD, the integrated trace gas concentration along the atmospheric light path) is derived. We quantify the dSCD of NO2 at different measurement conditions. From the measured NO2 SCDs we calculate the tropospheric vertical column density using the so called geometric approximation. The preliminary results of this MAX DOAS observations and the diurnal variation of the retrieved trace gas dSCDs will be presented. We also use the MAX-DOAS results for the validation of satellite observations.

  9. Intercomparison of MAX-DOAS NO2 retrieval algorithms

    NASA Astrophysics Data System (ADS)

    Peters, Enno; Pinardi, Gaia; Bösch, Tim; Wittrock, Folkard; Richter, Andreas; Burrows, John P.; Van Roozendael, Michel; Piters, Ankie; Wagner, Thomas; Drosoglou, Theano; Bais, Alkis; Wang, Shanshan; Saiz-Lopez, Alfonso

    2016-04-01

    Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements are a powerful method for monitoring of atmospheric composition in an automated way. The number of instruments and sites operated has been rapidly increasing over the last years. However, integrating the measurements from all these instruments into a consistent data set necessitates careful homogenization of measurements and data retrieval procedures. For this reason, several MAX-DOAS intercomparison campaigns have been carried out in the last years. Mostly, slant columns measured by different instruments and retrieved by different software were intercompared, i.e. observed differences were potentially caused by both, the instrument and/or the retrieval. In contrast, the approach presented here is a pure intercomparison of MAX-DOAS retrievals. In total, 16 international groups and institutes working in the field of MAX-DOAS participated. The work was performed as part of the EU-funded QA4ECV project. The intercomparison exercise is based on data recorded by the IUP-Bremen MAX-DOAS instrument during the MAD-CAT campaign (Multi-Axis DOAS comparison campaign for Aerosols and Trace gases), which was carried out at the Max-Planck-Institute of Chemistry in Mainz, Germany, in summer 2013. Each group participating in the exercise presented here performed MAX-DOAS fits using their own retrieval software but common input (IUP-Bremen spectra, same cross-sections, and same fit settings). The resulting slant columns show in general an excellent agreement (correlation coefficient > 99.9%). Surprisingly, the correlation is substantially smaller when using sequential Fraunhofer reference spectra instead of a noon reference indicating that groups calculate the sequential reference differently. Further differences were found to arise from treatment of the slit function and subsequent convolution of cross-sections as well as from wavelength calibration. The results indicate overall a high

  10. NOx emissions of various sources in Romania and the Rhein-Main region in Germany based on mobile MAX-DOAS measurements of NO2.

    NASA Astrophysics Data System (ADS)

    Riffel, Katharina; Sebastian, Donner; Shaiganfar, Reza; Wagner, Thomas; Dörner, Steffen

    2016-04-01

    The MAX DOAS-Method (Multi-AXis Differential Optical Absorption Spectroscopy) is used to analyze different trace gases (e.g. NO2, SO2, HCHO) at the same time and to determine the trace gas vertical column density (vertically integrated concentration). In summer 2015 we performed car-MAX-DOAS measurements in Romania during the AROMAT2 campaign. We encircled Bucharest at different weather situations and different times of the day. Afterwards the total NOx emissions were derived from the mobile MAX-DOAS observations in combination with wind data. In Germany we performed the same measurement procedure in fall/ winter/ spring 2015 /2016 by encircling the cities Mainz and Frankfurt. For the setting we mounted two MAX-DOAS instruments with different viewing directions (forward and backward) on the roof of a car. One instrument is a commercial mini MAX-DOAS that is built by the German company Hoffmann Messtechnik. The second one was built at the MPI in Mainz. This so-called Tube MAX-DOAS uses an AVANTES spectrometer with better optical characteristics than Hoffmann's mini MAX-DOAS. The advantage of two instruments working at the same time is (besides redundancy) that localized emission plumes can be measured from different directions at different locations. Thus, especially for emission plumes from power plants, tomographic methods can be applied to derive information about the plume altitude. Car-MAX-DOAS observations can cover large areas at a short time with reasonable resolution (depending on the speed of the car and the instruments integration time). Thus these measurements are well suited to validate satellites observations. This work will show the first AROMAT2 results of NOx emissions derived in Romania and in the Rhein-Main region, which is one of the most polluted area in Germany.

  11. Long-term measurements of trace gaseous pollutants over Beijing using Mini-MAX-DOAS instruments

    NASA Astrophysics Data System (ADS)

    Ma, Jianzhong; Jin, Junli; Shaiganfar, Reza; Wagner, Thomas

    2014-05-01

    Air quality in Beijing megacity has been of great concern in the atmospheric and environmental science community as well as public media. In addition to in situ measurements of ambient concentrations of air pollutants (e.g. NO2, SO2) near the ground, satellite data have also been used to analyze the long-term variation trend of urban pollution as well as the special emission control effect. However, the emission sources of pollutants in a megacity like Beijing are diverse and heterogeneously distributed in the urban canopy. Therefore, in situ surface measurement results may be quite different from one site to another depending on the representativeness of the chosen sites. Satellite measurements are found to have large biases in monitoring the air pollutant levels in a city due to both grid-smoothing and aerosol shielding effects. Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a passive remote sensing technology, which retrieves atmospheric trace gases by using scattered sun light from various elevation angles. Ground-based measurements by MAX-DOAS are especially sensitive to the tropospheric part of trace gas column, and can be used effectively to validate the satellite products for the troposphere. We have performed ground Mini-MAX-DOAS measurements at an urban site (39.95N, 116.32E) in Beijing since August 2008. The diurnal and seasonal variations of tropospheric NO2 vertical column densities were retrieved by analyzing the MAX-DOAS spectra obtained at this site. Such dataset were also used to validate the SCIMACHY and OMI satellite NO2 products for the period 2008-2009. Analyses of these MAX-DOAS spectra for SO2 and HCHO will be done in the near future to investigate the long-term variations of pollution level and character in Beijing over the past years.

  12. Inference of cloud altitude and optical properties from MAX-DOAS measurements

    NASA Astrophysics Data System (ADS)

    Nasse, Jan-Marcus; Zielcke, Johannes; Frieß, Udo; Lampel, Johannes; König-Langlo, Gert; Platt, Ulrich

    2015-04-01

    Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) is a widely used technique for the detection of atmospheric trace gases, e.g. NO2, SO2, BrO, HCHO, but also for the oxygen collision complex O4. The atmospheric distribution of the latter is proportional to the square of the molecular oxygen concentration and thus well known. By comparing measured O4 differential slant column densities (dSCDs) from MAX-DOAS measurements with modeled ones, information on aerosol distributions and optical properties, as well as on clouds can be obtained using an algorithm based on optimal estimation. Here the ability of MAX-DOAS observations to detect cloud altitude and cloud optical properties of different cloud covers based on measurements of O4 will be discussed. The analysis uses measurements made by a ship-borne instrument on two cruises of the German research vessel Polarstern to the Antarctic Weddell Sea from June to October 2013. During this time a broad range of cloud and aerosol conditions was encountered, in particular persistent low cloud cover with a high optical thickness. Aerosol and particle extinction profiles were retrieved with temporal resolutions of up to 15 minutes. For clouds at altitudes up to 2000 m the results show a very good agreement with co-located measurements of a commercial ceilometer and pictures from a cloud camera. Unless visibility was very poor due to fog, even rapid changes in cloud altitude or cover could be detected by MAX-DOAS. These results indicate that under homogeneous cloud cover an accurate retrieval of trace gas vertical profiles can be possible despite the strong influence of clouds on atmospheric light paths. We will discuss advantages and limitations of cloud detection with MAX-DOAS, implications for the subsequent retrieval of trace gas profiles and the possible use of external (ceilometer) data as a priori information for the profile retrieval algorithm.

  13. The effect of cloud screening on MAX-DOAS aerosol retrievals.

    NASA Astrophysics Data System (ADS)

    Gielen, Clio; Van Roozendael, Michel; Hendrik, Francois; Fayt, Caroline; Hermans, Christian; Pinardi, Gaia; De Backer, Hugo; De Bock, Veerle; Laffineur, Quentin; Vlemmix, Tim

    2014-05-01

    In recent years, ground-based multi-axis differential absorption spectroscopy (MAX-DOAS) has shown to be ideally suited for the retrieval of tropospheric trace gases and deriving information on the aerosol properties. These measurements are invaluable to our understanding of the physics and chemistry of the atmospheric system, and the impact on the Earth's climate. Unfortunately, MAX-DOAS measurements are often performed under strong non-clear-sky conditions, causing strong data quality degradation and uncertainties on the retrievals. Here we present the result of our cloud-screening method, using the colour index (CI), on aerosol retrievals from MAX-DOAS measurements (AOD and vertical profiles). We focus on two large data sets, from the Brussels and Beijing area. Using the CI we define 3 different sky conditions: bad (=full thick cloud cover/extreme aerosols), mediocre (=thin clouds/aerosols) and good (=clear sky). We also flag the presence of broken/scattered clouds. We further compare our cloud-screening method with results from cloud-cover fractions derived from thermic infrared measurements. In general, our method shows good results to qualify the sky and cloud conditions of MAX-DOAS measurements, without the need for other external cloud-detection systems. Removing data under bad-sky and broken-cloud conditions results in a strongly improved agreement, in both correlation and slope, between the MAX-DOAS aerosol retrievals and data from other instruments (e.g. AERONET, Brewer). With the improved AOD retrievals, the seasonal and diurnal variations of the aerosol content and vertical distribution at both sites can be investigated in further detail. By combining with additional information derived by other instruments (Brewer, lidar, ...) operated at the stations, we will further study the observed aerosol characteristics, and their influence on and by meteorological conditions such as clouds and/or the boundary layer height.

  14. Evaluation of MAX-DOAS aerosol retrievals by coincident observations using CRDS, lidar, and sky radiometer in Tsukuba, Japan

    NASA Astrophysics Data System (ADS)

    Irie, H.; Nakayama, T.; Shimizu, A.; Yamazaki, A.; Nagai, T.; Uchiyama, A.; Zaizen, Y.; Kagamitani, S.; Matsumi, Y.

    2015-01-01

    Coincident aerosol observations of Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS), Cavity Ring Down Spectroscopy (CRDS), lidar, and sky radiometer were conducted in Tsukuba, Japan on 5-18 October 2010. MAX-DOAS aerosol retrieval (for aerosol extinction coefficient and aerosol optical depth at 476 nm) was evaluated from the viewpoint of the need for a correction factor for oxygen collision complexes (O4 or O2-O2) absorption. The present study strongly supports this need, as systematic residuals at relatively high elevation angles (20 and 30°) were evident in MAX-DOAS profile retrievals conducted without the correction. However, adopting a single number for the correction factor (fO4 = 1.25) for all of the elevation angles led to systematic overestimation of near-surface aerosol extinction coefficients, as reported in the literature. To achieve agreement with all three observations, we limited the set of elevation angles to ≤ 10° and adopted an elevation-angle-dependent correction factor for practical profile retrievals with scattered light observations by a ground-based MAX-DOAS. With these modifications, we expect to minimize the possible effects of temperature-dependent O4 absorption cross section and uncertainty in DOAS fit on an aerosol profile retrieval, although more efforts are encouraged to quantitatively identify a physical explanation for the need of a correction factor.

  15. Evaluation of MAX-DOAS aerosol retrievals by coincident observations using CRDS, lidar, and sky radiometer inTsukuba, Japan

    NASA Astrophysics Data System (ADS)

    Irie, H.; Nakayama, T.; Shimizu, A.; Yamazaki, A.; Nagai, T.; Uchiyama, A.; Zaizen, Y.; Kagamitani, S.; Matsumi, Y.

    2015-07-01

    Coincident aerosol observations of multi-axis differential optical absorption spectroscopy (MAX-DOAS), cavity ring-down spectroscopy (CRDS), lidar, and sky radiometer were conducted in Tsukuba, Japan, on 5-18 October 2010. MAX-DOAS aerosol retrieval (for aerosol extinction coefficient and aerosol optical depth at 476 nm) was evaluated from the viewpoint of the need for a correction factor for oxygen collision complexes (O4 or O2-O2) absorption. The present study strongly supports this need, as systematic residuals at relatively high elevation angles (20 and 30°) were evident in MAX-DOAS profile retrievals conducted without the correction. However, adopting a single number for the correction factor (fO4 = 1.25) for all of the elevation angles led to systematic overestimation of near-surface aerosol extinction coefficients, as reported in the literature. To achieve agreement with all three observations, we limited the set of elevation angles to ≤10° and adopted an elevation-angle-dependent correction factor for practical profile retrievals with scattered light observations by a ground-based MAX-DOAS. With these modifications, we expect to minimize the possible effects of temperature-dependent O4 absorption cross section and uncertainty in DOAS fit on an aerosol profile retrieval, although more efforts are encouraged to quantitatively identify a physical explanation for the need of a correction factor.

  16. Direct sun and airborne MAX-DOAS measurements of the collision induced oxygen complex, O2O2 absorption with significant pressure and temperature differences

    NASA Astrophysics Data System (ADS)

    Spinei, E.; Cede, A.; Herman, J.; Mount, G. H.; Eloranta, E.; Morley, B.; Baidar, S.; Dix, B.; Ortega, I.; Koenig, T.; Volkamer, R.

    2014-09-01

    The collision induced O2 complex, O2O2, is a very important trace gas in remote sensing measurements of aerosol and cloud properties. Some ground based MAX-DOAS measurements of O2O2 slant column density require correction factors of 0.75 ± 0.1 to reproduce radiative transfer modeling (RTM) results for a near pure Rayleigh atmosphere. One of the potential causes of this discrepancy is believed to be uncertainty in laboratory measured O2O2 absorption cross section temperature and pressure dependence, due to difficulties in replicating atmospheric conditions in the laboratory environment. This paper presents direct-sun (DS) and airborne multi-axis (AMAX) DOAS measurements of O2O2 absorption optical depths under actual Earth atmospheric conditions in two wavelength regions (335-390 nm and 435-490 nm). DS irradiance measurements were made by the research grade MFDOAS instrument from 2007-2014 at seven sites with significant pressure (778-1013 hPa) and O2O2 profile weighted temperature (247-275 K) differences. Aircraft MAX-DOAS measurements were conducted by the University of Colorado AMAX-DOAS instrument on 29 January 2012 over the Southern Hemisphere subtropical Pacific Ocean. Scattered solar radiance spectra were collected at altitudes between 9 and 13.2 km, with O2O2 profile weighted temperatures of 231-244 K, and near pure Rayleigh scattering conditions. Due to the well defined DS air mass factors and extensively characterized atmospheric conditions during the AMAX-DOAS measurements, O2O2"pseudo" absorption cross sections, σ, are derived from the observed optical depths and estimated O2O2column densities. Vertical O2O2 columns are calculated from the atmospheric sounding temperature, pressure and specific humidity profiles. Based on the atmospheric DS observations, there is no pressure dependence of the O2O2 σ, within the measurement errors (3%). The two data sets are combined to derive peak σ temperature dependence of 360 and 477 nm absorption bands from 231

  17. Cloud and aerosol classification for 2 1/2 years of MAX-DOAS observations in Wuxi (China) and comparison to independent data sets

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Penning de Vries, M.; Xie, P. H.; Beirle, S.; Dörner, S.; Remmers, J.; Li, A.; Wagner, T.

    2015-05-01

    Multi-Axis-Differential Optical Absorption Spectroscopy (MAX-DOAS) observations of trace gases can be strongly influenced by clouds and aerosols. Thus it is important to identify clouds and characterise their properties. In a recent study Wagner et al. (2014) developed a cloud classification scheme based on the MAX-DOAS measurements themselves with which different "sky conditions" (e.g. clear sky, continuous clouds, broken clouds) can be distinguished. Here we apply this scheme to long term MAX-DOAS measurements from 2011 to 2013 in Wuxi, China (31.57° N, 120.31° E). The original algorithm has been modified, in particular in order to account for smaller solar zenith angles (SZA). Instrumental degradation is accounted for to avoid artificial trends of the cloud classification. We compared the results of the MAX-DOAS cloud classification scheme to several independent measurements: aerosol optical depth from a nearby AERONET station and from MODIS, visibility derived from a visibility meter; and various cloud parameters from different satellite instruments (MODIS, OMI, and GOME-2). The most important findings from these comparisons are: (1) most cases characterized as clear sky with low or high aerosol load were associated with the respective AOD ranges obtained by AERONET and MODIS, (2) the observed dependences of MAX-DOAS results on cloud optical thickness and effective cloud fraction from satellite indicate that the cloud classification scheme is sensitive to cloud (optical) properties, (3) separation of cloudy scenes by cloud pressure shows that the MAX-DOAS cloud classification scheme is also capable of detecting high clouds, (4) some clear sky conditions, especially with high aerosol load, classified from MAX-DOAS observations corresponding to the optically thin and low clouds derived by satellite observations probably indicate that the satellite cloud products contain valuable information on aerosols.

  18. Intercomparison of aerosol extinction profiles retrieved from MAX-DOAS measurements

    NASA Astrophysics Data System (ADS)

    Frieß, U.; Klein Baltink, H.; Beirle, S.; Clémer, K.; Hendrick, F.; Henzing, B.; Irie, H.; de Leeuw, G.; Li, A.; Moerman, M. M.; van Roozendael, M.; Shaiganfar, R.; Wagner, T.; Wang, Y.; Xie, P.; Yilmaz, S.; Zieger, P.

    2016-07-01

    A first direct intercomparison of aerosol vertical profiles from Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations, performed during the Cabauw Intercomparison Campaign of Nitrogen Dioxide measuring Instruments (CINDI) in summer 2009, is presented. Five out of 14 participants of the CINDI campaign reported aerosol extinction profiles and aerosol optical thickness (AOT) as deduced from observations of differential slant column densities of the oxygen collision complex (O4) at different elevation angles. Aerosol extinction vertical profiles and AOT are compared to backscatter profiles from a ceilometer instrument and to sun photometer measurements, respectively. Furthermore, the near-surface aerosol extinction coefficient is compared to in situ measurements of a humidity-controlled nephelometer and dry aerosol absorption measurements. The participants of this intercomparison exercise use different approaches for the retrieval of aerosol information, including the retrieval of the full vertical profile using optimal estimation and a parametrised approach with a prescribed profile shape. Despite these large conceptual differences, and also differences in the wavelength of the observed O4 absorption band, good agreement in terms of the vertical structure of aerosols within the boundary layer is achieved between the aerosol extinction profiles retrieved by the different groups and the backscatter profiles observed by the ceilometer instrument. AOTs from MAX-DOAS and sun photometer show a good correlation (R>0.8), but all participants systematically underestimate the AOT. Substantial differences between the near-surface aerosol extinction from MAX-DOAS and from the humidified nephelometer remain largely unresolved.

  19. Atmospheric aerosol characterization combining multi-wavelength Raman lidar and MAX-DOAS measurements in Gwanjgu

    NASA Astrophysics Data System (ADS)

    Chong, Jihyo; Shin, Dong Ho; Kim, Kwang Chul; Lee, Kwon-Ho; Shin, Sungkyun; Noh, Young M.; Müller, Detlef; Kim, Young J.

    2011-11-01

    Integrated approach has been adopted at the ADvanced Environmental Research Center (ADEMRC), Gwangju Institute of Science and Technology (GIST), Korea for effective monitoring of atmospheric aerosol. Various active and passive optical remote sensing techniques such as multi-wavelength (3β+2α+1δ) Raman LIDAR, sun-photometry, MAX-DOAS, and satellite retrieval have been utilized. This integrated monitoring system approach combined with in-situ surface measurement is to allow better characterization of physical and optical properties of atmospheric aerosol. Information on the vertical distribution and microphysical properties of atmospheric aerosol is important for understanding its transport characteristics as well as radiative effect. The GIST multi-wavelength (3β + 2α+1δ) Raman lidar system can measure vertical profiles of optical properties of atmospheric aerosols such as extinction coefficients at 355 and 532nm, particle backscatter coefficients at 355, 532 and 1064 nm, and depolarization ratio at 532nm. The incomplete overlap between the telescope field-of-view and beam divergence of the transmitting laser significantly affects lidar measurement, resulting in higher uncertainty near the surface where atmospheric aerosols of interest are concentrated. Differential Optical Absorption Spectroscopy (DOAS) technique is applied as a complementary tool for the detection of atmospheric aerosols near the surface. The passive Multi-Axis DOAS (MAX-DOAS) technique uses scattered sunlight as a light source from several viewing directions. Recently developed aerosol retrieval algorithm based on O4 slant column densities (SCDs) measured at UV and visible wavelengths has been utilized to derive aerosol information (e.g., aerosol optical depth (AOD) and aerosol extinction coefficients (AECs)) in the lower troposphere. The aerosol extinction coefficient at 356 nm was retrieved for the 0-1 and 1-2 km layers based on the MAX-DOAS measurements using the retrieval algorithm

  20. MAX-DOAS observations of the total atmospheric water vapour column and comparison with independent observations

    NASA Astrophysics Data System (ADS)

    Wagner, T.; Andreae, M. O.; Beirle, S.; Dörner, S.; Mies, K.; Shaiganfar, R.

    2013-01-01

    We developed an algorithm for the retrieval of the atmospheric water vapour column from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in the yellow and red spectral range. The retrieval is based on the so-called geometric approximation and does not depend on explicit a priori information for individual observations, extensive radiative transfer simulations, or the construction of large look-up tables. Disturbances of the radiative transfer due to aerosols and clouds are simply corrected using the simultaneously measured absorptions of the oxygen dimer, O4. We applied our algorithm to MAX-DOAS observations made at the Max Planck Institute for Chemistry in Mainz, Germany, from March to August 2011, and compared the results to independent observations. Good agreement with Aerosol Robotic Network (AERONET) and European Centre for Medium-Range Weather Forecasting (ECMWF) H2O vertical column densities (VCDs) is found, while the agreement with satellite observations is less good, most probably caused by the shielding effect of clouds for the satellite observations. Good agreement is also found with near-surface in situ observations, and it was possible to derive average daily H2O scale heights (between 1.5 km and 3 km). MAX-DOAS measurements use cheap and simple instrumentation and can be run automatically. One important advantage of our algorithm is that the H2O VCD can be retrieved even under cloudy conditions (except clouds with very high optical thickness).

  1. MAX-DOAS observations of the total atmospheric water vapour column and comparison with independent observations

    NASA Astrophysics Data System (ADS)

    Wagner, T.; Andreae, M. O.; Beirle, S.; Dörner, S.; Mies, K.; Shaiganfar, R.

    2012-09-01

    We developed an algorithm for the retrieval of the atmospheric water vapour column from Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in the yellow and red spectral range. The retrieval is based on the so called geometric approximation and does not depend on a-priori information, extensive radiative transfer simulations, or the construction of large look-up tables. Disturbances of the radiative transfer due to aerosols and clouds are simply corrected using the simultaneously measured absorptions of the oxygen dimer, O4. We applied our algorithm to MAX-DOAS observations made at the Max Planck Institute for Chemistry in Mainz, Germany, from March to August 2011 and compared the results to independent observations. Good agreement with Aerosol Robotic Network (AERONET) and European Centre for Medium-Range Weather Forecasting (ECMWF) H2O vertical column densities (VCDs) is found, while the agreement with satellite observations is less good, most probably caused by the shielding effect of clouds for the satellite observations. Good agreement is also found with near-surface in-situ observations, and it was possible to derive average daily H2O layer heights (between 1.5 km and 3 km). MAX-DOAS measurements use cheap and simple instrumentation and can be run automatically. One important advantage of our algorithm is that the H2O VCD can be retrieved even under cloudy conditions (except clouds with very high optical thickness).

  2. Inter-comparison of MAX-DOAS Retrieved Vertical Profiles of Aerosol Extinction, SO2 and NO2 in the Alberta Oil Sands with LIDAR Data and GEM-MACH Air Quality Model.

    NASA Astrophysics Data System (ADS)

    Davis, Zoe; Friess, Udo; Strawbridge, Kevin; Whiteway, James; Aggarwal, Monika; Makar, Paul; Li, Shao-Meng; O'Brien, Jason; Baray, Sabour; Schnitzler, Elijah; Olfert, Jason S.; Osthoff, Hans D.; Lobo, Akshay; McLaren, Robert

    2016-04-01

    Understanding industrial emissions of trace gas pollutants in the Alberta oil sands is essential to maintaining air quality standards and informing public policy. Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of trace gases can improve knowledge of pollutant levels, vertical distribution and chemical transformation. During an intensive air measurement campaign to study emissions, transport, transformation and deposition of oil sands air pollutants from August to September of 2013, a MAX-DOAS instrument was deployed at a site north of Fort McMurray, Alberta to determine the vertical profiles of aerosol extinction, NO2 and SO2 through retrieval from the MAX-DOAS spectral measurements using an optimal estimation method. The large complement of data collected from multiple instruments deployed during this field campaign provides a unique opportunity to validate and characterize the performance of the MAX-DOAS vertical profile retrievals. Aerosol extinction profiles determined from two Light Detection and Ranging (LIDAR) instruments, one collocated and the other on a Twin Otter aircraft that flew over the site during the study, will be compared to the MAX-DOAS aerosol extinction profile retrievals. Vertical profiles of NO2 and SO2 retrieved from the MAX-DOAS measurements will be further compared with the composite vertical profiles measured from the flights of a second aircraft, the NRC-Convair 580, over the field site during the same measurement period. Finally, the MAX-DOAS retrieved tropospheric vertical column densities (VCDs) of SO2 and NO2 will be compared to the predicted VCDs from Environment and Climate Change Canada's Global Environmental Multi-scale - Modelling Air quality and Chemistry (GEM-MACH) air quality model over the grid cell containing the field site. Emission estimates of SO2 from the major oil mining facility Syncrude Mildred Lake using the MAX-DOAS VCD results, validated through the detailed characterization above

  3. Cloud and aerosol classification for 2.5 years of MAX-DOAS observations in Wuxi (China) and comparison to independent data sets

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Penning de Vries, M.; Xie, P. H.; Beirle, S.; Dörner, S.; Remmers, J.; Li, A.; Wagner, T.

    2015-12-01

    Multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations of trace gases can be strongly influenced by clouds and aerosols. Thus it is important to identify clouds and characterize their properties. In a recent study Wagner et al. (2014) developed a cloud classification scheme based on the MAX-DOAS measurements themselves with which different "sky conditions" (e.g., clear sky, continuous clouds, broken clouds) can be distinguished. Here we apply this scheme to long-term MAX-DOAS measurements from 2011 to 2013 in Wuxi, China (31.57° N, 120.31° E). The original algorithm has been adapted to the characteristics of the Wuxi instrument, and extended towards smaller solar zenith angles (SZA). Moreover, a method for the determination and correction of instrumental degradation is developed to avoid artificial trends of the cloud classification results. We compared the results of the MAX-DOAS cloud classification scheme to several independent measurements: aerosol optical depth from a nearby Aerosol Robotic Network (AERONET) station and from two Moderate Resolution Imaging Spectroradiometer (MODIS) instruments, visibility derived from a visibility meter and various cloud parameters from different satellite instruments (MODIS, the Ozone Monitoring Instrument (OMI) and the Global Ozone Monitoring Experiment (GOME-2)). Here it should be noted that no quantitative comparison between the MAX-DOAS results and the independent data sets is possible, because (a) not exactly the same quantities are measured, and (b) the spatial and temporal sampling is quite different. Thus our comparison is performed in a semi-quantitative way: the MAX-DOAS cloud classification results are studied as a function of the external quantities. The most important findings from these comparisons are as follows: (1) most cases characterized as clear sky with low or high aerosol load were associated with the respective aerosol optical depth (AOD) ranges obtained by AERONET and MODIS

  4. Ground-based direct-sun DOAS and airborne MAX-DOAS measurements of the collision-induced oxygen complex, O2O2, absorption with significant pressure and temperature differences

    NASA Astrophysics Data System (ADS)

    Spinei, E.; Cede, A.; Herman, J.; Mount, G. H.; Eloranta, E.; Morley, B.; Baidar, S.; Dix, B.; Ortega, I.; Koenig, T.; Volkamer, R.

    2015-02-01

    The collision-induced O2 complex, O2O2, is a very important trace gas for understanding remote sensing measurements of aerosols, cloud properties and atmospheric trace gases. Many ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of the O2O2 optical depth require correction factors of 0.75 ± 0.1 to reproduce radiative transfer modeling (RTM) results for a nearly pure Rayleigh atmosphere. One of the potential causes of this discrepancy is uncertainty in laboratory-measured O2O2 absorption cross section temperature and pressure dependencies due to difficulties in replicating atmospheric conditions in the laboratory environment. This paper presents ground-based direct-sun (DS) and airborne multi-axis (AMAX) DOAS measurements of O2O2 absorption optical depths under actual atmospheric conditions in two wavelength regions (335-390 and 435-490 nm). DS irradiance measurements were made by the Washington State University research-grade Multi-Function Differential Spectroscopy Instrument instrument from 2007 to 2014 at seven sites with significant pressure (778 to 1013 hPa) and O2O2 profile-weighted temperature (247 to 275 K) differences. Aircraft MAX-DOAS measurements were conducted by the University of Colorado (CU) AMAX-DOAS instrument on 29 January 2012 over the Southern Hemispheric subtropical Pacific Ocean. Scattered solar radiance spectra were collected at altitudes between 9 and 13.2 km, with O2O2 profile-weighted temperatures of 231 to 244 K and nearly pure Rayleigh scattering conditions. Due to the well-defined DS air-mass factors during ground-based measurements and extensively characterized atmospheric conditions during the aircraft AMAX-DOAS measurements, O2O2 "pseudo" absorption cross sections, σ, are derived from the observed optical depths and estimated O2O2 column densities. Vertical O2O2 columns are calculated from the atmospheric sounding temperature, pressure and specific humidity profiles. Based on the ground

  5. Observations of tropospheric NO2 using ground based MAX-DOAS and OMI measurements during the Shanghai World Expo 2010

    NASA Astrophysics Data System (ADS)

    Chan, K. L.; Hartl, A.; Lam, Y. F.; Xie, P. H.; Liu, W. Q.; Cheung, H. M.; Lampel, J.; Pöhler, D.; Li, A.; Xu, J.; Zhou, H. J.; Ning, Z.; Wenig, M. O.

    2015-10-01

    During the Shanghai World Expo 2010 ground based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of tropospheric nitrogen dioxide (NO2) were performed to investigate the effects of emission control measures during that time. In this study we measured NO2 using four identical MAX-DOAS instruments in Shanghai from April 2009 to November 2010. We combined our MAX-DOAS data, the Ozone Monitoring Instrument (OMI) satellite observations and meteorological information from the National Centers for Environmental Prediction final reanalysis data (NCEP FNL) in order to investigate the spatial distribution of NO2 over Shanghai and the effects of emission control measures during the Expo. In general, the comparison of cloud screened MAX-DOAS data and OMI observations are in good correlation (Pearson correlation coefficient between 0.67 and 0.93 for the four measurement stations). In addition, we compared the MAX-DOAS and OMI NO2 data from the Shanghai Expo in 2010 to the same time of the year in 2009. The results show that the NO2 columns were reduced up to ∼ 30% in the area of central Shanghai during the Expo but no significant reduction of NO2 levels was found in the nearby industrial area. The overall NO2 reduction from May, July and September 2010 ranged from 7.5% to 14.5%, which is comparable to observations in previous studies. Our results revealed that the NO2 reduction was mainly achieved by emission control policies on transportation sources in the city rather than the controls from nearby provinces.

  6. Observations of atmospheric trace gases by MAX-DOAS in the coastal boundary layer over Jiaozhou Bay

    NASA Astrophysics Data System (ADS)

    Li, Xianxin; Wang, Zhangjun; Meng, Xiangqian; Zhou, Haijin; Du, Libin; Qu, Junle; Chen, Chao; An, Quan; Wu, Chengxuan; Wang, Xiufen

    2014-11-01

    Atmospheric trace gases exist in the atmosphere of the earth rarely. But the atmospheric trace gases play an important role in the global atmospheric environment and ecological balance by participating in the global atmospheric cycle. And many environmental problems are caused by the atmospheric trace gases such as photochemical smog, acid rain, greenhouse effect, ozone depletion, etc. So observations of atmospheric trace gases become very important. Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) developed recently is a kind of promising passive remote sensing technology which can utilize scattered sunlight received from multiple viewing directions to derive vertical column density of lower tropospheric trace gases like ozone, sulfur dioxide and nitrogen dioxide. It has advantages of simple structure, stable running, passive remote sensing and real-time online monitoring automatically. A MAX-DOAS has been developed at Shandong Academy of Sciences Institute of Oceanographic Instrumentation (SDIOI) for remote measurements of lower tropospheric trace gases (NO2, SO2, and O3). In this paper, we mainly introduce the stucture of the instrument, calibration and results. Detailed performance analysis and calibration of the instrument were made at Qingdao. We present the results of NO2, SO2 and O3 vertical column density measured in the coastal boundary layer over Jiaozhou Bay. The diurnal variation and the daily average value comparison of vertical column density during a long-trem observation are presented. The vertical column density of NO2 and SO2 measured during Qingdao oil pipeline explosion on November 22, 2013 by MAX-DOAS is also presented. The vertical column density of NO2 reached to a high value after the explosion. Finally, the following job and the outlook for future possible improvements are given. Experimental calibration and results show that the developed MAX-DOAS system is reliable and credible.

  7. [MAX-DOAS Tomography Reconstruction for Gas Plume].

    PubMed

    Wei, Min-hong; Tong, Min-ming; Li, Su-wen; Xiao, Jian-yu

    2015-08-01

    In order to achieve precisely two-dimensional spatial distribution reconstruction of smoke plume, passive MAX-DOAS tomography is established, the measurement of the spatial distribution of the exhaust plume is implemented by more passive multi-axis differential absorption spectrum system. First, the multi-axis differential absorption spectrum system and its mechanism of inverse gas concentration are introduced in the paper. Then, algebra iterative algorithm is adopted to extract the information of the trace gas concentration in reconstruction simulation with different models and different scanning optical path, and the reconstruction program is designed. Then, the numerical simulation results are compared. Finally, a platform of multi-axis differential absorption optical tomography system is set up, a field campaign was carried out. The numerical simulation results show that the MAX-DOAS tomography can accurately reconstruct two-dimensional spatial distribution of plume model, the re- construction error of MAX-DOAS tomography with four light sources is about a third of the reconstruction error with double light sources, moreover, the reconstruction time is about a quarter of the reconstruction time of double light sources, and the reconstruction error of the twin peaks model is greater than that of the one peak model. Field test results show that the integral data of reconstruction image is consistent with the measured projection data of multi-axis differential absorption spectrum, the spatial distribution reconstruction of plume is in line with the actual situation. Studies have shown that the result of numerical simulation and field test results have consistency. PMID:26672304

  8. [MAX-DOAS Tomography Reconstruction for Gas Plume].

    PubMed

    Wei, Min-hong; Tong, Min-ming; Li, Su-wen; Xiao, Jian-yu

    2015-08-01

    In order to achieve precisely two-dimensional spatial distribution reconstruction of smoke plume, passive MAX-DOAS tomography is established, the measurement of the spatial distribution of the exhaust plume is implemented by more passive multi-axis differential absorption spectrum system. First, the multi-axis differential absorption spectrum system and its mechanism of inverse gas concentration are introduced in the paper. Then, algebra iterative algorithm is adopted to extract the information of the trace gas concentration in reconstruction simulation with different models and different scanning optical path, and the reconstruction program is designed. Then, the numerical simulation results are compared. Finally, a platform of multi-axis differential absorption optical tomography system is set up, a field campaign was carried out. The numerical simulation results show that the MAX-DOAS tomography can accurately reconstruct two-dimensional spatial distribution of plume model, the re- construction error of MAX-DOAS tomography with four light sources is about a third of the reconstruction error with double light sources, moreover, the reconstruction time is about a quarter of the reconstruction time of double light sources, and the reconstruction error of the twin peaks model is greater than that of the one peak model. Field test results show that the integral data of reconstruction image is consistent with the measured projection data of multi-axis differential absorption spectrum, the spatial distribution reconstruction of plume is in line with the actual situation. Studies have shown that the result of numerical simulation and field test results have consistency.

  9. Development of photovoltaic-driven MAX-DOAS system (Eco-MAXDOAS) and its evaluation using 4AZ-MAXDOAS system at Chiba, Japan

    NASA Astrophysics Data System (ADS)

    Kato, T.; Irie, H.

    2015-12-01

    It is recognized that the Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) technique is suitable for routine observations of atmospheric constituents as its setup is simple, power consumption is low, and fully automated long-term operation without absolute radiometric calibration is possible. In addition, it is also a powerful technique with abilities enabling simultaneous measurements of aerosols and their gaseous precursors, such as nitrogen dioxide (NO2) and sulfur dioxide (SO2). To exploit its further applications, we are have developed the photovoltaic-driven MAX-DOAS system, called Eco-MAXDOAS. By utilizing the Eco-MAXDOAS, we expect to make multi-component air quality observations possible in areas with problems on stable power supply. For this development, we removed a temperature controller to reduce the power consumption. Instead, a shutter was introduced just before the entrance slit of the spectrometer. With this modification, it was made possible to take dark count measurements more often than for the normal MAX-DOAS instrument by closing the shutter between observations at different elevation angles. We tested the Eco-MAXDOAS and found that the spectrometer temperature varied by less than ±0.3 degrees for 3 minutes interval of changing elevation angles. Using dark count data taken before and after scattered sun light observations, the Signal-to-Noise Ratio(SNR) was estimated to be about 10000. This supports that analysis for a differential absorption as small as 10-4 (0.01%) is possible. In addition, we compared the aerosol and NO2 data retrieved from Eco-MAXDOAS and MAX-DOAS observations, and we confirmed that the two retrieved values were usually almost the same but occasionally showed significant differences. To investigate the cause, we devised the 4AZ-MAXDOAS system, a set of 4 MAX-DOAS instruments directed toward different azimuth angels of north, south, east, and west. The observation with the 4AZ-MAXDOAS confirmed that the

  10. MAX-DOAS measurements and satellite validation of tropospheric NO2 and SO2 vertical column densities at a rural site of North China

    NASA Astrophysics Data System (ADS)

    Jin, Junli; Ma, Jianzhong; Lin, Weili; Zhao, Huarong; Shaiganfar, Reza; Beirle, Steffen; Wagner, Thomas

    2016-05-01

    North China (NC), namely Huabei in Chinese, is one of the most severely polluted regions in China, and the air pollution issues in this region have received a worldwide attention. We performed ground-based Multi Axis Differential Absorption Spectroscopy (MAX-DOAS) measurements at Gucheng, (39°08‧N, 115°40‧E), a rural site of North China about 110 km southwest of Beijing, from September 2008 to September 2010. The tropospheric vertical column densities (VCDs) of NO2 and SO2 were retrieved using the so-called geometric approximation. The results show that the tropospheric NO2 and SO2 VCDs over NC have nearly the same seasonal variation pattern, with the maximum in winter and minimum in summer, while their diurnal variations are different. We also compared the tropospheric NO2 and SO2 VCDs from our MAX-DOAS measurements with several products of corresponding OMI (Ozone Monitoring Instrument) satellite observations. While in summer good agreement is found, the satellite observations systematically underestimate the tropospheric NO2 in winter over the polluted rural area of NC, probably mostly due to the so called aerosol shielding effect. In contrast, for SO2 no such clear conclusion can be drawn, probably owing to the larger uncertainties from MAX-DOAS and in particular satellite retrievals. This indicates that improvements of the retrieval algorithm for MAX-DOAS and off-line corrections of satellite measurements for the tropospheric SO2 VCDs should be given more emphasis in the future.

  11. Four years of ground-based MAX-DOAS observations of aerosols, NO2, SO2 and HCHO in Wuxi, China

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Lampel, Johannes; Wagner, Thomas; Li, Ang; Xie, Pinhua; Wu, Dexia; Beirle, Steffen

    2016-04-01

    Understanding the temporal variation and spatial distribution of the abundances of nitrogen dioxide (NO2), sulphur dioxide (SO2), formaldehyde (HCHO) and aerosols is necessary to study their role in tropospheric chemistry and to estimate their importance among anthropogenic emissions. To accomplish this, we operated a Multi AXis - Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument from May 2011 to Nov 2014 in Wuxi, China. A new inversion algorithm PriAM (profile inversion algorithm of aerosol extinction and trace gas concentration) developed at AIOFM in cooperation with MPIC based on the optimal estimation algorithm is applied to obtain tropospheric profiles of trace gases and aerosols from the long-term observations. The performance of the inversion algorithm is evaluated by comparisons with other independent techniques for a period longer than one year. The cloud effect on the retrieved column densities, surface concentrations and profiles of the trace gases and aerosols is evaluated using of a cloud classification scheme based on the MAX-DOAS measurements themselves. From this study recommendations for the quality of the MAX-DOAS results for different cloud scenarios are given. Further, the MAX-DOAS results are used to characterize the seasonal, diurnal, and weekly variations of NO2, SO2, HCHO and aerosols. Systematic weekly variations are found for all the species, indicating a significant contribution of anthropogenic emissions to the observed abundances. The good correlations between the trace gases and aerosols, especially for HCHO, indicate a significant contribution of secondary aerosols from the precursors to the total aerosol load. We use the wind dependence of the pollutants to identify the dominating sources. High values are observed when the wind comes from the direction of industrial areas.

  12. MAX-DOAS measurements and satellite validation of tropospheric NO2 and SO2 vertical column densities at a rural site of North China

    NASA Astrophysics Data System (ADS)

    Jin, Junli; Ma, Jianzhong; Lin, Weili; Zhao, Huarong; Shaiganfar, Reza; Beirle, Steffen; Wagner, Thomas

    2016-05-01

    North China (NC), namely Huabei in Chinese, is one of the most severely polluted regions in China, and the air pollution issues in this region have received a worldwide attention. We performed ground-based Multi Axis Differential Absorption Spectroscopy (MAX-DOAS) measurements at Gucheng, (39°08‧N, 115°40‧E), a rural site of North China about 110 km southwest of Beijing, from September 2008 to September 2010. The tropospheric vertical column densities (VCDs) of NO2 and SO2 were retrieved using the so-called geometric approximation. The results show that the tropospheric NO2 and SO2 VCDs over NC have nearly the same seasonal variation pattern, with the maximum in winter and minimum in summer, while their diurnal variations are different. We also compared the tropospheric NO2 and SO2 VCDs from our MAX-DOAS measurements with several products of corresponding OMI (Ozone Monitoring Instrument) satellite observations. While in summer good agreement is found, the satellite observations systematically underestimate the tropospheric NO2 in winter over the polluted rural area of NC, probably mostly due to the so called aerosol shielding effect. In contrast, for SO2 no such clear conclusion can be drawn, probably owing to the larger uncertainties from MAX-DOAS and in particular satellite retrievals. This indicates that improvements of the retrieval algorithm for MAX-DOAS and off-line corrections of satellite measurements for the tropospheric SO2 VCDs should be given more emphasis in the future.

  13. Development of 2-D-MAX-DOAS and retrievals of trace gases and aerosols optical properties

    NASA Astrophysics Data System (ADS)

    Ortega, Ivan

    Air pollution is a major problem worldwide that adversely a_ects human health, impacts ecosystems and climate. In the atmosphere, there are hundreds of important compounds participating in complex atmospheric reactions linked to air quality and climate. Aerosols are relevant because they modify the radiation balance, a_ect clouds, and thus Earth albedo. The amount of aerosol is often characterized by the vertical integral through the entire height of the atmosphere of the logarithm fraction of incident light that is extinguished called Aerosol Optical Depth (AOD). The AOD at 550 nm (AOD550) over land is 0.19 (multi annual global mean), and that over oceans is 0.13. About 43 % of the Earth surface shows AOD550 smaller than 0.1. There is a need for measurement techniques that are optimized to measure aerosol optical properties under low AOD conditions, sample spatial scales that resemble satellite ground-pixels and atmospheric models, and help integrate remote sensing and in-situ observations to obtain optical closure on the effects of aerosols and trace gases in our changing environment. In this work, I present the recent development of the University of Colorado two dimensional (2-D) Multi-AXis Differential Optical Absorption Spectroscopy (2-D-MAX-DOAS) instrument to measure the azimuth and altitude distribution of trace gases and aerosol optical properties simultaneously with a single instrument. The instrument measures solar scattered light from any direction in the sky, including direct sun light in the hyperspectral domain. In Chapter 2, I describe the capabilities of 2-D measurements in the context of retrievals of azimuth distributions of nitrogen dioxide (NO2), formaldehyde (HCHO), and glyoxal (CHOCHO), which are precursors for tropospheric O3 and aerosols. The measurements were carried out during the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) campaign in Mainz, Germany and show the ability to bridge spatial scales to

  14. New concepts for the comparison of tropospheric NO2 column densities derived from car-MAX-DOAS observations, OMI satellite observations and the regional model CHIMERE during two MEGAPOLI campaigns in Paris 2009/10

    NASA Astrophysics Data System (ADS)

    Shaiganfar, R.; Beirle, S.; Petetin, H.; Zhang, Q.; Beekmann, M.; Wagner, T.

    2015-03-01

    We compare tropospheric column densities (vertically integrated concentrations) of NO2 from three data sets for the metropolitan area of Paris during two extensive measurement campaigns (25 days in summer 2009 and 29 days in winter 2010) within the European research project MEGAPOLI. The selected data sets comprise a regional chemical transport model (CHIMERE) as well as two observational data sets: ground based mobile Multi-AXis-Differential Optical Absorption Spectroscopy (car-MAX-DOAS) measurements and satellite measurements from the Ozone Monitoring Instrument (OMI). On most days, car-MAX-DOAS measurements were carried out along large circles (diameter ~35 km) around Paris. The car-MAX-DOAS results are compared to coincident data from CHIMERE and OMI. All three data sets have their specific strengths and weaknesses, especially with respect to their spatio-temporal resolution and coverage as well as their uncertainties. Thus we compare them in two different ways: first, we simply consider the original data sets. Second, we compare modified versions making synergistic use of the complementary information from different data sets. For example, profile information from the regional model is used to improve the satellite data, observations of the horizontal trace gas distribution are used to adjust the respective spatial patterns of the model simulations, or the model is used as a transfer tool to bridge the spatial scales between car-MAX-DOAS and satellite observations. Using the modified versions of the data sets, the comparison results substantially improve compared to the original versions. In general, good agreement between the data sets is found outside the emission plume, but inside the emission plumes the tropospheric NO2 VCDs are systematically underestimated by the CHIMERE model and the satellite observations (compared to the car-MAX-DOAS observations). One major result from our study is that for satellite validation close to strong emission sources (like

  15. New concepts for the comparison of tropospheric NO2 column densities derived from car-MAX-DOAS observations, OMI satellite observations and the regional model CHIMERE during two MEGAPOLI campaigns in Paris 2009/10

    NASA Astrophysics Data System (ADS)

    Shaiganfar, R.; Beirle, S.; Petetin, H.; Zhang, Q.; Beekmann, M.; Wagner, T.

    2015-07-01

    We compare tropospheric column densities (vertically integrated concentrations) of NO2 from three data sets for the metropolitan area of Paris during two extensive measurement campaigns (25 days in summer 2009 and 29 days in winter 2010) within the European research project MEGAPOLI. The selected data sets comprise a regional chemical transport model (CHIMERE) as well as two observational data sets: ground-based mobile Multi-AXis-Differential Optical Absorption Spectroscopy (car-MAX-DOAS) measurements and satellite measurements from the Ozone Monitoring Instrument (OMI). On most days, car-MAX-DOAS measurements were carried out along large circles (diameter ~ 35 km) around Paris. The car-MAX-DOAS results are compared to coincident data from CHIMERE and OMI. All three data sets have their specific strengths and weaknesses, especially with respect to their spatiotemporal resolution and coverage as well as their uncertainties. Thus we compare them in two different ways: first, we simply consider the original data sets. Second, we compare modified versions making synergistic use of the complementary information from different data sets. For example, profile information from the regional model is used to improve the satellite data, observations of the horizontal trace gas distribution are used to adjust the respective spatial patterns of the model simulations, or the model is used as a transfer tool to bridge the spatial scales between car-MAX-DOAS and satellite observations. Using the modified versions of the data sets, the comparison results substantially improve compared to the original versions. In general, good agreement between the data sets is found outside the emission plume, but inside the emission plumes the tropospheric NO2 vertical column densities (VCDs). are systematically underestimated by the CHIMERE model and the satellite observations (compared to the car-MAX-DOAS observations). One major result from our study is that for satellite validation close to

  16. [MAX-DOAS measurements of NO2 column densities and vertical distribution at Ny-Alesund, Arctic during summer].

    PubMed

    Luo, Yu-Han; Sun, Li-Guang; Liu, Wen-Qing; Xie, Pin-Hua; Si, Fu-Qi; Zhou, Hai-Jin

    2012-09-01

    The multi-axis differential optical absorption spectroscopy (MAX-DOAS), one of the remote sensing techniques for trace gases measurements, is sensitive to the lower atmosphere by eliminating the influence of stratosphere retrieved from zenith-sky spectroscopy. Ground-based MAX-DOAS measurements were carried out to observe NO2 at Ny-Alesund, Arctic from 5th Jul to 1st Aug 2011. The differential slant column densities (DSCDs) of NO2 at four off-axis angles showed typical pattern of tropospheric absorbers. Based on the assumption that NO2 was well mixed in 0-1 km of the troposphere, the mean mixing ratio of NO2 during the measurement period was 1.023E11 molec x cm(-3). The fluctuation of NO2 might be related to the fossil fuel combustions and the photochemical reactions. The vertical distribution of NO2 at 0-3 km showed that NO2 was mainly originated from boundary layer of sea surface. PMID:23240391

  17. Ship-based MAX-DOAS measurements of nitrogen dioxide in the South China Sea

    NASA Astrophysics Data System (ADS)

    Schreier, Stefan F.; Peters, Enno; Richter, Andreas; Wittrock, Folkard; Burrows, John P.

    2014-05-01

    In November 2011, the SHIVA-Sonne campaign took place in the South China Sea in order to investigate the transport of very short-lived substances to the stratosphere for a better understanding of their role in ozone depletion. Among other instruments, a Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument was placed on board the RV Sonne to measure scattered sunlight at different elevation angles. These measurements can be used for the retrieval of vertical columns of several trace gases (e.g. nitrogen dioxide (NO2), formaldehyde (HCHO), and iodine monoxide (IO)) by applying the DOAS method. In this study, we present tropospheric NO2 vertical columns (TVC NO2) retrieved from the MAX-DOAS measurements between 17 and 28 November 2011. During this period, the tropospheric NO2 levels were rather low (< 1 x 1015 molec cm-2) in the open sea most of the time. However, elevated NO2 levels (> 5 x 1015 molec cm-2) were observed when other large vessels navigated in the proximity of RV Sonne. Moreover, elevated levels of TVC NO2 (> 3 x 1015 molec cm-2) were also observed close to the coast of the island Borneo. The web-based version of the Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT) was used for the calculation of 24 h backward trajectories to better identify the sources of these elevated levels of TVC NO2. The analysis of the backward trajectories indicated that some cases with elevated tropospheric NO2 levels could be the result of NO2 transport from biomass burning and urban/industrial sources. In summary, the highest levels of TVC NO2 were found to be the result of the combustion process of large vessel engines. The contribution of biomass burning and urban/industrial sources to the tropospheric NO2 level in the South China Sea is rather low, at least during this part of the season.

  18. MAX-DOAS measurements of nitrogen dioxide at the high altitude sites Zugspitze (2964 m) and Pico Espejo (4765 m)

    NASA Astrophysics Data System (ADS)

    Schreier, Stefan F.; Richter, Andreas; Wittrock, Folkard; Burrows, John P.

    2015-04-01

    Spectral measurements at two mountain sites were performed with a MAX-DOAS (Multi AXis Differential Optical Absorption Spectroscopy) instrument from February to July 2003 (Zugspitze, Germany) and from March 2004 to November 2008 (Pico Espejo, Venezuela). Here, these measurements are used for the retrieval of slant column densities (SCDs) of nitrogen dioxide (NO2). While at the altitude of observations the NO2 levels are usually small, uplifting of anthropogenic emissions from the valley and in Venezuela also transport of emissions from biomass burning can lead to significant enhancements. Daily, weekly, and seasonal cycles of NO2 SCDs are shown for the two stations, linked to different meteorological conditions and compared between the two sites. In a next step, a preliminary approach to derive vertical column densities (VCDs) is presented. VCDs of NO2 from ground-based MAX-DOAS instruments provide useful information for the validation of satellite instruments such as SCIAMACHY, OMI, and GOME-2. Comparisons between ground-based and satellite-based NO2 VCDs are shown for selected periods.

  19. Operational MAX-DOAS Tropospheric Column Observations of NO2 used for Validation of OMI and SCIAMACHY

    NASA Astrophysics Data System (ADS)

    Vlemmix, T.; Piters, A. J. M.; Levelt, P. F.; Wang, P.; Stammes, P.

    2009-04-01

    Worldwide the number of observation sites where nitrogen dioxide (NO2) columns are monitored on an operational basis by atmospheric remote sensing is sparse. Few small networks exist so there is no global coverage which is essential for satellite validation. Since November 2007 multi axes differential optical absorption spectroscopy (MAX-DOAS) observations of NO2 are performed on an operational basis at the Royal Netherlands Meteorological Institute (KNMI). For this a Mini MAX-DOAS instrument is used. This poster will show the algorithm that is used to retrieve tropospheric vertical columns of NO2 which includes a correction for aerosols. Information on the aerosol optical thickness (AOT) and the height of the boundary layer is derived from O4 differential slant columns combined with observations of the radiation intensity at various viewing angles. The Doubling Adding KNMI (DAK) radiative transfer model is used to create a look up table for the AOT and boundary layer height retrieval. A comparison will be shown of retrieved AOT with CIMEL direct sun observations of AOT done at the CESAR site in Cabauw (25 kilometers from KNMI). Additionally we will show retrieved tropospheric vertical columns of NO2 in this highly polluted region throughout more than one year of observations. Finally a comparison is shown with satellite observations of SCIAMACHY and OMI. The results show the potential of this relatively low cost instrument for a global network of NO2 remote sensing sites.

  20. MAX-DOAS measurements of shipping emissions

    NASA Astrophysics Data System (ADS)

    Seyler, André; Wittrock, Folkard; Kattner, Lisa; Mathieu-Üffing, Barbara; Peters, Enno; Richter, Andreas; Schmolke, Stefan; Theobald, Norbert; Burrows, John P.

    2015-04-01

    Air pollution from ships contributes to overall air quality problems and it has direct health effects on the population in particular in coastal regions, and in harbor cities. In order to reduce the emissions the International Maritime Organisation (IMO) have tightened the regulations for air pollution. E.g. Sulfur Emission Control Areas (SECA) have been introduced where the sulfur content of marine fuel is limited. Recently, on the 1st of January 2015, the allowed sulfur content of marine fuels inside Sulfur Emission Control Areas has been significantly decreased from 1.0% to 0.1%. However, up to now there is no regular monitoring system available to verify that ships are complying with the new regulations. Furthermore measurements of reactive trace gases in marine environments are in general sparse. The project MeSMarT (Measurements of shipping emissions in the marine troposphere, www.mesmart.de) has been established as a cooperation between the University of Bremen and the German Bundesamt für Seeschifffahrt und Hydrographie (Federal Maritime and Hydrographic Agency) with support of the Helmholtz Research Centre Geesthacht to estimate the influence of ship emissions on the chemistry of the atmospheric boundary layer and to establish a monitoring system for main shipping routes. Here we present MAX-DOAS observations of NO2 and SO2 carried out from two permanent sites close to the Elbe river (Wedel, Germany) and on the island Neuwerk close to the mouths of Elbe and Weser river since the year 2013. Mixing ratios of both trace gases have been retrieved using different approaches (pure geometric and taking into account the radiative transfer) and compared to in situ observations (see Kattner et al., Monitoring shipping fuel sulfur content regulations with in-situ measurements of shipping emissions). Furthermore, simple approaches have been used to calculate emission factors of NOx and SO2 for single ships.

  1. Long-term MAX-DOAS measurement of trace gases and aerosol in the Environmental Research Station Schneefernerhaus

    NASA Astrophysics Data System (ADS)

    Wang, Zhuoru; Hao, Nan; Hendrick, François; Van Roozendael, Michel; Holla, Robert; Valks, Pieter

    2016-04-01

    The Environmental Research Station Schneefernerhaus (Umwelt Forschungsstation Schneefernerhaus, UFS) is located immediately under the summit of Zugspitze (2962 m), the highest mountain of Germany, at a height of 2650 m. The UFS is a rare observation site in Germany with mostly clean and unpolluted air. It is ideal for both stratospheric composition measurements and trace gas measurements in the free-troposphere. It is optimal for detecting pollution events in the free-troposphere, which are indications of short- or long-range transport of air pollutants. A MAX-DOAS instrument has been working in the UFS since February 2011. With the zenith spectrum of each cycle used as the reference, the differential slant column densities (DSCDs) of trace gases are calculated from the spectra with Differential Optical Absorption Spectroscopy (DOAS) method. The DSCDs of both O4 and NO2 are calculated in two different wavelength intervals, 338-370 nm in the UV region and 440-490 nm in the VIS region. For HCHO and HONO, optimal fitting windows have been determined in the UV region. A retrieval algorithm, based on the radiative transfer model LIDORT and the optimal estimation technique, is used to provide information on the vertical profiles and vertical column densities (VCDs) of aerosol and trace gases. Meanwhile, zenith-sky radiance spectra during twilight hours are analyzed using DOAS method to derive the total vertical column densities (VCDs) of O3 and NO2. A zenith spectrum measured in the noon of a summer day was chosen as the reference spectrum. The slant column densities (SCDs) of O3 and NO2, which are the direct product of the DOAS analysis, are then converted into VCDs using the air mass factors (AMFs) derived by radiative transfer calculations. This work presents the results of the MAX-DOAS measurement in the UFS from 2012 to 2015, including aerosol (derived from O4 measurement), NO2, HCHO, and HONO, etc. The vertical profiles as well as the seasonal and diurnal variation

  2. Temporal variations of aerosol, glyoxal, and formaldehyde at urban sites of Japan as observed by MAX-DOAS based on detailed error analysis

    NASA Astrophysics Data System (ADS)

    Irie, H.; Chin, S.; Ni, W.; Nakayama, T.; Shimizu, A.; Yamazaki, A.; Nagai, T.; Takamura, T.; Khatri, P.

    2014-12-01

    The degradation of volatile organic compounds (VOCs) results in the formation of ozone (O3) and secondary organic aerosols (SOA) in the troposphere. This process consists of the oxidation of VOCs by hydroxyl radical (OH), O3, and nitrate radical (NO3). Detailed understanding of the VOC degradation mechanism is challenged by the co-existence of vast variety of VOC species in the atmosphere. However, investigations on ubiquitous oxidation intermediates, e.g., formaldehyde (HCHO) and glyoxal (CHOCHO), can help us improve the current knowledge of the VOC sources and degradation pathways. We installed one ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) system in Meteorological Research Institute (MRI) located at Tsukuba, Japan (36.06N, 130.13E) in June 2010. In addition, two more systems were installed in Chiba University at Chiba, Japan (35.63N, 140.10E) in June and December 2012, respectively. Since then, we have retrieved lower-tropospheric vertical profile information for eight components; aerosol extinction coefficients at two wavelengths, 357 and 476 nm, and NO2, HCHO, CHOCHO, H2O, SO2, and O3 concentrations. For a detailed evaluation for the aerosol retrieval, which is a key step in the MAX-DOAS eight-component retrieval, simultaneous aerosol observations with the Cavity Ring-Down Spectroscopy (CRDS), lidar, and sky radiometer were conducted at Tsukuba on October 5-18, 2010. At Chiba, in addition to the comparison with sky radiometer data, a self-consistency test was performed by comparing results obtained from two MAX-DOAS systems operated at the same place. Through these detailed evaluations, our retrieval method was improved significantly, attaining excellent agreement with CRDS, lidar, and sky radiometer data. On the basis of these efforts, we find clear seasonal and diurnal temporal variations in HCHO and CHOCHO concentrations and their ratios (RGF) retrieved from MAX-DOAS systems. Using NO2 retrieved together with HCHO and

  3. MAX-DOAS measurements of atmospheric trace gases in Ny-Ålesund

    NASA Astrophysics Data System (ADS)

    Wittrock, F.; Oetjen, H.; Richter, A.; Fietkau, S.; Medeke, T.; Rozanov, A.; Burrows, J. P.

    2003-12-01

    A new approach to derive tropospheric concentrations of some atmospheric trace gases from ground-based UV/vis measurements is described. The instrument, referred to as the MAX-DOAS, is based on the well-known UV/vis instruments, which use the sunlight scattered in the zenith sky as the light source and the method of Differential Optical Absorption Spectroscopy (DOAS) to derive column amounts of absorbers like ozone and nitrogen dioxide. Substantial enhancements have been applied to this standard setup to use different lines of sight near to the horizon as additional light sources (MAX - multi axis). Results from measurements at Ny-Ålesund (79° N, 12° E) are presented and interpreted with the full-spherical radiation transport model SCIATRAN. In particular, measurements of the oxygen dimer O4 which has a known column and vertical distribution in the atmosphere are used to evaluate the sensitivity of the retrieval to parameters such as multiple scattering, solar azimuth, surface albedo and refraction in the atmosphere and also to validate the radiative transport model. As a first application, measurements of NO2 emissions from a ship lying in Ny-Ålesund harbour are presented. The results of this study demonstrate the feasibility of long term UV/vis multi axis measurement that can be used to derive not only column amounts of different trace gases but also some information on the vertical location of these absorbers.

  4. Transport of gaseous NO2 and SO2 by MAX-DOAS in Beijing and surrounding area

    NASA Astrophysics Data System (ADS)

    Xu, Jin; Li, Ang; Xie, Pinhua; Liu, Jianguo; Liu, Wenqing

    2016-04-01

    With the development of industry and urbanization, regional pollution is increasing seriously, and the cross influence between cities is becoming more frequently. Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) has been successfully applied in the remote sensing of gaseous pollutants during the past decade, it is based on scattered light of the sun, and can measure spectral in different directions, measure tropospheric and the whole atmospheric column densities of trace gases combining with radiative transfer model (RTM). This approach is very useful for the investigation of the main path of air pollution transportation. Fifteen MAX-DOAS stations which are in urban and in the path of pollution transport are set up in Beijing and surrounding area including Tianjin and Hebei province to observe the spatial and temporal distributions and regional transport of gaseous NO2 and SO2. The NO2 VCDs and profiles and SO2 VCDs are obtained. The results show that the NO2 column densities in urban are higher than surroundings, it shows that the NO2 in Beijing is mainly from the local; The SO2 column densities in other cities to the south of Beijing are obviously higher than in Beijing, so regional transport from the south of Hebei province will have a significant impact on Beijing. From the results of NO2 and SO2, the whole pollution process including incubation, generation, duration, and dispersion was observed. The vertical distribution show that NO2 concentration is mainly near the surface from 0 to 400m, and SO2 is higher in the transport process.

  5. Five Years of Ground-Based MAX-DOAS Observations of CHOCHO and HCHO in the Beijing Area

    NASA Astrophysics Data System (ADS)

    Hendrick, F.; Lerot, C.; De Smedt, I.; Stavrakou, T.; Fayt, C.; Gielen, C.; Hermans, C.; Muller, J. F.; Pinardi, G.; Van Roozendael, M.

    2015-12-01

    Glyoxal (CHOCHO) and formaldehyde (HCHO) are among the most important carbonyl compounds in the atmosphere. Given their short lifetime (typically a few hours) and since they are mainly produced by the oxidation of biogenic and anthropogenic volatile organic compounds (VOCs), they are very good proxy for detecting active VOCs chemistry which can be responsible for the formation of pollutants such as tropospheric ozone and secondary organic aerosols. Both CHOCHO and HCHO are also directly released by biomass burning and fossil fuel combustion. Measuring these species is therefore of major importance for air quality monitoring, especially given the scarcity of available observational data sets. In this presentation, CHOCHO and HCHO vertical profiles and corresponding column densities are retrieved from ground-based MAX-DOAS (Multi-AXis Differential Optical Absorption Spectroscopy) measurements in the Beijing city center and at the suburban site of Xianghe located at 60km East of Beijing. The periods covered by the observations are June 2008-April 2009 in Beijing and March 2010-December 2014 in Xianghe. We first investigate the capability of the MAX-DOAS technique to measure these species in such highly-polluted environment. Then the diurnal and seasonal cycles of CHOCHO and HCHO near-surface concentrations and vertical column densities as well as the corresponding CHOCHO/HCHO ratios (RGF) are examined on a long-term basis at both locations. This RGF ratio is often used as an indicator of changes in the atmospheric VOC mixture. Finally, these diurnal and seasonal cycles are further assessed using simulations from the 3D chemistry transport model IMAGES and observations from the OMI and GOME-2 satellite nadir sensors.

  6. Inter-comparison of glyoxal retrievals from MAX-DOAS during the MAD-CAT campaign

    NASA Astrophysics Data System (ADS)

    Ortega, Ivan; Wagner, Thomas; Lampel, Johannes; van Roozendael, Michel; Richter, Andreas; Sinha, Vinayak; Xie, Pinhua; Volkamer, Rainer

    2015-04-01

    Over the past few years the smallest α-dicarbonyl compound glyoxal (CHOCHO) has received attention in order to inform relevant atmospheric chemistry processes such as oxidative capacity and secondary organic aerosol (SOA) formation. A method to detect glyoxal in the atmosphere is through the Differential Optical Absorption Spectroscopy (DOAS) applied to solar scattered light passive remote sensing measurements on different platforms, including ground based, aircrafts, and satellites. Although these measurements are often described still many questions about DOAS fitting parameters need to be investigated. We present results from a comprehensive Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) comparison effort during the Multi Axis DOAS-Comparison campaign for Aerosols and Trace gases (MAD-CAT) held at the Max Planck institute for Chemistry in Mainz, Germany with an intensive operation period from June to August 2013. We evaluate the comparison for glyoxal differential Slant Column Densities (dSCD) from 6 different research groups during the MAD-CAT campaign. The data analysis is performed following three retrieval common settings. In general, good agreement between different groups is found, especially for days with low cloud coverage. Based on the diurnal variability of the glyoxal-to-formaldehyde ratio we identified that Mainz is influenced mostly by anthropogenic volatile organic compounds (AVOC) emission type. Also, for most of the days glyoxal was often clearly above the respective detection limits. We will present results of sensitivity studies in order to know influence of the wavelength window, dependence of the NO2 air mass factor, cross correlation with H2O, among others. Finally, synthetic spectra created with the SCIATRAN radiative transfer model using measurement related inputs are analysed and first results are presented.

  7. Vertical Profiles of SO2 and NO2 in the Alberta Oil Sands: MAX-DOAS Measurements and Comparison to in-situ Instrumentation

    NASA Astrophysics Data System (ADS)

    Davis, Zoe; Lobo, Akshay; McLaren, Robert

    2015-04-01

    Understanding the levels of industrially emitted gas pollutants in the Alberta oil sands is essential to making quality environmental management decisions but is currently limited due to scarcity of top-down quantification studies. Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrogen dioxide (NO2) and sulfur dioxide (SO2) , important tropospheric trace gas pollutants, contributes to improved knowledge of these pollutants' levels, vertical distributions and chemical transformations. A mini-MAX-DOAS instrument measured spectra at multiple viewing elevation angles in order to retrieve NO2 and SO2 differential slant column densities (dSCDs) at an Environment Canada research site north of Fort McMurray, Alberta in the fall of 2013. For the first time in the oil sands, tropospheric vertical profiles of NO2 and SO2 were retrieved by applying the optimal estimation technique to the MAX-DOAS measurements. The DOAS fit retrievals of SO2 dSCDs were validated by comparison with retrievals obtained with a quartz calibration cell with known SO2 SCD placed in front of the MAX-DOAS telescope at multiple elevation angles on a clean day. Retrieved SO2 dSCDs varied significantly from the true value depending on the chosen wavelength fitting interval. At the lowest wavelength intervals, interference by stray light and O3 differential structures significantly reduced dSCDs and caused an elevation angle dependence. These results indicate that MAX-DOAS dSCD retrieval settings, particularly for weak absorbers with differential absorption structures in low-intensity spectral regions, must be chosen carefully in order to achieve the most accurate results. Tropospheric vertical column densities (VCDs) and vertical profile retrievals of NO2, SO2 and aerosol extinction during significant pollution events will be illustrated. Trace gas vertical profiles exhibited significant variability between days and at different times of day and were often spatially

  8. The New MAX-DOAS Network in Mexico City for Trace Gas Detection

    NASA Astrophysics Data System (ADS)

    Arellano, E. J.; Krüger, A.; Rivera, C. I.; Stremme, W.; Friedrich, M. M.; Grutter, M.

    2014-12-01

    Atmospheric studies in large cities are of great relevance since pollution affects air quality and human health. We have designed and built instruments based on the Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) technique and established a network in strategic sites within the Mexico City metropolitan area. Four instruments are now in operation with the aim to study the variability and spatial distribution of key pollutants, which will bring new insight in the current knowledge of transport patterns, emissions as well as frequency and origin of extraordinary events. The instruments measure UV/visible spectra of the sky at different elevation angles in the 280 nm to 510 nm wavelength region along one axis. Currently, 36 measurements constitute a full scan performed from west until East direction (-90 to +90°). The scanning unit, which is installed outdoors, holds a small telescope and the motor control unit. Light is transmitted via an optical fiber to the main box, which holds a compact USB spectrometer and the main control electronics. The spectrometer is accurately temperature controlled and all the spectra of each scan, together with elevation angle and other parameters, are recorded on a compact PC. Post processing of these data with the QDOAS software results in slant column densities (SCD) of the atmospheric gases. This information is then converted to vertical profiles through a process described in a companion presentation. Preliminary results will be presented for formaldehyde, fitted in the region 324-360 nm. The data obtained is useful for the comparison with satellite data for example OMI.

  9. Car MAX-DOAS measurements of the tropospheric Formaldehyde (HCHO) column around Bucharest (Romania) and in the Rhein-Main area (Germany)

    NASA Astrophysics Data System (ADS)

    Donner, Sebastian; Shaiganfar, Reza; Riffel, Katharina; Dörner, Steffen; Lampel, Johannes; Remmers, Julia; Wagner, Thomas

    2016-04-01

    The DOAS (differential optical absorption spectroscopy)-method analyses the absorptions of atmospheric trace gases in spectra of scattered sun light. It is an excellent way to determine the concentrations of different trace gases (e.g. NO2, SO2, HCHO…) simultaneously. MAX (Multi-AXis)-DOAS measurements observe scattered sun light under different elevation angles. From such measurements tropospheric vertical column densities (VCDs) or even vertical profiles of the measured trace gases and aerosols can be determined. We performed mobile MAX-DOAS measurements using two instruments on the roof of a car in summer 2015 in Romania during the AROMAT2 campaign and in the Winter/Spring 2016 in the Rhein-Main area (Germany). The latter is one of the densest populated areas in Germany. One instrument is a commercial Mini-MAX-DOAS instrument from the Hoffmann company, the other a self-built instrument using an AVANTES spectrometer with better optical characteristics. The instruments were looking in two different directions (one forward and one backward). Mobile MAX-DOAS measurements cover a quite large area in a short period of time. This enables to map existing gradients of concentrations of tropospheric trace gases, e.g. NO2 and HCHO. The results of those measurements then can be used to validate satellite measurements or can be compared to model results. In this study we focus on formaldehyde (HCHO). In small amounts it is emitted directly by industries and other anthropogenic and biogenic activities. Large amounts are mostly secondary produced. As it is an intermediate product of basic oxidation cycles of other hydrocarbons its concentrations are determined by the abundances of other hydrocarbons. Therefore it can be used as an indicator for volatile organic compounds (VOCs). Furthermore HCHO plays an important role in photochemical smog chemistry and tropospheric O3 chemistry. In this work we present the measurement setup and preliminary HCHO results of the AROMAT2

  10. MAX-DOAS measurements of atmospheric trace gases in Ny-Ålesund - Radiative transfer studies and their application

    NASA Astrophysics Data System (ADS)

    Wittrock, F.; Oetjen, H.; Richter, A.; Fietkau, S.; Medeke, T.; Rozanov, A.; Burrows, J. P.

    2004-06-01

    A new approach to derive tropospheric concentrations of some atmospheric trace gases from ground-based UV/vis measurements is described. The instrument, referred to as the MAX-DOAS, is based on the well-known UV/vis instruments, which use the sunlight scattered in the zenith sky as the light source and the method of Differential Optical Absorption Spectroscopy (DOAS) to derive column amounts of absorbers like ozone and nitrogen dioxide. Substantial enhancements have been applied to this standard setup to use different lines of sight near to the horizon as additional light sources (MAX - multi axis). Results from measurements at Ny-Ålesund (79° N, 12° E) are presented and interpreted with the full-spherical radiative transfer model SCIATRAN. In particular, measurements of the oxygen dimer O4 which has a known column and vertical distribution in the atmosphere are used to evaluate the sensitivity of the retrieval to parameters such as multiple scattering, solar azimuth, surface albedo and refraction in the atmosphere and also to validate the radiative transfer model. As a first application, measurements of NO2 emissions from a ship lying in Ny-Ålesund harbour are presented. The results of this study demonstrate the feasibility of long term UV/vis multi axis measurement that can be used to derive not only column amounts of different trace gases but also some information on the vertical location of these absorbers.

  11. Estimation of NOx emissions from the Megacity of Lahore, Pakistan using car MAX-DOAS observations and comparison with OMI satellite data

    NASA Astrophysics Data System (ADS)

    Razi, Maria; Shaiganfar, Reza; Fahim Khokhar, Muhammad; Dörner, Steffen; Ahmad, Noor; Donner, Sebastian; Beirle, Steffen; Wagner, Thomas

    2016-04-01

    Lahore is a metropolitan city of Pakistan with about more than 10 million inhabitants and thus a strong emission source of atmospheric pollutants. The quantification of these emission sources is usually accomplished by so-called bottom-up inventories, based on the summation of the emissions of individual emission sources for all relevant emission categories. Such inventories are subject to large errors because of uncertainties in the emission estimates for individual sources as well as their numbers and characteristics. Here we present results of a top-down emission inventory for Lahore based on car multi-axis differential optical absorption spectroscopy (car-MAX-DOAS) observations. We performed such measurements around the city on Lahore on six days in December 2015. From the measured spectra we derive the vertically integrated concentration of NO2 along the driving route (the so called tropospheric vertical column density, VCD). By combining these observations with wind data we estimate the total NO2 emissions from the city of Lahore. Since from the measured spectra only NO2 (but not NO) can be retrieved, we convert the NO2 emissions to total NOx (NO2 plus NO) emissions. We also apply corrections for the decay of NOx on the way between the emission source and the location of the measurements. We compare the derived NOx emissions to existing emission inventories. We also compare the spatial distributions of the tropospheric NO2 VCDs observed by car MAX-DOAS with collocated results from satellite observations of the Ozone Monitoring Instrument (OMI).

  12. Vertical and horizontal NO2 transport in urban area associated with land-sea breeze as observed by ground-based MAX-DOAS

    NASA Astrophysics Data System (ADS)

    Takashima, H.; Kanaya, Y.

    2013-12-01

    Since July 2012, continuous NO2 profile observations have been performed by using ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) at Fukuoka (33.55N, 130.36E), an urban site in Japan. MAX-DOAS is a passive remote sensing technique using scatted visible and ultraviolet solar radiation at several elevation angles, and it can allow us to retrieve vertical information on several trace gasses. In this study, the vertical resolution of the profiles is roughly 1 km below 2 km height. We investigate inhomogeneity of NO2 over Fukuoka by observing at two azimuth angles, Tenjin (downtown area) direction and Itoshima (out of downtown area) direction. Understanding of the spatial inhomogeneity of NO2 in urban area is important for measuring a priori profiles for satellite and for validating chemical transport model. Diurnal variation with maximum in the morning is clearly observed in both directions throughout the year for 0-1 km. Diurnal variation with maximum around noon is sometimes observed in Itoshima direction, which is delayed by 1-2 hours from maxima in Tenjin direction. The NO2 maximum for upper level (1-2 km) is also delayed from the maximum in Tenjin direction. From the analysis of surface wind field, these variations seems to be strongly related to vertical/horizontal transport of high concentration of NO2 from the downtown area (and development of the boundary layer) and horizontal transport of low concentration from ocean associated with land-sea breeze. We also present a comparison of NO2 data measured with the Ozone Monitoring Instrument (OMI) satellite sensor.

  13. NO2 and HCHO variability in Mexico City from MAX-DOAS measurements

    NASA Astrophysics Data System (ADS)

    Grutter, M.; Friedrich, M. M.; Rivera, C. I.; Arellano, E. J.; Stremme, W.

    2015-12-01

    Atmospheric studies in large cities are of great relevance since pollution affects air quality and human health. A network of Multi Axis Differential Optical Absorption Spectrometers (MAX-DOAS) has been established in strategic sites within the Mexico City metropolitan area. Four instruments are now in operation with the aim to study the variability and spatial distribution of key pollutants, providing results of O4, NO2 and HCHO slant column densities (SCD). A numerical code has been written to retrieve gas profiles of NO2 and HCHO using radiative transfer simulations. We present the first results of the variability of these trace gases which will bring new insight in the current knowledge of transport patterns, emissions as well as frequency and origin of extraordinary events. Results of the vertical column densities (VCD) valiability of NO2 and HCHO in Mexico City are presented. These studies are useful to validate current and future satellite observatopns such as OMI, TROPOMI and TEMPO.

  14. Retrieval of aerosol optical and micro-physical properties with 2D-MAX-DOAS

    NASA Astrophysics Data System (ADS)

    Ortega, Ivan; Coburn, Sean; Hostetler, Chris; Ferrare, Rich; Hair, Johnathan; Kassianov, Evgueni; Barnard, James; Berg, Larry; Schmid, Beat; Tomlinson, Jason; Hodges, Gary; Lantz, Kathy; Wagner, Thomas; Volkamer, Rainer

    2015-04-01

    Recent retrievals of 2 dimensional (2D) Multi-AXis Differential Optical Absorption Spectroscopy (2D-MAX-DOAS) have highlighted its importance in order to infer diurnal horizontal in-homogeneities around the measurement site. In this work, we expand the capabilities of 2D measurements in order to estimate simultaneously aerosol optical and micro-physical properties. Specifically, we present a retrieval method to obtain: (1) aerosol optical thickness (AOT) in the boundary layer (BL) and free troposphere (FT) and (2) the effective complex refractive index and the effective radius of the aerosol column size distribution. The retrieval method to obtain AOT is based on an iterative comparison of measured normalized radiances, oxygen collision pair (O4), and absolute Raman Scattering Probability (RSP) with the forward model calculations derived with the radiative transfer model McArtim based on defined aerosol extinction profiles. Once the aerosol load is determined we use multiple scattering phase functions and single scattering albedo (SSA) obtained with Mie calculations which then constrain the RTM to forward model solar almucantar normalized radiances. The simulated almucantar normalized radiances are then compared to the measured normalized radiances. The best-fit, determined by minimizing the root mean square, retrieves the complex refractive index, and effective radius. We apply the retrieval approach described above to measurements carried out during the 2012 intensive operation period of the Two Column Aerosol Project (TCAP) held on Cape Cod, MA, USA. Results are presented for two ideal case studies with both large and small aerosol loading and similar air mass outflow from the northeast coast of the US over the West Atlantic Ocean. The aerosol optical properties are compared with several independent instruments, including the NASA Langley airborne High Spectral Resolution Lidar (HSRL-2) for highly resolved extinction profiles during the overpasses, and with the

  15. Slant column MAX-DOAS measurements of nitrogen dioxide, formaldehyde, glyoxal and oxygen dimer in the urban environment of Athens

    NASA Astrophysics Data System (ADS)

    Gratsea, Myrto; Vrekoussis, Mihalis; Richter, Andreas; Wittrock, Folkard; Schönhardt, Anja; Burrows, John; Kazadzis, Stelios; Mihalopoulos, Nikos; Gerasopoulos, Evangelos

    2016-06-01

    Slant column (SC) densities of nitrogen dioxide (NO2), formaldehyde (HCHO), glyoxal (CHOCHO) and oxygen dimer (O4) were successfully retrieved for the first time in Athens, by using spectral measurements from a ground-based multi-azimuth Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) system. The data span the period from October 2012 to March 2014 and measurements were conducted at NOA's (National Observatory of Athens) station in Penteli (38.0°N, 23.9°E, 527 m a.s.l.) at eight azimuth angles and eight off-axis elevation angles. The SCNO2, SCHCHO and SCCHOCHO measurements at +1ο elevation angle, pointing towards the urban area, range from 0.6 to 24·1016, 0.8-9.6·1016 and 0.3-5.2·1015 molec cm-2 (mean daily values throughout the whole period), respectively. Seasonal modulation characterised by summertime maximum and wintertime minimum was observed for HCHO and CHOCHO, while for NO2 the maximum values were recorded during winter. Changes in the diurnal variability of all trace gases with season and day of the week are investigated suggesting a strong link to primary anthropogenic sources for NO2 and a weaker one, compared to photochemistry, for HCHO and CHOCHO. In addition, the impact of the reduced anthropogenic emissions during weekends on the measured SC values was quantified and 30%-50% lower SCNO2 values were found during weekends. The contribution of local urban emissions to the overall recorded amounts of the selected species was assessed. Using meteorological data from NOA's station in Penteli, the impact of the local circulation patterns on the SC levels was estimated, and a strong relation between western wind direction, which is related to the industrial area, and enhanced SC measurements was found.

  16. [Retrieval of tropospheric NO2 by multi axis differential optical absorption spectroscopy].

    PubMed

    Xu, Jin; Xie, Pin-hua; Si, Fu-qi; Dou, Ke; Li, Ang; Liu, Yu; Liu, Wen-qing

    2010-09-01

    A method of retrieving NO2 in troposphere based on multi axis differential optical absorption spectroscopy (MAX-DOAS) was introduced. The differential slant column density (dSCD) of NO2 was evaluated by differential optical absorption spectroscopy (DOAS), removing the Fraunhofer structure and Ring effect. Combining the results of different observing directions, the tropospheric NO2 differential slant column density (deltaSCD) was evaluated, and the air mass factor (AMF) was calculated with the radiative transfer model SCIATRAN and the tropospheric NO2 vertical column density (VCD) was retrieved. To ensure the accuracy of the results, it was compared with the results of long path differential optical absorption spectroscopy (LP-DOAS), a good accordance was shown with the correlation coefficients of 0.94027 and 0.96924. PMID:21105419

  17. Long-term MAX-DOAS network observations of NO2 in Russia and Asia (MADRAS) during the period 2007-2012: instrumentation, elucidation of climatology, and comparisons with OMI satellite observations and global model simulations

    NASA Astrophysics Data System (ADS)

    Kanaya, Y.; Irie, H.; Takashima, H.; Iwabuchi, H.; Akimoto, H.; Sudo, K.; Gu, M.; Chong, J.; Kim, Y. J.; Lee, H.; Li, A.; Si, F.; Xu, J.; Xie, P.-H.; Liu, W.-Q.; Dzhola, A.; Postylyakov, O.; Ivanov, V.; Grechko, E.; Terpugova, S.; Panchenko, M.

    2014-08-01

    We conducted long-term network observations using standardized Multi-Axis Differential optical absorption spectroscopy (MAX-DOAS) instruments in Russia and ASia (MADRAS) from 2007 onwards and made the first synthetic data analysis. At seven locations (Cape Hedo, Fukue and Yokosuka in Japan, Hefei in China, Gwangju in Korea, and Tomsk and Zvenigorod in Russia) with different levels of pollution, we obtained 80 927 retrievals of tropospheric NO2 vertical column density (TropoNO2VCD) and aerosol optical depth (AOD). In the technique, the optimal estimation of the TropoNO2VCD and its profile was performed using aerosol information derived from O4 absorbances simultaneously observed at 460-490 nm. This large data set was used to analyze NO2 climatology systematically, including temporal variations from the seasonal to the diurnal scale. The results were compared with Ozone Monitoring Instrument (OMI) satellite observations and global model simulations. Two NO2 retrievals of OMI satellite data (NASA ver. 2.1 and Dutch OMI NO2 (DOMINO) ver. 2.0) generally showed close correlations with those derived from MAX-DOAS observations, but had low biases of up to ~50%. The bias was distinct when NO2 was abundantly present near the surface and when the AOD was high, suggesting a possibility of incomplete accounting of NO2 near the surface under relatively high aerosol conditions for the satellite observations. Except for constant biases, the satellite observations showed nearly perfect seasonal agreement with MAX-DOAS observations, suggesting that the analysis of seasonal features of the satellite data were robust. Weekend reduction in the TropoNO2VCD found at Yokosuka and Gwangju was absent at Hefei, implying that the major sources had different weekly variation patterns. While the TropoNO2VCD generally decreased during the midday hours, it increased exceptionally at urban/suburban locations (Yokosuka, Gwangju, and Hefei) during winter. A global chemical transport model, MIROC

  18. Ship-based MAX-DOAS measurements of tropospheric NO2 and SO2 in the South China and Sulu Sea

    NASA Astrophysics Data System (ADS)

    Schreier, S. F.; Peters, E.; Richter, A.; Lampel, J.; Wittrock, F.; Burrows, J. P.

    2015-02-01

    In November 2011, ship-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements were performed within the SHIVA campaign on board RV Sonne in the South China and Sulu Sea. Spectral measurements for a total of eleven days could be used to retrieve tropospheric slant column densities (SCDs) of nitrogen dioxide (NO2) and sulfur dioxide (SO2) in the marine environment. The NO2 fit was performed following recommendations developed during the CINDI campaign and adapted for the ship-based measurements. We found that the inclusion of a cross section for liquid water and an empirical correction spectrum accounting for the effects of liquid water and vibrational Raman scattering (VRS) slightly improved the NO2 fit quality, especially at lower elevation angles and for lower NO2 levels. The conversion of SCDs into tropospheric NO2 vertical columns (TVC NO2) has been achieved using both a simple geometric approach and the Bremian advanced MAX-DOAS Retrieval Algorithm (BREAM), which is based on the optimal estimation method and accounts for atmospheric radiative transfer. We found good agreement between the geometric approach using the 15° measurements and BREAM, revealing that measurements at 15° elevation angle can be used for retrieving TVC NO2 in tropical marine environments when SZA is smaller than 75°. As expected, the values of TVC NO2 were generally low (<0.5 × 1015 molec cm-2) when no sources of NOx were in proximity to the RV Sonne. However, we found increased values of TVC NO2 (>2 × 1015 molec cm-2) in the morning when the RV Sonne was heading along the coast of Borneo. This is in good agreement with satellite measurements. The results of the profile retrieval show that the boundary layer values of NO2 are <30 pptv in the open and clean tropical marine environment. Interestingly, we also found elevated tropospheric SO2 amounts for measurements taken in a busy shipping lane, consistent with the time series of tropospheric NO2.

  19. The CU 2-D-MAX-DOAS instrument - Part 1: Retrieval of 3-D distributions of NO2 and azimuth-dependent OVOC ratios

    NASA Astrophysics Data System (ADS)

    Ortega, I.; Koenig, T.; Sinreich, R.; Thomson, D.; Volkamer, R.

    2015-06-01

    We present an innovative instrument telescope and describe a retrieval method to probe three-dimensional (3-D) distributions of atmospheric trace gases that are relevant to air pollution and tropospheric chemistry. The University of Colorado (CU) two-dimensional (2-D) multi-axis differential optical absorption spectroscopy (CU 2-D-MAX-DOAS) instrument measures nitrogen dioxide (NO2), formaldehyde (HCHO), glyoxal (CHOCHO), oxygen dimer (O2-O2, or O4), and water vapor (H2O); nitrous acid (HONO), bromine monoxide (BrO), and iodine monoxide (IO) are among other gases that can in principle be measured. Information about aerosols is derived through coupling with a radiative transfer model (RTM). The 2-D telescope has three modes of operation: mode 1 measures solar scattered photons from any pair of elevation angle (-20° < EA < +90° or zenith; zero is to the horizon) and azimuth angle (-180° < AA < +180°; zero being north); mode 2 measures any set of azimuth angles (AAs) at constant elevation angle (EA) (almucantar scans); and mode 3 tracks the direct solar beam via a separate view port. Vertical profiles of trace gases are measured and used to estimate mixing layer height (MLH). Horizontal distributions are then derived using MLH and parameterization of RTM (Sinreich et al., 2013). NO2 is evaluated at different wavelengths (350, 450, and 560 nm), exploiting the fact that the effective path length varies systematically with wavelength. The area probed is constrained by O4 observations at nearby wavelengths and has a diurnal mean effective radius of 7.0 to 25 km around the instrument location; i.e., up to 1960 km2 can be sampled with high time resolution. The instrument was deployed as part of the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany, from 7 June to 6 July 2013. We present first measurements (modes 1 and 2 only) and describe a four-step retrieval to derive (a) boundary layer vertical profiles and MLH of NO2; (b

  20. Estimates of free-tropospheric NO2 and HCHO mixing ratios derived from high-altitude mountain MAX-DOAS observations in the mid-latitudes and tropics

    NASA Astrophysics Data System (ADS)

    Schreier, S. F.; Richter, A.; Wittrock, F.; Burrows, J. P.

    2015-11-01

    In this study, mixing ratios of NO2 (XNO2) and HCHO (XHCHO) in the free troposphere are derived from two Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) data sets collected at Zugspitze (2650 m a.s.l., Germany) and Pico Espejo (4765 m a.s.l., Venezuela). The estimation of NO2 and HCHO mixing ratios is based on the modified geometrical approach, which assumes a single-scattering geometry and a scattering point altitude close to the instrument. Firstly, the horizontal optical path length (hOPL) is obtained from O4 differential slant column densities (DSCDs) in the horizontal (0°) and vertical (90°) viewing directions. Secondly, XNO2 and XHCHO are estimated from the NO2 and HCHO DSCDs at the 0 and 90° viewing directions and averaged along the obtained hOPLs. As the MAX-DOAS instrument was performing measurements in the ultraviolet region, wavelength ranges of 346-372 and 338-357 nm are selected for the DOAS analysis to retrieve NO2 and HCHO DSCDs, respectively. In order to compare the measured O4 DSCDs and moreover to perform some sensitivity tests, the radiative transfer model SCIATRAN with adapted altitude settings for mountainous terrain is operated to simulate synthetic spectra, on which the DOAS analysis is also applied. The overall agreement between measured and synthetic O4 DSCDs is better for the higher Pico Espejo station than for Zugspitze. Further sensitivity analysis shows that a change in surface albedo (from 0.05 to 0.7) can influence the O4 DSCDs, with a larger absolute difference observed for the horizontal viewing direction. Consequently, the hOPL can vary by about 5 % throughout the season, for example when winter snow cover fully disappears in summer. Typical values of hOPLs during clear sky conditions are 19 km (14 km) at Zugspitze and 34 km (26.5 km) at Pico Espejo when using the 346-372 nm (338-357 nm) fitting window. The estimated monthly values of XNO2 (XHCHO), averaged over these hOPLs during clear sky conditions, are in

  1. Estimates of free-tropospheric NO2 and HCHO mixing ratios derived from high-altitude mountain MAX-DOAS observations at midlatitudes and in the tropics

    NASA Astrophysics Data System (ADS)

    Schreier, Stefan F.; Richter, Andreas; Wittrock, Folkard; Burrows, John P.

    2016-03-01

    In this study, mixing ratios of NO2 (XNO2) and HCHO (XHCHO) in the free troposphere are derived from two multi-axis differential optical absorption spectroscopy (MAX-DOAS) data sets collected at Zugspitze (2650 m a.s.l., Germany) and Pico Espejo (4765 m a.s.l., Venezuela). The estimation of NO2 and HCHO mixing ratios is based on the modified geometrical approach, which assumes a single-scattering geometry and a scattering point altitude close to the instrument altitude. Firstly, the horizontal optical path length (hOPL) is obtained from O4 differential slant column densities (DSCDs) in the horizontal (0°) and vertical (90°) viewing directions. Secondly, XNO2 and XHCHO are estimated from the NO2 and HCHO DSCDs at the 0° and 90° viewing directions and averaged along the obtained hOPLs. As the MAX-DOAS instrument was performing measurements in the ultraviolet region, wavelength ranges of 346-372 and 338-357 nm are selected for the DOAS analysis to retrieve NO2 and HCHO DSCDs, respectively. In order to compare the measured O4 DSCDs and moreover to perform some sensitivity tests, the radiative transfer model SCIATRAN with adapted altitude settings for mountainous terrain is operated to simulate synthetic spectra, on which the DOAS analysis is also applied. The overall agreement between measured and synthetic O4 DSCDs is better for the higher Pico Espejo station than for Zugspitze. Further sensitivity analysis shows that a change in surface albedo (from 0.05 to 0.7) can influence the O4 DSCDs, with a larger absolute difference observed for the horizontal viewing direction. Consequently, the hOPL can vary by about 5 % throughout the season, for example when winter snow cover fully disappears in summer. Typical values of hOPLs during clear-sky conditions are 19 km (14 km) at Zugspitze and 34 km (26.5 km) at Pico Espejo when using the 346-372 (338-357 nm) fitting window. The estimated monthly values of XNO2 (XHCHO), averaged over these hOPLs during clear-sky conditions

  2. The CU 2-dimensional MAX-DOAS instrument - Part 1: Retrieval of NO2 in 3 dimensions and azimuth dependent OVOC ratios

    NASA Astrophysics Data System (ADS)

    Ortega, I.; Koenig, T.; Sinreich, R.; Thomson, D.; Volkamer, R.

    2014-11-01

    We present an innovative instrument telescope, and describe a retrieval method to probe 3-D distributions of atmospheric trace gases that are relevant to air pollution and tropospheric chemistry. The University of Colorado (CU) two dimensional (2-D) Multi-AXis-Differential Optical Absorption Spectroscopy (CU 2D-MAX-DOAS) instrument measures nitrogen dioxide (NO2), formaldehyde (HCHO), glyoxal (CHOCHO), oxygen dimer (O2-O2, or O4) and water vapor (H2O); also nitrous acid (HONO), bromine monoxide (BrO), iodine monoxide (IO) among other gases can in principle be measured. Information about aerosols is derived through coupling with a radiative transfer model (RTM). The 2-D telescope has 3 modes of operation: (mode 1) measures solar scattered photons from any pair of elevation angle (-20° < EA < +90° or zenith; zero is to the horizon) and azimuth angle (-180° < AA < +180°; zero being North), (mode 2) measures any set of AA at constant EA (almucantar scans); and (mode 3) tracks the direct solar beam via a separate view port. Vertical profiles of trace gases are measured, and used to estimate planetary boundary layer height (PBL). Horizontal distributions are then derived using PBL and parameterization of RTM (Sinreich et al., 2013). NO2 is evaluated at different wavelengths (350, 450, and 560 nm), exploiting the fact that the effective path length varies systematically with wavelength. The area probed is constrained by O4 observations at nearby wavelengths, and has an effective radius of 7.5 to 20 km around the instrument location; i.e., up to 1250 km2 can be sampled near-instantaneously, and with high time resolution. The instrument was deployed as part of the Multi Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany from 7 June to 6 July 2013. We present first measurements (modes 1 and 2 only) and describe a four-step retrieval to derive (a) boundary layer vertical profiles of NO2 and PBL; (b) near-surface horizontal distributions

  3. Spatiotemporal inhomogeneity in atmospheric trace-gas over Fukuoka, an urban area in Japan, observed by ground-based MAX-DOAS

    NASA Astrophysics Data System (ADS)

    Takashima, H.; Kanaya, Y.; Irie, H.

    2015-12-01

    Continuous trace-gas observations have been made using ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) at Fukuoka (33.55N, 130.36E), an urban area in Japan. The maximum of the NOx emissions at Fukuoka is estimated to be at the city center, and the monitoring site is located ~5 km southwest of the city center, outside of the central area. To clarify the inhomogeneity as well as the transport/mixing processes of the polluted air in the urban area, continuous profile measurements have been conducted in two azimuth directions: towards and away from the city center. From NO2 observations, we sometimes observed spatial inhomogeneity associated with vertical/horizontal transport of high concentrations of NO2 from the city center, and horizontal transport of low concentrations from the ocean via a land-sea breeze. On the other hand, we observed spatial inhomogeneity in HONO and HCHO during summer, which was probably due to photochemical production over the city center.

  4. From slant column densities to trace gas profiles: Post processing data from the new MAX-DOAS network in Mexico City

    NASA Astrophysics Data System (ADS)

    Friedrich, M. M.; Stremme, W.; Rivera, C. I.; Arellano, E. J.; Grutter, M.

    2014-12-01

    The new MAX-DOAS network in Mexico City provides results of O4, HCHO and NO2 slant column densities (SCD). Here, we present a new numerical code developed to retrieve gas profiles of NO2 and HCHO using radiative transfer simulations. We present first results of such profiles from the MAX-DOAS station located at UNAM campus. The code works in two steps: First, the O4 slant column density information is used to retrieve an aerosol profile. As an a-priori aerosol profile, we use averaged ceilometer data measured at UNAM and scaled to the total optical depth provided by the Aeronet data base. In the second step, the retrieved aerosol profile information is used together with the trace gas (HCHO or NO2) SCDs to retrieve the trace gas profiles. The inversion is based on a gauss-newton iteration scheme and uses constrained least square fitting with either optimal estimation or Tihkonov regularization. For the latter, the regulation matrix is currently constructed from the discrete first derivative operator. The forward model uses the radiative transfer code VLIDORT. The inputs to VLIDORT are calculated using temperature and pressure information from daily radiosounde measurements and aerosol single scattering optical depths and asymmetry factors from the Aeronet data base for Mexico City. For the gas absorption cross sections we use the same values as were used for the SCD calculation from the recorded spectra using QDOAS. Besides demonstrating the functionality of the algorithm showing profile retrievals of simulated SCDs with added random noise, we present HCHO and NO2 profiles retrieved from SCDs calculated from the MAX-DOAS measurements at UNAM campus at selected days.

  5. Intercomparison of HONO SCDs and profiles from MAX-DOAS observations during the MAD-CAT campaign and comparison to chemical model simulations

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Wagner, Thomas; Xie, Pinhua; Remmers, Julia; Li, Ang; Lampel, Johannes; Friess, Udo; Peters, Enno; Wittrock, Folkard; Richter, Andreas; Hilboll, Andreas; Volkamer, Rainer; Ortega, Ivan; Hendrick, Francois; Van Roozendael, Michel; Ma, Jianzhong; Jin, Junli; Su, Hang; Cheng, Yafang

    2015-04-01

    In order to promote the development of the passive DOAS technique and to improve the retrieval algorithms of trace gases and aerosols the Multi Axis DOAS - Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany from June to October 2013. MAX-DOAS (Multi-Axis Differential Optical Absorption Spectroscopy) instruments of various designs recorded UV-visible spectra of scattered sunlight at different elevation and azimuth angles. We present intercomparison results for slant column densities (SCDs) of nitrous acid (HONO) retrieved during this campaign by several research groups. Data analysis was performed in two steps, starting with the preferred settings of the individual groups, followed by an analysis using common retrieval settings. In general good agreement of the resulting HONO SCD sets was found. Furthermore, we performed various sensitivity analyses to improve and evaluate the uncertainties in the HONO SCD retrieval, such as the influence of the wavelength dependence of the NO2 air mass factor, the selection of the wavelength interval of the retrieval, the choice of the Fraunhofer reference spectrum, or the offset correction. Finally we compared the results from different kinds of inversion algorithms for the vertical profiles of trace gases and aerosols. The derived HONO profiles, VMR near surface and tropospheric vertical column densities are compared with each other and with the results of regional chemical model simulations. We found a high HONO VMR near surface of about 200 ppt, which is much higher than the typical daytime VMR of lower than 10 ppt at the early noon (around 9:30 local time), probably indicating a strong source of HONO. The strong vertical gradient in the profile of HONO VMR probably indicates the HONO source is close to the surface.

  6. Retrieval of CHOCHO from MAX-DOAS measurements in the Beijing area

    NASA Astrophysics Data System (ADS)

    Hendrick, Francois; Lerot, Christophe; Stavrakou, Trissevgeni; De Smedt, Isabelle; Fayt, Caroline; Gielen, Clio; Hermans, Christian; Müller, Jean-Francois; Pinardi, Gaia; Van Roozendael, Michel

    2015-04-01

    Glyoxal (CHOCHO) is one of the most important carbonyl compounds in the atmosphere. It is produced mainly by the oxidation of biogenic and anthropogenic non-methane volatile organic compounds (NMVOCs) which participate to the formation of tropospheric ozone and secondary organic aerosols. CHOCHO is also directly released by biomass burning and fossil fuel combustion. Measuring this species is therefore of major importance for air quality monitoring, especially given the scarcity of available CHOCHO observational data sets. In this presentation, CHOCHO vertical profiles and corresponding column densities are retrieved from MAX-DOAS measurements in the Beijing city center and at the suburban site of Xianghe located at 60km East of Beijing. The periods covered by the observations are June 2008-April 2009 in Beijing and March 2010-December 2014 in Xianghe. We first investigate the capability of the MAX-DOAS technique to measure this species in such highly-polluted environment. Then the diurnal and seasonal cycles of CHOCHO near-surface concentrations and vertical column densities as well as the corresponding CHOCHO/HCHO ratios are examined on a long-term basis at both locations. The CHOCHO/HCHO ratios are derived from MAX-DOAS HCHO vertical profiles retrieved in parallel to the CHOCHO profiles. These diurnal and seasonal cycles are further assessed using simulations from the 3D-CTM IMAGES and observations from the OMI and GOME-2 satellite nadir instruments. The impact of these results on our knowledge about the CHOCHO budget is discussed.

  7. The CU 2-D-MAX-DOAS instrument - Part 2: Raman scattering probability measurements and retrieval of aerosol optical properties

    NASA Astrophysics Data System (ADS)

    Ortega, Ivan; Coburn, Sean; Berg, Larry K.; Lantz, Kathy; Michalsky, Joseph; Ferrare, Richard A.; Hair, Johnathan W.; Hostetler, Chris A.; Volkamer, Rainer

    2016-08-01

    The multiannual global mean of aerosol optical depth at 550 nm (AOD550) over land is ˜ 0.19, and that over oceans is ˜ 0.13. About 45 % of the Earth surface shows AOD550 smaller than 0.1. There is a need for measurement techniques that are optimized to measure aerosol optical properties under low AOD conditions. We present an inherently calibrated retrieval (i.e., no need for radiance calibration) to simultaneously measure AOD and the aerosol phase function parameter, g, based on measurements of azimuth distributions of the Raman scattering probability (RSP), the near-absolute rotational Raman scattering (RRS) intensity. We employ radiative transfer model simulations to show that for solar azimuth RSP measurements at solar elevation and solar zenith angle (SZA) smaller than 80°, RSP is insensitive to the vertical distribution of aerosols and maximally sensitive to changes in AOD and g under near-molecular scattering conditions. The University of Colorado two-dimensional Multi-AXis Differential Optical Absorption Spectroscopy (CU 2-D-MAX-DOAS) instrument was deployed as part of the Two Column Aerosol Project (TCAP) at Cape Cod, MA, during the summer of 2012 to measure direct sun spectra and RSP from scattered light spectra at solar relative azimuth angles (SRAAs) between 5 and 170°. During two case study days with (1) high aerosol load (17 July, 0.3 < AOD430 < 0.6) and (2) near-molecular scattering conditions (22 July, AOD430 < 0.13) we compare RSP-based retrievals of AOD430 and g with data from a co-located CIMEL sun photometer, Multi-Filter Rotating Shadowband Radiometer (MFRSR), and an airborne High Spectral Resolution Lidar (HSRL-2). The average difference (relative to DOAS) for AOD430 is +0.012 ± 0.023 (CIMEL), -0.012 ± 0.024 (MFRSR), -0.011 ± 0.014 (HSRL-2), and +0.023 ± 0.013 (CIMELAOD - MFRSRAOD) and yields the following expressions for correlations between different instruments

  8. An intercomparison study of tropospheric NO2 columns retrieved from MAX-DOAS and simulated by regional air quality models

    NASA Astrophysics Data System (ADS)

    Blechschmidt, Anne-Marlene

    2016-04-01

    Tropospheric NO2 is hazardous to human health and can lead to tropospheric ozone formation, eutrophication of ecosystems and acid rain production. It is therefore very important to accurately observe and simulate tropospheric NO2 on a regional and global scale. In the present study, MAX-DOAS tropospheric NO2 column retrievals from three European measurement stations are applied for validation of a regional model ensemble. In general, there is a good agreement between simulated and retrieved NO2 column values for individual MAX-DOAS measurements, indicating that the model ensemble does well represent the emission and tropospheric chemistry of NOx. However, the model ensemble tends to overestimate low and underestimate high tropospheric NO2 column values, respectively. Pollution transport towards the stations is on average well represented by the models. However, large differences can be found for individual pollution plumes. Seasonal cycles are overestimated by the model ensemble, which could point to problems in simulating photochemistry. While weekly cycles are reproduced well by the models, model performance is rather poor for diurnal cycles. In particular, simulated morning rush hour peaks are not confirmed by MAX-DOAS retrievals, which may result from inappropriate hourly scaling of NOx emissions, possibly combined with errors in chemistry. Our results demonstrate that a large number of validation points are available from MAX-DOAS data, which should therefore be used more extensively in future regional air quality modelling studies.

  9. Mobile MAX-DOAS observation of NO2 and comparison with OMI satellite data in the western coastal areas of the Korean peninsula.

    PubMed

    Chong, Jihyo; Kim, Young J; Gu, Myojeong; Wagner, Thomas; Song, Chul H

    2016-01-01

    Ground-based MAX-DOAS measurements have been used to retrieve column densities of atmospheric absorbers such as NO2, SO2, HCHO, and O3. In this study, mobile MAX-DOAS measurements were conducted to map the 2-D distributions of atmospheric NO2 in the western coastal areas of the Korean peninsula. A Mini-MAX-DOAS instrument was mounted on the rooftop of a mobile lab vehicle with a telescope mounted parallel to the driving direction, pointing forward. The measurements were conducted from 21 to 24 December 2010 along the western coastal areas from Gomso harbor (35.59N, 126.61E) to Gunsan harbor (35.98N, 126.67E). During mobile MAX-DOAS observations, high elevation angles were used to avoid shades from nearby obstacles. For the determination of the tropospheric vertical column density (VCD), the air mass factor (AMF) was retrieved by the so-called geometric approximation. The NO2 VCDs from 20 and 45 degree elevation angles were retrieved from mobile MAX-DOAS measurements. The tropospheric NO2 VCDs derived from mobile MAX-DOAS measurements were compared directly to those retrieved by the OMI satellite observations. Mobile MAX-DOAS VCD was in good agreement with OMI tropospheric VCD on most days. However, OMI tropospheric VCD was much higher than that of mobile MAX-DOAS on 23 December 2010. One probable reason for this difference is that OMI retrieval might overestimate NO2 VCD under haze conditions, when a pollution plume was transported over the measurement site. The mobile MAX-DOAS observations reveal much finer spatial patterns of NO2 distributions, which can provide useful information for the validation of satellite observation of atmospheric trace gases.

  10. Mobile MAX-DOAS observation of NO2 and comparison with OMI satellite data in the western coastal areas of the Korean peninsula.

    PubMed

    Chong, Jihyo; Kim, Young J; Gu, Myojeong; Wagner, Thomas; Song, Chul H

    2016-01-01

    Ground-based MAX-DOAS measurements have been used to retrieve column densities of atmospheric absorbers such as NO2, SO2, HCHO, and O3. In this study, mobile MAX-DOAS measurements were conducted to map the 2-D distributions of atmospheric NO2 in the western coastal areas of the Korean peninsula. A Mini-MAX-DOAS instrument was mounted on the rooftop of a mobile lab vehicle with a telescope mounted parallel to the driving direction, pointing forward. The measurements were conducted from 21 to 24 December 2010 along the western coastal areas from Gomso harbor (35.59N, 126.61E) to Gunsan harbor (35.98N, 126.67E). During mobile MAX-DOAS observations, high elevation angles were used to avoid shades from nearby obstacles. For the determination of the tropospheric vertical column density (VCD), the air mass factor (AMF) was retrieved by the so-called geometric approximation. The NO2 VCDs from 20 and 45 degree elevation angles were retrieved from mobile MAX-DOAS measurements. The tropospheric NO2 VCDs derived from mobile MAX-DOAS measurements were compared directly to those retrieved by the OMI satellite observations. Mobile MAX-DOAS VCD was in good agreement with OMI tropospheric VCD on most days. However, OMI tropospheric VCD was much higher than that of mobile MAX-DOAS on 23 December 2010. One probable reason for this difference is that OMI retrieval might overestimate NO2 VCD under haze conditions, when a pollution plume was transported over the measurement site. The mobile MAX-DOAS observations reveal much finer spatial patterns of NO2 distributions, which can provide useful information for the validation of satellite observation of atmospheric trace gases. PMID:26239513

  11. MAX-DOAS measurements of NO2, HCHO and CHOCHO at a rural site in Southern China

    NASA Astrophysics Data System (ADS)

    Li, X.; Brauers, T.; Hofzumahaus, A.; Lu, K.; Li, Y. P.; Shao, M.; Wagner, T.; Wahner, A.

    2013-02-01

    We performed MAX-DOAS measurements during the PRIDE-PRD2006 campaign in the Pearl River Delta region (PRD), China, for 4 weeks in July 2006 at a site located 60 km north of Guangzhou. The vertical distributions of NO2, HCHO, and CHOCHO were independently retrieved by an automated iteration method. The NO2 mixing ratios measured by MAX-DOAS showed reasonable agreement with the simultaneous, ground based in-situ data. The tropospheric NO2 vertical column densities (VCDs) observed by OMI on board EOS-Aura satellite were higher than with those by MAX-DOAS. The 3-D chemical transport model CMAQ overestimated the NO2 VCDs as well as the surface concentrations by about 65%. From this observation, a reduction of NOx emission strength in CMAQ seems to be necessary in order to well reproduce the NO2 observations. The average mixing ratios of HCHO and CHOCHO were 7 ppb and 0.4 ppb, respectively, higher than in other rural or semirural environments. The high ratio of 0.062 between CHOCHO and HCHO corresponds to the high VOCs reactivity and high HOx turnover rate consistent with other observations during the campaign.

  12. MAX-DOAS observations and their application to the validation of satellite and model data in Wuxi, China

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Wagner, T.; Xie, P.; Theys, N.; De Smedt, I.; Koukouli, M.; Stavrakou, T.; Beirle, S.; Li, A.

    2015-12-01

    Thomas Wagner1, Pinhua Xie2, Nicolas Theys3, Isabelle De Smedt3, MariLiza Koukouli4, Trissevgeni Stavrakou3, Steffen Beirle1, Ang Li2,1) Satellite group, Max Planck institute for Chemistry, Mainz, Germany2) Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei, China 3) BIRA-IASB, Brussels, Belgium 4) Laboratory of Atmospheric Physics, Aristotle University of Thessaloniki, Greece From 2011 to 2014 a MAX-DOAS instrument developed by the Anhui Institute of Optics and Fine Mechanics institute is operated in Wuxi, China, which is locatd about 100 km west of Shanghai. We determine the tropospheric vertical column densities (VCDs), near surface concentrations and vertical profiles of aerosols, NO2, SO2, HCHO from the MAX-DOAS observations using the optimal estimation profile retrieval algorithm (refered to as "PriAM"). We verified the results by comparing them with results from independent techniques, such as sun photometer (AERONET), a visibility meter and a long-path DOAS instrument. We acquire the cloud and aerosol conditions using a cloud classification scheme based on the MAX-DOAS observations (Wang et al., AMTD, 2015). Based on the obtained results, we characterize the effect of the clouds on the trace gas and aerosol profiles retrieved from MAX-DOAS. Then we characterize the diurnal, annual and weekly variations of the trace gases and aerosols and validate the tropospheric trace gas VCDs derived from the Ozone Monitoring instrument (OMI) on the Aura satellite platform as well as the model results from the IMAGES, CHIMERE and Lotos-Euros models and analyse the agreement depending on the cloud and aerosol conditions. Besides the direct comparison with the satellite data, we also use the trace gas and aerosol profiles derived from MAX-DOAS to recalculate the air mass factor (AMF) for the satellite observations and to evaluate the corresponding improvement of the satellite VCDs. In some periods with strong aerosol pollution, we evaluate the

  13. Characterisation of Central-African emissions based on MAX-DOAS measurements, satellite observations and model simulations over Bujumbura, Burundi.

    NASA Astrophysics Data System (ADS)

    Gielen, Clio; Hendrick, Francois; Pinardi, Gaia; De Smedt, Isabelle; Stavrakou, Trissevgeni; Yu, Huan; Fayt, Caroline; Hermans, Christian; Bauwens, Maité; Ndenzako, Eugene; Nzohabonayo, Pierre; Akimana, Rachel; Niyonzima, Sébastien; Müller, Jean-Francois; Van Roozendael, Michel

    2016-04-01

    Central Africa is known for its strong biogenic, pyrogenic, and to a lesser extent anthropogenic emissions. Satellite observations of species like nitrogen dioxide (NO2) and formaldehyde (HCHO), as well as inverse modelling results have shown that there are large uncertainties associated with the emissions in this region. There is thus a need for additional measurements, especially from the ground, in order to better characterise the biomass-burning and biogenic products emitted in this area. We present MAX-DOAS measurements of NO2, HCHO, and aerosols performed in Central Africa, in the city of Bujumbura, Burundi (3°S, 29°E, 850m). A MAX-DOAS instrument has been operating at this location by BIRA-IASB since late 2013. Aerosol-extinction and trace-gases vertical profiles are retrieved by applying the optimal-estimation-based profiling tool bePRO to the measured O4, NO2 and HCHO slant-column densities. The MAX-DOAS vertical columns and profiles are used for investigating the diurnal and seasonal cycles of NO2, HCHO, and aerosols. Regarding the aerosols, the retrieved AODs are compared to co-located AERONET sun photometer measurements for verification purpose, while in the case of NO2 and HCHO, the MAX-DOAS vertical columns and profiles are used for validating GOME-2 and OMI satellite observations. To characterise the biomass-burning and biogenic emissions in the Bujumbura region, the trace gases and aerosol MAX-DOAS retrievals are used in combination to MODIS fire counts/radiative-power and GOME-2/OMI NO2 and HCHO satellite data, as well as simulations from the NOAA backward trajectory model HYSPLIT. First results show that HCHO seasonal variation around local noon is driven by the alternation of rain and dry periods, the latter being associated with intense biomass-burning agricultural activities and forest fires in the south/south-east and transport from this region to Bujumbura. In contrast, NO2 is seen to depend mainly on local emissions close to the city, due

  14. Monitoring shipping emissions with MAX-DOAS measurements of reactive trace gases

    NASA Astrophysics Data System (ADS)

    Wittrock, Folkard; Peters, Enno; Seyler, André; Kattner, Lisa; Mathieu-Üffing, Barbara; Burrows, John P.; Chirkov, Maksym; Meier, Andreas C.; Richter, Andreas; Schönhardt, Anja; Schmolke, Stefan; Theobald, Norbert

    2014-05-01

    Air pollution from ships contributes to overall air quality problems and it has direct health effects on the population in particular in coastal regions, and in harbor cities. In order to reduce the emissions the International Maritime Organisation (IMO) have tightened the regulations for air pollution. E.g. Sulfur Emission Control Areas (SECA) have been introduced where the sulfur content of marine fuel is limited. However, up to now there is no regular monitoring system available to verify that ships are complying with the new regulations. Furthermore measurements of reactive trace gases in marine environments are in general sparse. The project MeSMarT (Measurements of shipping emissions in the marine troposphere, www.mesmart.de) has been established as a cooperation between the University of Bremen and the German Bundesamt für Seeschifffahrt und Hydrographie (Federal Maritime and Hydrographic Agency) with support of the Helmholtz Research Centre Geesthacht to estimate the influence of ship emissions on the chemistry of the atmospheric boundary layer and to establish a monitoring system for main shipping routes. Here we present MAX-DOAS observations of NO2 and SO2 carried out during ship campaigns in the North and Baltic Sea and from two permanent sites close to the Elbe river (Wedel, Germany) and on the island Neuwerk close to the mouths of Elbe and Weser river. Mixing ratios of both trace gases have been retrieved using different approaches (pure geometric and taking into account the radiative transfer) and compared to in situ and air borne observations (see Kattner et al., Monitoring shipping emissions with in-situ measurements of trace gases, and Meier et al., Airborne measurements of NO2 shipping emissions using imaging DOAS) observations. Furthermore simple approaches have been used to calculate emission factors of NOx and SO2 for single ships.

  15. Photothermal absorption correlation spectroscopy.

    PubMed

    Octeau, Vivien; Cognet, Laurent; Duchesne, Laurence; Lasne, David; Schaeffer, Nicolas; Fernig, David G; Lounis, Brahim

    2009-02-24

    Fluorescence correlation spectroscopy (FCS) is a popular technique, complementary to cell imaging for the investigation of dynamic processes in living cells. Based on fluorescence, this single molecule method suffers from artifacts originating from the poor fluorophore photophysics: photobleaching, blinking, and saturation. To circumvent these limitations we present here a new correlation method called photothermal absorption correlation spectroscopy (PhACS) which relies on the absorption properties of tiny nano-objects. PhACS is based on the photothermal heterodyne detection technique and measures akin FCS, the time correlation function of the detected signals. Application of this technique to the precise determination of the hydrodynamic sizes of different functionalized gold nanoparticles are presented, highlighting the potential of this method. PMID:19236070

  16. Comparison of glyoxal, BrO, and IO vertical profiles derived from both ground-based and airborne MAX-DOAS measurements

    NASA Astrophysics Data System (ADS)

    Coburn, Sean; Volkamer, Rainer; Baidar, Sunil; Dix, Barbara; Koenig, Theodore; Ortega, Ivan; Sinreich, Roman; van Roozendael, Michel; Hendrick, Francois; Kinnison, Doug

    2015-04-01

    The information content of ground-based MAX-DOAS retrievals is assessed by collocated aircraft measurements for a ship MAX-DOAS setup over the Eastern tropical Pacific Ocean (TORERO RF17), and a mountain-top MAX-DOAS setup at Mauna Loa Observatory, Hawaii (CONTRAST RF17). During both case studies the CU airborne MAX-DOAS (AMAX-DOAS) instrument aboard the NSF/NCAR GV aircraft measured profiles of glyoxal, BrO, and IO with 12-20 degrees of freedom and up to 500 m vertical resolution. The TORERO field campaign took place in 2012, while CONTRAST in 2014; both campaigns covered the months of January and February. Additional measurements aboard the aircraft helped to provide information/validation of the AMAX-DOAS derived profiles, such as in-situ water vapor from the Vertical-Cavity Surface-Emitting Laser hygrometer (VCSEL), in-situ hydrocarbon measurements from the Trace Organic Gas Analyzer (TOGA), and aerosol information constrained by the Ultra High Sensitivity Aerosol Spectrometer (UHSAS). The AMAX-DOAS profiles are compared with ground-based MAX-DOAS inversions. The latter explores the effect of using either the measured differential slant column density (dSCD) or SCD as input to the optimal estimation inversion, where SCD = dSCD + SCD_ref. SCD_ref is the residual column amount of the trace gas contained within the reference spectrum. For the AMAX-DOAS data, the values of SCD_ref were actively minimized, while SCD_ref is usually unknown for ground-based MAX-DOAS retrievals. In absence of independent measurements to constrain SCD_ref, the current state-of-the-art with ground-based MAX-DOAS applications is to use dSCDs as input to the inversion. Here we assess the effect of uncertain SCD_ref for ground-based MAX-DOAS profiles in form of a sensitivity study. Additionally for the ground-based data, different methods are compared for the determination of SCD_ref: 1) the collocated aircraft profiles described above present the opportunity to forward calculate the SCD

  17. Tomographic multiaxis-differential optical absorption spectroscopy observations of Sun-illuminated targets: a technique providing well-defined absorption paths in the boundary layer.

    PubMed

    Frins, Erna; Bobrowski, Nicole; Platt, Ulrich; Wagner, Thomas

    2006-08-20

    A novel experimental procedure to measure the near-surface distribution of atmospheric trace gases by using passive multiaxis differential absorption optical spectroscopy (MAX-DOAS) is proposed. The procedure consists of pointing the receiving telescope of the spectrometer to nonreflecting surfaces or to bright targets placed at known distances from the measuring device, which are illuminated by sunlight. We show that the partial trace gas absorptions between the top of the atmosphere and the target can be easily removed from the measured total absorption. Thus it is possible to derive the average concentration of trace gases such as NO(2), HCHO, SO(2), H(2)O, Glyoxal, BrO, and others along the line of sight between the instrument and the target similar to the well-known long-path DOAS observations (but with much less expense). If tomographic arrangements are used, even two- or three-dimensional trace gas distributions can be retrieved. The basic assumptions of the proposed method are confirmed by test measurements taken across the city of Heidelberg. PMID:16892129

  18. Assessing the need for a O4 scaling factor for MAX-DOAS measurements during the MAD-CAT campaign in Mainz Germany, Summer 2013

    NASA Astrophysics Data System (ADS)

    Wagner, Thomas; Remmers, Julia; Shaiganfar, Reza; Lampel, Johannes; Wang, Yang; Beirle, Steffen; Dörner, Steffen

    2016-04-01

    MAX-DOAS measurements of the atmospheric absorption of the oxygen dimer O4 are often used to derive information about the tropospheric aerosol distribution. For that purpose measured absorptions are compared to results of a forward model based on radiative transfer simulations and assumptions about the atmospheric state. Many studies demonstrated good agreement of the derived aerosol results with independent observations. Nevertheless, in some studies also systematic differences between the measurements and the forward model were found. E.g. measured O4 absorptions on clear days were found to be even larger than the forward model results for an assumed aerosol-free atmosphere. These discrepancies motivated the use of a scaling factor for the retrieved O4 absorptions. Reported values of this scaling factor range from about 0.7 to 0.9. On the other hand, several studies found excellent agreement between measurements and forward model without the need of a scaling factor. So far, there is no convincing explanation for these conflicting findings. In this study we compare measurements and forward model results for two clear days during the MAD-CAT (Multi Axis DOAS - Comparison campaign of Aerosols and Trace gases) campaign in Mainz, Germany in Summer 2013. On these days the aerosol extinction profiles were well constraint by measurements of a ceilometer and a sun photometer. For almost all of these measurements (made in 4 azimuth directions) we find a systematic underestimation of the measured O4 absorptions by the forward model indicating the need for a scaling factor of about 0.65 to 0.9. We investigate several potential reasons for the observed discrepancy including the influence of the profiles of temperature, pressure and aerosol extinction as well as the aerosol optical properties.

  19. Relic Neutrino Absorption Spectroscopy

    SciTech Connect

    Eberle, b

    2004-01-28

    Resonant annihilation of extremely high-energy cosmic neutrinos on big-bang relic anti-neutrinos (and vice versa) into Z-bosons leads to sizable absorption dips in the neutrino flux to be observed at Earth. The high-energy edges of these dips are fixed, via the resonance energies, by the neutrino masses alone. Their depths are determined by the cosmic neutrino background density, by the cosmological parameters determining the expansion rate of the universe, and by the large redshift history of the cosmic neutrino sources. We investigate the possibility of determining the existence of the cosmic neutrino background within the next decade from a measurement of these absorption dips in the neutrino flux. As a by-product, we study the prospects to infer the absolute neutrino mass scale. We find that, with the presently planned neutrino detectors (ANITA, Auger, EUSO, OWL, RICE, and SalSA) operating in the relevant energy regime above 10{sup 21} eV, relic neutrino absorption spectroscopy becomes a realistic possibility. It requires, however, the existence of extremely powerful neutrino sources, which should be opaque to nucleons and high-energy photons to evade present constraints. Furthermore, the neutrino mass spectrum must be quasi-degenerate to optimize the dip, which implies m{sub {nu}} 0.1 eV for the lightest neutrino. With a second generation of neutrino detectors, these demanding requirements can be relaxed considerably.

  20. Car MAX-DOAS measurements around entire cities: quantification of NOx emissions from the cities of Mannheim and Ludwigshafen (Germany)

    NASA Astrophysics Data System (ADS)

    Ibrahim, O.; Shaiganfar, R.; Sinreich, R.; Stein, T.; Platt, U.; Wagner, T.

    2010-06-01

    We present car Multi-Axis (MAX-) DOAS observations of tropospheric NO2 carried out on circles around the cities of Mannheim and Ludwigshafen (Germany) on 24 August 2006. Together with information on wind speed and direction, the total emissions of the encircled source(s) are quantified from these measurements. In contrast to recent similar studies based on zenith scattered sun light (elevation angle of 90°), we use a MAX-DOAS instrument mounted on a car, which observes scattered sun light under different elevation angles (here 45°, and 90°). Compared to simple zenith sky observations, MAX-DOAS observations have higher sensitivity and reduced uncertainty, and avoid systematic offsets in the determination of the vertically integrated trace gas concentration. The determination of the absolute value of the integrated tropospheric trace gas concentrations is especially important for the calculation of absolute trace gas fluxes through arbitrary transects. However, even if emission sources are completely surrounded, systematic offsets in the measured vertically integrated trace gas concentration can lead to errors in the determined total emissions, especially for observations around extended areas. In this study we discuss and quantify different error sources. In most cases, the largest error source is the variability and imperfect knowledge of the wind field. In addition - depending on the trace species observed - also chemical transformations between the emission sources and the measurement location have to be considered. For that purpose we use local observations within the encircled area to quantify and/or correct these errors. From our observations we derive a total NOx emission from the Mannheim/Ludwigshafen area of (7.4±1.8)×1024 molec/sec, which if assumed to be constant throughout the year would correspond to a total emission of 17 830±4340 t/yr (calculated with the mass of NO2 t/yr, consistent with existing emission estimates. From our observations it is

  1. [Retrieval of NO2 total vertical columns by direct-sun differential optical absorption spectroscopy].

    PubMed

    Wang, Yang; Xie, Pin-hua; Li, Ang; Xu, Jin; Zeng, Yi; Si, Fu-qi; Wu, Feng-cheng

    2012-04-01

    An appropriate reference spectrum is essential for the direct-sun differential optical absorption spectroscopy (DS-DOAS). It depends on the real reference spectrum to retrieve the total vertical column density (VCD). The spectrum detected at the time with minimum sun zenith angle under the relative clear atmospheric condition in the measurement period was conventionally selected as the reference spectrum. Because there is still untracked NO2 absorption structure in the reference spectrum, the VCD retrieved based on the above spectrum is actually relative VCD, which results in larger error. To solve this problem, a new method was investigated. A convolution of extraterrestrial high-precision solar Fraunhofer spectrum and the instrumental function of the spectrometer was computed and chosen as the reference spectrum. The error induced by NO2 absorption structure in the reference spectrum was removed. Then the fitting error of slant column density (SCD) retrieved by this method was analyzed. The correlation between the absolute SCD and the differential slant column density (dSCD) was calculated. The result shows that the error of SCD retrieved by this new method is below 1.6 x 10(16) molecules x cm(-2) on March 7, 2011, while the error generated by the normal method is about 4.25 x 10(16) molecules x cm(-2). The new method decreased more than 62% error. In addition, the results throughout the day were compared to the troposphere VCD from MAX-DOAS and they are in good agreement. It indicates that the new method could effectively reduce the VCD error of the common way. PMID:22715747

  2. Evaluation wavelength range mapping, a tool to optimize the evaluation window in differential absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vogel, L.; Sihler, H.; Lampel, J.; Wagner, T.; Platt, U.

    2012-04-01

    Optical remote sensing via Differential Optical Absorption Spectroscopy (DOAS) has become a standard technique to assess various trace gases in the atmosphere. Measurement instruments are usually classified into active instruments applying an artificial light source and passive instruments using natural light sources, e.g., scattered or direct sunlight. Platforms range from ground based to satellites and trace gases are studied in all kinds of different environments. Naturally, the evaluation of gathered spectra needs to be tuned to each specific case and trace gas of interest due to the wide range of measurement conditions, atmospheric compositions and instruments used. A well chosen evaluation wavelength range is crucial to the DOAS technique. It should be as large as possible and include the largest differential absorption features of the trace gas of interest in order to maximize sensitivity. However, the differential optical densities of other absorbers should be minimized in order to prevent interferences between different absorption cross sections. Furthermore, instrumental specific features and wavelength dependent radiative transfer effects may have malicious effects and lead to erroneous values. Usually a compromise needs to be found depending on the conditions at hand. Evaluation wavelength range mapping is an easily applied tool to visualize wavelength depending evaluation features of DOAS and to find the optimal retrieval wavelength range. As an example, synthetic spectra are studied which simulate passive DOAS measurements of stratospheric bromine monoxide (BrO) by Zenith-DOAS and Multi-Axis DOAS (MAX-DOAS) measurements of BrO in volcanic plumes. The influence of the I0-effect and the Ring-effect on the respective retrievals are demonstrated. However, due to the general nature of the tool it is applicable to any DOAS measurement and the technique also allows to study any other wavelength dependent influences on retrieved trace gas columns.

  3. X-ray Absorption Spectroscopy

    SciTech Connect

    Yano, Junko; Yachandra, Vittal K.

    2009-07-09

    This review gives a brief description of the theory and application of X-ray absorption spectroscopy, both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), especially, pertaining to photosynthesis. The advantages and limitations of the methods are discussed. Recent advances in extended EXAFS and polarized EXAFS using oriented membranes and single crystals are explained. Developments in theory in understanding the XANES spectra are described. The application of X-ray absorption spectroscopy to the study of the Mn4Ca cluster in Photosystem II is presented.

  4. The CU 2-D-MAX-DOAS instrument – Part 2: Raman scattering probability measurements and retrieval of aerosol optical properties

    DOE PAGES

    Ortega, Ivan; Coburn, Sean; Berg, Larry K.; Lantz, Kathy; Michalsky, Joseph; Ferrare, Richard A.; Hair, Johnathan W.; Hostetler, Chris A.; Volkamer, Rainer

    2016-08-23

    The multiannual global mean of aerosol optical depth at 550 nm (AOD550) over land is ∼ 0.19, and that over oceans is ∼ 0.13. About 45 % of the Earth surface shows AOD550 smaller than 0.1. There is a need for measurement techniques that are optimized to measure aerosol optical properties under low AOD conditions. We present an inherently calibrated retrieval (i.e., no need for radiance calibration) to simultaneously measure AOD and the aerosol phase function parameter, g, based on measurements of azimuth distributions of the Raman scattering probability (RSP), the near-absolute rotational Raman scattering (RRS) intensity. We employ radiative transfer model simulations tomore » show that for solar azimuth RSP measurements at solar elevation and solar zenith angle (SZA) smaller than 80°, RSP is insensitive to the vertical distribution of aerosols and maximally sensitive to changes in AOD and g under near-molecular scattering conditions. The University of Colorado two-dimensional Multi-AXis Differential Optical Absorption Spectroscopy (CU 2-D-MAX-DOAS) instrument was deployed as part of the Two Column Aerosol Project (TCAP) at Cape Cod, MA, during the summer of 2012 to measure direct sun spectra and RSP from scattered light spectra at solar relative azimuth angles (SRAAs) between 5 and 170°. During two case study days with (1) high aerosol load (17 July, 0.3  <  AOD430 < 0.6) and (2) near-molecular scattering conditions (22 July, AOD430 < 0.13) we compare RSP-based retrievals of AOD430 and g with data from a co-located CIMEL sun photometer, Multi-Filter Rotating Shadowband Radiometer (MFRSR), and an airborne High Spectral Resolution Lidar (HSRL-2). The average difference (relative to DOAS) for AOD430 is +0.012 ± 0.023 (CIMEL), −0.012 ± 0.024 (MFRSR), −0.011 ± 0.014 (HSRL-2), and +0.023 ± 0.013 (CIMELAOD − MFRSRAOD) and yields the following expressions for correlations between different instruments

  5. Airborne MAX-DOAS Measurements Over California: Testing the NASA OMI Tropospheric NO2 Product

    NASA Technical Reports Server (NTRS)

    Oetjen, Hilke; Baidar, Sunil; Krotkov, Nickolay A.; Lamsal, Lok N.; Lechner, Michael; Volkamer, Rainer

    2013-01-01

    Airborne Multi-AXis Differential Optical Absorption Spectroscopy (AMAX-DOAS) measurements of NO2 tropospheric vertical columns were performed over California for two months in summer 2010. The observations are compared to the NASA Ozone Monitoring Instrument (OMI) tropospheric vertical columns (data product v2.1) in two ways: (1) Median data were compared for the whole time period for selected boxes, and the agreement was found to be fair (R = 0.97, slope = 1.4 +/- 0.1, N= 10). (2) A comparison was performed on the mean of coincident AMAX-DOAS measurements within the area of the corresponding OMI pixels with the tropospheric NASA OMI NO2 assigned to that pixel. The effects of different data filters were assessed. Excellent agreement and a strong correlation (R = 0.85, slope = 1.05 +/- 0.09, N= 56) was found for (2) when the data were filtered to eliminate large pixels near the edge of the OMI orbit, the cloud radiance fraction was<50%, the OMI overpass occurred within 2 h of the AMAX-DOAS measurements, the flight altitude was>2 km, and a representative sample of the footprint was taken by the AMAX-DOAS instrument. The AMAX-DOAS and OMI data sets both show a reduction of NO2 tropospheric columns on weekends by 38 +/- 24% and 33 +/- 11%, respectively. The assumptions in the tropospheric satellite air mass factor simulations were tested using independent measurements of surface albedo, aerosol extinction, and NO2 profiles for Los Angeles for July 2010 indicating an uncertainty of 12%.

  6. Concentration-modulated absorption spectroscopy.

    PubMed

    Langley, A J; Beaman, R A; Baran, J; Davies, A N; Jones, W J

    1985-07-01

    Concentration modulation is demonstrated to be a technique capable of markedly extending sensitivity limits in absorption spectroscopy. The gain generated relates in such a manner to sample transmittance that for the first reported time direct spectroscopic concentration measurements become possible. When concentration modulation is used with picosecond lasers, state lifetimes can be determined to a limit of approximately 20 psec.

  7. Inter-Comparison of Nitrogen Dioxide Column Densities Retrieved by Ground-Based Max-Doas Under Different Instrumental Conditions Over Mainz

    NASA Astrophysics Data System (ADS)

    Bruchkouski, I.; Dziomin, V.; Ortega, I.; Volkamer, R.; Krasouski, A.

    2013-12-01

    This study is dedicated to the instrumental differences between ground-based MAX-DOAS measurement devices. Our MAX-DOAS instrument, which has been developed at the National Ozone Monitoring Research & Education Center of the Belarusian State University for the purpose of nitrogen dioxide and other atmospheric trace gases monitoring over Belarus, features a rotating mirror and a telescope directly connected to the spectrometer with a two-dimensional CCD detector. Using a mirror instead of an optical fibre makes it possible to change the field of view of the telescope, and the whole instrument is rather compact and all its components are placed outdoors in the open air. However, this makes it quite difficult to ensure a top-quality thermostabilization. In the course of the MAX-DOAS campaign, which took place in the Max Planck Institute for Chemistry in Mainz, Germany in summer of 2013, we had a great opportunity to compare our instrument with other devices of different types. In the present study we make a comparison of nitrogen dioxide slant column densities (SCDs) during several days obtained by our instrument with that measured by the device from the Department of Chemistry and Biochemistry, University of Colorado (Boulder), which has a thermostabilization level of about 0.01 degrees Celsius. We investigate the influence of the spectrometer parts thermostabilization on nitrogen dioxide SCDs retrieval. Furthermore, it was possible to modify the telescope field of view for our instrument from 0.005 to 1.3 degrees, so we performed nitrogen dioxide SCDs retrieval for different fields of view at the same angle of elevation. We analyze these measurement results and obtain an optimal field of view with the aim to achieve the highest possible signal to noise ratio.

  8. Graphene intracavity spaser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lozovik, Yu. E.; Nechepurenko, I. A.; Dorofeenko, A. V.

    2016-09-01

    We propose an intracavity plasmon absorption spectroscopy method based on graphene active plasmonics. It is shown that the plasmonic cavity contribution to the sensitivity is proportional to the quality factor Q of the graphene plasmonic cavity and reaches two orders of magnitude. The addition of gain medium into the cavity increases the sensitivity of method. Maximum sensitivity is reached in the vicinity of the plasmon generation threshold. The gain contribution to the sensitivity is proportional to Q1/2. The giant amplification of sensitivity in the graphene plasmon generator is associated with a huge path length, limited only by the decoherence processes. An analytical estimation of the sensitivity to loss caused by analyzed particles (molecules, nanoparticles, etc.) normalized by the single pass plasmon scheme is derived. Usage of graphene nanoflakes as plasmonic cavity allows a high spatial resolution to be reached, in addition to high sensitivity.

  9. Evaluation of NOx emission uncertainties based on car-MAX-DOAS observations and CHIMERE model simulations during the MEGAPOLI campaigns in Paris in Summer 2009 and Winter 2009/10

    NASA Astrophysics Data System (ADS)

    Shaiganfar, Reza; Petetin, Herve; Beirle, Steffen; Beekmann, Matthias; Wagner, Thomas

    2016-04-01

    Within the European project MEGAPOLI we performed two extensive car-MAX-DOAS campaigns around Paris in August 2009 and January/February 2010. The car-MAX-DOAS observations are conducted on circles with different radii around the city with the aim to quantify the NOx emissions from the area inside the circles. The method is based on the combination of the retrieved tropospheric NO2 column densities with wind fields. In this way the influx and the outflux can be calculated; the difference of both represents emissions from the encircled area. Since the car-MAX-DOAS observations are only sensitive to NO2, the derived NO2 emissions have to be upscaled to the total NOx (NO + NO2) emissions from megacity. Also corrections for the rather short lifetime of NOx have to be applied. In our study we investigate the uncertainty of the method with respect to different measurement parameters and wind conditions. For that purpose we make use of model simulations from the regional CHIMERE model. First we sample the modelled NO2 fields at the exact locations and times of the car-MAX-DOAS measurements. Second, we apply the method for the determination of the NOx emissions to this sampled model data. Third, we compare the derived emissions to the input emissions used in the model simulations. From the comparison we identify critical parameters for the application of our method and develop a method for the determination of the uncertainty of the derived emissions. Largest errors are found for situations with low wind speed and/or high variability of the wind speed or direction during the period of the measurements. Also gaps or road segments close to the citiy center cause larger errors. Finally, we apply the method to the car-MAX-DOAS observations and compare the derived emissions to existing emission inventories.

  10. 3 dimensional distributions of NO2, CHOCHO, and HCHO measured by the University of Colorado 2D-MAX-DOAS during MAD-CAT

    NASA Astrophysics Data System (ADS)

    Ortega, Ivan; Sinreich, Roman; Volkamer, Rainer

    2014-05-01

    We present results of 2 dimensional Multi Axis-DOAS (2D-MAX-DOAS) measurements to infer 3-dimensional measurements of trace gases by characterizing boundary layer vertical profiles and near surface azimuth horizontal distribution of NO2 (14 angles covering 360°). We combine the established optimal estimation inversion with a new parameterization approach; the first method to derive NO2 tropospheric vertical profiles and boundary layer height and the second one to retrieve the azimuth horizontal distribution of near surface NO2 mixing ratios, both at multiple wavelengths (350 nm, 450 nm, and 560 nm). This was conducted for three cloud-free days in the framework of the intensive Multi Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany 2013. By retrieving NO2 at multiple wavelengths range-resolved distributions of NO2 are derived using an 'Onion-peeling' approach, i.e., exploiting the fact that the optical path lengths at different wavelengths probe different horizontal air masses. We also measure glyoxal (CHOCHO) and formaldehyde (HCHO) distributions, and present to our knowledge the first 3-dimesional trace-gas distribution measurements of CHOCHO by a ground-based instrument. We expand the 2D-MAX-DOAS capabilities to calculate azimuth ratios of HCHO-to-NO2 (RFN) and CHOCHO-to-NO2 (RGN) to pinpoint volatile organic compound (VOC) oxidation chemistry and CHOCHO-to-HCHO (RGF) ratios as an indicator of biogenic and/or anthropogenic VOC emissions. The results of RFN correlate well with RGN and we identify azimuth variations that indicate gradients in the VOC/NOx chemistry that leads to O3 and secondary aerosol production. While there is a clear diurnal pattern in the RFN and RGN, no such variations are observed in the RGF, which shows rather constant values below 0.04 throughout the day, consistent with previous measurements, and indicative of urban air masses.

  11. Retrieval of free-tropospheric BrO from MAX-DOAS measurements at the high-altitude alpine station of Jungfraujoch

    NASA Astrophysics Data System (ADS)

    Van Roozendael, Michel; Hendrick, Francois; De Smedt, Isabelle; Fayt, Caroline; Gielen, Clio; Hermans, Christian; Pinardi, Gaia; Tack, Frederik; Theys, Nicolas

    2014-05-01

    There are currently many open questions about the sources, transport, and photochemical processing that control the abundance of BrO and its precursors in the global troposphere. Recent experimental studies based on various platforms and instrumentations indicate contrasting results reflecting the scarcity of the measurements and the experimental challenge of quantifying the typically low abundance levels of BrO. Modeling studies indicate however that the presence of only 1-2 pptv levels of reactive bromine has important consequences for free tropospheric ozone with indirect climate implications. The MAX-DOAS technique offers high sensitivity for near-surface trace gas measurements and it is well suited to BrO detection. From a high altitude site such as the Jungfraujoch which is located in the Swiss Alps at about 3600 m ASL, the free-troposphere can be sampled under favourable conditions. We report on attempts to quantify the free tropospheric BrO level based on MAXDOAS measurements performed by BIRA-IASB in the period from June 2010 until December 2012. Retrievals are based on the DOAS method followed by vertical profile inversion using an Optimal Estimation scheme. The possible sources of bias that can affect the spectral retrieval of BrO are carefully investigated and various sensitivity tests are performed to assess the stability of the inversion. Results are compared with independent estimates of the mid-latitude tropospheric BrO based on satellite measurements.

  12. Further advancement of differential optical absorption spectroscopy: theory of orthogonal optical absorption spectroscopy.

    PubMed

    Liudchik, Alexander M

    2014-08-10

    A modified version of the differential optical absorption spectroscopy (DOAS) method is presented. The technique is called orthogonal optical absorption spectroscopy (OOAS). A widespread variant of DOAS with smoothing of the registered spectrum and absorption cross sections being made employing a polynomial regression is a particular case of OOAS. The concept of OOAS provides a variety of new possibilities for constructing computational schemes and analyzing the influence of different error sources on calculated concentrations. PMID:25320931

  13. Absorption spectroscopy: technique provides extremely high sensitivity.

    PubMed

    Provencal, R A; Paul, J B; Michael, E; Saykally, R J

    1998-06-01

    Technology associated with cavity ringdown laser absorption spectroscopy is reviewed. The technique is used to study general trace analysis, free radicals in flames and chemical reactors, molecular ions in electrical discharges, biological molecules and water clusters in supersonic jets, and vibrational overtones of stable molecules. Its specific enough to detect about 1-ppm fractional absorption by a gaseous sample in about 10 microseconds. The use of mirrors in ringdown sepctroscopy is explained. Other topics include the generation of pulsed infrared rays and the adaptation of ringdown spectroscopy for use with narrow-bandwidth continuous-wave lasers. PMID:11541906

  14. X-ray absorption spectroscopy of metalloproteins.

    PubMed

    Ward, Jesse; Ollmann, Emily; Maxey, Evan; Finney, Lydia A

    2014-01-01

    Metalloproteins are enormously important in biology. While a variety of techniques exist for studying metals in biology, X-ray absorption spectroscopy is particularly useful in that it can determine the local electronic and physical structure around the metal center, and is one of the few avenues for studying "spectroscopically silent" metal ions like Zn(II) and Cu(I) that have completely filled valence bands. While X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) are useful for studying metalloprotein structure, they suffer the limitation that the detected signal is an average of all the various metal centers in the sample, which limits its usefulness for studying metal centers in situ or in cell lysates. It would be desirable to be able to separate the various proteins in a mixture prior to performing X-ray absorption studies, so that the derived signal is from one species only. Here we describe a method for performing X-ray absorption spectroscopy on protein bands following electrophoretic separation and western blotting.

  15. Triplet absorption spectroscopy and electromagnetically induced transparency

    NASA Astrophysics Data System (ADS)

    Ghafoor, F.; Nazmitdinov, R. G.

    2016-09-01

    Coherence phenomena in a four-level atomic system, cyclically driven by three coherent fields, are investigated thoroughly at zero and weak magnetic fields. Each strongly interacting atomic state is converted to a triplet due to a dynamical Stark effect. Two dark lines with a Fano-like profile arise in the triplet absorption spectrum with anomalous dispersions. We provide conditions to control the widths of the transparency windows by means of the relative phase of the driving fields and the intensity of the microwave field, which closes the optical system loop. The effect of Doppler broadening on the results of the triplet absorption spectroscopy is analysed in detail.

  16. Absorption spectroscopy with quantum cascade lasers

    NASA Technical Reports Server (NTRS)

    Kosterev, A. A.; Curl, R. F.; Tittel, F. K.; Gmachl, C.; Capasso, F.; Sivco, D. L.; Baillargeon, J. N.; Hutchinson, A. L.; Cho, A. Y.

    2001-01-01

    Novel pulsed and cw quantum cascade distributed feedback (QC-DFB) lasers operating near lambda=8 micrometers were used for detection and quantification of trace gases in ambient air by means of sensitive absorption spectroscopy. N2O, 12CH4, 13CH4, and different isotopic species of H2O were detected. Also, a highly selective detection of ethanol vapor in air with a sensitivity of 125 parts per billion by volume (ppb) was demonstrated.

  17. OH absorption spectroscopy in a flame using spatial heterodyne spectroscopy

    NASA Astrophysics Data System (ADS)

    Bartula, Renata J.; Ghandhi, Jaal B.; Sanders, Scott T.; Mierkiewicz, Edwin J.; Roesler, Fred L.; Harlander, John M.

    2007-12-01

    We demonstrate measurements of OH absorption spectra in the post-flame zone of a McKenna burner using spatial heterodyne spectroscopy (SHS). SHS permits high-resolution, high-throughput measurements. In this case the spectra span ~308-310 nm with a resolution of 0.03 nm, even though an extended source (extent of ~2×10-7 m2 rad2) was used. The high spectral resolution is important for interpreting spectra when multiple absorbers are present for inferring accurate gas temperatures from measured spectra and for monitoring weak absorbers. The present measurement paves the way for absorption spectroscopy by SHS in practical combustion devices, such as reciprocating and gas-turbine engines.

  18. Comparison of tropospheric NO2 columns from ground based MAX-DOAS systems with satellite retrievals: A case study in the greater area of Thessaloniki.

    NASA Astrophysics Data System (ADS)

    Drosoglou, Theano; Bais, Alkis; Kouremeti, Natalia; Koukouli, Mariliza; Balis, Dimitris

    2015-04-01

    Phaethon is a low-cost ground-based MAX-DOAS system that is used to acquire fast direct solar irradiance and sky radiance spectrally resolved measurements in the region 300-450 nm and deliver total and tropospheric columns of atmospheric trace gases. Phaethon, which comprises a cooled miniature CCD spectrograph (AvaSpec-ULS2048LTEC) and a 2-axes tracker, was designed for easy deployment at different sites to address specific air quality problems and to support satellite validation studies at locations of particular scientific interest. In the framework of the Optimization and expansion of ground infrastructure for the validation of satellite-derived column densities of atmospheric species, AVANTI project, three Phaethon systems have been deployed in the greater area of Thessaloniki, Greece, within an area of about 15 km by 30 km, comparable to the size of a satellite pixel, with the aim to link modeling of tropospheric trace gases with satellite products. The locations of the three systems are characterized by diverse local atmospheric pollution loadings representing urban, industrial and rural conditions. The systems have been first operated for a few days in parallel at the station in the University campus to establish their inter-comparison behaviour and possible systematic differences. Tropospheric NO2 columns derived at these different locations are presented and compared with the "area-averaged" columns derived from OMI/Aura and GOME-2/MetopA and /MetopB satellites. During days with high levels of NO2 at the urban site, the measurements at the rural site compare better with the satellite products. This finding has been attributed to the fact that the satellite products are representative of the average pollution levels in the sub-satellite pixel area which, in the case of Thessaloniki, corresponds mostly to rural conditions. This validation campaign precedes a full-scale validation to be performed within the EU FP7 Monitoring and Assessment of Regional air

  19. Gas in scattering media absorption spectroscopy - GASMAS

    NASA Astrophysics Data System (ADS)

    Svanberg, Sune

    2008-09-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. GASMAS combines narrow-band diode-laser spectroscopy with diffuse media optical propagation. While solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures, typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. So far molecular oxygen and water vapour have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen. Also other dynamic processes such as drying of materials can be studied. The techniques have also been extended to remote-sensing applications (LIDAR-GASMAS).

  20. Aerosol optical absorption measurements with photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Kun; Wang, Lei; Liu, Qiang; Wang, Guishi; Tan, Tu; Zhang, Weijun; Chen, Weidong; Gao, Xiaoming

    2015-04-01

    Many parameters related to radiative forcing in climate research are known only with large uncertainties. And one of the largest uncertainties in global radiative forcing is the contribution from aerosols. Aerosols can scatter or absorb the electromagnetic radiation, thus may have negative or positive effects on the radiative forcing of the atmosphere, respectively [1]. And the magnitude of the effect is directly related to the quantity of light absorbed by aerosols [2,3]. Thus, sensitivity and precision measurement of aerosol optical absorption is crucial for climate research. Photoacoustic spectroscopy (PAS) is commonly recognized as one of the best candidates to measure the light absorption of aerosols [4]. A PAS based sensor for aerosol optical absorption measurement was developed. A 532 nm semiconductor laser with an effective power of 160 mW was used as a light source of the PAS sensor. The PAS sensor was calibrated by using known concentration NO2. The minimum detectable optical absorption coefficient (OAC) of aerosol was determined to be 1 Mm-1. 24 hours continues measurement of OAC of aerosol in the ambient air was carried out. And a novel three wavelength PAS aerosol OAC sensor is in development for analysis of aerosol wavelength-dependent absorption Angstrom coefficient. Reference [1] U. Lohmann and J. Feichter, Global indirect aerosol effects: a review, Atmos. Chem. Phys. 5, 715-737 (2005) [2] M. Z. Jacobson, Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols, Nature 409, 695-697 (2001) [3] V. Ramanathan and G. Carmichae, Global and regional climate changes due to black carbon, nature geoscience 1, 221-227 (2008) [4] W.P Arnott, H. Moosmuller, C. F. Rogers, T. Jin, and R. Bruch, Photoacoustic spectrometer for measuring light absorption by aerosol: instrument description. Atmos. Environ. 33, 2845-2852 (1999).

  1. UV laser long-path absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Dorn, Hans-Peter; Brauers, Theo; Neuroth, Rudolf

    1994-01-01

    Long path Differential Optical Absorption Spectroscopy (DOAS) using a picosecond UV laser as a light source was developed in our institute. Tropospheric OH radicals are measured by their rotational absorption lines around 308 nm. The spectra are obtained using a high resolution spectrograph. The detection system has been improved over the formerly used optomechanical scanning device by application of a photodiode array which increased the observed spectral range by a factor of 6 and which utilizes the light much more effectively leading to a considerable reduction of the measurement time. This technique provides direct measurements of OH because the signal is given by the product of the absorption coefficient and the OH concentration along the light path according to Lambert-Beers law. No calibration is needed. Since the integrated absorption coefficient is well known the accuracy of the measurement essentially depends on the extent to which the OH absorption pattern can be detected in the spectra. No interference by self generated OH radicals in the detection lightpath has been observed. The large bandwidth (greater than 0.15 nm) and the high spectral resolution (1.5 pm) allows absolute determination of interferences by other trace gas absorptions. The measurement error is directly accessible from the absorption-signal to baseline-noise ratio in the spectra. The applicability of the method strongly depends on visibility. Elevated concentrations of aerosols lead to considerable attenuation of the laser light which reduces the S/N-ratio. In the moderately polluted air of Julich, where we performed a number of OH measurement spectra. In addition absorption features of unidentified species were frequently detected. A quantitative deconvolution even of the known species is not easy to achieve and can leave residual structures in the spectra. Thus interferences usually increase the noise and deteriorate the OH detection sensitivity. Using diode arrays for sensitive

  2. Eruptive SO2-plume measurements at Piton de la Fournaise (Ile de La Réunion) by stationary NOVAC scanning MAX-DOAS instruments

    NASA Astrophysics Data System (ADS)

    Garofalo, K.; Staudacher, T.; Ferrazzini, V.; Kowalski, P.; Boissier, P.; Dupont, A.; Peltier, A.; Villemant, B.; Boudon, G.

    2009-04-01

    Since September 2007 stationary scanning MAX-DOAS instruments are installed on the Enclos Fouqué caldera around Piton de la Fournaise volcano (PdF), integrating the volcano monitoring network of the OVPF (Observatoire Volcanologique du Piton de la Fournaise). The instruments are about 4 km away from the summit and can measure volcanic SO2 degassing downwind from Dolomieu crater or from a source located inside the caldera, since activity is mostly concentrated here. The instruments work during daylight between 7:00 a.m. and 6:00 p.m. local time, acquiring data on average every 7 minutes during favorable weather conditions. During the first year, corresponding to a pause in eruptive activity, the DOAS network did not record any SO2 as PdF shows no significant degassing except during eruptions. Since then the volcano has erupted three times recently (September 2008, November 2008 and December 2008, the latter is still ongoing). Volcanic unrest started in August 2008 with an increase in seismicity and deformation. Numerous seismic crises were recorded beneath the summit of the volcano, but still no SO2 emission was detected by the instruments during these events. On September 12th the DOAS network detected for the first time SO2 degassing from the volcano. It was associated to volcanic tremor under the summit indicating the presence of magma at shallow level in the volcano edifice. Volcanic tremor and SO2 degassing lasted only some few hours, announcing the forthcoming resumption in eruptive activity, which started nine days later. On September 21st, after a short seismic crisis, eruptive tremor appeared at 11:38 (UT), SO2 degassing followed immediately at 11:47 (UT). Lava emission occurred from a vent in the West wall of the Dolomieu crater, probably from a relatively shallow magma reservoir. The eruption continued for 12 days. In the months that followed several seismic crises were recorded, the last one on November 27th that shortly preceded eruptive tremor at the

  3. Atmospheric Measurements by Cavity Enhanced Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Yi, Hongming; Wu, Tao; Coeur-Tourneur, Cécile; Fertein, Eric; Gao, Xiaoming; Zhao, Weixiong; Zhang, Weijun; Chen, Weidong

    2015-04-01

    Since the last decade, atmospheric environmental monitoring has benefited from the development of novel spectroscopic measurement techniques owing to the significant breakthroughs in photonic technology from the UV to the infrared spectral domain [1]. In this presentation, we will overview our recent development and applications of cavity enhanced absorption spectroscopy techniques for in situ optical monitoring of chemically reactive atmospheric species (such as HONO, NO3, NO2, N2O5) in intensive campaigns [2] and/or in smog chamber studies [3]. These field deployments demonstrated that modern photonic technologies (newly emergent light sources combined with high sensitivity spectroscopic techniques) can provide a useful tool to improve our understanding of tropospheric chemical processes which affect climate, air quality, and the spread of pollution. Experimental detail and preliminary results will be presented. Acknowledgements. The financial support from the French Agence Nationale de la Recherche (ANR) under the NexCILAS (ANR-11-NS09-0002) and the CaPPA (ANR-10-LABX-005) contracts is acknowledged. References [1] X. Cui, C. Lengignon, T. Wu, W. Zhao, G. Wysocki, E. Fertein, C. Coeur, A. Cassez,L. Croisé, W. Chen, et al., "Photonic Sensing of the Atmosphere by absorption spectroscopy", J. Quant. Spectrosc. Rad. Transfer 113 (2012) 1300-1316 [2] T. Wu, Q. Zha, W. Chen, Z. XU, T. Wang, X. He, "Development and deployment of a cavity enhanced UV-LED spectrometer for measurements of atmospheric HONO and NO2 in Hong Kong", Atmos. Environ. 95 (2014) 544-551 [3] T. Wu, C. Coeur-Tourneur, G. Dhont,A. Cassez, E. Fertein, X. He, W. Chen,"Application of IBBCEAS to kinetic study of NO3 radical formation from O3 + NO2 reaction in an atmospheric simulation chamber", J. Quant. Spectrosc. Rad. Transfer 133 (2014)199-205

  4. Precision Saturated Absorption Spectroscopy of H3+

    NASA Astrophysics Data System (ADS)

    Guan, Yu-chan; Liao, Yi-Chieh; Chang, Yung-Hsiang; Peng, Jin-Long; Shy, Jow-Tsong

    2016-06-01

    In our previous work on the Lamb dips of the νb{2} fundamental band of H3+, the saturated absorption spectrum was obtained by the third-derivative spectroscopy using frequency modulation [1]. However, the frequency modulation also causes error in absolute frequency determination. To solve this problem, we have built an offset-locking system to lock the OPO pump frequency to an iodine-stabilized Nd:YAG laser. With this modification, we are able to scan the OPO idler frequency precisely and obtain the profile of the Lamb dips. Double modulation (amplitude modulation of the idler power and concentration modulation of the ion) is employed to subtract the interference fringes of the signal and increase the signal-to-noise ratio effectively. To Determine the absolute frequency of the idler wave, the pump wave is offset locked on the R(56) 32-0 a10 hyperfine component of 127I2, and the signal wave is locked on a GPS disciplined fiber optical frequency comb (OFC). All references and lock systems have absolute frequency accuracy better than 10 kHz. Here, we demonstrate its performance by measuring one transition of methane and sixteen transitions of H3+. This instrument could pave the way for the high-resolution spectroscopy of a variety of molecular ions. [1] H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, and J.-T. Shy, Phys. Rev. Lett. 109, 263002 (2012).

  5. Transient absorption spectroscopy of laser shocked explosives

    SciTech Connect

    Mcgrane, Shawn D; Dang, Nhan C; Whitley, Von H; Bolome, Cindy A; Moore, D S

    2010-01-01

    Transient absorption spectra from 390-890 nm of laser shocked RDX, PETN, sapphire, and polyvinylnitrate (PVN) at sub-nanosecond time scales are reported. RDX shows a nearly linear increase in absorption with time after shock at {approx}23 GPa. PETN is similar, but with smaller total absorption. A broad visible absorption in sapphire begins nearly immediately upon shock loading but does not build over time. PVN exhibits thin film interference in the absorption spectra along with increased absorption with time. The absorptions in RDX and PETN are suggested to originate in chemical reactions happening on picosecond time scales at these shock stresses, although further diagnostics are required to prove this interpretation.

  6. Applications of absorption spectroscopy using quantum cascade lasers.

    PubMed

    Zhang, Lizhu; Tian, Guang; Li, Jingsong; Yu, Benli

    2014-01-01

    Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis.

  7. Applications of Absorption Spectroscopy Using Quantum Cascade Lasers.

    PubMed

    2014-10-01

    Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis.

  8. Detection of water vapour absorption around 363nm in measured atmospheric absorption spectra and its effect on DOAS evaluations

    NASA Astrophysics Data System (ADS)

    Lampel, Johannes; Polyansky, Oleg. L.; Kyuberis, Alexandra A.; Zobov, Nikolai F.; Tennyson, Jonathan; Lodi, Lorenzo; Pöhler, Denis; Frieß, Udo; Platt, Ulrich; Beirle, Steffen; Wagner, Thomas

    2016-04-01

    Water vapour is known to absorb light from the microwave region to the blue part of the visible spectrum at a decreasing magnitude. Ab-initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines until its dissociation limit at 243 nm. We present first evidence of water vapour absorption at 363 nm from field measurements based on the POKAZATEL absorption line list by Polyansky et al. (2016) using data from Multi-Axis differential optical absorption spectroscopy (MAX-DOAS) and Longpath (LP)-DOAS measurements. The predicted absorptions contribute significantly to the observed optical depths with up to 2 × 10‑3. Their magnitude correlates well (R2 = 0.89) to simultaneously measured well-established water vapour absorptions in the blue spectral range from 452-499 nm, but is underestimated by a factor of 2.6 ± 0.6 in the ab-initio model. At a spectral resolution of 0.5nm this leads to a maximum absorption cross-section value of 5.4 × 10‑27 cm2/molec at 362.3nm. The results are independent of the employed cross-section data to compensate for the overlayed absorption of the oxygen dimer O4. The newly found absorption can have a significant impact on the spectral retrieval of absorbing trace-gas species in the spectral range around 363 nm. Its effect on the spectral analysis of O4, HONO and OClO are discussed.

  9. Absorption and fluorescence spectroscopy on a smartphone

    NASA Astrophysics Data System (ADS)

    Hossain, Md. Arafat; Canning, John; Cook, Kevin; Ast, Sandra; Rutledge, Peter J.; Jamalipour, Abbas

    2015-07-01

    A self-powered smartphone-based field-portable "dual" spectrometer has been developed for both absorption and fluorescence measurements. The smartphone's existing flash LED has sufficient optical irradiance to undertake absorption measurements within a 3D-printed case containing a low cost nano-imprinted polymer diffraction grating. A UV (λex ~ 370 nm) and VIS (λex ~ 450 nm) LED are wired into the circuit of the flash LED to provide an excitation source for fluorescence measurements. Using a customized app on the smartphone, measurements of absorption and fluorescence spectra are demonstrated using pH-sensitive and Zn2+-responsive probes. Detection over a 300 nm span with 0.42 nm/pixel spectral resolution is demonstrated. Despite the low cost and small size of the portable spectrometer, the results compare well with bench top instruments.

  10. Applications of absorption spectroscopy using quantum cascade lasers.

    PubMed

    Zhang, Lizhu; Tian, Guang; Li, Jingsong; Yu, Benli

    2014-01-01

    Infrared laser absorption spectroscopy (LAS) is a promising modern technique for sensing trace gases with high sensitivity, selectivity, and high time resolution. Mid-infrared quantum cascade lasers, operating in a pulsed or continuous wave mode, have potential as spectroscopic sources because of their narrow linewidths, single mode operation, tunability, high output power, reliability, low power consumption, and compactness. This paper reviews some important developments in modern laser absorption spectroscopy based on the use of quantum cascade laser (QCL) sources. Among the various laser spectroscopic methods, this review is focused on selected absorption spectroscopy applications of QCLs, with particular emphasis on molecular spectroscopy, industrial process control, combustion diagnostics, and medical breath analysis. PMID:25239063

  11. Development and characterization of the CU ground MAX-DOAS instrument: lowering RMS noise and first measurements of BrO, IO, and CHOCHO near Pensacola, FL

    NASA Astrophysics Data System (ADS)

    Coburn, S.; Dix, B.; Sinreich, R.; Volkamer, R.

    2011-01-01

    We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO2) and the oxygen dimer O4 in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is directly proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS values of ~6 × 10-6 without apparent limitations other than photon shot noise. Laboratory tests revealed two factors that, in practice, limit the RMS: (1) detector non-linearity noise, RMSNLin, and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMSFWHM. The non-linearity of our detector is low (~10-3) yet - unless actively controlled - is sufficiently large to create a RMSNLin limit of up to 1.4 × 10-4. The optical resolution is sensitive to temperature changes (0.03 detector pixels/°C at 334 nm), and temperature variations of 0.1 °C can cause residual RMSFWHM of ~1 × 10-4. Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. The CU GMAX-DOAS was set up at a coastal site near Pensacola, FL, where we detected BrO, IO and CHOCHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities, VCDs, of ~2 × 1013 molec cm-2, 8 × 1012 molec cm-2 and 4 × 1014 molec cm-2, respectively. HCHO and NO2 were also detected with typical MBL VCDs of 1 × 1016 and 3 × 1015. These are the first measurements of BrO, IO and CHOCHO over the Gulf of Mexico. The atmospheric implications of these observations for elevated mercury wet deposition rates in this area are briefly

  12. [Study of retrieving formaldehyde with differential optical absorption spectroscopy].

    PubMed

    Li, Yu-Jin; Xie, Pin-Hua; Qin, Min; Qu, Xiao-Ying; Hu, Lin

    2009-01-01

    The present paper introduces the method of retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS). The authors measured ambient HCHO in Beijing region with the help of differential optical absorption spectroscopy instrument made by ourself, and discussed numerous factors in retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS), especially, the choice of HCHO wave band, how to avoid absorption of ambient SO2, NO2 and O3, and the influence of the Xenon lamp spectrum structure on the absorption of ambient HCHO. The authors achieved the HCHO concentration by simultaneously retrieving the concentrations of HCHO, SO2, NO2 and O3 with non-linear least square fitting method, avoiding the effect of choosing narrow wave of HCHO and the residual of SO2, NO2, O3 and the Xenon lamp spectrum structure in retrieving process to attain the concentration of HCHO, Finally the authors analyzed the origin of error in retrieving the concentration of HCHO with differential optical absorption spectroscopy (DOAS), and the total error is within 13.7% in this method. PMID:19385238

  13. Atomic absorption spectroscopy with high temperature flames.

    PubMed

    Willis, J B

    1968-07-01

    An account is given of the history of the development of high temperature flames for the atomic absorption measurement of metals forming refractory oxides. The principles governing the design of premix burners for such flames, and the relative merits of different types of nebulizer burner systems are described. After a brief account of the structure and emission characteristics of the premixed oxygen-acetylene and nitrous oxide-acetylene flames, the scope and limitations of the latter flame in chemical analysis are discussed.

  14. The CU ground MAX-DOAS instrument: characterization of RMS noise limitations and first measurements near Pensacola, FL of BrO, IO, and CHOCHO

    NASA Astrophysics Data System (ADS)

    Coburn, S.; Dix, B.; Sinreich, R.; Volkamer, R.

    2011-11-01

    We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO2) and the oxygen dimer (O4) in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS of ∼6 × 10-6 from solar stray light noise tests using high photon count spectra (compatible within a factor of two with photon shot noise). Laboratory tests revealed two critical instrument properties that, in practice, can limit the RMS: (1) detector non-linearity noise, RMSNLin, and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMSFWHM. The non-linearity of our detector is low (∼10-2) yet - unless actively controlled - is sufficiently large to create RMSNLin of up to 2 × 10-4. The optical resolution is sensitive to temperature changes (0.03 detector pixels °C-1 at 334 nm), and temperature variations of 0.1°C can cause RMSFWHM of ~1 × 10-4. Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. With an integration time of 60 s the instrument can reach RMS noise of 3 × 10-5, and typical RMS in field measurements ranged from 6 × 10-5 to 1.4 × 10-4. The CU GMAX-DOAS was set up at a coastal site near Pensacola, Florida, where we detected BrO, IO and CHOCHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities (average of data above the detection limit), VCDs, of ∼2 × 1013 molec cm-2, 8 × 1012 molec cm-2 and 4 × 1014 molec cm-2, respectively

  15. Diode laser absorption spectroscopy of lithium isotopes

    NASA Astrophysics Data System (ADS)

    Olivares, Ignacio E.; González, Iván A.

    2016-10-01

    We study Doppler-limited laser intensity absorption, in a thermal lithium vapor containing 7Li and 6Li atoms in a 9 to 1 ratio, using a narrow-linewidth single-longitudinal-mode tunable external cavity diode laser at the wavelength of 670.8 nm. The lithium vapor was embedded in helium or argon buffer gas. The spectral lineshapes were rigorously predicted for D_1 and D_2 for the lithium 6 and 7 isotope lines using reduced optical Bloch equations, specifically derived, from a density matrix analysis. Here, a detailed comparison is provided of the predicted lineshapes with the measured 7Li-D_2, 7Li-D_1, 6Li-D_2 and 6Li-D_1 lines, in the case of high vapor density and with intensity above the saturation intensity. To our knowledge, this is the first time that such detailed comparison is reported in the open literature. The calculations were also extended to saturated absorption spectra and compared to measured Doppler-free 7Li-D_2 and 6Li-D_2 hyperfine lines.

  16. Molecular shock response of explosives: electronic absorption spectroscopy

    SciTech Connect

    Mcgrne, Shawn D; Moore, David S; Whitley, Von H; Bolme, Cindy A; Eakins, Daniel E

    2009-01-01

    Electronic absorption spectroscopy in the range 400-800 nm was coupled to ultrafast laser generated shocks to begin addressing the question of the extent to which electronic excitations are involved in shock induced reactions. Data are presented on shocked polymethylmethacrylate (PMMA) thin films and single crystal pentaerythritol tetranitrate (PETN). Shocked PMMA exhibited thin film interference effects from the shock front. Shocked PETN exhibited interference from the shock front as well as broadband increased absorption. Relation to shock initiation hypotheses and the need for time dependent absorption data (future experiments) is briefly discussed.

  17. Developing a Transdisciplinary Teaching Implement for Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Drew, John

    2008-01-01

    In this article I explain why I wrote the set of teaching notes on Atomic Absorption Spectroscopy (AAS) and why they look the way they do. The notes were intended as a student reference to question, highlight and write over as much as they wish during an initial practical demonstration of the threshold concept being introduced, in this case…

  18. Atomic Absorption Spectroscopy. The Present and the Future.

    ERIC Educational Resources Information Center

    Slavin, Walter

    1982-01-01

    The status of current techniques and methods of atomic absorption (AA) spectroscopy (flame, hybrid, and furnace AA) is discussed, including limitations. Technological opportunities and how they may be used in AA are also discussed, focusing on automation, microprocessors, continuum AA, hybrid analyses, and others. (Author/JN)

  19. Visualizing the Solute Vaporization Interference in Flame Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Dockery, Christopher R.; Blew, Michael J.; Goode, Scott R.

    2008-01-01

    Every day, tens of thousands of chemists use analytical atomic spectroscopy in their work, often without knowledge of possible interferences. We present a unique approach to study these interferences by using modern response surface methods to visualize an interference in which aluminum depresses the calcium atomic absorption signal. Calcium…

  20. Laser photothermal spectroscopy of light-induced absorption

    SciTech Connect

    Skvortsov, L A

    2013-01-31

    Basic methods of laser photothermal spectroscopy, which are used to study photoinduced absorption in various media, are briefly considered. Comparative analysis of these methods is performed and the latest results obtained in this field are discussed. Different schemes and examples of their practical implementation are considered. (review)

  1. Absorption and Emission Spectroscopy of a Lasing Material: Ruby

    ERIC Educational Resources Information Center

    Esposti, C. Degli; Bizzocchi, L.

    2007-01-01

    Ruby is a crystalline material, which comes very expensive and is of great significance, as it helped in the creation of first laser. An experiment to determine the absorption and emission spectroscopy, in addition to the determination of the room-temperature lifetime of the substance is being described.

  2. Tropospheric NO2 and HCHO columns derived from ground-based MAX-DOAS system in Guangzhou, China and comparison with satellite observations: First results within the EU FP7 project MarcoPolo

    NASA Astrophysics Data System (ADS)

    Drosoglou, Theano; Kouremeti, Natalia; Bais, Alkis; Zyrichidou, Irene; Li, Shu; Balis, Dimitris; Huang, Zhonghui

    2016-04-01

    A miniature MAX-DOAS system, Phaethon, has been developed at the Laboratory of Atmospheric Physics of the Aristotle University of Thessaloniki, Greece, for ground-based monitoring of column densities of atmospheric gases. Simultaneous measurements with two Phaethon systems at the city centre of Thessaloniki and at a rural location about 30 km away have shown that Phaethon provides NO2 and HCHO tropospheric column measurements of acceptable accuracy under both low and high air-pollution levels. Currently three systems have been deployed in areas with different pollution patterns to support air quality and satellite validation studies. In the framework of the EU FP7 Monitoring and Assessment of Regional air quality in China using space Observations, Project Of Long-term sino-european co-Operation, MarcoPolo project, one of the Phaethon systems has been installed since April 2015 in the Guangzhou region in China. Tropospheric NO2 and HCHO columns derived at Guangzhou during the first 10 months of operation are compared with corresponding retrievals from OMI/Aura and GOME-2/Metop-A and /Metop-B satellite sensors. The area is characterized by humid subtropical monsoon climate and cloud-free conditions are rather rare from early March to mid-October. Despite this limitation and the short period of operation of Phaethon in Guangzhou, the agreement between ground-based and satellite observations is generally good for both NO2 and HCHO. It appears that GOME-2 sensors seem to underestimate the tropospheric NO2, possibly due to their large pixel size, whereas the comparison with OMI data is better, especially when a small cloud fraction (< 0.2) is used for cloud screening.

  3. Communication: XUV transient absorption spectroscopy of iodomethane and iodobenzene photodissociation

    NASA Astrophysics Data System (ADS)

    Drescher, L.; Galbraith, M. C. E.; Reitsma, G.; Dura, J.; Zhavoronkov, N.; Patchkovskii, S.; Vrakking, M. J. J.; Mikosch, J.

    2016-07-01

    Time-resolved extreme ultraviolet (XUV) transient absorption spectroscopy of iodomethane and iodobenzene photodissociation at the iodine pre-N4,5 edge is presented, using femtosecond UV pump pulses and XUV probe pulses from high harmonic generation. For both molecules the molecular core-to-valence absorption lines fade immediately, within the pump-probe time-resolution. Absorption lines converging to the atomic iodine product emerge promptly in CH3I but are time-delayed in C6H5I. We attribute this delay to the initial π → σ* excitation in iodobenzene, which is distant from the iodine reporter atom. We measure a continuous shift in energy of the emerging atomic absorption lines in CH3I, attributed to relaxation of the excited valence shell. An independent particle model is used to rationalize the observed experimental findings.

  4. Biological X-ray absorption spectroscopy and metalloproteomics.

    PubMed

    Ascone, Isabella; Strange, Richard

    2009-05-01

    In the past seven years the size of the known protein sequence universe has been rapidly expanding. At present, more then five million entries are included in the UniProtKB/TrEMBL protein database. In this context, a retrospective evaluation of recent X-ray absorption studies is undertaken to assess its potential role in metalloproteomics. Metalloproteomics is the structural and functional characterization of metal-binding proteins. This is a new area of active research which has particular relevance to biology and for which X-ray absorption spectroscopy is ideally suited. In the last three years, biological X-ray absorption spectroscopy (BioXAS) has been included among the techniques used in post-genomics initiatives for metalloprotein characterization. The emphasis of this review is on the progress in BioXAS that has emerged from recent meetings in 2007-2008. Developments required to enable BioXAS studies to better contribute to metalloproteomics throughput are also discussed. Overall, this paper suggests that X-ray absorption spectroscopy could have a higher impact on metalloproteomics, contributing significantly to the understanding of metal site structures and of reaction mechanisms for metalloproteins. PMID:19395808

  5. Electron Wavepacket Interference Observed by Attosecond Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Gallmann, L.; Holler, M.; Schapper, F.; Keller, U.

    Attosecond time-resolved transient absorption spectroscopy is performed in a dense helium target by superimposing an attosecond pulse train (APT) with a moderately strong infrared field. We observe rapid oscillations of the absorption of the individual harmonics as a function of time-delay between the APT and IR field even for harmonic energies well below the ionization threshold. The phase dependence of these modulations on atto-chirp and IR intensity yields direct evidence for the interference of transiently bound electronic wavepackets as the underlying mechanism.

  6. Infrared absorption spectroscopy and chemical kinetics of free radicals

    SciTech Connect

    Curl, R.F.; Glass, G.P.

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  7. Multiphoton cascade absorption in single molecule fluorescence saturation spectroscopy.

    PubMed

    Winckler, Pascale; Jaffiol, Rodolphe

    2013-05-01

    Saturation spectroscopy is a relevant method to investigate photophysical parameters of single fluorescent molecules. Nevertheless, the impact of a gradual increase, over a broad range, of the laser excitation on the intramolecular dynamics is not completely understood, particularly concerning their fluorescence emission (the so-called brightness). Thus, we propose a comprehensive theoretical and experimental study to interpret the unexpected evolution of the brightness with the laser power taking into account the cascade absorption of two and three photons. Furthermore, we highlight the key role played by the confocal observation volume in fluorescence saturation spectroscopy of single molecules in solution.

  8. Beta-decay studies using total absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    GSI-TAS Collaboration; LUCRECIA-TAgS Collaboration; Algora, A.; Batist, L.; Borge, M. J. G.; Cano-Ott, D.; Collatz, R.; Courtin, S.; Dessagne, Ph; Fraile, L. M.; Gadea, A.; Gelletly, W.; Hellström, M.; Janas, Z.; Jungclaus, A.; Kirchner, R.; Karny, M.; Le Scornet, G.; Miehé, Ch; Maréchal, F.; Moroz, F.; Nácher, E.; Poirier, E.; Roeckl, E.; Rubio, B.; Rykaczewski, K.; Tain, J. L.; Tengblad, O.; Wittmann, V.

    2003-04-01

    . Beta-decay experiments are a primary source of information for nuclear-structure studies and at the same time complementary to in-beam investigations of nuclei far from stability. Although both types of experiment are mainly based on γ -ray spectroscopy, they face different experimental problems. The so-called Pandemonium effect is a critical problem in β -decay if we are to test theoretically calculated transition probabilities. In this contribution we will present a solution to this problem using total absorption spectroscopy methods. We will also present some examples of experiments carried out with the Total Absorption Spectrometer (TAS) at GSI an describe a new device LUCRECIA recently installed at CERN.

  9. Label free detection of phospholipids by infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahmed, Tahsin; Foster, Erick; Vigil, Genevieve; Khan, Aamir A.; Bohn, Paul; Howard, Scott S.

    2014-08-01

    We present our study on compact, label-free dissolved lipid sensing by combining capillary electrophoresis separation in a PDMS microfluidic chip online with mid-infrared (MIR) absorption spectroscopy for biomarker detection. On-chip capillary electrophoresis is used to separate the biomarkers without introducing any extrinsic contrast agent, which reduces both cost and complexity. The label free biomarker detection could be done by interrogating separated biomarkers in the channel by MIR absorption spectroscopy. Phospholipids biomarkers of degenerative neurological, kidney, and bone diseases are detectable using this label free technique. These phospholipids exhibit strong absorption resonances in the MIR and are present in biofluids including urine, blood plasma, and cerebrospinal fluid. MIR spectroscopy of a 12-carbon chain phosphatidic acid (PA) (1,2-dilauroyl-snglycero- 3-phosphate (sodium salt)) dissolved in N-methylformamide, exhibits a strong amide peak near wavenumber 1660 cm-1 (wavelength 6 μm), arising from the phosphate headgroup vibrations within a low-loss window of the solvent. PA has a similar structure to many important phospholipids molecules like phosphatidylcholine (PC), phosphatidylinositol (PI), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), and phosphatidylserine (PS), making it an ideal molecule for initial proof-of-concept studies. This newly proposed detection technique can lead us to minimal sample preparation and is capable of identifying several biomarkers from the same sample simultaneously.

  10. Terahertz vibrational absorption spectroscopy using microstrip-line waveguides

    NASA Astrophysics Data System (ADS)

    Byrne, M. B.; Cunningham, J.; Tych, K.; Burnett, A. D.; Stringer, M. R.; Wood, C. D.; Dazhang, L.; Lachab, M.; Linfield, E. H.; Davies, A. G.

    2008-11-01

    We demonstrate that terahertz microstrip-line waveguides can be used to measure absorption spectra of polycrystalline materials with a high frequency resolution (˜2 GHz) and with a spatial resolution that is determined by the microstrip-line dimensions, rather than the free-space wavelength. The evanescent terahertz-bandwidth electric field extending above the microstrip line interacts with, and is modified by, overlaid dielectric samples, thus enabling the characteristic vibrational absorption resonances in the sample to be probed. As an example, the terahertz absorption spectrum of polycrystalline lactose monohydrate was investigated; the lowest lying mode was observed at 534(±2) GHz, in excellent agreement with free-space measurements. This microstrip technique offers both a higher spatial and frequency resolution than free-space terahertz time-domain spectroscopy and requires no contact between the waveguide and sample.

  11. Use of absorption spectroscopy for refined petroleum product discrimination

    NASA Astrophysics Data System (ADS)

    Short, Michael

    1991-07-01

    On-line discrimination between arbitrary petroleum products is necessary for optimal control of petroleum refinery and pipeline operation and process control involving petroleum distillates. There are a number of techniques by which petroleum products can be distinguished from one another. Among these, optical measurements offer fast, non-intrusive, real-time characterization. The application examined here involves optically monitoring the interface between dissimilar batches of fluids in a gasoline pipeline. After examination of near- infrared and mid-infrared absorption spectroscopy and Raman spectroscopy, Fourier transform mid-infrared (FTIR) spectroscopy was chosen as the best candidate for implementation. On- line FTIR data is presented, verifying the applicability of the technique for batch interface detection.

  12. Pathlength Determination for Gas in Scattering Media Absorption Spectroscopy

    PubMed Central

    Mei, Liang; Somesfalean, Gabriel; Svanberg, Sune

    2014-01-01

    Gas in scattering media absorption spectroscopy (GASMAS) has been extensively studied and applied during recent years in, e.g., food packaging, human sinus monitoring, gas diffusion studies, and pharmaceutical tablet characterization. The focus has been on the evaluation of the gas absorption pathlength in porous media, which a priori is unknown due to heavy light scattering. In this paper, three different approaches are summarized. One possibility is to simultaneously monitor another gas with known concentration (e.g., water vapor), the pathlength of which can then be obtained and used for the target gas (e.g., oxygen) to retrieve its concentration. The second approach is to measure the mean optical pathlength or physical pathlength with other methods, including time-of-flight spectroscopy, frequency-modulated light scattering interferometry and the frequency domain photon migration method. By utilizing these methods, an average concentration can be obtained and the porosities of the material are studied. The last method retrieves the gas concentration without knowing its pathlength by analyzing the gas absorption line shape, which depends upon the concentration of buffer gases due to intermolecular collisions. The pathlength enhancement effect due to multiple scattering enables also the use of porous media as multipass gas cells for trace gas monitoring. All these efforts open up a multitude of different applications for the GASMAS technique. PMID:24573311

  13. APPLICATION OF ABSORPTION SPECTROSCOPY TO ACTINIDE PROCESS ANALYSIS AND MONITORING

    SciTech Connect

    Lascola, R.; Sharma, V.

    2010-06-03

    The characteristic strong colors of aqueous actinide solutions form the basis of analytical techniques for actinides based on absorption spectroscopy. Colorimetric measurements of samples from processing activities have been used for at least half a century. This seemingly mature technology has been recently revitalized by developments in chemometric data analysis. Where reliable measurements could formerly only be obtained under well-defined conditions, modern methods are robust with respect to variations in acidity, concentration of complexants and spectral interferents, and temperature. This paper describes two examples of the use of process absorption spectroscopy for Pu analysis at the Savannah River Site, in Aiken, SC. In one example, custom optical filters allow accurate colorimetric measurements of Pu in a stream with rapid nitric acid variation. The second example demonstrates simultaneous measurement of Pu and U by chemometric treatment of absorption spectra. The paper concludes with a description of the use of these analyzers to supplement existing technologies in nuclear materials monitoring in processing, reprocessing, and storage facilities.

  14. Absorption spectroscopy with sub-angstrom beams: ELS in STEM

    NASA Astrophysics Data System (ADS)

    Spence, John C. H.

    2006-03-01

    Electron-energy loss spectroscopy (EELS) performed using a modern transmission scanning electron microscope (STEM) now offers sub-nanometre spatial resolution and an energy resolution down to 200 meV or less, in favourable cases. The absorption spectra, which probe empty states, cover the soft x-ray region and may be obtained under conditions of well-defined momentum transfer (angle-resolved), providing a double projection onto crystallographic site and symmetry within the density of states. By combining the very high brightness of field-emission electron sources (brighter than a synchrotron) with the high cross-section of electron scattering, together with parallel detection (not possible with scanning x-ray absorption spectroscopy), a form of spectroscopy ideally suited to the study of nanostructures, interfacial states and defects in materials is obtained with uniquely high spatial resolution. We review the basic theory, the relationship of EELS to optical properties and the dielectric response function, the removal of multiple scattering artefacts and channelling effects. We consider applications in the light of recent developments in aberration corrector and electron monochromator design. Examples are cited of inner-shell spectra obtained from individual atoms within thin crystals, of the detection of interfacial electronic states in semiconductors, of inner-shell near edge structure mapped with sub-nanometre spatial resolution in glasses and of spectra obtained from individual carbon nanotubes, amongst many others.

  15. X-ray absorption spectroscopy of liquid surface

    NASA Astrophysics Data System (ADS)

    Watanabe, Iwao; Tanida, Hajime; Kawauchi, Sigehiro; Harada, Makoto; Nomura, Masaharu

    1997-09-01

    An apparatus has been constructed for x-ray absorption spectroscopy of elements at air/aqueous solution interface. Its surface sensitivity is gained from glancing incidence of synchrotron radiation under total reflection condition. The absorption is detected by total conversion He ion-yield method. This apparatus was operated at the beam line 7C of Photon Factory, where the incident photon beam comes from a sagittal focus double-crystal monochromator via a 70-cm-long bent mirror. The mirror focuses the beam vertically and changes the beam direction downward by 1 mrad to irradiate solution surface. The essential requirement of this technique, ripple-free liquid surface at accurate position, was attained by introducing a trough on a floating boat, continuous surface level monitoring, and an automatic Z-stage control. The x-ray absorption edge jump demonstrated that surface concentration of bromide ion follows the Langmuir type adsorption for tetraalkylammonuim bromide solution. By comparing the jump values for surface-active and -inactive bromide salt solutions, the detecting depth of the present technique was determined to be 8.8 nm. An extended x-ray absorption fine structure analysis of bromide ion segregated to the surface by stearyltrimethylammonium cation indicated that its solvation structure is different from that of bulk.

  16. Diagnostic potential of cosmic-neutrino absorption spectroscopy

    SciTech Connect

    Barenboim, Gabriela; Mena Requejo, Olga; Quigg, Chris; /Fermilab

    2004-12-01

    Annihilation of extremely energetic cosmic neutrinos on the relic-neutrino background can give rise to absorption lines at energies corresponding to formation of the electroweak gauge boson Z{sup 0}. The positions of the absorption dips are set by the masses of the relic neutrinos. Suitably intense sources of extremely energetic (10{sup 21} - 10{sup 25}-eV) cosmic neutrinos might therefore enable the determination of the absolute neutrino masses and the flavor composition of the mass eigenstates. Several factors--other than neutrino mass and composition--distort the absorption lines, however. We analyze the influence of the time-evolution of the relic-neutrino density and the consequences of neutrino decay. We consider the sensitivity of the lineshape to the age and character of extremely energetic neutrino sources, and to the thermal history of the Universe, reflected in the expansion rate. We take into account Fermi motion arising from the thermal distribution of the relic-neutrino gas. We also note the implications of Dirac vs. Majorana relics, and briefly consider unconventional neutrino histories. We ask what kinds of external information would enhance the potential of cosmic-neutrino absorption spectroscopy, and estimate the sensitivity required to make the technique a reality.

  17. The determination of vanadium in brines by atomic absorption spectroscopy

    USGS Publications Warehouse

    Crump-Wiesner, Hans J.; Feltz, H.R.; Purdy, W.C.

    1971-01-01

    A standard addition method is described for the determination of vanadium in brines by atomic absorption spectroscopy with a nitrous oxide-acetylene flame. Sample pH is adjusted to 1.0 with concentrated hydrochloric acid and the vanadium is directly extracted with 5% cupferron in methyl isobutyl ketone (MIBK). The ketone layer is then aspirated into the flame and the recorded absorption values are plotted as a function of the concentration of the added metal. As little as 2.5 ??g l-1 of vanadium can be detected under the conditions of the procedure. Tungsten and tin interfere when present in excess of 5 and 10 ??g ml-1, respectively. The concentrations of the two interfering ions normally found in brines are well below interference levels. ?? 1971.

  18. Spatially resolved concentration measurements based on backscatter absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Ze; Sanders, Scott T.; Robinson, Michael A.

    2016-06-01

    We demonstrate the feasibility of spatially resolved measurements of gas properties using direct absorption spectroscopy in conjunction with backscattered signals. We report a 1-D distribution of H2O mole fraction with a spatial resolution of 5 mm. The peak and average discrepancy between the measured and expected mole fraction are 21.1 and 8.0 %, respectively. The demonstration experiment is related to a diesel aftertreatment system; a selective catalytic reduction brick made of cordierite is used. The brick causes volume scattering interference; advanced baseline fitting based on a genetic algorithm is used to reduce the effects of this interference by a factor of 2.3.

  19. Atmospheric absorption spectroscopy using Tm: fiber sources around two microns

    NASA Astrophysics Data System (ADS)

    Kadwani, Pankaj; Chia, Jeffrey; Altal, Faleh; Sims, Robert A.; Willis, Christina; Shah, Lawrence; Killinger, Dennis; Richardson, Martin C.

    2011-03-01

    We report on a thulium doped silica fiber ASE source for absorption spectroscopy of CO2. The average spectral power of this source was 2.3-6.1 μW/nm. This low spectral power of this source posed limitation in the sensitivity of the system which was overcome by using an ultrashort pulsed Raman amplifier system with 50-125 μW/nm average spectral power. This system produced CO2 sensitivity better than 300 ppm making measurement of CO2 possible at standard atmospheric concentrations.

  20. Piezo-locking a diode laser with saturated absorption spectroscopy

    SciTech Connect

    Debs, J. E.; Robins, N. P.; Lance, A.; Kruger, M. B.; Close, J. D

    2008-10-01

    We demonstrate modulation-based frequency locking of an external cavity diode laser, utilizing a piezo-electrically actuated mirror, external to the laser cavity, to create an error signal from saturated absorption spectroscopy. With this method, a laser stabilized to a rubidium hyperfine transition has a FWHM of 130 kHz over seconds, making the locked laser suitable for experiments in atomic physics, such as creating and manipulating Bose-Einstein condensates. This technique combines the advantages of low-amplitude modulation, simplicity, performance, and price, factors that are usually considered to be mutually exclusive.

  1. Laser absorption spectroscopy system for vaporization process characterization and control

    NASA Astrophysics Data System (ADS)

    Galkowski, Joseph J.; Hagans, Karla G.

    1994-03-01

    In support of the Lawrence Livermore National Laboratory's (LLNL's) Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) Program, a laser atomic absorption spectroscopy (LAS) system has been developed. This multilaser system is capable of simultaneously measuring the line densities of 238U ground and metastable states, 235U ground and metastable states, iron, and ions at up to nine locations within the separator vessel. Supporting enrichment experiments that last over one hundred hours, this laser spectroscopy system is employed to diagnose and optimize separator system performance, control the electron beam vaporizer and metal feed systems, and provide physics data for the validation of computer models. As a tool for spectroscopic research, vapor plume characterization, vapor deposition monitoring, and vaporizer development, LLNL's LAS laboratory with its six argon-ion-pumped ring dye lasers and recently added Ti:Sapphire and external-cavity diode- lasers has capabilities far beyond the requirements of its primary mission.

  2. Monitoring PVD metal vapors using laser absorption spectroscopy

    SciTech Connect

    Braun, D.G.; Anklam, T.M.; Berzins, L.V.; Hagans, K.G.

    1994-04-01

    Laser absorption spectroscopy (LAS) has been used by the Atomic Vapor Laser Isotope Separation (AVLIS) program for over 10 years to monitor the co-vaporization of uranium and iron in its separators. During that time, LAS has proven to be an accurate and reliable method to monitor both the density and composition of the vapor. It has distinct advantages over other rate monitors, in that it is completely non-obtrusive to the vaporization process and its accuracy is unaffected by the duration of the run. Additionally, the LAS diagnostic has been incorporated into a very successful process control system. LAS requires only a line of sight through the vacuum chamber, as all hardware is external to the vessel. The laser is swept in frequency through an absorption line of interest. In the process a baseline is established, and the line integrated density is determined from the absorption profile. The measurement requires no hardware calibration. Through a proper choice of the atomic transition, a wide range of elements and densities have been monitored (e.g. nickel, iron, cerium and gadolinium). A great deal of information about the vapor plume can be obtained from the measured absorption profiles. By monitoring different species at the same location, the composition of the vapor is measured in real time. By measuring the same density at different locations, the spatial profile of the vapor plume is determined. The shape of the absorption profile is used to obtain the flow speed of the vapor. Finally, all of the above information is used evaluate the total vaporization rate.

  3. Mid-infrared absorption spectroscopy using quantum cascade lasers

    NASA Astrophysics Data System (ADS)

    Haibach, Fred; Erlich, Adam; Deutsch, Erik

    2011-06-01

    Block Engineering has developed an absorption spectroscopy system based on widely tunable Quantum Cascade Lasers (QCL). The QCL spectrometer rapidly cycles through a user-selected range in the mid-infrared spectrum, between 6 to 12 μm (1667 to 833 cm-1), to detect and identify substances on surfaces based on their absorption characteristics from a standoff distance of up to 2 feet with an eye-safe laser. It can also analyze vapors and liquids in a single device. For military applications, the QCL spectrometer has demonstrated trace explosive, chemical warfare agent (CWA), and toxic industrial chemical (TIC) detection and analysis. The QCL's higher power density enables measurements from diffuse and highly absorbing materials and substrates. Other advantages over Fourier Transform Infrared (FTIR) spectroscopy include portability, ruggedness, rapid analysis, and the ability to function from a distance through free space or a fiber optic probe. This paper will discuss the basic technology behind the system and the empirical data on various safety and security applications.

  4. Sensitive detection of weak absorption signals in photoacoustic spectroscopy by using derivative spectroscopy and wavelet transform

    NASA Astrophysics Data System (ADS)

    Zheng, Jincun; Tang, Zhilie; He, Yongheng; Guo, Lina

    2008-05-01

    This report presents a practical analytical method of photoacoustic (PA) spectroscopy that is based on wavelet transform (WT) and the first-derivative PA spectrum. An experimental setup is specially designed to obtain the first-derivative spectrum, which aims to identify some unnoticeable absorption peaks in the normal PA spectrum. To enhance the detectability of overlapping spectral bands, the WT is used to decompose the PA spectrum signals into a series of localized contributions (details and approximation) on the basis of the frequency. For the decomposed contributions do not change the absorption peak position of PA spectrum, one can retrieve the weak absorption signals by the decomposed result of WT. Because of the use of derivative spectroscopy and WT, three unnoticeable absorption peaks that are hidden in the PA spectrum of carbon absorption are precisely retrieved, the wavelengths of which are 699.7, 752.7, and 775.5nm, respectively. This analytical method, which has the virtue of using a physical method and using a computer software method, can achieve great sensitivity and accuracy for PA spectral analysis.

  5. Femtosecond transient absorption spectroscopy of silanized silicon quantum dots

    NASA Astrophysics Data System (ADS)

    Kuntermann, Volker; Cimpean, Carla; Brehm, Georg; Sauer, Guido; Kryschi, Carola; Wiggers, Hartmut

    2008-03-01

    Excitonic properties of colloidal silicon quantum dots (Si qdots) with mean sizes of 4nm were examined using stationary and time-resolved optical spectroscopy. Chemically stable silicon oxide shells were prepared by controlled surface oxidation and silanization of HF-etched Si qdots. The ultrafast relaxation dynamics of photogenerated excitons in Si qdot colloids were studied on the picosecond time scale from 0.3psto2.3ns using femtosecond-resolved transient absorption spectroscopy. The time evolution of the transient absorption spectra of the Si qdots excited with a 150fs pump pulse at 390nm was observed to consist of decays of various absorption transitions of photoexcited electrons in the conduction band which overlap with both the photoluminescence and the photobleaching of the valence band population density. Gaussian deconvolution of the spectroscopic data allowed for disentangling various carrier relaxation processes involving electron-phonon and phonon-phonon scatterings or arising from surface-state trapping. The initial energy and momentum relaxation of hot carriers was observed to take place via scattering by optical phonons within 0.6ps . Exciton capturing by surface states forming shallow traps in the amorphous SiOx shell was found to occur with a time constant of 4ps , whereas deeper traps presumably localized in the Si-SiOx interface gave rise to exciton trapping processes with time constants of 110 and 180ps . Electron transfer from initially populated, higher-lying surface states to the conduction band of Si qdots (>2nm) was observed to take place within 400 or 700fs .

  6. Rapid Scan Absorption Spectroscopy with Applications for Remote Sensing

    NASA Astrophysics Data System (ADS)

    Douglass, K.; Maxwell, S. E.; Truong, G.; Van Zee, R. D.; Hodges, J. T.; Plusquellic, D.; Long, D.; Whetstone, J. R.

    2013-12-01

    Our objective is to develop accurate and reliable methods for quantifying distributed carbon sources and sinks to support both mitigation efforts and climate change research. The presentation will describe a method for rapid step-scan absorption spectroscopy in the near-infrared wavelength range for the measurement of greenhouse gases. The method utilizes a fiber coupled laser system and a free space confocal cavity to effectively scan the laser system over a bandwidth of 37.5 GHz (1.25 cm-1), with a step size of 300 MHz (0.01 cm-1) and a scan rate of 40 kHz. The laser system is scanned with microwave precision over a full absorption lineshape profile. Measurements have been demonstrated in a 45 m long multipass cell for detection of carbon dioxide near 1602.4 nm (6240.6 cm-1) and for methane near 1645.5 nm (6077.2 cm 1). Ambient level detection is demonstrated using the multipass cell with a signal-to-noise ratio of ~5:1 in a 5 ms integration time. The scan speed, resolution and bandwidth are well suited for remote sensing using integrated path and differential absorption LIDAR techniques.

  7. Precision atomic beam density characterization by diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Oxley, Paul; Wihbey, Joseph

    2016-09-01

    We provide experimental and theoretical details of a simple technique to determine absolute line-of-sight integrated atomic beam densities based on resonant laser absorption. In our experiments, a thermal lithium beam is chopped on and off while the frequency of a laser crossing the beam at right angles is scanned slowly across the resonance transition. A lock-in amplifier detects the laser absorption signal at the chop frequency from which the atomic density is determined. The accuracy of our experimental method is confirmed using the related technique of wavelength modulation spectroscopy. For beams which absorb of order 1% of the incident laser light, our measurements allow the beam density to be determined to an accuracy better than 5% and with a precision of 3% on a time scale of order 1 s. Fractional absorptions of order 10-5 are detectable on a one-minute time scale when we employ a double laser beam technique which limits laser intensity noise. For a lithium beam with a thickness of 9 mm, we have measured atomic densities as low as 5 × 104 atoms cm-3. The simplicity of our technique and the details we provide should allow our method to be easily implemented in most atomic or molecular beam apparatuses.

  8. Optical re-injection in cavity-enhanced absorption spectroscopy.

    PubMed

    Leen, J Brian; O'Keefe, Anthony

    2014-09-01

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10(-10) cm(-1)/√Hz; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features. PMID:25273701

  9. Optical re-injection in cavity-enhanced absorption spectroscopy

    PubMed Central

    Leen, J. Brian; O’Keefe, Anthony

    2014-01-01

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10−10 cm−1/\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{upgreek} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} }{}$\\sqrt {{\\rm Hz;}}$\\end{document} Hz ; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features. PMID:25273701

  10. Optical re-injection in cavity-enhanced absorption spectroscopy

    SciTech Connect

    Leen, J. Brian O’Keefe, Anthony

    2014-09-15

    Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10{sup −10} cm{sup −1}/√(Hz;) an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features.

  11. Intracavity laser absorption spectroscopy of platinum fluoride, PtF

    NASA Astrophysics Data System (ADS)

    Handler, Kimberly G.; Harris, Rachel A.; O'Brien, Leah C.; O'Brien, James J.

    2011-01-01

    Two vibrational bands of an electronic transition of PtF occurring at 11 940 cm -1 and 12 496 cm -1 were recorded and analyzed. These transitions are identified as the (0,0) and (1,0) bands of an [11.9] Ω = 3/2 - XΩ = 3/2 electronic transition. Gas phase PtF was produced in a copper hollow cathode lined with platinum foil using a trace amount of SF 6, and the spectrum was recorded at Doppler resolution by intracavity laser absorption spectroscopy. This work represents the first published spectroscopic data on PtF. Molecular constants for the ground and excited electronic states are presented.

  12. High Resolution Absorption Spectroscopy using Externally Dispersed Interferometry

    SciTech Connect

    Edelstein, J; Erskine, D J

    2005-07-06

    We describe the use of Externally Dispersed Interferometry (EDI) for high-resolution absorption spectroscopy. By adding a small fixed-delay interferometer to a dispersive spectrograph, a precise fiducial grid in wavelength is created over the entire spectrograph bandwidth. The fiducial grid interacts with narrow spectral features in the input spectrum to create a moire pattern. EDI uses the moire pattern to obtain new information about the spectra that is otherwise unavailable, thereby improving spectrograph performance. We describe the theory and practice of EDI instruments and demonstrate improvements in the spectral resolution of conventional spectrographs by a factor of 2 to 6. The improvement of spectral resolution offered by EDI can benefit space instruments by reducing spectrograph size or increasing instantaneous bandwidth.

  13. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals

    SciTech Connect

    Curl, Robert F; Glass, Graham

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  14. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    SciTech Connect

    Serrano, A.; Rodriguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Castro, G. R.; Monton, C.; Garcia, M. A.

    2012-08-15

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10{sup -3} to 10{sup -5}, depending on the particular experiment.

  15. Investigating Actinide Molecular Adducts From Absorption Edge Spectroscopy

    SciTech Connect

    Den Auwer, C.; Conradson, S.D.; Guilbaud, P.; Moisy, P.; Mustre de Leon, J.; Simoni, E.; /SLAC, SSRL

    2006-10-27

    Although Absorption Edge Spectroscopy has been widely applied to the speciation of actinide elements, specifically at the L{sub III} edge, understanding and interpretation of actinide edge spectra are not complete. In that sense, semi-quantitative analysis is scarce. In this paper, different aspects of edge simulation are presented, including semi-quantitative approaches. Comparison is made between various actinyl (U, Np) aquo or hydroxy compounds. An excursion into transition metal osmium chemistry allows us to compare the structurally related osmyl and uranyl hydroxides. The edge shape and characteristic features are discussed within the multiple scattering picture and the role of the first coordination sphere as well as contributions from the water solvent are described.

  16. Simultaneous surface plasmon resonance and x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Serrano, A.; Rodríguez de la Fuente, O.; Collado, V.; Rubio-Zuazo, J.; Monton, C.; Castro, G. R.; García, M. A.

    2012-08-01

    We present an experimental setup for the simultaneous measurement of surface plasmon resonance (SPR) and x-ray absorption spectroscopy (XAS) on metallic thin films at a synchrotron beamline. The system allows measuring in situ and in real time the effect of x-ray irradiation on the SPR curves to explore the interaction of x-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to study changes in the films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be also carried out. The relative variations in the SPR and XAS spectra that can be detected with this setup range from 10-3 to 10-5, depending on the particular experiment.

  17. La Saturated Absorption Spectroscopy for Applications in Quantum Information

    NASA Astrophysics Data System (ADS)

    Becker, Patrick; Donoghue, Liz; Dungan, Kristina; Liu, Jackie; Olmschenk, Steven

    2015-05-01

    Quantum information may revolutionize computation and communication by utilizing quantum systems based on matter quantum bits and entangled light. Ions are excellent candidates for quantum bits as they can be well-isolated from unwanted external influences by trapping and laser cooling. Doubly-ionized lanthanum in particular shows promise for use in quantum information as it has infrared transitions in the telecom band, with low attenuation in standard optical fiber, potentially allowing for long distance information transfer. However, the hyperfine splittings of the lowest energy levels, required for laser cooling, have not been measured. We present progress and recent results towards measuring the hyperfine splittings of these levels in lanthanum by saturated absorption spectroscopy with a hollow cathode lamp. This research is supported by the Army Research Office, Research Corporation for Science Advancement, and Denison University.

  18. Non-destructive plant health sensing using absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Bledsoe, Jim; Manukian, Ara; Pearce, Michael; Weiss, Lee

    1988-01-01

    The sensor group of the 1988 EGM 4001 class, working on NASA's Controlled Ecological Life Support Systems (CELSS) project, investigated many different plant health indicators and the technologies used to test them. The project selected by the group was to measure chlorophyll levels using absorption spectroscopy. The spectrometer measures the amount of chlorophyll in a leaf by measuring the intensity of light of a specific wavelength that is passed through a leaf. The three wavelengths of light being used corresponded to the near-IR absorption peaks of chlorophyll a, chlorophyll b, and chlorophyll-free structures. Experimentation showed that the sensor is indeed measuring levels of chlorophyll a and b and their changes before the human eye can see any changes. The detector clamp causes little damage to the leaf and will give fairly accurate readings on similar locations on a leaf, freeing the clamp from having to remain on the same spot of a leaf for all measurements. External light affects the readings only slightly so that measurements may be taken in light or dark environments. Future designs and experimentation will concentrate on reducing the size of the sensor and adapting it to a wider range of plants.

  19. Temperature and pressure measurement based on tunable diode laser absorption spectroscopy with gas absorption linewidth detection

    NASA Astrophysics Data System (ADS)

    Meng, Yunxia; Liu, Tiegen; Liu, Kun; Jiang, Junfeng; Wang, Tao; Wang, Ranran

    2014-11-01

    A gas temperature and pressure measurement method based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) detecting linewidth of gas absorption line was proposed in this paper. Combined with Lambert-Beer Law and ideal gas law, the relationship between temperature, pressure and gas linewidth with Lorentzian line shape was investigated in theory. Taking carbon monoxide (CO) at 1567.32 nm for example, the linewidths of gas absorption line in different temperatures and pressures were obtained by simulation. The relationship between the linewidth of second harmonic and temperature, pressure with the coefficient 0.025 pm/K and 0.0645 pm/kPa respectively. According to the relationship of simulation results and detected linewidth, the undefined temperature and pressure of CO gas were measured. The gas temperature and pressure measurement based on linewidth detection, avoiding the influence of laser intensity, is an effective temperature and pressure measurement method. This method also has the ability to detect temperature and pressure of other gases with Lorentzian line shape.

  20. Gas in Scattering Media Absorption Spectroscopy -- Laser Spectroscopy in Unconventional Environments

    NASA Astrophysics Data System (ADS)

    Svanberg, Sune

    2010-02-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. The GASMAS technique combines narrow-band diode-laser spectroscopy with optical propagation in diffuse media. Whereas solids and liquids have broad absorption features, free gas in pores and cavities in the material is characterized by sharp spectral signatures. These are typically 10,000 times sharper than those of the host material. Many applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. Molecular oxygen and water vapor have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, allowing propagation. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities have been studied, demonstrating new possibilities for characterization and diagnostics. Transport of gas in porous media can readily be studied by first immersing the material in, e.g., pure nitrogen gas, and then observing the rate at which normal air, containing oxygen, reinvades the material. The conductance of the human sinus connective passages can be measured in this way by flushing the nasal cavity with nitrogen, while breathing normally through the mouth. A clinical study comprising 40 patients has been concluded.

  1. X-Ray Absorption Spectroscopy of Strontium(II) Coordination.

    PubMed

    Sahai; Carroll; Roberts; O'Day

    2000-02-15

    Sorption of dissolved strontium on kaolinite, amorphous silica, and goethite was studied as a function of pH, aqueous strontium concentration, the presence or absence of atmospheric CO(2) or dissolved phosphate, and aging over a 57-day period. Selected sorption samples ([Sr(aq)](i) approximately 0.5-1x10(-3) m) were examined with synchrotron X-ray absorption spectroscopy (XAS) at low (13-23 K) and room temperatures to determine the local molecular coordination around strontium. Quantitative analyses of the extended X-ray absorption fine structure (EXAFS) of kaolinite, amorphous silica, and most goethite sorption samples showed a single first shell of 9-10 (+/-1) oxygen atoms around strontium at an average Sr-O bond-distance of 2.61 (+/-0.02) Å, indicating hydrated surface complexes. The EXAFS spectra were unchanged after reaction for up to 57 days. Likewise, in kaolinite sorption samples prepared in 100% nitrogen atmosphere, the presence of dissolved phosphate (0.5x10(-3) m) in addition to strontium did not change the local coordination around strontium. In two goethite sorption samples reacted in air at pH approximately 8.5, the EXAFS spectra (collected at low and room temperature) clearly showed that the local structure around strontium is that of strontianite (SrCO(3)(s)). We also noted an increase in strontium uptake on goethite in the presence of atmospheric CO(2) in batch experiments, relative to CO(2)-free experiments. These observations suggest that sorption of carbonate may nucleate the precipitation of SrCO(3) in the pH range in which carbonate sorption on goethite is near a maximum. At higher pH, carbonate surface sorption decreases as dissolved CO(2) decreases. For goethite sorption samples above pH 8.6, hydrated surface complexes, rather than a precipitate, were observed in the EXAFS spectra. Copyright 2000 Academic Press.

  2. Indirect absorption spectroscopy using quantum cascade lasers: mid-infrared refractometry and photothermal spectroscopy.

    PubMed

    Pfeifer, Marcel; Ruf, Alexander; Fischer, Peer

    2013-11-01

    We record vibrational spectra with two indirect schemes that depend on the real part of the index of refraction: mid-infrared refractometry and photothermal spectroscopy. In the former, a quantum cascade laser (QCL) spot is imaged to determine the angles of total internal reflection, which yields the absorption line via a beam profile analysis. In the photothermal measurements, a tunable QCL excites vibrational resonances of a molecular monolayer, which heats the surrounding medium and changes its refractive index. This is observed with a probe laser in the visible. Sub-monolayer sensitivities are demonstrated.

  3. Cavity-Enhanced Absorption Spectroscopy and Photoacoustic Spectroscopy for Human Breath Analysis

    NASA Astrophysics Data System (ADS)

    Wojtas, J.; Tittel, F. K.; Stacewicz, T.; Bielecki, Z.; Lewicki, R.; Mikolajczyk, J.; Nowakowski, M.; Szabra, D.; Stefanski, P.; Tarka, J.

    2014-12-01

    This paper describes two different optoelectronic detection techniques: cavity-enhanced absorption spectroscopy and photoacoustic spectroscopy. These techniques are designed to perform a sensitive analysis of trace gas species in exhaled human breath for medical applications. With such systems, the detection of pathogenic changes at the molecular level can be achieved. The presence of certain gases (biomarkers), at increased concentration levels, indicates numerous human diseases. Diagnosis of a disease in its early stage would significantly increase chances for effective therapy. Non-invasive, real-time measurements, and high sensitivity and selectivity, capable of minimum discomfort for patients, are the main advantages of human breath analysis. At present, monitoring of volatile biomarkers in breath is commonly useful for diagnostic screening, treatment for specific conditions, therapy monitoring, control of exogenous gases (such as bacterial and poisonous emissions), as well as for analysis of metabolic gases.

  4. Absorption and emission spectroscopy of individual semiconductor nanostructures

    NASA Astrophysics Data System (ADS)

    McDonald, Matthew P.

    The advent of controllable synthetic methods for the production of semiconductor nanostructures has led to their use in a host of applications, including light-emitting diodes, field effect transistors, sensors, and even television displays. This is, in part, due to the size, shape, and morphologically dependent optical and electrical properties that make this class of materials extremely customizable; wire-, rod- and sphere-shaped nanocrystals are readily synthesized through common wet chemical methods. Most notably, confining the physical dimension of the nanostructure to a size below its Bohr radius (aB) results in quantum confinement effects that increase its optical energy gap. Not only the size, but the shape of a particle can be exploited to tailor its optical and electrical properties. For example, confined CdSe quantum dots (QDs) and nanowires (NWs) of equivalent diameter possess significantly different optical gaps. This phenomenon has been ascribed to electrostatic contributions arising from dielectric screening effects that are more pronounced in an elongated (wire-like) morphology. Semiconducting nanostructures have thus received significant attention over the past two decades. However, surprisingly little work has been done to elucidate their basic photophysics on a single particle basis. What has been done has generally been accomplished through emission-based measurements, and thus does not fully capture the full breadth of these intriguing systems. What is therefore needed then are absorption-based studies that probe the size and shape dependent evolution of nanostructure photophysics. This thesis summarizes the single particle absorption spectroscopy that we have carried out to fill this knowledge gap. Specifically, the diameter-dependent progression of one-dimensional (1D) excitonic states in CdSe NWs has been revealed. This is followed by a study that focuses on the polarization selection rules of 1D excitons within single CdSe NWs. Finally

  5. Near Edge X-ray Absorption Spectroscopy of Polymers

    NASA Astrophysics Data System (ADS)

    Dhez, Olivier; Ade, Harald; Urquhart, Stephen

    2001-03-01

    Synthetic and natural polymers exhibit a rich carbon, nitrogen and oxygen K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS). The spectroscopic variations with chemical structure and composition are interesting in their own right. In addition, the large spectroscopic variability can be utilized for the compositional analysis of materials. This is particularly useful for high spatial resolution NEXAFS microanalysis at lateral spatial resolutions exceeding that achievable with more traditional compositional analysis tools such as Infrared and NMR spectroscopy. To increase our understanding of NEXAFS spectra and to start a database for microanalysis, we acquired carbon NEXAFS spectra of the following polymers: polycarbonate, poly(oxybenzoate-co-2,6oxynaphthoate), poly (p-phenylene terephtalamide), toluene diisocyanate polyurethane, toluene diisocyanate polyurea, 4,4'-methylene di-p-phenylene isocyanate polyurethane, 4,4'-methylene di-p-phenylene isocyanate polyurea, poly(ether ether ketone), poly(alpha-methylstyrene), poly-styrene, poly bromostyrene, poly(2-vinyl styrene), polyethylene, poly(ethylene oxide), polypropylene, poly(propylene oxide), polyisobutylene, ethylene propylene rubber, poly(methyl -metacrylate). These spectra were obtained in transmission with an energy resolution of 150 meV. The energy scale was carefully calibrated in-situ utilizing C02 gas as a reference. Spectral assignments are made based on model compounds and theoretical calculations.

  6. Urban ozone measurements using differential optical absorption spectroscopy.

    PubMed

    Morales, J A; Treacy, J; Coffey, S

    2004-05-01

    In order to improve the air quality in Europe the European Commission has issued a number of directives with regard to acceptable levels of a range of gaseous pollutants, which includes ozone. Therefore, monitoring of this compound is necessary to comply with EU legislation, to provide improved pollution warnings for those who are sensitive to air pollutants as well as providing valuable data for environmental planning. Open-path spectroscopic techniques, such as differential optical absorption spectroscopy (DOAS), are ideal for monitoring pollutants because of the advantages they offer over classical methods and point-source analysers. A DOAS system has been installed in Dublin city centre to monitor a range of criteria pollutants including ozone. Observations of urban background ozone concentrations are presented. The measurements are compared with those obtained using a UV point-source analyser and are presented in the context of the current EU directive. The influence of trans-boundary pollution from mainland Europe leading to ozone episodes is also discussed. Observations of high ozone during this measurement campaign coincided with the influx of photochemically polluted air masses which originated over continental Europe. For the analysed time interval, the data suggest that the ground ozone level in Dublin might be significantly influenced by long-range transport from the United Kingdom and continental Europe. PMID:14963627

  7. Decay Heat Measurements Using Total Absorption Gamma-ray Spectroscopy

    NASA Astrophysics Data System (ADS)

    Rice, S.; Valencia, E.; Algora, A.; Taín, J. L.; Regan, P. H.; Podolyák, Z.; Agramunt, J.; Gelletly, W.; Nichols, A. L.

    2012-09-01

    A knowledge of the decay heat emitted by thermal neutron-irradiated nuclear fuel is an important factor in ensuring safe reactor design and operation, spent fuel removal from the core, and subsequent storage prior to and after reprocessing, and waste disposal. Decay heat can be readily calculated from the nuclear decay properties of the fission products, actinides and their decay products as generated within the irradiated fuel. Much of the information comes from experiments performed with HPGe detectors, which often underestimate the beta feeding to states at high excitation energies. This inability to detect high-energy gamma emissions effectively results in the derivation of decay schemes that suffer from the pandemonium effect, although such a serious problem can be avoided through application of total absorption γ-ray spectroscopy (TAS). The beta decay of key radionuclei produced as a consequence of the neutron-induced fission of 235U and 239Pu are being re-assessed by means of this spectroscopic technique. A brief synopsis is given of the Valencia-Surrey (BaF2) TAS detector, and their method of operation, calibration and spectral analysis.

  8. External Cavity Quantum Cascade Laser for Quartz Tuning Fork Photoacoustic Spectroscopy of Broad Absorption Features

    SciTech Connect

    Phillips, Mark C.; Myers, Tanya L.; Wojcik, Michael D.; Cannon, Bret D.

    2007-05-01

    We demonstrate mid-infrared spectroscopy of large molecules with broad absorption features using a tunable external cavity quantum cascade laser. Absorption spectra for two different Freons are measured over the range 1130-1185 cm-1 with 0.2 cm-1 resolution via laser photoacoustic spectroscopy with quartz tuning forks as acoustic transducers. The measured spectra are in excellent agreement with published reference absorption spectra.

  9. Nocturnal Measurements of HONO by Differential Optical Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wojtal, P.; McLaren, R.

    2011-12-01

    Differential optical absorption spectroscopy (DOAS) was used to quantify the concentration of HONO, NO2 and SO2 in the nocturnal urban atmosphere at York University over a period of one year. These measurements form a comprehensive HONO data set, including a large range of temperatures, relative humidity, surface conditions (snow, water, dry, etc.) and NO2 concentrations. Laboratory studies and observations within the nocturnal boundary layer reported in the literature suggest heterogeneous conversion of NO2 on surface adsorbed water as the major nighttime source of HONO. HONO formation and photolysis is believed to represent a major source term in the hydroxyl radical budget in polluted continental regions. Currently, most air quality models tend to significantly underpredict HONO, caused by the lack of understanding of HONO formation processes and the parameters that affect its concentration. Recently, we reported nocturnal pseudo steady states (PSS) of HONO in an aqueous marine environment and a conceptual model for HONO formation on aqueous surfaces was proposed. The data set collected at York University is being analyzed with a view towards further understanding the nighttime HONO formation mechanism and testing several hypotheses: 1) A HONO PSS can exist during certain times at night in an urban area in which the HONO concentration is independent of NO2, given the surface contains sufficient water coverage and is saturated with nitrogen containing precursors; 2) The concentration of HONO is positively correlated with temperature during periods where a PSS exists; 3) Different conversion efficiencies of NO2 to HONO exist on dry, wet and snow surfaces; 4) HONO formation has a NO2 order dependence between 0 and 2nd order, dependant on NO2 concentration, relative humidity, etc. The data set will be presented along with statistical analysis that sheds new light on the source of HONO in urban areas at night.

  10. Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.

    1975-01-01

    Data were obtained which will provide a test of the accuracy of the differential absorption method for trace contaminant detection in many-component gas mixtures. The necessary accurate absorption coefficient determinations were carried out for several gases; acetonitrile, 1,2-dichloroethane, Freon-113, furan, methyl ethyl ketone, and t-butyl alcohol. The absorption coefficients are displayed graphically. An opto-acoustic method was tested for measuring absorbance, similar to the system described by Dewey.

  11. A cavity type absorption cell for double resonance microwave spectroscopy.

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; White, W. F.

    1972-01-01

    Description of an experimental dual resonant cavity absorption cell for observing microwave spectroscopic double-resonance effects. The device is composed of two Fabry-Perot interferometers excited by independent microwave sources and mounted at right angles in a suitable vacuum enclosure. The pumping transition is modulated by one source and the modulation induced on the rf absorption in the orthogonal cavity is detected.

  12. The use of UV-Vis absorption spectroscopy for studies of natively disordered proteins.

    PubMed

    Permyakov, Eugene A

    2012-01-01

    Absorption spectroscopy can be used to monitor structural changes upon transitions from ordered to disordered state in proteins. Changes in environment of tryptophan, tyrosine, and phenylalanine residues result in changes of their absorption spectra. In most cases the changes are small and can be measured only in a differential mode.

  13. Direct and quantitative photothermal absorption spectroscopy of individual particulates

    SciTech Connect

    Tong, Jonathan K.; Hsu, Wei-Chun; Eon Han, Sang; Burg, Brian R.; Chen, Gang; Zheng, Ruiting; Shen, Sheng

    2013-12-23

    Photonic structures can exhibit significant absorption enhancement when an object's length scale is comparable to or smaller than the wavelength of light. This property has enabled photonic structures to be an integral component in many applications such as solar cells, light emitting diodes, and photothermal therapy. To characterize this enhancement at the single particulate level, conventional methods have consisted of indirect or qualitative approaches which are often limited to certain sample types. To overcome these limitations, we used a bilayer cantilever to directly and quantitatively measure the spectral absorption efficiency of a single silicon microwire in the visible wavelength range. We demonstrate an absorption enhancement on a per unit volume basis compared to a thin film, which shows good agreement with Mie theory calculations. This approach offers a quantitative approach for broadband absorption measurements on a wide range of photonic structures of different geometric and material compositions.

  14. The use of CNDO in spectroscopy. XV. Two photon absorption

    NASA Astrophysics Data System (ADS)

    Marchese, Francis T.; Seliskar, C. J.; Jaffé, H. H.

    1980-04-01

    Two-photon absorptivities have been calculated within the CNDO/S-CI molecular orbital framework of Del Bene and Jaffé utilizing the second order time dependent perturbation equations of Göppert-Mayer and polarization methods of McClain. Good agreement is found between this theory and experiment for transition energies, symmetries, and two-photon absorptivities for the following molecules: biphenyl, terphenyl, 2,2'-difluorobiphenyl, 2,2'-bipyridyl, phenanthrene, and the isoelectronic series: fluorene, carbazole, dibenzofuran.

  15. Trace gas absorption spectroscopy using laser difference-frequency spectrometer for environmental application

    NASA Technical Reports Server (NTRS)

    Chen, W.; Cazier, F.; Boucher, D.; Tittel, F. K.; Davies, P. B.

    2001-01-01

    A widely tunable infrared spectrometer based on difference frequency generation (DFG) has been developed for organic trace gas detection by laser absorption spectroscopy. On-line measurements of concentration of various hydrocarbons, such as acetylene, benzene, and ethylene, were investigated using high-resolution DFG trace gas spectroscopy for highly sensitive detection.

  16. Method and apparatus for aerosol particle absorption spectroscopy

    DOEpatents

    Campillo, Anthony J.; Lin, Horn-Bond

    1983-11-15

    A method and apparatus for determining the absorption spectra, and other properties, of aerosol particles. A heating beam source provides a beam of electromagnetic energy which is scanned through the region of the spectrum which is of interest. Particles exposed to the heating beam which have absorption bands within the band width of the heating beam absorb energy from the beam. The particles are also illuminated by light of a wave length such that the light is scattered by the particles. The absorption spectra of the particles can thus be determined from an analysis of the scattered light since the absorption of energy by the particles will affect the way the light is scattered. Preferably the heating beam is modulated to simplify the analysis of the scattered light. In one embodiment the heating beam is intensity modulated so that the scattered light will also be intensity modulated when the particles absorb energy. In another embodiment the heating beam passes through an interferometer and the scattered light reflects the Fourier Transform of the absorption spectra.

  17. Review on VUV to MIR absorption spectroscopy of atmospheric pressure plasma jets

    NASA Astrophysics Data System (ADS)

    Reuter, Stephan; Santos Sousa, Joao; Stancu, Gabi Daniel; Hubertus van Helden, Jean-Pierre

    2015-10-01

    Absorption spectroscopy (AS) represents a reliable method for the characterization of cold atmospheric pressure plasma jets. The method’s simplicity stands out in comparison to competing diagnostic techniques. AS is an in situ, non-invasive technique giving absolute densities, free of calibration procedures, which other diagnostics, such as laser-induced fluorescence or optical emission spectroscopy, have to rely on. Ground state densities can be determined without the knowledge of the influence of collisional quenching. Therefore, absolute densities determined by absorption spectroscopy can be taken as calibration for other methods. In this paper, fundamentals of absorption spectroscopy are presented as an entrance to the topic. In the second part of the manuscript, a review of AS performed on cold atmospheric pressure plasma jets, as they are used e.g. in the field of plasma medicine, is presented. The focus is set on special techniques overcoming not only the drawback of spectrally overlapping absorbing species, but also the line-of-sight densities that AS usually provides or the necessity of sufficiently long absorption lengths. Where references are not available for measurements on cold atmospheric pressure plasma jets, other plasma sources including low-pressure plasmas are taken as an example to give suggestions for possible approaches. The final part is a table summarizing examples of absorption spectroscopic measurements on cold atmospheric pressure plasma jets. With this, the paper provides a ‘best practice’ guideline and gives a compendium of works by groups performing absorption spectroscopy on cold atmospheric pressure plasma jets.

  18. Direct and quantitative broadband absorptance spectroscopy with multilayer cantilever probes

    SciTech Connect

    Hsu, Wei-Chun; Tong, Jonathan Kien-Kwok; Liao, Bolin; Chen, Gang

    2015-04-21

    A system for measuring the absorption spectrum of a sample is provided that includes a broadband light source that produces broadband light defined within a range of an absorptance spectrum. An interferometer modulates the intensity of the broadband light source for a range of modulation frequencies. A bi-layer cantilever probe arm is thermally connected to a sample arm having at most two layers of materials. The broadband light modulated by the interferometer is directed towards the sample and absorbed by the sample and converted into heat, which causes a temperature rise and bending of the bi-layer cantilever probe arm. A detector mechanism measures and records the deflection of the probe arm so as to obtain the absorptance spectrum of the sample.

  19. Time-resolved diffuse optical spectroscopy: a differential absorption approach

    NASA Astrophysics Data System (ADS)

    Taroni, Paola; Bassi, Andrea; Spinelli, Lorenzo; Cubeddu, Rinaldo; Pifferi, Antonio

    2009-07-01

    A method was developed to estimate spectral changes of the absorption properties of turbid media from time-resolved reflectance/transmittance measurements. It was derived directly from the microscopic Beer-Lambert law, and tested against simulations and phantom measurements.

  20. [The Research for Trace Ammonia Escape Monitoring System Based on Tunable Diode Laser Absorption Spectroscopy].

    PubMed

    Zhang, Li-fang; Wang, Fei; Yu, Li-bin; Yan, Jian-hua; Cen, Ke-fa

    2015-06-01

    In order to on-line measure the trace ammonia slip of the commercial power plant in the future, this research seeks to measure the trace ammonia by using tunable diode laser absorption spectroscopy under ambient temperature and pressure, and at different temperatures, and the measuring temperature is about 650 K in the power plant. In recent years lasers have become commercially available in the near-infrared where the transitions are much stronger, and ammonia's spectroscopy is pretty complicated and the overlapping lines are difficult to resolve. A group of ammonia transitions near 4 433.5 cm(-1) in the v2 +v3 combination band have been thoroughly selected for detecting lower concentration by analyzing its absorption characteristic and considering other absorption interference in combustion gases where H2O and CO2 mole fraction are very large. To illustrate the potential for NH3 concentration measurements, predictions for NH3, H2O and CO2 are simultaneously simulated, NH3 absorption lines near 4 433.5 cm(-1) wavelength meet weaker H2O absorption than the commercial NH3 lines, and there is almost no CO2 absorption, all the parameters are based on the HITRAN database, and an improved detection limit was obtained for interference-free NH3 monitoring, this 2.25 μm band has line strengths several times larger than absorption lines in the 1.53 μm band which was often used by NH3 sensors for emission monitoring and analyzing. The measurement system was developed with a new Herriott cell and a heated gas cell realizing fast absorption measurements of high resolution, and combined with direct absorption and wavelenguh modulation based on tunable diode laser absorption spectroscopy at different temperatures. The lorentzian line shape is dominant at ambient temperature and pressure, and the estimated detectivity is approximately 0.225 x 10(-6) (SNR = 1) for the directed absorption spectroscopy, assuming a noise-equivalent absorbance of 1 x 10(-4). The heated cell

  1. X-ray absorption spectroscopy of chicken sulfite oxidase crystals

    SciTech Connect

    George, G.N.; Pickering, I.J.; Kisker, C.

    1999-05-17

    Sulfite oxidase catalyzes the physiologically vital oxidation of sulfite to sulfate. Recently, the crystal structure of chicken sulfite oxidase has been reported at 1.9 {angstrom} resolution. In contrast to the information available from previous X-ray absorption spectroscopic studies, the active site indicated by crystallography was a mono-oxo species. Because of this the possibility that the crystals did in fact contain a reduced molybdenum species was considered in the crystallographic work. The authors report herein an X-ray absorption spectroscopic study of polycrystalline sulfite oxidase prepared in the same manner as the previous single-crystal samples, and compare this with data for frozen solutions of oxidized and reduced enzyme.

  2. Differential optical spectroscopy for absorption characterization of scattering media.

    PubMed

    Billet, Cyril; Sablong, Raphaël

    2007-11-15

    Reflectance techniques are commonly used to characterize the optical properties of tissues. However, the precise determination of local chromophore concentrations in turbid media is usually difficult because of the nonlinear dependence of light intensity as a function of scattering and absorption coefficients. A technique is presented to easily determine absorbent compound concentration ratios in a turbid media from three optical reflectance spectra, in the visible range, measured for source-detector distances less than 1cm. The validity of the method is experimentally established, in cases of sets of diluted milk containing absorbent inks, over a relatively wide range of absorption (0.05-0.5 cm(-1)) and reduced scattering (10-20 cm(-1)) coefficients.

  3. Ultrafast Extreme Ultraviolet Absorption Spectroscopy of Methylammonium Lead Iodide Perovskite

    NASA Astrophysics Data System (ADS)

    Verkamp, Max A.; Lin, Ming-Fu; Ryland, Elizabeth S.; Vura-Weis, Josh

    2016-06-01

    Methylammonium lead iodide (perovskite) is a leading candidate for use in next-generation solar cell devices. However, the photophysics responsible for its strong photovoltaic qualities are not fully understood. Ultrafast extreme ultraviolet (XUV) absorption was used to investigate electron and hole dynamics in perovskite by observing transitions from a common inner-shell level (I 4d) to the valence and conduction bands. Ultrashort (30 fs) pulses of XUV radiation with a broad spectrum (40-70 eV) were generated via high-harmonic generation using a tabletop instrument. Transient absorption measurements with visible pump and XUV probe directly observed the relaxation of charge carriers in perovskite after above-band excitation in the femtosecond and picosecond time ranges.

  4. Two-photon absorption spectroscopy of rubrene single crystals

    NASA Astrophysics Data System (ADS)

    Irkhin, Pavel; Biaggio, Ivan

    2014-05-01

    We determine the wavelength dependence of the two-photon absorption cross section in rubrene single crystals both by direct measurement of nonlinear transmission and from the two-photon excitation spectrum of the photoluminescence. The peak two-photon absorption coefficient for b-polarized light was found to be (4.6±1)×10-11 m/W at a wavelength of 850±10 nm. It is 2.3 times larger for c-polarized light. The lowest energy two-photon excitation peak corresponds to an excited state energy of 2.92±0.04 eV and it is followed by a vibronic progression of higher energy peaks separated by ˜0.14 eV.

  5. X-Ray Absorption Spectroscopy Of Thin Foils Irradiated By An Ultra-short Laser Pulse

    NASA Astrophysics Data System (ADS)

    Renaudin, P.; Lecherbourg, L.; Blancard, C.; Cossé, P.; Faussurier, G.; Audebert, P.; Bastiani-Ceccotti, S.; Geindre, J.-P.; Shepherd, R.

    2007-08-01

    Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum and the 2p-3d absorption lines of bromine were measured over an extended range of densities in a low-temperature regime. Independent plasma characterization was obtained using frequency domain interferometry diagnostic (FDI) that allows the interpretation of the absorption spectra in terms of spectral opacities. Assuming local thermodynamic equilibrium, spectral opacity calculations have been performed using the density and temperature inferred from the FDI diagnostic to compare to the measured absorption spectra. A good agreement is obtained when non-equilibrium effects due to non-stationary atomic physics are negligible at the x-ray probe time.

  6. A heated chamber burner for atomic absorption spectroscopy.

    PubMed

    Venghiattis, A A

    1968-07-01

    A new heated chamber burner is described. The burner is of the premixed type, and burner heads of the types conventionally used in atomic absorption may be readily adapted to it. This new sampling system has been tested for Ag, Al, Ca, Cu, Fe, Mg, Mn, Ni, Pb, Si, Ti, and Zn in aqueous solutions. An improvement of the order of ten times has been obtained in sensitivity, and in detection limits as well, for the elements determined. Interferences controllable are somewhat more severe than in conventional burners but are controllable.

  7. A GAS TEMPERATURE PROFILE BY INFRARED EMISSION-ABSORPTION SPECTROSCOPY

    NASA Technical Reports Server (NTRS)

    Buchele, D. R.

    1994-01-01

    This computer program calculates the temperature profile of a flame or hot gas. Emphasis is on profiles found in jet engine or rocket engine exhaust streams containing water vapor or carbon dioxide as radiating gases. The temperature profile is assumed to be axisymmetric with a functional form controlled by two variable parameters. The parameters are calculated using measurements of gas radiation at two wavelengths in the infrared spectrum. Infrared emission and absorption measurements at two or more wavelengths provide a method of determining a gas temperature profile along a path through the gas by using a radiation source and receiver located outside the gas stream being measured. This permits simplified spectral scanning of a jet or rocket engine exhaust stream with the instrumentation outside the exhaust gas stream. This program provides an iterative-cyclic computation in which an initial assumed temperature profile is altered in shape until the computed emission and absorption agree, within specified limits, with the actual instrument measurements of emission and absorption. Temperature determination by experimental measurements of emission and absorption at two or more wavelengths is also provided by this program. Additionally, the program provides a technique for selecting the wavelengths to be used for determining the temperature profiles prior to the beginning of the experiment. By using this program feature, the experimenter has a higher probability of selecting wavelengths which will result in accurate temperature profile measurements. This program provides the user with a technique for determining whether this program will be sufficiently accurate for his particular application, as well as providing a means of finding the solution. The input to the program consists of four types of data: (1) computer program control constants, (2) measurements of gas radiance and transmittance at selected wavelengths, (3) tabulations from the literature of gas

  8. Absorption spectroscopy of a laboratory photoionized plasma experiment at Z

    SciTech Connect

    Hall, I. M.; Durmaz, T.; Mancini, R. C.; Bailey, J. E.; Rochau, G. A.; Golovkin, I. E.; MacFarlane, J. J.

    2014-03-15

    The Z facility at the Sandia National Laboratories is the most energetic terrestrial source of X-rays and provides an opportunity to produce photoionized plasmas in a relatively well characterised radiation environment. We use detailed atomic-kinetic and spectral simulations to analyze the absorption spectra of a photoionized neon plasma driven by the x-ray flux from a z-pinch. The broadband x-ray flux both photoionizes and backlights the plasma. In particular, we focus on extracting the charge state distribution of the plasma and the characteristics of the radiation field driving the plasma in order to estimate the ionisation parameter.

  9. Simulation-based comparison of noise effects in wavelength modulation spectroscopy and direct absorption TDLAS

    NASA Astrophysics Data System (ADS)

    Lins, B.; Zinn, P.; Engelbrecht, R.; Schmauss, B.

    2010-08-01

    A simulative investigation of noise effects in wavelength modulation spectroscopy (WMS) and direct absorption diode laser absorption spectroscopy is presented. Special attention is paid to the impact of quantization noise of the analog-to-digital conversion (ADC) of the photodetector signal in the two detection schemes with the goal of estimating the necessary ADC resolution for each technique. With laser relative intensity noise (RIN), photodetector shot noise and thermal amplifier noise included, the strategies used for noise reduction in direct and wavelength modulation spectroscopy are compared by simulating two respective systems. Results show that because of the combined effects of dithering by RIN and signal averaging, the resolutions required for the direct absorption setup are only slightly higher than for the WMS setup. Only for small contributions of RIN an increase in resolution will significantly improve signal quality in the direct scheme.

  10. Properties of Liquid Silicon Observed by Time-Resolved X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, S. L.; Heimann, P. A.; Lindenberg, A. M.; Jeschke, H. O.; Garcia, M. E.; Chang, Z.; Lee, R. W.; Rehr, J. J.; Falcone, R. W.

    2003-10-01

    Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.

  11. Total absorption spectroscopy of N = 51 nucleus 85Se

    NASA Astrophysics Data System (ADS)

    Goetz, K. C.; Grzywacz, R. K.; Rykaczewski, K. P.; Karny, M.; Fialkowska, A.; Wolinska-Cichocka, M.; Rasco, B. C.; Zganjar, E. F.; Johnson, J. W.; Gross, C. J.

    2014-09-01

    An experimental campaign utilizing the Modular Total Absorption Spectrometer (MTAS) was conducted at the HRIBF facility in January of 2012. The campaign studied 22 isotopes, many of which were identified as the highest priority for decay heat analysis during a nuclear fuel cycle, see the report by the OECD-IAEA Nuclear Energy Agency in 2007. The case of 85Se will be discussed. 85Se is a Z = 34, N = 51 nucleus with the valence neutron located in the positive parity sd single particle state. Therefore, its decay properties are determined by interplay between first forbidden decays of the valence neutron and Gamow-Teller decay of a 78Ni core. Analysis of the data obtained during the January 2012 run indicates a significant increase of the beta strength function when compared with previous measurements, see Ref..

  12. Monitoring spacecraft atmosphere contaminants by laser absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.

    1976-01-01

    Laser-based spectrophotometric methods which have been proposed for the detection of trace concentrations of gaseous contaminants include Raman backscattering (LIDAR) and passive radiometry (LOPAIR). Remote sensing techniques using laser spectrometry are presented and in particular a simple long-path laser absorption method (LOLA), which is capable of resolving complex mixtures of closely related trace contaminants at ppm levels is discussed. A number of species were selected for study which are representative of those most likely to accumulate in closed environments, such as submarines or long-duration manned space flights. Computer programs were developed which will permit a real-time analysis of the monitored atmosphere. Estimates of the dynamic range of this monitoring technique for various system configurations, and comparison with other methods of analysis, are given.

  13. Examination of the local structure in composite and lowdimensional semiconductor by X-ray Absorption Spectroscopy

    SciTech Connect

    Lawniczak-Jablonska, K.; Demchenko, I.N.; Piskorska, E.; Wolska,A.; Talik, E.; Zakharov, D.N.; Liliental-Weber, Z.

    2006-09-25

    X-ray absorption methods have been successfully used to obtain quantitative information about local atomic composition of two different materials. X-ray Absorption Near Edge Structure analysis and X-Ray Photoelectron Spectroscopy allowed us to determine seven chemical compounds and their concentrations in c-BN composite. Use of Extended X-ray Absorption Fine Structure in combination with Transmission Electron Microscopy enabled us to determine the composition and size of buried Ge quantum dots. It was found that the quantum dots consisted out of pure Ge core covered by 1-2 monolayers of a layer rich in Si.

  14. [Novel analysis algorithms for differential optical absorption spectroscopy for pollution monitoring].

    PubMed

    Zhang, Xue-Dian; Huang, Xian; Xu, Ke-Xin

    2007-11-01

    Differential optical absorption spectroscopy, or DOAS, is a widely used method to determine concentrations of atmospheric species. The principle of DOAS for measuring the concentration of air pollutants is presented in briefly. Using the linear relationship between the area of the measured differential absorbance curve and that of the differential absorption cross-section curve as taken from the literature, an alternative method for calculating the gas concentration on the basis of the proportionality between differential absorbance and differential absorption cross section of the gas under study was developed. The method can be used on its own for single-component analysis or as a complement to the standard technique in multi-component cases. The procedure can be used with differential absorption cross sections measured in the laboratory or taken from the literature. In addition, the method provides a criterion to discriminate between different species having absorption features in the same wavelength range.

  15. Absorption and Scattering Coefficients: A Biophysical-Chemistry Experiment Using Reflectance Spectroscopy

    ERIC Educational Resources Information Center

    Cordon, Gabriela B.; Lagorio, M. Gabriela

    2007-01-01

    A biophysical-chemistry experiment, based on the reflectance spectroscopy for calculating the absorption and scattering coefficients of leaves is described. The results show that different plants species exhibit different values for both the coefficients because of their different pigment composition.

  16. Application of x-ray absorption spectroscopy to the study of corrosion and inhibition

    SciTech Connect

    Davenport, A.J.; Isaacs, H.S.

    1991-01-01

    X-ray absorption spectroscopy is a powerful technique for determination of valency and coordination. Measurements can be made in air or in situ under electrochemical control. The technique will be described and its application to the analysis of passive oxide films, corrosion products, and inhibitors will be reviewed.

  17. Circuit Board Analysis for Lead by Atomic Absorption Spectroscopy in a Course for Nonscience Majors

    ERIC Educational Resources Information Center

    Weidenhammer, Jeffrey D.

    2007-01-01

    A circuit board analysis of the atomic absorption spectroscopy, which is used to measure lead content in a course for nonscience majors, is being presented. The experiment can also be used to explain the potential environmental hazards of unsafe disposal of various used electronic equipments.

  18. DETERMINING BERYLLIUM IN DRINKING WATER BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROSCOPY

    EPA Science Inventory

    A direct graphite furnace atomic absorption spectroscopy method for the analysis of beryllium in drinking water has been derived from a method for determining beryllium in urine. Ammonium phosphomolybdate and ascorbic acid were employed as matrix modifiers. The matrix modifiers s...

  19. Gas concentration measurement by optical similitude absorption spectroscopy: methodology and experimental demonstration.

    PubMed

    Anselmo, Christophe; Welschinger, Jean-Yves; Cariou, Jean-Pierre; Miffre, Alain; Rairoux, Patrick

    2016-06-13

    We propose a new methodology to measure gas concentration by light-absorption spectroscopy when the light source spectrum is larger than the spectral width of one or several molecular gas absorption lines. We named it optical similitude absorption spectroscopy (OSAS), as the gas concentration is derived from a similitude between the light source and the target gas spectra. The main OSAS-novelty lies in the development of a robust inversion methodology, based on the Newton-Raphson algorithm, which allows retrieving the target gas concentration from spectrally-integrated differential light-absorption measurements. As a proof, OSAS is applied in laboratory to the 2ν3 methane absorption band at 1.66 µm with uncertainties revealed by the Allan variance. OSAS has also been applied to non-dispersive infra-red and the optical correlation spectroscopy arrangements. This all-optics gas concentration retrieval does not require the use of a gas calibration cell and opens new tracks to atmospheric gas pollution and greenhouse gases sources monitoring.

  20. Gas concentration measurement by optical similitude absorption spectroscopy: methodology and experimental demonstration.

    PubMed

    Anselmo, Christophe; Welschinger, Jean-Yves; Cariou, Jean-Pierre; Miffre, Alain; Rairoux, Patrick

    2016-06-13

    We propose a new methodology to measure gas concentration by light-absorption spectroscopy when the light source spectrum is larger than the spectral width of one or several molecular gas absorption lines. We named it optical similitude absorption spectroscopy (OSAS), as the gas concentration is derived from a similitude between the light source and the target gas spectra. The main OSAS-novelty lies in the development of a robust inversion methodology, based on the Newton-Raphson algorithm, which allows retrieving the target gas concentration from spectrally-integrated differential light-absorption measurements. As a proof, OSAS is applied in laboratory to the 2ν3 methane absorption band at 1.66 µm with uncertainties revealed by the Allan variance. OSAS has also been applied to non-dispersive infra-red and the optical correlation spectroscopy arrangements. This all-optics gas concentration retrieval does not require the use of a gas calibration cell and opens new tracks to atmospheric gas pollution and greenhouse gases sources monitoring. PMID:27410280

  1. Spectrum sensing of trace C(2)H(2) detection in differential optical absorption spectroscopy technique.

    PubMed

    Chen, Xi; Dong, Xiaopeng

    2014-09-10

    An improved algorithm for trace C(2)H(2) detection is presented in this paper. The trace concentration is accurately calculated by focusing on the absorption spectrum from the frequency domain perspective. The advantage of the absorption spectroscopy frequency domain algorithm is its anti-interference capability. First, the influence of the background noise on the minimum detectable concentration is greatly reduced. Second, the time-consuming preprocess of spectra calibration in the differential optical absorption spectroscopy technique is skipped. Experimental results showed the detection limit of 50 ppm is achieved at a lightpath length of 0.2 m. This algorithm can be used in real-time spectrum analysis with high accuracy.

  2. X-ray absorption spectroscopy on the basis of hybrid X-pinch radiation

    SciTech Connect

    Tilikin, I. N. Shelkovenko, T. A.; Pikuz, S. A.; Knapp, P. F.; Hammer, D. A.

    2015-07-15

    Results of experiments on X-ray absorption spectroscopy carried out at the BIN (270 kA, 100 ns) and XP (450 kA, 45 ns) facilities are presented. Continuum radiation of a Mo hybrid X-pinch was used as probing radiation, against which absorption lines of the plasma of exploded Al wires placed in the return current circuit of a hybrid X-pinch, as well as in a two- and four-wire array, were observed. The experiments have demonstrated that the radiation of a hybrid X-pinch hot spot can be used as probing radiation for X-ray absorption spectroscopy and that, in many parameters, such a source surpasses those on the basis of laser-produced plasma. The plasma parameters in arrays made of two and four Al wires were studied experimentally.

  3. Surface relaxation in liquid water and methanol studied by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wilson, Kevin R.; Schaller, R. D.; Co, D. T.; Saykally, R. J.; Rude, Bruce S.; Catalano, T.; Bozek, J. D.

    2002-10-01

    X-ray absorption spectroscopy is a powerful probe of local electronic structure in disordered media. By employing extended x-ray absorption fine structure spectroscopy of liquid microjets, the intermolecular O-O distance has been observed to undergo a 5.9% expansion at the liquid water interface, in contrast to liquid methanol for which there is a 4.6% surface contraction. Despite the similar properties of liquid water and methanol (e.g., abnormal heats of vaporization, boiling points, dipole moments, etc.), this result implies dramatic differences in the surface hydrogen bond structure, which is evidenced by the difference in surface tension of these liquids. This result is consistent with surface vibrational spectroscopy, which indicates both stronger hydrogen bonding and polar ordering at the methanol surface as a consequence of "hydrophobic packing" of the methyl group.

  4. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A. ); Mitchell, G.E.; Dekoven, B.M. ); Yeh, A.T.; Gland, J.L. ); Moodenbaugh, A.R. )

    1993-01-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  5. Ultra-soft x-ray absorption spectroscopy: A bulk and surface probe of materials

    SciTech Connect

    Fischer, D.A.; Mitchell, G.E.; Dekoven, B.M.; Yeh, A.T.; Gland, J.L.; Moodenbaugh, A.R.

    1993-06-01

    Direct comparisons between surface and bulk of diverse materials can be made by simultaneous electron yield (5 nm depth sensitivity) and fluorescence yield (200 nm) ultra soft x-ray absorption spectroscopy measurements utilizing a rapid sample interchange apparatus. For example the orientations of functional groups have been characterized at and near the surface of a series of model polymeric materials highlighting the chemical and molecular sensitivity of ultra soft x-ray absorption spectroscopy. In addition we discuss a bulk sensitive use of fluorescence yield to non destructively study a buried metal polymer interface. A second bulk sensitive example is the use of fluorescence yield oxygen K near edge x-ray spectroscopy as a method to determine the hole state density of high Tc materials.

  6. [Influence of silver/silicon dioxide on infrared absorption spectroscopy of sodium nitrate].

    PubMed

    Yang, Shi-Ling; Yue, Li; Jia, Zhi-Jun

    2014-09-01

    Quickly detecting of ocean nutrient was one important task in marine pollution monitoring. We discovered the application of surface-enhanced infrared absorption spectroscopy in the detection of ocean nutrient through researching the evaporation of sodium nitrate solution. The silicon dioxide (SiO2) with highly dispersion was prepared by Stober method, The silver/silica (Ag/SiO2) composite materials were prepared by mixing ammonia solution and silicon dioxide aqueous solution. Three kinds of composite materials with different surface morphology were fabricated through optimizing the experimental parameter and changing the experimental process. The surface morphology, crystal orientation and surface plasmon resonance were investigated by means of the scanning electronic microscope (SEM), X-ray diffraction (XRD), UV-Visible absorption spectrum and infrared ab- sorption spectroscopy. The SEM images showed that the sample A was purified SiO2, sample B and sample C were mixture of silver nanoparticle and silicon dioxide, while sample D was completed nanoshell structure. The absorption spectroscopy showed that there was surface plasmon resonance in the UV-visible region, while there was possibility of surface plasmon resonance in the Infrared absorption region. The effect of Ag/SiO2 composite material on the infrared absorption spectra of sodium nitrite solution was investigated through systematically analyzing the infrared absorption spectroscopy of sodium nitrate solution during its evaporation, i. e. the peak integration area of nitrate and the peak integration area of water molecule. The experimental results show that the integration area of nitrate was enhanced greatly during the evaporation process while the integration area of water molecule decreased continuously. The integration area of nitrate comes from the anti-symmetric stretch vibration and the enhancement of the vibration is attributed to the interface effect of Ag/SiO2 which is consistent with Jensen T

  7. [The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

    PubMed

    Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

    2016-03-01

    Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results

  8. [The Diagnostics of Detonation Flow External Field Based on Multispectral Absorption Spectroscopy Technology].

    PubMed

    Lü, Xiao-jing; Li, Ning; Weng, Chun-sheng

    2016-03-01

    Compared with traditional sampling-based sensing method, absorption spectroscopy technology is well suitable for detonation flow diagnostics, since it can provide with us fast response, nonintrusive, sensitive solution for situ measurements of multiple flow-field parameters. The temperature and concentration test results are the average values along the laser path with traditional absorption spectroscopy technology, while the boundary of detonation flow external field is unknown and it changes all the time during the detonation engine works, traditional absorption spectroscopy technology is no longer suitable for detonation diagnostics. The trend of line strength with temperature varies with different absorption lines. By increasing the number of absorption lines in the test path, more information of the non-uniform flow field can be obtained. In this paper, based on multispectral absorption technology, the reconstructed model of detonation flow external field distribution was established according to the simulation results of space-time conservation element and solution element method, and a diagnostic method of detonation flow external field was given. The model deviation and calculation error of the least squares method adopted were studied by simulation, and the maximum concentration and temperature calculation error was 20.1% and 3.2%, respectively. Four absorption lines of H2O were chosen and detonation flow was scanned at the same time. The detonation external flow testing system was set up for the valveless gas-liquid continuous pulse detonation engine with the diameter of 80 mm. Through scanning H2O absorption lines with a high frequency of 10 kHz, the on-line detection of detonation external flow was realized by direct absorption method combined with time-division multiplexing technology, and the reconstruction of dynamic temperature distribution was realized as well for the first time, both verifying the feasibility of the test method. The test results

  9. Measurements of the mass absorption cross section of atmospheric soot particles using Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Nordmann, S.; Birmili, W.; Weinhold, K.; Müller, K.; Spindler, G.; Wiedensohler, A.

    2013-11-01

    Soot particles are a major absorber of shortwave radiation in the atmosphere. The mass absorption cross section is an essential quantity to describe this light absorption process. This work presents new experimental data on the mass absorption cross section of soot particles in the troposphere over Central Europe. Mass absorption cross sections were derived as the ratio between the light absorption coefficient determined by multiangle absorption photometry (MAAP) and the soot mass concentration determined by Raman spectroscopy. The Raman method is sensitive to graphitic structures present in the particle samples and was calibrated in the laboratory using Printex®90 model particles. Mass absorption cross sections were determined for a number of seven observation sites, ranging between 3.9 and 7.4 m2 g-1depending on measurement site and observational period. The highest values were found in a continentally aged air mass in winter, where soot particles were assumed to be mainly internally mixed. Our values are in the lower range of previously reported values, possibly due to instrumental differences to the former photometer and mass measurements. Overall, a value of 5.3m2 g-1from orthogonal regression over all samples is considered to be representative for the soot mass absorption cross section in the troposphere over Central Europe.

  10. Determination of Calcium in Cereal with Flame Atomic Absorption Spectroscopy: An Experiment for a Quantitative Methods of Analysis Course

    ERIC Educational Resources Information Center

    Bazzi, Ali; Kreuz, Bette; Fischer, Jeffrey

    2004-01-01

    An experiment for determination of calcium in cereal using two-increment standard addition method in conjunction with flame atomic absorption spectroscopy (FAAS) is demonstrated. The experiment is intended to introduce students to the principles of atomic absorption spectroscopy giving them hands on experience using quantitative methods of…

  11. Recovery of acetylene absorption line profile basing on tunable diode laser spectroscopy with intensity modulation and photoacoustic spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Li; Thursby, Graham; Stewart, George; Arsad, Norhana; Uttamchandani, Deepak; Culshaw, Brian; Wang, Yiding

    2010-04-01

    A novel and direct absorption line recovery technique based on tunable diode laser spectroscopy with intensity modulation is presented. Photoacoustic spectroscopy is applied for high sensitivity, zero background and efficient acoustic enhancement at a low modulation frequency. A micro-electromechanical systems (MEMS) mirror driven by an electrothermal actuator is used for generating laser intensity modulation (without wavelength modulation) through the external reflection. The MEMS mirror with 10μm thick structure material layer and 100nm thick gold coating is formed as a circular mirror of 2mm diameter attached to an electrothermal actuator and is fabricated on a chip that is wire-bonded and placed on a PCB holder. Low modulation frequency is adopted (since the resonant frequencies of the photoacoustic gas cell and the electrothermal actuator are different) and intrinsic high signal amplitude characteristics in low frequency region achieved from measured frequency responses for the MEMS mirror and the gas cell. Based on the property of photoacoustic spectroscopy and Beer's law that detectable sensitivity is a function of input laser intensity in the case of constant gas concentration and laser path length, a Keopsys erbium doped fibre amplifier (EDFA) with opto-communication C band and high output power up to 1W is chosen to increase the laser power. High modulation depth is achieved through adjusting the MEMS mirror's reflection position and driving voltage. In order to scan through the target gas absorption line, the temperature swept method is adopted for the tunable distributed feed-back (DFB) diode laser working at 1535nm that accesses the near-infrared vibration-rotation spectrum of acetylene. The profile of acetylene P17 absorption line at 1535.39nm is recovered ideally for ~100 parts-per-million (ppm) acetylene balanced by nitrogen. The experimental signal to noise ratio (SNR) of absorption line recovery for 500mW laser power was ~80 and hence the

  12. Photocarrier dynamics in anatase TiO{sub 2} investigated by pump-probe absorption spectroscopy

    SciTech Connect

    Matsuzaki, H. E-mail: okamotoh@k.u-tokyo.ac.jp; Matsui, Y.; Uchida, R.; Yada, H.; Terashige, T.; Li, B.-S.; Sawa, A.; Kawasaki, M.; Tokura, Y.; Okamoto, H. E-mail: okamotoh@k.u-tokyo.ac.jp

    2014-02-07

    The dynamics of photogenerated electrons and holes in undoped anatase TiO{sub 2} were studied by femtosecond absorption spectroscopy from the visible to mid-infrared region (0.1–2.0 eV). The transient absorption spectra exhibited clear metallic responses, which were well reproduced by a simple Drude model. No mid-gap absorptions originating from photocarrier localization were observed. The reduced optical mass of the photocarriers obtained from the Drude-model analysis is comparable to theoretically expected one. These results demonstrate that both photogenerated holes and electrons act as mobile carriers in anatase TiO{sub 2}. We also discuss scattering and recombination dynamics of photogenerated electrons and holes on the basis of the time dependence of absorption changes.

  13. Ultrafast carrier dynamics of titanic acid nanotubes investigated by transient absorption spectroscopy.

    PubMed

    Wang, Li; Zhao, Hui; Pan, Lin Yun; Weng, Yu Xiang; Nakato, Yoshihiro; Tamai, Naoto

    2010-12-01

    Carrier dynamics of titanic acid nanotubes (phase of H2Ti2O5.H2O) deposited on a quartz plate was examined by visible/near-IR transient absorption spectroscopy with an ultraviolet excitation. The carrier dynamics of titanic acid nanotubes follows the fast trapping process which attributed to the intrinsic tubular structure, the relaxation of shallow trapped carriers and the recombination as a second-order kinetic process. Transient absorption of titanic acid nanotubes was dominated by the absorption of surface-trapped holes in visible region around 500 nm, which was proved by the faster decay dynamics in the presence of polyvinyl alcohol as a hole-scavenger. However, the slow relaxation of free carriers was much more pronounced in the TiO2 single crystals, as compared with the transient absorption spectra of titanic acid nanotubes under the similar excitation.

  14. Minute Concentration Measurements of Simple Hydrocarbon Species Using Supercontinuum Laser Absorption Spectroscopy.

    PubMed

    Yoo, Jihyung; Traina, Nicholas; Halloran, Michael; Lee, Tonghun

    2016-06-01

    Minute concentration measurements of simple hydrocarbon gases are demonstrated using near-infrared supercontinuum laser absorption spectroscopy. Absorption-based gas sensors, particularly when combined with optical fiber components, can significantly enhance diagnostic capabilities to unprecedented levels. However, these diagnostic techniques are subject to limitations under certain gas sensing applications where interference and harsh conditions dominate. Supercontinuum laser absorption spectroscopy is a novel laser-based diagnostic technique that can exceed the above-mentioned limitations and provide accurate and quantitative concentration measurement of simple hydrocarbon species while maintaining compatibility with telecommunications-grade optical fiber components. Supercontinuum radiation generated using a highly nonlinear photonic crystal fiber is used to probe rovibrational absorption bands of four hydrocarbon species using full-spectral absorption diagnostics. Absorption spectra of methane (CH4), acetylene (C2H2), and ethylene (C2H4) were measured in the near-infrared spectrum at various pressures and concentrations to determine the accuracy and feasibility of the diagnostic strategy. Absorption spectra of propane (C3H8) were subsequently probed between 1650 nm and 1700 nm, to demonstrate the applicability of the strategy. Measurements agreed very well with simulated spectra generated using the HITRAN database as well as with previous experimental results. Absorption spectra of CH4, C2H2, and C2H4 were then analyzed to determine their respective measurement accuracy and detection limit. Concentration measurements integrated from experimental results were in very good agreement with independent concentration measurements. Calculated detection limits of CH4, C2H2, and C2H4 at room temperature and atmospheric pressure are 0.1%, 0.09%, and 0.17%, respectively. PMID:27091905

  15. [The principle and technical analysis of methane detection using infrared absorption spectroscopy].

    PubMed

    Zhang, Yu; Wang, Yi-Ding; Li, Li; Zheng, Chuan-Tao; An, Yu-Peng; Song, Zhen-Yu

    2008-11-01

    There has been considerable interest recently in methane sensor based on infrared absorption spectroscopy for industrial detection and environment monitoring. The present paper presents the intensites of methane mid-infrared fundamental absorption bands, near-infrared combination band of v2 + 2v3 and overtone band of 2v3, and it was found that the absorption strengths of fundamental bands are two orders of magnitude higher than those of overtone bands and three orders of magnitude higher than those of the combinations. Theoretically, mid-infrared detection system is much better. However, because the near-infrared source and detector are more maturely developed and cheaper, near-infrared technology is widely used. Furthermore, the near-infrared radiation can be transmitted through ordinary low-loss silica fiber, suitable for long-distance methane sensing system, meeting the needs of industrial mining and other aspects. But with the development of mid-infrared detector and high-power high-sensitivity devices, low priced micro sensor modules will be more and more developed. The development of optical methane sensors is reported in this paper. Several detection technologies were investigated such as differential absorption, harmonic detection, cavity spectroscopy enhancement and photoacoustic spectroscopy. The theoretical formula, sensitivity and system structure of these technologies are presented. PMID:19271479

  16. Rapid, Time-Division Multiplexed, Direct Absorption- and Wavelength Modulation-Spectroscopy

    PubMed Central

    Klein, Alexander; Witzel, Oliver; Ebert, Volker

    2014-01-01

    We present a tunable diode laser spectrometer with a novel, rapid time multiplexed direct absorption- and wavelength modulation-spectroscopy operation mode. The new technique allows enhancing the precision and dynamic range of a tunable diode laser absorption spectrometer without sacrificing accuracy. The spectroscopic technique combines the benefits of absolute concentration measurements using calibration-free direct tunable diode laser absorption spectroscopy (dTDLAS) with the enhanced noise rejection of wavelength modulation spectroscopy (WMS). In this work we demonstrate for the first time a 125 Hz time division multiplexed (TDM-dTDLAS-WMS) spectroscopic scheme by alternating the modulation of a DFB-laser between a triangle-ramp (dTDLAS) and an additional 20 kHz sinusoidal modulation (WMS). The absolute concentration measurement via the dTDLAS-technique allows one to simultaneously calibrate the normalized 2f/1f-signal of the WMS-technique. A dTDLAS/WMS-spectrometer at 1.37 μm for H2O detection was built for experimental validation of the multiplexing scheme over a concentration range from 50 to 3000 ppmV (0.1 MPa, 293 K). A precision of 190 ppbV was achieved with an absorption length of 12.7 cm and an averaging time of two seconds. Our results show a five-fold improvement in precision over the entire concentration range and a significantly decreased averaging time of the spectrometer. PMID:25405508

  17. Determining Concentrations and Temperatures in Semiconductor Manufacturing Plasmas via Submillimeter Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Helal, Yaser H.; Neese, Christopher F.; De Lucia, Frank C.; Ewing, Paul R.; Agarwal, Ankur; Craver, Barry; Stout, Phillip J.; Armacost, Michael D.

    2016-06-01

    Plasmas used in the manufacturing processes of semiconductors are similar in pressure and temperature to plasmas used in studying the spectroscopy of astrophysical species. Likewise, the developed technology in submillimeter absorption spectroscopy can be used for the study of industrial plasmas and for monitoring manufacturing processes. An advantage of submillimeter absorption spectroscopy is that it can be used to determine absolute concentrations and temperatures of plasma species without the need for intrusive probes. A continuous wave, 500 - 750 GHz absorption spectrometer was developed for the purpose of being used as a remote sensor of gas and plasma species. An important part of this work was the optical design to match the geometry of existing plasma reactors in the manufacturing industry. A software fitting routine was developed to simultaneously fit for the background and absorption signal, solving for concentration, rotational temperature, and translational temperature. Examples of measurements made on inductively coupled plasmas will be demonstrated. We would like to thank the Texas Analog Center of Excellence/Semiconductor Research Corporation (TxACE/SRC) and Applied Materials for their support of this work.

  18. Redox Chemisty of Tantalum Clusters on Silica Characterized by X-ray Absorption Spectroscopy

    SciTech Connect

    Nemana,S.; Gates, B.

    2006-01-01

    SiO{sub 2}-supported clusters of tantalum were synthesized from adsorbed Ta(CH{sub 2}Ph){sub 5} by treatment in H{sub 2} at 523 K. The surface species were characterized by X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray absorption near edge spectroscopy (XANES)) and ultraviolet-visible spectroscopy. The EXAFS data show that SiOO{sub 2}-supported tantalum clusters were characterized by a Ta-Ta coordination number of approximately 2, consistent with the presence of tritantalum clusters, on average. When these were reduced in H{sub 2} and reoxidized in O{sub 2}, the cluster nuclearity remained essentially unchanged, although reduction and oxidation occurred, respectively, as shown by XANES and UV-vis spectra; in the reoxidation, the tantalum oxidation state change was approximately two electronic charges per tritantalum cluster. The data demonstrate an analogy between the chemistry of group 5 metals on the SiO{sub 2} support and their chemistry in solution, as determined by the group of Cotton.

  19. High sensitivity ultra-broad-band absorption spectroscopy of inductively coupled chlorine plasma

    NASA Astrophysics Data System (ADS)

    Marinov, Daniil; Foucher, Mickaël; Campbell, Ewen; Brouard, Mark; Chabert, Pascal; Booth, Jean-Paul

    2016-06-01

    We propose a method to measure the densities of vibrationally excited Cl2(v) molecules in levels up to v  =  3 in pure chlorine inductively coupled plasmas (ICPs). The absorption continuum of Cl2 in the 250-450 nm spectral range is deconvoluted into the individual components originating from the different vibrational levels of the ground state, using a set of ab initio absorption cross sections. It is shown that gas heating at constant pressure is the major depletion mechanism of the Cl2 feedstock in the plasma. In these line-integrated absorption measurements, the absorption by the hot (and therefore rarefied) Cl2 gas in the reactor centre is masked by the cooler (and therefore denser) Cl2 near the walls. These radial gradients in temperature and density make it difficult to assess the degree of vibrational excitation in the centre of the reactor. The observed line-averaged vibrational distributions, when analyzed taking into account the radial temperature gradient, suggest that vibrational and translational degrees of freedom in the plasma are close to local equilibrium. This can be explained by efficient vibrational-translational (VT) relaxation between Cl2 and Cl atoms. Besides the Cl2(v) absorption band, a weak continuum absorption is observed at shorter wavelengths, and is attributed to photodetachment of Cl- negative ions. Thus, line-integrated densities of negative ions in chlorine plasmas can be directly measured using broad-band absorption spectroscopy.

  20. Photodissociation of thioglycolic acid studied by femtosecond time-resolved transient absorption spectroscopy

    SciTech Connect

    Attar, Andrew R.; Blumling, Daniel E.; Knappenberger, Kenneth L. Jr.

    2011-01-14

    Steady-state and time-resolved spectroscopies were employed to study the photodissociation of both the neutral (HS-CH{sub 2}-COOH) and doubly deprotonated ({sup -}S-CH{sub 2}-COO{sup -}) forms of thioglycolic acid (TGA), a common surface-passivating ligand used in the aqueous synthesis and organization of semiconducting nanostructures. Room temperature UV-Vis absorption spectroscopy indicated strong absorption by the S{sub 1} and S{sub 2} excited states at 250 nm and 185 nm, respectively. The spectrum also contained a weaker absorption band that extended to approximately 550 nm, which was assigned to the {pi}{sub CO}{sup *}(leftarrow)n{sub O} transition. Femtosecond time-resolved transient absorption spectroscopy was performed on TGA using 400 nm excitation and a white-light continuum probe to provide the temporally and spectrally resolved data. Both forms of TGA underwent a photoinduced dissociation from the excited state to form an {alpha}-thiol-substituted acyl radical ({alpha}-TAR, S-CH{sub 2}-CO). For the acidic form of TGA, radical formation occurred with an apparent time constant of 60 {+-} 5 fs; subsequent unimolecular decay took 400 {+-} 60 fs. Similar kinetics were observed for the deprotonated form of TGA (70 {+-} 10 fs radical formation; 420 {+-} 40 fs decay). The production of the {alpha}-TAR was corroborated by the observation of its characteristic optical absorption. Time-resolved data indicated that the photoinduced dissociation of TGA via cleavage of the C-OH bond occurred rapidly ({<=}100 fs). The prevalence of TGA in aqueous semiconducting nanoparticles makes its absorption in the visible spectral region and subsequent dissociation key to understanding the behavior of nanoscale systems.

  1. Infrared-laser spectroscopy using a long-pathlength absorption cell

    SciTech Connect

    Kim, K.C.; Briesmeister, R.A.

    1983-01-01

    The absorption measurements in an ordinary cell may require typically a few torr pressure of sample gas. At these pressures the absorption lines are usually pressure-broadened and, therefore, closely spaced transitions are poorly resolved even at diode-laser resolution. This situation is greatly improved in Doppler-limited spectroscopy at extremely low sample pressures. Two very long-pathlength absorption cells were developed to be used in conjunction with diode lasers. They were designed to operate at controlled temperatures with the optical pathlength variable up to approx. 1.5 km. Not only very low sample pressures are used for studies with such cells but also the spectroscopic sensitivity is enhanced over conventional methods by a factor of 10/sup 3/ to 10/sup 4/, improving the analytical capability of measuring particle densities to the order of 1 x 10'' molecules/cm/sup 3/. This paper presents some analytical aspects of the diode laser spectroscopy using the long-pathlength absorption cells in the areas of absorption line widths, pressure broadening coefficients, isotope composition measurements and trace impurity analysis.

  2. Spatial variance and assessment of nitrogen dioxide pollution in major cities of Pakistan along N5-Highway.

    PubMed

    Shabbir, Yasir; Khokhar, Muhammad Fahim; Shaiganfar, Reza; Wagner, Thomas

    2016-05-01

    This paper discusses the findings of the first car MAX-DOAS (multi-axis differential optical absorption spectroscopy) field campaign (300km long) along the National Highway-05 (N5-Highway) of Pakistan conducted on 13 and 14 November, 2012. The main objective of the field campaign was to assess the spatial distribution of tropospheric nitrogen dioxide (NO2) columns and corresponding concentrations along the N5-Highway from Islamabad to Lahore. Source identification of NO2 revealed that the concentrations were higher within major cities along the highway. The highest NO2 vertical column densities (NO2 VCDs) were found around two major cities of Rawalpindi and Lahore. This study also presents a comparison of NO2 VCDs measured by the ozone monitoring instrument (OMI) and car MAX-DOAS observations. The comparison revealed similar spatial distribution of the NO2 columns with both car MAX-DOAS and satellite observations, but the car MAX-DOAS observations show much more spatial details. Maximum NO2 VCD retrieved from car MAX-DOAS observations was up to an order of magnitude larger than the OMI observations in urban areas.

  3. Spatial variance and assessment of nitrogen dioxide pollution in major cities of Pakistan along N5-Highway.

    PubMed

    Shabbir, Yasir; Khokhar, Muhammad Fahim; Shaiganfar, Reza; Wagner, Thomas

    2016-05-01

    This paper discusses the findings of the first car MAX-DOAS (multi-axis differential optical absorption spectroscopy) field campaign (300km long) along the National Highway-05 (N5-Highway) of Pakistan conducted on 13 and 14 November, 2012. The main objective of the field campaign was to assess the spatial distribution of tropospheric nitrogen dioxide (NO2) columns and corresponding concentrations along the N5-Highway from Islamabad to Lahore. Source identification of NO2 revealed that the concentrations were higher within major cities along the highway. The highest NO2 vertical column densities (NO2 VCDs) were found around two major cities of Rawalpindi and Lahore. This study also presents a comparison of NO2 VCDs measured by the ozone monitoring instrument (OMI) and car MAX-DOAS observations. The comparison revealed similar spatial distribution of the NO2 columns with both car MAX-DOAS and satellite observations, but the car MAX-DOAS observations show much more spatial details. Maximum NO2 VCD retrieved from car MAX-DOAS observations was up to an order of magnitude larger than the OMI observations in urban areas. PMID:27155404

  4. Diamond solid state ionization chambers for x-ray absorption spectroscopy applications

    SciTech Connect

    De Sio, A.; Bocci, A.; Pace, E.; Castellano, C.; Cinque, G.; Tartoni, N.; D'Acapito, F.

    2008-08-25

    The photoresponse of a diamond detector has been compared with a standard ionization chamber in x-ray absorption spectroscopy applications. A photoconductive device based on a nitrogen-doped single crystal diamond has been tested by synchrotron radiation. Time stability and linearity have been studied by x rays at 10 keV to assess its performances. Finally, extended x-ray absorption fine structure at the Fe K-edge was carried on a standard iron target using both the diamond device and the IC. Spectroscopical results have been compared including references to literature.

  5. Assignment of benzodiazepine UV absorption spectra by the use of photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Khvostenko, O. G.; Tzeplin, E. E.; Lomakin, G. S.

    2002-04-01

    Correlations between singlet transition energies and energy gaps of corresponding pairs of occupied and unoccupied molecular orbitals were revealed in a series of benzodiazepines. The occupied orbital energies were taken from the photoelectron spectra of the compound investigated, the unoccupied ones were obtained from MNDO/d calculations, and the singlet energies were taken from the UV absorption spectra. The correspondence of the singlet transitions to certain molecular orbitals was established using MNDO/d calculations and comparing between UV and photoelectron spectra. It has been concluded that photoelectron spectroscopy can be applied for interpretation of UV absorption spectra of various compounds on the basis of similar correlations.

  6. Electrochemical flowcell for in-situ investigations by soft x-ray absorption and emission spectroscopy

    SciTech Connect

    Schwanke, C.; Lange, K. M.; Golnak, R.; Xiao, J.

    2014-10-15

    A new liquid flow-cell designed for electronic structure investigations at the liquid-solid interface by soft X-ray absorption and emission spectroscopy is presented. A thin membrane serves simultaneously as a substrate for the working electrode and solid state samples as well as for separating the liquid from the surrounding vacuum conditions. In combination with counter and reference electrodes this approach allows in-situ studies of electrochemical deposition processes and catalytic reactions at the liquid-solid interface in combination with potentiostatic measurements. As model system in-situ monitoring of the deposition process of Co metal from a 10 mM CoCl{sub 2} aqueous solution by X-ray absorption and emission spectroscopy is presented.

  7. Atomic structure of machined semiconducting chips: An x-ray absorption spectroscopy study

    SciTech Connect

    Paesler, M.; Sayers, D.

    1988-12-01

    X-ray absorption spectroscopy (XAS) has been used to examine the atomic structure of chips of germanium that were produced by single point diamond machining. It is demonstrated that although the local (nearest neighbor) atomic structure is experimentally quite similar to that of single crystal specimens information from more distant atoms indicates the presence of considerable stress. An outline of the technique is given and the strength of XAS in studying the machining process is demonstrated.

  8. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-10-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  9. X-ray absorption spectroscopy beyond the core-hole lifetime

    SciTech Connect

    Haemaelaeinen, K.; Hastings, J.B.; Siddons, D.P.; Berman, L.

    1992-01-01

    A new technique to overcome the core-hole lifetime broadening in x-ray absorption spectroscopy is presented. It utilizes a high resolution fluorescence spectrometer which can be used to analyze the fluorescence photon energy with better resolution than the natural lifetime width. Furthermore, the high resolution spectrometer can also be used to select the final state in the fluorescence process which can offer spin selectivity even without long range magnetic order in the sample.

  10. Narrow-band, tunable, semiconductor-laser-based source for deep-UV absorption spectroscopy.

    PubMed

    Kliner, D A; Koplow, J P; Goldberg, L

    1997-09-15

    Tunable, narrow-bandwidth (<200-MHz), ~215-nm radiation was produced by frequency quadrupling the ~860-nm output of a high-power, pulsed GaAlAs tapered amplifier seeded by an external-cavity diode laser. Pulsing the amplifier increased the 860 nm?215 nm conversion efficiency by 2 orders of magnitude with respect to cw operation. Detection of nitric oxide and sulfur dioxide by high-resolution absorption spectroscopy was demonstrated. PMID:18188256

  11. Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy.

    PubMed

    Stockett, M H; Houmøller, J; Brøndsted Nielsen, S

    2016-09-14

    Nile blue is used extensively in biology as a histological stain and fluorescent probe. Its absorption and emission spectra are strongly solvent dependent, with variations larger than 100 nm. The molecule is charged due to an iminium group, and it is therefore an obvious target for gas-phase ion spectroscopy. Here we report the absorption and emission spectra of the mass-selected bare ions isolated in vacuo, and based on our results we revisit the interpretation of solution-phase spectra. An accelerator mass spectrometer was used for absorption spectroscopy where the absorption is represented by the yield of photofragment ions versus excitation wavelength (action spectroscopy). The luminescence experiments were done with a newly built ion trap setup equipped with an electrospray ion source, and some details on the mass selection technique will be given which have not been described before. In vacuo, the absorption and emission maxima are at 580 ± 10 nm and 628 ± 1 nm. These values are somewhat blue-shifted relative to those obtained in most solvents; however, they are much further to the red than those in some of the most non-polar solvents. Furthermore, the Stokes shift in the gas phase (1300 cm(-1)) is much smaller than that in these non-polar solvents but similar to that in polar ones. An explanation based on charge localization by solvent dipoles, or by counterions in some non-polar solvents, can fully account for these findings. Hence in the case of ions, it is nontrivial to establish intrinsic electronic transition energies from solvatochromic shifts alone. PMID:27634256

  12. Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy.

    PubMed

    Stockett, M H; Houmøller, J; Brøndsted Nielsen, S

    2016-09-14

    Nile blue is used extensively in biology as a histological stain and fluorescent probe. Its absorption and emission spectra are strongly solvent dependent, with variations larger than 100 nm. The molecule is charged due to an iminium group, and it is therefore an obvious target for gas-phase ion spectroscopy. Here we report the absorption and emission spectra of the mass-selected bare ions isolated in vacuo, and based on our results we revisit the interpretation of solution-phase spectra. An accelerator mass spectrometer was used for absorption spectroscopy where the absorption is represented by the yield of photofragment ions versus excitation wavelength (action spectroscopy). The luminescence experiments were done with a newly built ion trap setup equipped with an electrospray ion source, and some details on the mass selection technique will be given which have not been described before. In vacuo, the absorption and emission maxima are at 580 ± 10 nm and 628 ± 1 nm. These values are somewhat blue-shifted relative to those obtained in most solvents; however, they are much further to the red than those in some of the most non-polar solvents. Furthermore, the Stokes shift in the gas phase (1300 cm(-1)) is much smaller than that in these non-polar solvents but similar to that in polar ones. An explanation based on charge localization by solvent dipoles, or by counterions in some non-polar solvents, can fully account for these findings. Hence in the case of ions, it is nontrivial to establish intrinsic electronic transition energies from solvatochromic shifts alone.

  13. Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy

    NASA Astrophysics Data System (ADS)

    Stockett, M. H.; Houmøller, J.; Brøndsted Nielsen, S.

    2016-09-01

    Nile blue is used extensively in biology as a histological stain and fluorescent probe. Its absorption and emission spectra are strongly solvent dependent, with variations larger than 100 nm. The molecule is charged due to an iminium group, and it is therefore an obvious target for gas-phase ion spectroscopy. Here we report the absorption and emission spectra of the mass-selected bare ions isolated in vacuo, and based on our results we revisit the interpretation of solution-phase spectra. An accelerator mass spectrometer was used for absorption spectroscopy where the absorption is represented by the yield of photofragment ions versus excitation wavelength (action spectroscopy). The luminescence experiments were done with a newly built ion trap setup equipped with an electrospray ion source, and some details on the mass selection technique will be given which have not been described before. In vacuo, the absorption and emission maxima are at 580 ± 10 nm and 628 ± 1 nm. These values are somewhat blue-shifted relative to those obtained in most solvents; however, they are much further to the red than those in some of the most non-polar solvents. Furthermore, the Stokes shift in the gas phase (1300 cm-1) is much smaller than that in these non-polar solvents but similar to that in polar ones. An explanation based on charge localization by solvent dipoles, or by counterions in some non-polar solvents, can fully account for these findings. Hence in the case of ions, it is nontrivial to establish intrinsic electronic transition energies from solvatochromic shifts alone.

  14. X-RAY ABSORPTION SPECTROSCOPY OF YB3+-DOPED OPTICAL FIBERS

    SciTech Connect

    Citron, Robert; Kropf, A.J.

    2008-01-01

    Optical fibers doped with Ytterbium-3+ have become increasingly common in fiber lasers and amplifiers. Yb-doped fibers provide the capability to produce high power and short pulses at specific wavelengths, resulting in highly effective gain media. However, little is known about the local structure, distribution, and chemical coordination of Yb3+ in the fibers. This information is necessary to improve the manufacturing process and optical qualities of the fibers. Five fibers doped with Yb3+ were studied using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES), in addition to Yb3+ mapping. The Yb3+ distribution in each fiber core was mapped with 2D and 1D intensity scans, which measured X-ray fluorescence over the scan areas. Two of the five fibers examined showed highly irregular Yb3+ distributions in the core center. In four of the five fibers Yb3+ was detected outside of the given fiber core dimensions, suggesting possible Yb3+ diffusion from the core, manufacturing error, or both. X-ray absorption spectroscopy (XAS) analysis has so far proven inconclusive, but did show that the fibers had differing EXAFS spectra. The Yb3+ distribution mapping proved highly useful, but additional modeling and examination of fiber preforms must be conducted to improve XAS analysis, which has been shown to have great potential for the study of similar optical fi bers.

  15. X-ray microprobe for micro x-ray fluorescence and absorption spectroscopies at GSECARS

    NASA Astrophysics Data System (ADS)

    Newville, M.; Sutton, S.; Rivers, M.

    2002-12-01

    The hard x-ray microprobe for x-ray fluorescence and absorption spectroscopy at GeoSoilEnviroCARS is presented. Using focused synchrotron radiation from an undulator beamline at the Advanced Photon Source at Argonne National Lab, the x-ray microprobe provides bright, monochromatic x-rays with typical spot sizes down to 1x1 μm for x-ray fluorescence and absorption spectroscopies. Quantitative x-ray fluorescence (XRF) analysis gives precise elemental composition and correlations, while x-ray absorption spectroscopy (XAS) gives the chemical state and local atomic coordination for a selected atomic species. These two techniques can be used in conjunction with one another on a wide range of samples, including minerals, glasses, fluid inclusions, soils, sediments, and plant tissue. This x-ray microprobe is part of the GeoSoilEnviroCARS user facility, available for use in all areas geological, soil, and environmental sciences, and selected examples from these fields will be given.

  16. Absorption spectroscopy setup for determination of whole human blood and blood-derived materials spectral characteristics

    NASA Astrophysics Data System (ADS)

    Wróbel, M. S.; Gnyba, M.; Milewska, D.; Mitura, K.; Karpienko, K.

    2015-09-01

    A dedicated absorption spectroscopy system was set up using tungsten-halogen broadband source, optical fibers, sample holder, and a commercial spectrometer with CCD array. Analysis of noise present in the setup was carried out. Data processing was applied to the absorption spectra to reduce spectral noise, and improve the quality of the spectra and to remove the baseline level. The absorption spectra were measured for whole blood samples, separated components: plasma, saline, washed erythrocytes in saline and human whole blood with biomarkers - biocompatible nanodiamonds (ND). Blood samples had been derived from a number of healthy donors. The results prove a correct setup arrangement, with adequate preprocessing of the data. The results of blood-ND mixtures measurements show no toxic effect on blood cells, which proves the NDs as a potential biocompatible biomarkers.

  17. Deep ultraviolet Raman spectroscopy: A resonance-absorption trade-off illustrated by diluted liquid benzene

    NASA Astrophysics Data System (ADS)

    Chadwick, C. T.; Willitsford, A. H.; Philbrick, C. R.; Hallen, H. D.

    2015-12-01

    The magnitude of resonance Raman intensity, in terms of the real signal level measured on-resonance compared to the signal level measured off-resonance for the same sample, is investigated using a tunable laser source. Resonance Raman enhancements, occurring as the excitation energy is tuned through ultraviolet absorption lines, are used to examine the 1332 cm-1 vibrational mode of diamond and the 992 cm-1 ring-breathing mode of benzene. Competition between the wavelength dependent optical absorption and the magnitude of the resonance enhancement is studied using measured signal levels as a function of wavelength. Two system applications are identified where the resonance Raman significantly increases the real signal levels despite the presence of strong absorption: characterization of trace species in laser remote sensing and spectroscopy of the few molecules in the tiny working volumes of near-field optical microscopy.

  18. The potential of UV-VIS-NIR absorption spectroscopy in glass studies

    NASA Astrophysics Data System (ADS)

    Meulebroeck, Wendy; Baert, Kitty; Ceglia, Andrea; Cosyns, Peter; Wouters, Hilde; Nys, Karin; Terryn, Herman; Thienpont, Hugo

    Absorption spectroscopy is the technique that measures the absorption of radiation as a function of wavelength, due to its interaction with the material. During a research project funded by our home university, we were able to investigate the possibilities of this technique to study ancient glasses. One of our main conclusions is that UV-VIS-NIR absorption spectroscopy is especially suited to characterize colored artifacts in terms of composition and furnace conditions. Moreover, for naturally colored window glasses, we have shown that this technique allows us to classify fragments based on differences in iron impurity levels. It is a semi-quantitative analysis tool that can be applied for a first-line analysis of (large) glass collections. Thanks to the commercial available portable instruments, these measurements can be performed at relative high speed and this in-situ if necessary. To illustrate the possibilities of this technique, we describe in this paper two case-studies. In a first test-case we analyze 63 naturally colored window glasses and demonstrate how groups with different iron concentrations can be identified by calculating the absorption edge position from the measured optical spectrum. In a second case-study 8 modern naturally colored and 31 intentionally colored Roman glass fragments are the point of focus. For these samples we first estimate which samples are potentially fabricated under the same furnace conditions. This is done based on the calculated color values. Finally we identify the type of applied colorants.

  19. Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

    PubMed Central

    Dunlop, Iain E.; Zorn, Stefan; Richter, Gunther; Srot, Vesna; Kelsch, Marion; van Aken, Peter A.; Skoda, Maximilian; Gerlach, Alexander; Spatz, Joachim P.; Schreiber, Frank

    2010-01-01

    We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ~6 nm sputtered silicon oxide film on a ~200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure. PMID:20418963

  20. Theory of dynamic absorption spectroscopy of nonstationary states. 4. Application to 12-fs resonant impulsive Raman spectroscopy of bacteriorhodopsin

    SciTech Connect

    Pollard, W.T.; Peteanu, L.A.; Mathies, R.A.

    1992-07-23

    A time-dependent theory for femtosecond dynamic absorption spectroscopy is used to describe the creation and observation of molecular ground-state vibrational coherence through the resonance impulsive stimulated Raman mechanism. Model calculations show that the oscillatory absorption signal that arises from this ground-state coherence is maximized for a limited range of pulse lengths and that there is a complex relationship between the probe wavelength and the strength of the spectral oscillations. The generalized time-dependent linear susceptibility of the nonstationary system created by the impulsive pump pulse is defined and used to discuss the strong dependence of the measured signals on the properties of the probe pulse. Finally, calculations are presented to analyze the high-frequency oscillations ({approximately}20-fs period) recently observed in the transient absorption spectra of light-adapted bacteriorhodopsin (BR{sub 568}) following excitation with a 12-fs optical pulse. At the probe wavelengths used in this experiment, the contribution of stimulated emission is negligible at long times because of the extremely rapid excited-state isomerization; as a result, the spectral oscillations observed after this time are due to the impulsive excitation of coherent vibrations in the ground state. The transient response observed for BR{sub 568} is calculated using a 29-mode harmonic potential surface derived from a prior resonance Raman intensity analysis. Both the oscillatory signals and their dependence on the probe wavelength are satisfactorily reproduced. 68 refs., 11 figs.

  1. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy.

    PubMed

    Hager, J D; Lanier, N E; Kline, J L; Flippo, K A; Bruns, H C; Schneider, M; Saculla, M; McCarville, T

    2014-11-01

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO2 foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured. PMID:25430177

  2. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy

    SciTech Connect

    Hager, J. D. Lanier, N. E.; Kline, J. L.; Flippo, K. A.; Bruns, H. C.; Schneider, M.; Saculla, M.; McCarville, T.

    2014-11-15

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO{sub 2} foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured.

  3. [Study on removing the lamp spectrum structure in differential optical absorption spectroscopy].

    PubMed

    Qu, Xiao-ying; Li, Yu-jin

    2010-11-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range, and nowadays this technique has been widely utilized to measure trace polluted gases in the atmosphere e.g. SO2, NO2, O3, HCHO, etc. However, there exists lamp (xenon lamp or deuteriumlamp) spectrum structure in the measured band (300-700 nm) of the absorption spectra of atmosphere, which badly impacts on precision of retrieving the concentration of trace gases in the atmosphere. People home and abroad generally employ two ways to handle this problem, one is segmenting band retrieving method, another is remedial retrieving method. In the present paper, a new retrieving method to deal with this trouble is introduced. The authors used moving-window average smoothing method to obtain the slow part of the absorption spectra of atmosphere, then achieved the lamp (xenon lamp in the paper) spectrum structure in the measured band of the absorption spectra of atmosphere. The authors analyzed and retrieved the measured spectrum of the atmosphere, and the result is better than the forenamed ways. Chi-square of residuum is 2.995 x 10(-4), and this method was proved to be able to avoid shortcoming of choosing narrowband and disadvantage of discovering the new component of atmosphere in retrieving the concentration of air pollutants and measuring the air pollutants. PMID:21284148

  4. Infrared Cavity Ringdown Laser Absorption Spectroscopy of jet-cooled clusters

    NASA Astrophysics Data System (ADS)

    Provencal, Robert Allen

    Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS) employing stimulated Raman scattering (SRS) of pulsed dye lasers as the tunable IR source has been developed. This technique allows highly sensitive (ca. 1 ppm fractional absorption) direct absorption measurements to be performed in the 2-8 μm spectral range with complete wavelength coverage. Basic CR-LAS principles and essential SRS theory are reviewed. IR- CRLAS spectrometers based on both a Raman shifted dye laser and a pulsed Alexandrite ring laser are described. The IR-CRLAS spectrometer has been used in a comparative study of the O-H-stretching vibrations of small alcohol clusters. Results indicate an increase in the hydrogen bond strength as the alcohol chain length increases. An IR-CRLAS investigation of the aromatic C-H stretches of benzene and berizene/methane mixtures, performed in an effort to provide experimental support for a theoretically proposed ``antihydrogen bond'', produced negative results. Similarly, negative results from a visible CRLAS search for water cluster absorptions in connection with the anomalous atmospheric absorption of solar radiation are presented. Infrared laser spectroscopic studies of the structures and bonding in jet-cooled carbon clusters are discussed. The measurement and analysis of a rovibrational band at 2074 cm-1, tentatively assigned to linear C10 is presented. The astrophysical significance of carbon clusters is also discussed in conjunction with the first detection of a non polar molecule (C3) in a cold interstellar dust forming region, performed using far-infrared heterodyne spectroscopy aboard the Kuiper Airborne Observatory.

  5. Use of X-ray absorption spectroscopy in the search for the best LIGO mirror coatings

    NASA Astrophysics Data System (ADS)

    McGuire, Stephen C.

    2008-03-01

    The Laser Interferometer Gravitational-wave Observatory (LIGO) seeks to improve its sensitivity for gravity-wave detection by a factor of ten during its next phase of operation, Advanced LIGO. In order to achieve this goal it is necessary to design and fabricate test mass mirrors that help minimize the noise in the interferometers and in doing so maximize gravity-wave detection capability. In this talk we will present recent results from our program of X-ray absorption spectroscopy measurements to obtain detailed chemical composition and structure of titania (TiO2)-doped tantala (Ta2O5) multilayers fabricated via ion beam sputtering on SiO2 substrates. Our investigations focus on how the microscopic features of the coatings influence their macroscopic mechanical loss properties. Our goal is to obtain correlations between chemical impurities and/or dopants and the optical absorption and mechanical loss characteristics of these multilayer coatings. To examine our samples we use synchrotron-based X-ray absorption Spectroscopy (XAS) techniques including Extended X-ray Absorption Fine Structure (EXAFS), X-ray Absorption Near Edge Structure (XANES) and X-ray Fluorescence (XRF). We present chemical and structural data obtained at the titanium K-edge and tantalum LIII-edge as well as relative elemental distribution information (Ti/Ta, Fe/Ta, and Cr/Ta) obtained via XRF. Following a brief description of the LIGO experiment, our program of research in optical materials for use in advanced versions of the interferometer will be described.

  6. UV-Vis Reflection-Absorption Spectroscopy at air-liquid interfaces.

    PubMed

    Rubia-Payá, Carlos; de Miguel, Gustavo; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

    2015-11-01

    UV-Visible Reflection-Absorption Spectroscopy (UVRAS) technique is reviewed with a general perspective on fundamental and applications. UVRAS is formally identical to IR Reflection-Absorption Spectroscopy (IRRAS), and therefore, the methodology developed for this IR technique can be applied in the UV-visible region. UVRAS can be applied to air-solid, air-liquid or liquid-liquid interfaces. This review focuses on the use of UVRAS for studying Langmuir monolayers. We introduce the theoretical framework for a successful understanding of the UVRAS data, and we illustrate the usage of this data treatment to a previous study from our group comprising an amphiphilic porphyrin. For ultrathin films with a thickness of few nm, UVRAS produces positive or negative bands when p-polarized radiation is used, depending on the incidence angle and the orientation of dipole absorption. UVRAS technique provides highly valuable information on tilt of chromophores at the air-liquid interface, and moreover allows the determination of optical parameters. We propose UVRAS as a powerful technique to investigate the in situ optical properties of Langmuir monolayers. PMID:26385430

  7. Surface arsenic speciation of a drinking-water treatment residual using X-ray absorption spectroscopy.

    PubMed

    Makris, Konstantinos C; Sarkar, Dibyendu; Parsons, Jason G; Datta, Rupali; Gardea-Torresdey, Jorge L

    2007-07-15

    Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing >90% of the initial added As (15,000 mg kg(-1)) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg(-1)) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.

  8. High Speed H2O Concentration Measurements Using Absorption Spectroscopy to Monitor Exhaust Gas

    SciTech Connect

    Kranendonk, Laura; Parks, II, James E; Prikhodko, Vitaly Y; Partridge Jr, William P

    2008-01-01

    This paper demonstrates the potential for fast absorption spectroscopy measurements in diesel-engine exhaust to track H2O concentration transients. Wavelength-agile absorption spectroscopy is an optical technique that measures broadband absorption spectra between 10kHz and 100 MHz. From these measured spectra, gas temperature and absorber concentration can be determined. The Fourier-domain mode-locking (FDML) laser is becoming recognized as one of the most robust and reliable wavelength-agile sources available. H2O concentration measurements during combustion events at crank angle resolved speeds are beneficial for a wide variety of applications, such as product improvements for industry, control and reliability checks for experimental researchers, and measures of fit for numerical simulations. The difficulties associated with measuring diesel exhaust compared to in-cylinder measurements are discussed. A full description of the experimental configuration and data processing is explained. Measurements of engine exhaust H2O transients with 10- s temporal resolution are presented for a range of engine conditions.

  9. [Signal analysis and spectrum distortion correction for tunable diode laser absorption spectroscopy system].

    PubMed

    Bao, Wei-Yi; Zhu, Yong; Chen, Jun; Chen, Jun-Qing; Liang, Bo

    2011-04-01

    In the present paper, the signal of a tunable diode laser absorption spectroscopy (TDLAS) trace gas sensing system, which has a wavelength modulation with a wide range of modulation amplitudes, is studied based on Fourier analysis method. Theory explanation of spectrum distortion induced by laser intensity amplitude modulation is given. In order to rectify the spectrum distortion, a method of synchronous amplitude modulation suppression by a variable optical attenuator is proposed. To validate the method, an experimental setup is designed. Absorption spectrum measurement experiments on CO2 gas were carried out. The results show that the residual laser intensity modulation amplitude of the experimental system is reduced to -0.1% of its original value and the spectrum distortion improvement is 92% with the synchronous amplitude modulation suppression. The modulation amplitude of laser intensity can be effectively reduced and the spectrum distortion can be well corrected by using the given correction method and system. By using a variable optical attenuator in the TDLAS (tunable diode laser absorption spectroscopy) system, the dynamic range requirements of photoelectric detector, digital to analog converter, filters and other aspects of the TDLAS system are reduced. This spectrum distortion correction method can be used for online trace gas analyzing in process industry.

  10. Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics

    NASA Astrophysics Data System (ADS)

    Neville, Simon P.; Averbukh, Vitali; Ruberti, Marco; Yun, Renjie; Patchkovskii, Serguei; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

    2016-10-01

    We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L 2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

  11. High-performance dispersive Raman and absorption spectroscopy as tools for drug identification

    NASA Astrophysics Data System (ADS)

    Pawluczyk, Olga; Andrey, Sam; Nogas, Paul; Roy, Andrew; Pawluczyk, Romuald

    2009-02-01

    Due to increasing availability of pharmaceuticals from many sources, a need is growing to quickly and efficiently analyze substances in terms of the consistency and accuracy of their chemical composition. Differences in chemical composition occur at very low concentrations, so that highly sensitive analytical methods become crucial. Recent progress in dispersive spectroscopy with the use of 2-dimensional detector arrays, permits for signal integration along a long (up to 12 mm long) entrance slit of a spectrometer, thereby increasing signal to noise ratio and improving the ability to detect small concentration changes. This is achieved with a non-scanning, non-destructive system. Two different methods using P&P Optica high performance spectrometers were used. High performance optical dispersion Raman and high performance optical absorption spectroscopy were employed to differentiate various acetaminophen-containing drugs, such as Tylenol and other generic brands, which differ in their ingredients. A 785 nm excitation wavelength was used in Raman measurements and strong Raman signals were observed in the spectral range 300-1800 cm-1. Measurements with the absorption spectrometer were performed in the wavelength range 620-1020 nm. Both Raman and absorption techniques used transmission light spectrometers with volume phase holographic gratings and provided sufficient spectral differences, often structural, allowing for drug differentiation.

  12. Femtosecond x-ray absorption spectroscopy with hard x-ray free electron laser

    SciTech Connect

    Katayama, Tetsuo; Togashi, Tadashi; Tono, Kensuke; Kameshima, Takashi; Inubushi, Yuichi; Sato, Takahiro; Hatsui, Takaki; Yabashi, Makina; Obara, Yuki; Misawa, Kazuhiko; Bhattacharya, Atanu; Kurahashi, Naoya; Ogi, Yoshihiro; Suzuki, Toshinori

    2013-09-23

    We have developed a method of dispersive x-ray absorption spectroscopy with a hard x-ray free electron laser (XFEL), generated by a self-amplified spontaneous emission (SASE) mechanism. A transmission grating was utilized for splitting SASE-XFEL light, which has a relatively large bandwidth (ΔE/E ∼ 5 × 10{sup −3}), into several branches. Two primary split beams were introduced into a dispersive spectrometer for measuring signal and reference spectra simultaneously. After normalization, we obtained a Zn K-edge absorption spectrum with a photon-energy range of 210 eV, which is in excellent agreement with that measured by a conventional wavelength-scanning method. From the analysis of the difference spectra, the noise ratio was evaluated to be ∼3 × 10{sup −3}, which is sufficiently small to trace minute changes in transient spectra induced by an ultrafast optical laser. This scheme enables us to perform single-shot, high-accuracy x-ray absorption spectroscopy with femtosecond time resolution.

  13. Infrared reflection-absorption spectroscopy of hyperfine layers on surfaces of semiconductors and dielectrics

    NASA Astrophysics Data System (ADS)

    Gruzinov, S. N.; Tolstoy, V. P.

    1988-02-01

    Infrared reflection-absorption spectroscopy of film son surfaces of transparent or weakly absorbing semiconductor and dielectric substrates is analyzed theoretically, the purpose being to establish the conditions for maximum sensitivity of this method. The absorption factor, namely the relative change of the reflection coefficient upon formation of a film on the substrate surface, is selected as the sensitivity criterion. The analysis is based on exact relations, one for a homogeneous isotopic absorbing film between substrate and ambient medium with plane-parallel boundaries and one for a reflecting layer with the possibility of multiple reflections taken into account. Calculations have been programmed on a computer for up to 60 nm thick SiO2 films on various substrates and infrared radiation within the 8 to 11 gmm waveband. The results indicate that the dependence of the absorption factor on the radiation wavelength and on the film thickness is different with the radiation s-polarized than with the radiation p-polarized. Calculations have also yielded the dispersion of optical constants characterizing a SiO2 film. According to these results, infrared spectroscopy is most sensitive to films on substrates with a small refractive index and when done with p-polarized radiation incident at exactly or approximately the Brewster angle for a determination of their presence and their composition respectively, also when no multiple reflections occur.

  14. Time resolved metal line profile by near-ultraviolet tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vitelaru, C.; de Poucques, L.; Minea, T. M.; Popa, G.

    2011-03-01

    Pulsed systems are extensively used to produce active species such as atoms, radicals, excited states, etc. The tunable diode laser absorption spectroscopy (TD-LAS) is successfully used to quantify the density of absorbing species, but especially for stationary or slow changing systems. The time resolved-direct absorption profile (TR-DAP) measurement method by TD-LAS, with time resolution of μs is proposed here as an extension of the regular use of diode laser absorption spectroscopy. The spectral narrowness of laser diodes, especially in the blue range (˜0.01 pm), combined with the nanosecond fast trigger of the magnetron pulsed plasma and long trace recording on the oscilloscope (period of second scale) permit the detection of the sputtered titanium metal evolution in the afterglow (˜ms). TR-DAP method can follow the time-dependence of the temperature (Doppler profile) and the density (deduced from the absorbance) of any medium and heavy species in a pulsed system.

  15. Surface Arsenic Speciation of a Drinking-Water Treatment Residual Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Makris, K.C.; Sarkar, D.; Parsons, J.G.; Datta, R.; Gardea-Torresdey, J.L.

    2009-06-03

    Drinking-water treatment residuals (WTRs) present a low-cost geosorbent for As-contaminated waters and soils. Previous work has demonstrated the high affinity of WTRs for As, but data pertaining to the stability of sorbed As is missing. Sorption/desorption and X-ray absorption spectroscopy (XAS), both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) studies, were combined to determine the stability of As sorbed by an Fe-based WTR. Arsenic(V) and As(III) sorption kinetics were biphasic in nature, sorbing <90% of the initial added As (15,000 mg kg{sup -1}) after 48 h of reaction. Subsequent desorption experiments with a high P load (7500 mg kg{sup -1}) showed negligible As desorption for both As species, approximately <3.5% of sorbed As; the small amount of desorbed As was attributed to the abundance of sorption sites. XANES data showed that sorption kinetics for either As(III) or As(V) initially added to solution had no effect on the sorbed As oxidation state. EXAFS spectroscopy suggested that As added either as As(III) or as As(V) formed inner-sphere mononuclear, bidentate complexes, suggesting the stability of the sorbed As, which was further corroborated by the minimum As desorption from the Fe-WTR.

  16. Broadband spectroscopy with external cavity quantum cascade lasers beyond conventional absorption measurements.

    PubMed

    Lambrecht, Armin; Pfeifer, Marcel; Konz, Werner; Herbst, Johannes; Axtmann, Felix

    2014-05-01

    Laser spectroscopy is a powerful tool for analyzing small molecules, i.e. in the gas phase. In the mid-infrared spectral region quantum cascade lasers (QCLs) have been established as the most frequently used laser radiation source. Spectroscopy of larger molecules in the gas phase, of complex mixtures, and analysis in the liquid phase requires a broader tuning range and is thus still the domain of Fourier transform infrared (FTIR) spectroscopy. However, the development of tunable external cavity (EC) QCLs is starting to change this situation. The main advantage of QCLs is their high spectral emission power that is enhanced by a factor of 10(4) compared with thermal light sources. Obviously, transmission measurements with EC-QCLs in strongly absorbing samples are feasible, which can hardly be measured by FTIR due to detector noise limitations. We show that the high power of EC-QCLs facilitates spectroscopy beyond simple absorption measurements. Starting from QCL experiments with liquid samples, we show results of fiber evanescent field analysis (FEFA) to detect pesticides in drinking water. FEFA is a special case of attenuated total reflection spectroscopy. Furthermore, powerful CW EC-QCLs enable fast vibrational circular dichroism (VCD) spectroscopy of chiral molecules in the liquid phase - a technique which is very time consuming with standard FTIR equipment. We present results obtained for the chiral compound 1,1'-bi-2-naphthol (BINOL). Finally, powerful CW EC-QCLs enable the application of laser photothermal emission spectroscopy (LPTES). We demonstrate this for a narrowband and broadband absorber in the gas phase. All three techniques have great potential for MIR process analytical applications.

  17. Cavity Enhanced absorption spectroscopy with an Optical Comb: Detection of atmospheric radicals in the near UV.

    NASA Astrophysics Data System (ADS)

    Méjean, G.; Kassi, S.; Romanini, D.

    2009-04-01

    The atmospheric chemistry community suffers a lack of fast, reliable and space resolved measurement for a wide set of very reactive molecules (e.g. radicals such as OH, NO3, BrO, IO, etc.). Due to their high reactivity, these molecules largely control the lifetime and concentration of numerous key atmospheric species. The concentrations of radicals are extremely low (ppbv or less) and highly variable in time and space. Measuring their concentration is often extremely laborious, expensive and requires heavy equipment (chemical sampling and treatment followed by mass spectrometry and/or chromatography). We recently introduced an optical spectroscopy technique based on a femtosecond laser oscillator, "Mode-Locked Cavity-Enhanced Absorption Spectroscopy", that we propose to develop into an instrument for in situ measurement of local concentration of traces of reactive molecules [1-3]. We have already demonstrated the possibility of measuring part in 1E12 by volume concentrations of radicals of high atmospheric interest, such as IO or BrO [4], as needed for monitoring these species in the environment. We apply cavity-enhanced absorption spectroscopy in the near UV range using a frequency-doubled Ti:Sa modelocked femtosecond laser. Efficient broadband injection of a high finesse cavity is obtained by matching this optical frequency-comb source to the comb of cavity transmission resonances. A grating spectrograph and a detector array disperse and detect the spectrum transmitted by the cavity carrying the absorption features of intracavity molecules. IO traces were obtained by mixing together controlled flows of gaseous iodine and ozone inside a high finesse cavity (F~6000). A Chameleon Ultra II ML-Laser (gracefully lent during 1 month by Coherent Inc.) was frequency doubled to address an absorption band of IO at 436 nm. A locking scheme allowed the cavity transmission to be smooth and stable. The transmitted light was dispersed using a high resolution (0.07nm) grating

  18. The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

    PubMed

    Liu, Ping; Li, Zhu; Li, Bo; Shi, Guolong; Li, Minqiang; Yu, Daoyang; Liu, Jinhuai

    2013-08-01

    Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

  19. Temperature and multi-species measurements by supercontinuum absorption spectroscopy for IC engine applications.

    PubMed

    Werblinski, Thomas; Engel, Sascha R; Engelbrecht, Rainer; Zigan, Lars; Will, Stefan

    2013-06-01

    The first supercontinuum (SC) absorption spectroscopy measurements showing the feasibility of quantitative temperature evaluation are presented to the best of the authors' knowledge. Temperature and multi-species measurements were carried out at a detection rate of ~2 MHz in a high-temperature flow cell within a temperature range from 450 K to 750 K at 0.22 MPa, representing conditions during the suction and compression stroke in an internal combustion (IC) engine. The broadband SC pulses were temporally dispersed into fast wavelength sweeps, covering the overtone absorption bands 2ν(1), 2ν(3), ν(1) + ν(3) of H2O and 3ν(3) of CO2 in the near-infrared region from 1330 nm to 1500 nm. The temperature information is inferred from the peak ratio of a temperature sensitive (1362.42 nm) and insensitive (1418.91 nm) absorption feature in the ν(1) + ν(3) overtone bands of water. The experimental results are in very good agreement with theoretical intensity ratios calculated from absorption spectra based on HiTran data. PMID:23736618

  20. Simple Monte Carlo methods to estimate the spectra evaluation error in differential-optical-absorption spectroscopy.

    PubMed

    Hausmann, M; Brandenburger, U; Brauers, T; Dorn, H P

    1999-01-20

    Differential-optical-absorption spectroscopy (DOAS) permits the sensitive measurement of concentrations of trace gases in the atmosphere. DOAS is a technique of well-defined accuracy; however, the calculation of a statistically sound measurement precision is still an unsolved problem. Usually one evaluates DOAS spectra by performing least-squares fits of reference absorption spectra to the measured atmospheric absorption spectra. Inasmuch as the absorbance from atmospheric trace gases is usually very weak, with optical densities in the range from 10(-5) to 10(-3), interference caused by the occurrence of nonreproducible spectral artifacts often determines the detection limit and the measurement precision. These spectral artifacts bias the least-squares fitting result in two respects. First, spectral artifacts to some extent are falsely interpreted as real absorption, and second, spectral artifacts add nonstatistical noise to spectral residuals, which results in a significant misestimation of the least-squares fitting error. We introduce two new approaches to investigate the evaluation errors of DOAS spectra accurately. The first method, residual inspection by cyclic displacement, estimates the effect of false interpretation of the artifact structures. The second method applies a statistical bootstrap algorithm to estimate properly the error of fitting, even in cases when the condition of random and independent scatter of the residual signal is not fulfilled. Evaluation of simulated atmospheric measurement spectra shows that a combination of the results of both methods yields a good estimate of the spectra evaluation error to within an uncertainty of ~10%.

  1. Stability of widely tuneable, continuous wave external-cavity quantum cascade laser for absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kasyutich, Vasili L.; Raja Ibrahim, R. K.; Martin, Philip A.

    2010-09-01

    The performance of widely tuneable, continuous wave (cw) external-cavity quantum cascade laser (EC-QCL) has been evaluated for direct absorption spectroscopy measurements of nitric oxide (NO) in the wavenumber range 1872-1958 cm -1 and with a 13.5 cm long optical cell. In order to reduce the absorption measurement errors due to the large variations of laser intensity, normalisation with a reference channel was used. Wavelength stability within the scans was analysed using the Allan plot technique for the reduced wavenumber range of 1892.4-1914.5 cm -1. The Allan variances of the NO absorption peak centres and areas were observed to increase with successive scan averaging for all absorption peaks across the wavelength scan, thus revealing short- and long-term drifts of the cw EC-QCL wavelength between successive scans. As an example application, the cw EC-QCL was used for NO measurements in the exhaust of an atmospheric pressure packed-bed plasma reactor applied to the decomposition of dichloromethane in waste gas streams. Etalon noise was reduced by subtracting a reference spectrum recorded when the plasma was off. The NO limit of detection (SNR = 1) was estimated to be ˜2 ppm at atmospheric pressure in a 20.5 cm long optical cell with a double pass and a single 7 s scan over 1892.4-1914.5 cm -1.

  2. Multiwavelength diode-laser absorption spectroscopy using external intensity modulation by semiconductor optical amplifiers.

    PubMed

    Karagiannopoulos, Solon; Cheadle, Edward; Wright, Paul; Tsekenis, Stylianos; McCann, Hugh

    2012-12-01

    A novel opto-electronic scheme for line-of-sight Near-IR gas absorption measurement based on direct absorption spectroscopy (DAS) is reported. A diode-laser-based, multiwavelength system is designed for future application in nonintrusive, high temporal resolution tomographic imaging of H2O in internal combustion engines. DAS is implemented with semiconductor optical amplifiers (SOAs) to enable wavelength multiplexing and to induce external intensity modulation for phase-sensitive detection. Two overtone water transitions in the Near-IR have been selected for ratiometric temperature compensation to enable concentration measurements, and an additional wavelength is used to account for nonabsorbing attenuation. A wavelength scanning approach was used to evaluate the new modulation technique, and showed excellent absorption line recovery. Fixed-wavelength, time-division-multiplexing operation with SOAs has also been demonstrated. To the best of our knowledge this is the first time SOAs have been used for modulation and switching in a spectroscopic application. With appropriate diode laser selection this scheme can be also used for other chemical species absorption measurements. PMID:23207374

  3. Temperature and multi-species measurements by supercontinuum absorption spectroscopy for IC engine applications.

    PubMed

    Werblinski, Thomas; Engel, Sascha R; Engelbrecht, Rainer; Zigan, Lars; Will, Stefan

    2013-06-01

    The first supercontinuum (SC) absorption spectroscopy measurements showing the feasibility of quantitative temperature evaluation are presented to the best of the authors' knowledge. Temperature and multi-species measurements were carried out at a detection rate of ~2 MHz in a high-temperature flow cell within a temperature range from 450 K to 750 K at 0.22 MPa, representing conditions during the suction and compression stroke in an internal combustion (IC) engine. The broadband SC pulses were temporally dispersed into fast wavelength sweeps, covering the overtone absorption bands 2ν(1), 2ν(3), ν(1) + ν(3) of H2O and 3ν(3) of CO2 in the near-infrared region from 1330 nm to 1500 nm. The temperature information is inferred from the peak ratio of a temperature sensitive (1362.42 nm) and insensitive (1418.91 nm) absorption feature in the ν(1) + ν(3) overtone bands of water. The experimental results are in very good agreement with theoretical intensity ratios calculated from absorption spectra based on HiTran data.

  4. Multiwavelength diode-laser absorption spectroscopy using external intensity modulation by semiconductor optical amplifiers.

    PubMed

    Karagiannopoulos, Solon; Cheadle, Edward; Wright, Paul; Tsekenis, Stylianos; McCann, Hugh

    2012-12-01

    A novel opto-electronic scheme for line-of-sight Near-IR gas absorption measurement based on direct absorption spectroscopy (DAS) is reported. A diode-laser-based, multiwavelength system is designed for future application in nonintrusive, high temporal resolution tomographic imaging of H2O in internal combustion engines. DAS is implemented with semiconductor optical amplifiers (SOAs) to enable wavelength multiplexing and to induce external intensity modulation for phase-sensitive detection. Two overtone water transitions in the Near-IR have been selected for ratiometric temperature compensation to enable concentration measurements, and an additional wavelength is used to account for nonabsorbing attenuation. A wavelength scanning approach was used to evaluate the new modulation technique, and showed excellent absorption line recovery. Fixed-wavelength, time-division-multiplexing operation with SOAs has also been demonstrated. To the best of our knowledge this is the first time SOAs have been used for modulation and switching in a spectroscopic application. With appropriate diode laser selection this scheme can be also used for other chemical species absorption measurements.

  5. [Concentration retrieving method of SO2 using differential optical absorption spectroscopy based on statistics].

    PubMed

    Liu, Bin; Sun, Chang-Ku; Zhang, Chi; Zhao, Yu-Mei; Liu, Jun-Ping

    2011-01-01

    A concentration retrieving method using statistics is presented, which is applied in differential optical absorption spectroscopy (DOAS) for measuring the concentration of SO2. The method uses the standard deviation of the differential absorption to represents the gas concentration. Principle component analysis (PCA) method is used to process the differential absorption spectrum. In the method, the basis data for the concentration retrieval of SO2 is the combination of the PCA processing result, the correlation coefficient, and the standard deviation of the differential absorption. The method is applied to a continuous emission monitoring system (CEMS) with optical path length of 0.3 m. Its measuring range for SO2 concentration is 0-5 800 mg x m(-3). The nonlinear calibration and the temperature compensation for the system were executed. The full scale error of the retrieving concentration is less than 0.7% FS. And the measuring result is -4.54 mg x m(-3) when the concentration of SO2 is zero. PMID:21428087

  6. An x-ray absorption spectroscopy study of Mo oxidation in Pb at elevated temperatures

    SciTech Connect

    Liu, Shanshan; Olive, Daniel; Terry, Jeff; Segre, Carlo U.

    2009-06-30

    The corrosion of fuel cladding and structural materials by lead and lead-bismuth eutectic in the liquid state at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. In this work, lead corrosion studies of molybdenum were performed to investigate the interaction layer as a function of temperature by X-ray absorption spectroscopy. In situ X-ray absorption measurements on a Mo substrate with a 3-6 {micro}m layer of Pb deposited by thermal evaporation were performed at temperatures up to 900 C and at a 15{sup o} angle to the incident X-rays. The changes in the local atomic structure of the corrosion layer are visible in the difference extended X-ray absorption fine structure and the linear combination fitting of the X-ray absorption near-edge structure to as-deposited molybdenum sample and molybdenum oxide (MoO{sub 2} and MoO{sub 3}) standards. The data are consistent with the appearance of MoO{sub 3} in an intermediate temperature range (650-800 C) and the more stable MoO{sub 2} phase dominating at high and low temperatures.

  7. Absorption spectroscopy of wire-array plasma at the non-radiative stage

    NASA Astrophysics Data System (ADS)

    Ivanov, V. V.; Hakel, P.; Mancini, R. C.; Wiewior, P.; Durmaz, T.; Anderson, A.; Astanovitskiy, A.; Chalyy, O.; Altemara, S. D.; Papp, D.; McKee, E.; Chittenden, J. P.; Niasse, N.; Shevelko, A. P.

    2010-11-01

    Absorption spectroscopy was applied to 1 MA wire-array Z-pinches. The 50 TW Leopard laser was coupled with the Zebra generator for x-ray backlighting of wire arrays. Wire-array plasmas were investigated at the ablation and implosion stages. Broadband x-ray radiation from a laser produced Sm plasma was used to backlight Al star wire arrays in the range of 7-9 å. Two time-integrated x-ray conical spectrometers recorded reference and main spectra. The backlighting radiation was separated from the powerful Z-pinch x-ray burst by collimators. A comparison of the backlighting radiation spectra that passed through the plasma with reference spectra indicates absorption lines in the range of 8.2-8.4 å. A plasma density profile was simulated with a 3D resistive MHD code. Simulations with atomic kinetics models derived an electron temperature of Al wire-array plasma.

  8. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa

    PubMed Central

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-01-01

    Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa. PMID:26371317

  9. Melting of iron determined by X-ray absorption spectroscopy to 100 GPa.

    PubMed

    Aquilanti, Giuliana; Trapananti, Angela; Karandikar, Amol; Kantor, Innokenty; Marini, Carlo; Mathon, Olivier; Pascarelli, Sakura; Boehler, Reinhard

    2015-09-29

    Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa.

  10. Measurement of temperature profiles in flames by emission-absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Simmons, F. S.; Arnold, C. B.; Lindquist, G. H.

    1972-01-01

    An investigation was conducted to explore the use of infrared and ultraviolet emission-absorption spectroscopy for determination of temperature profiles in flames. Spectral radiances and absorptances were measured in the 2.7-micron H2O band and the 3064-A OH band in H2/O2 flames for several temperature profiles which were directly measured by a sodium line-reversal technique. The temperature profiles, determined by inversion of the infrared and ultraviolet spectra, showed an average disagreement with line-reversal measurements of 50 K for the infrared and 200 K for the ultraviolet at a temperature of 2600 K. The reasons for these discrepancies are discussed in some detail.

  11. Note: cavity enhanced self-absorption spectroscopy: a new diagnostic tool for light emitting matter.

    PubMed

    Walsh, Anton J; Zhao, Dongfeng; Linnartz, Harold

    2013-02-01

    We introduce the concept of Cavity Enhanced Self-Absorption Spectroscopy (CESAS), a new sensitive diagnostic tool for analyzing light-emitting samples. The technique works without an additional light source and its implementation is straight forward. In CESAS, a sample (plasma, flame, or combustion source) is located in an optically stable cavity consisting of two high reflectivity mirrors, and here it acts both as light source and absorbing medium. A modest portion of the emitted light is trapped inside the cavity, making 10(4)-10(5) cavity round trips while crossing the sample and an artificial augmentation of the path length of the absorbing medium occurs as the light transverses the cavity. Light leaking out of the cavity simultaneously provides emission and absorption features. The performance is illustrated by CESAS results on supersonically expanding pulsed hydrocarbon plasma. We expect CESAS to become a generally applicable analytical tool for real time and in situ diagnostics.

  12. Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Cheng, Yan; Chini, Michael; Wang, Xiaowei; González-Castrillo, Alberto; Palacios, Alicia; Argenti, Luca; Martín, Fernando; Chang, Zenghu

    2016-08-01

    Attosecond science promises to allow new forms of quantum control in which a broadband isolated attosecond pulse excites a molecular wave packet consisting of a coherent superposition of multiple excited electronic states. This electronic excitation triggers nuclear motion on the molecular manifold of potential energy surfaces and can result in permanent rearrangement of the constituent atoms. Here, we demonstrate attosecond transient absorption spectroscopy (ATAS) as a viable probe of the electronic and nuclear dynamics initiated in excited states of a neutral molecule by a broadband vacuum ultraviolet pulse. Owing to the high spectral and temporal resolution of ATAS, we are able to reconstruct the time evolution of a vibrational wave packet within the excited B'Σ1u+ electronic state of H2 via the laser-perturbed transient absorption spectrum.

  13. Measurement of exhaled nitric oxide in beef cattle using tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Roller, C. B.; Holland, B. P.; McMillen, G.; Step, D. L.; Krehbiel, C. R.; Namjou, K.; McCann, P. J.

    2007-03-01

    Measurement of nitric oxide (NO) in the expired breath of crossbred calves received at a research facility was performed using tunable diode laser absorption spectroscopy. Exhaled NO (eNO) concentrations were measured using NO absorption lines at 1912.07 cm-1 and employing background subtraction. The lower detection limit and measurement precision were determined to be ˜330 parts in 1012 per unit volume. A custom breath collection system was designed to collect lower airway breath of spontaneously breathing calves while in a restraint chute. Breath was collected and analyzed from calves upon arrival and periodically during a 42 day receiving period. There was a statistically significant relationship between eNO, severity of bovine respiratory disease (BRD) in terms of number of times treated, and average daily weight gain over the first 15 days postarrival. In addition, breathing patterns and exhaled CO2 showed a statistically significant relationship with BRD morbidity.

  14. Intra-cavity absorption spectroscopy with narrow-ridge microfluidic quantum cascade lasers.

    PubMed

    Belkin, Mikhail A; Loncar, Marko; Lee, Benjamon G; Pflugl, Christian; Audet, Ross; Diehl, Laurent; Capasso, Federico; Bour, David; Corzine, Scott; Hofler, Gloria

    2007-09-01

    We demonstrate microfluidic laser intra-cavity absorption spectroscopy with mid-infrared lambda approximately 9mum quantum cascade lasers. A deepetched narrow ridge waveguide laser is placed in a microfluidic chamber. The evanescent tails of the laser mode penetrate into a liquid on both sides of the ridge. The absorption lines of the liquid modify the laser waveguide loss, resulting in significant changes in the laser emission spectrum and the threshold current. A volume of liquid as small as ~10pL may, in principle, be sufficient for sensing using the proposed technique. This method, similar to the related gas-phase technique, shows promise as a sensitive means of detecting chemicals in small volumes of solutions.

  15. Reflection-Absorption Infrared Spectroscopy of Thin Films Using an External Cavity Quantum Cascade Laser

    SciTech Connect

    Phillips, Mark C.; Craig, Ian M.; Blake, Thomas A.

    2013-02-04

    We present experimental demonstrations using a broadly tunable external cavity quantum cascade laser (ECQCL) to perform Reflection-Absorption InfraRed Spectroscopy (RAIRS) of thin layers and residues on surfaces. The ECQCL compliance voltage was used to measure fluctuations in the ECQCL output power and improve the performance of the RAIRS measurements. Absorption spectra from self-assembled monolayers of a fluorinated alkane thiol and a thiol carboxylic acid were measured and compared with FTIR measurements. RAIRS spectra of the explosive compounds PETN, RDX, and tetryl deposited on gold substrates were also measured. Rapid measurement times and low noise were demonstrated, with < 1E-3 absorbance noise for a 10 second measurement time.

  16. Tunable erbium-doped fiber ring laser for applications of infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ryu, Han Young; Lee, Won-Kyu; Moon, Han Seb; Suh, Ho Suhng

    2007-07-01

    We fabricate a low noise erbium-doped fiber ring laser that can be continuously tuned over 102 nm by insertion of the fiber Fabry-Perot tunable filter (FFP-TF) in the ring cavity with a novel cavity structure and the optimal gain medium length. As an application of this fiber ring laser, we performed the absorption spectroscopy of acetylene (13C2H2) and hydrogen cyanide (H13C14N) and measure the absorption spectra of more than 50 transition lines of these gases with an excellent signal to noise ratio (SNR). The pressure broadening coefficients of four acetylene transition lines are obtained using this fiber ring laser and an external cavity laser diode.

  17. Picosecond time-resolved X-ray absorption spectroscopy of ultrafast aluminum plasmas.

    PubMed

    Audebert, P; Renaudin, P; Bastiani-Ceccotti, S; Geindre, J-P; Chenais-Popovics, C; Tzortzakis, S; Nagels-Silvert, V; Shepherd, R; Matsushima, I; Gary, S; Girard, F; Peyrusse, O; Gauthier, J-C

    2005-01-21

    We have used point-projection K-shell absorption spectroscopy to infer the ionization and recombination dynamics of transient aluminum plasmas. Two femtosecond beams of the 100 TW laser at the LULI facility were used to produce an aluminum plasma on a thin aluminum foil (83 or 50 nm), and a picosecond x-ray backlighter source. The short-pulse backlighter probed the aluminum plasma at different times by adjusting the delay between the two femtosecond driving beams. Absorption x-ray spectra at early times are characteristic of a dense and rather homogeneous plasma. Collisional-radiative atomic physics coupled with hydrodynamic simulations reproduce fairly well the measured average ionization as a function of time. PMID:15698184

  18. Electronic structure investigation of highly compressed aluminum with K edge absorption spectroscopy.

    PubMed

    Benuzzi-Mounaix, A; Dorchies, F; Recoules, V; Festa, F; Peyrusse, O; Levy, A; Ravasio, A; Hall, T; Koenig, M; Amadou, N; Brambrink, E; Mazevet, S

    2011-10-14

    The electronic structure evolution of highly compressed aluminum has been investigated using time resolved K edge x-ray absorption spectroscopy. A long laser pulse (500 ps, I(L)≈8×10(13) W/cm(2)) was used to create a uniform shock. A second ps pulse (I(L)≈10(17)  W/cm(2)) generated an ultrashort broadband x-ray source near the Al K edge. The main target was designed to probe aluminum at reshocked conditions up to now unexplored (3 times the solid density and temperatures around 8 eV). The hydrodynamical conditions were obtained using rear side visible diagnostics. Data were compared to ab initio and dense plasma calculations, indicating potential improvements in either description. This comparison shows that x-ray-absorption near-edge structure measurements provide a unique capability to probe matter at these extreme conditions and severally constrains theoretical approaches currently used. PMID:22107398

  19. Infrared and near infrared transient absorption spectroscopy of molecular free radicals

    SciTech Connect

    Sears, T.J.; Wu, M.; Hall, G.E.; Chang, B.C.; Hansford, G.; Bloch, J.C.; Field, R.W.

    1993-12-31

    The advantages of absorption spectroscopy at low absorbances include a linear relationship between signal size and number of absorbing molecules, line of sight measurement, and easily interpretable lineshape functions. The main disadvantage is due to the necessity of measuring a small change in light intensity, usually in the presence of a strong background, which limits the sensitivity. In this work, recent results obtained using absorption techniques with continuous wave lasers to measure vibrational and electronic spectra in the mid- and near-infrared of small free radicals are reported. The radical of interest was generated by excimer laser photolysis of a chemically stable precursor molecule and detected by measuring the transient decrease in power of a continuous wave probe laser that traversed the photolyzed volume before being imaged onto a detector.

  20. Space Launch System Base Heating Test: Tunable Diode Laser Absorption Spectroscopy

    NASA Technical Reports Server (NTRS)

    Parker, Ron; Carr, Zak; MacLean, Matthew; Dufrene, Aaron; Mehta, Manish

    2016-01-01

    This paper describes the Tunable Diode Laser Absorption Spectroscopy (TDLAS) measurement of several water transitions that were interrogated during a hot-fire testing of the Space Launch Systems (SLS) sub-scale vehicle installed in LENS II. The temperature of the recirculating gas flow over the base plate was found to increase with altitude and is consistent with CFD results. It was also observed that the gas above the base plate has significant velocity along the optical path of the sensor at the higher altitudes. The line-by-line analysis of the H2O absorption features must include the effects of the Doppler shift phenomena particularly at high altitude. The TDLAS experimental measurements and the analysis procedure which incorporates the velocity dependent flow will be described.

  1. Application of terahertz absorption spectroscopy to evaluation of aging variation of medicine.

    PubMed

    Kawase, Masaya; Saito, Tadashi; Ogawa, Masafumi; Uejima, Hideki; Hatsuda, Yasutoshi; Kawanishi, Sonoyo; Hirotani, Yoshihiko; Myotoku, Michiaki; Ikeda, Kenji; Konishi, Hiroki; Iga, Ikumi; Yamakawa, Junji; Nishizawa, Seizi; Yamamoto, Kohji; Tani, Masahiko

    2011-01-01

    The absorption spectra of three kinds of medicines both before and after the expiration date: Amlodin OD(®) (5 mg), Basen OD(®) (0.2 mg) and Gaster D(®) (10 mg) have been measured by terahertz time domain spectroscopy (THz-TDS). All the medicines show some differences in the THz absorption spectra between medicines before and after the expiration dates. X-Ray powder diffraction (XRD) studies of all medicines suggest that the polymorph of the main effective compound is not changed before and after the expiration date. Therefore, the differences in the THz spectra between medicines before and after the expiration dates arise from aging variation of diluting agents and/or from modifications of intermolecular interaction between the effective compounds and diluting agents. PMID:21321447

  2. Ground-based imaging differential optical absorption spectroscopy of atmospheric gases.

    PubMed

    Lohberger, Falko; Hönninger, Gerd; Platt, Ulrich

    2004-08-20

    We describe a compact remote-sensing instrument that permits spatially resolved mapping of atmospheric trace gases by passive differential optical absorption spectroscopy (DOAS) and present our first applications of imaging of the nitrogen dioxide contents of the exhaust plumes of two industrial emitters. DOAS permits the identification and quantification of various gases, e.g., NO2, SO2, and CH2O, from their specific narrowband (differential) absorption structures with high selectivity and sensitivity. With scattered sunlight as the light source, DOAS is used with an imaging spectrometer that is simultaneously acquiring spectral information on the incident light in one spatial dimension (column). The second spatial dimension is scanned by a moving mirror. PMID:15352396

  3. [Measurement of OH radicals in flame with high resolution differential optical absorption spectroscopy].

    PubMed

    Liu, Yu; Liu, Wen-Qing; Kan, Rui-Feng; Si, Fu-Qi; Xu, Zhen-Yu; Hu, Ren-Zhi; Xie, Pin-Hua

    2011-10-01

    The present paper describes a new developed high resolution differential optical absorption spectroscopy instrument used for the measurement of OH radicals in flame. The instrument consists of a Xenon lamp for light source; a double pass high resolution echelle spectrometer with a resolution of 3.3 pm; a multiple-reflection cell of 20 meter base length, in which the light reflects in the cell for 176 times, so the whole path length of light can achieve 3 520 meters. The OH radicals'6 absorption lines around 308 nm were simultaneously observed in the experiment. By using high resolution DOAS technology, the OH radicals in candles, kerosene lamp, and alcohol burner flames were monitored, and their concentrations were also inverted. PMID:22250529

  4. Fluorescence and UV/VIS absorption spectroscopy studies on polymer blend films for photovoltaics

    NASA Astrophysics Data System (ADS)

    van Stam, Jan; Lindqvist, Camilla; Hansson, Rickard; Ericsson, Leif; Moons, Ellen

    2015-08-01

    The quinoxaline-based polymer TQ1 (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5- diyl]) is a promising candidate as electron donor in organic solar cells. In combination with the electron acceptor [6,6]- phenyl-C71- butyric acid methyl ester (PC70BM), TQ1 has resulted in solar cells with power conversion efficiencies of 7 %. We have studied TQ1 films, with and without PC70BM, spin-casted from different solvents, by fluorescence spectroscopy and UV/VIS absorption spectroscopy. We used chloroform (CF), chlorobenzene (CB), and odichlorobenzene (o-DCB) as solvents for the coating solutions and 1-chloronaphthalene (CN) as solvent additive. CN addition has been shown to enhance photo-conversion efficiency of these solar cells. Phase-separation causes lateral domain formation in the films and the domain size depends on the solvent . These morphological differences coincide with changes in the spectroscopic patterns of the films. From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC70BM as quencher. The degree of fluorescence quenching is coupled to the morphology through the distance between TQ1 and PC70BM. Furthermore, if using a bad solvent for PC70BM, morphological regions rich in the fullerene yield emission characteristic for aggregated PC70BM. Clear differences were found, comparing the TQ1:PC70BM blend films casted from different solvents and at different ratios between the donor and acceptor. The morphology also influences the UV/VIS absorption spectra, yielding further information on the composition. The results show that fluorescence and UV/VIS absorption spectroscopy can be used to detect aggregation in blended films and that these methods extend the morphological information beyond the scale accessible with microscopy.

  5. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy.

    PubMed

    Miaja-Avila, L; O'Neil, G C; Uhlig, J; Cromer, C L; Dowell, M L; Jimenez, R; Hoover, A S; Silverman, K L; Ullom, J N

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

  6. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    DOE PAGES

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also presentmore » data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.« less

  7. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy.

    PubMed

    Miaja-Avila, L; O'Neil, G C; Uhlig, J; Cromer, C L; Dowell, M L; Jimenez, R; Hoover, A S; Silverman, K L; Ullom, J N

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  8. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    SciTech Connect

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments.

  9. Laser plasma x-ray source for ultrafast time-resolved x-ray absorption spectroscopy

    PubMed Central

    Miaja-Avila, L.; O'Neil, G. C.; Uhlig, J.; Cromer, C. L.; Dowell, M. L.; Jimenez, R.; Hoover, A. S.; Silverman, K. L.; Ullom, J. N.

    2015-01-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >107 laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

  10. Wavelength modulation spectroscopy--digital detection of gas absorption harmonics based on Fourier analysis.

    PubMed

    Mei, Liang; Svanberg, Sune

    2015-03-20

    This work presents a detailed study of the theoretical aspects of the Fourier analysis method, which has been utilized for gas absorption harmonic detection in wavelength modulation spectroscopy (WMS). The lock-in detection of the harmonic signal is accomplished by studying the phase term of the inverse Fourier transform of the Fourier spectrum that corresponds to the harmonic signal. The mathematics and the corresponding simulation results are given for each procedure when applying the Fourier analysis method. The present work provides a detailed view of the WMS technique when applying the Fourier analysis method.

  11. A quality control technique based on UV-VIS absorption spectroscopy for tequila distillery factories

    NASA Astrophysics Data System (ADS)

    Barbosa Garcia, O.; Ramos Ortiz, G.; Maldonado, J. L.; Pichardo Molina, J.; Meneses Nava, M. A.; Landgrave, Enrique; Cervantes, M. J.

    2006-02-01

    A low cost technique based on the UV-VIS absorption spectroscopy is presented for the quality control of the spirit drink known as tequila. It is shown that such spectra offer enough information to discriminate a given spirit drink from a group of bottled commercial tequilas. The technique was applied to white tequilas. Contrary to the reference analytic methods, such as chromatography, for this technique neither special personal training nor sophisticated instrumentations is required. By using hand-held instrumentation this technique can be applied in situ during the production process.

  12. The determination of aluminum, copper, iron, and lead in glycol formulations by atomic absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Initial screening tests and the results obtained in developing procedures to determine Al, Cu, Fe, and Pb in glycol formulations are described. Atomic absorption completion was selected for Cu, Fe and Pb, and after comparison with emission spectroscopy, was selected for Al also. Before completion, carbon, iron, and lead are extracted with diethyl dithio carbamate (DDC) into methyl isobutyl ketone (MIBK). Aluminum was also extracted into MIBK using 8-hydroxyquinoline as a chelating agent. As little as 0.02 mg/l carbon and 0.06 mg/l lead or iron may be determined in glycol formulations. As little as 0.3 mg/l aluminum may be determined.

  13. Determining beryllium in drinking water by graphite furnace atomic absorption spectroscopy

    SciTech Connect

    Lytle, D.A.; Schock, M.R.; Dues, N.R.; Doerger, J.U.

    1993-01-01

    A direct graphite furnace atomic absorption spectroscopy method for the analysis of beryllium in drinking water has been derived from a method for determining beryllium in urine. Ammonium phosphomolybdate and ascorbic acid were employed as matrix modifiers. The matrix modifiers successfully eliminated common chemical interferences in drinking water samples analyzed for beryllium content, as well as interferences encountered during jar testing of beryllium removal by alum coagulation. The method proved to be a simple, accurate, and precise alternative to the method of standard additions. Method detection limit was 0.09 microgram/l, with a linear calibration range of 0 to 6 microgram/l.

  14. X-Ray Absorption Spectroscopy Study of Copper Doped ZnO Thin Films

    SciTech Connect

    Ma Qing

    2007-02-02

    X-ray absorption spectroscopy technique is used to study copper-doped ZnO thin films, prepared by pulsed-laser deposition. The samples with various doping levels are examined. It is found that the samples contain metallic clusters with the sizes {<=} 2 nm as well as Cu1+ and Cu2+ states. The Cu1+ states exist as stable oxide clusters, while the Cu2+ ones participate in the ZnO lattice some of which may be pertaining to the surfaces of the Cu clusters as well. The copper clusters of {approx}1 nm are unstable and fragment under monochromatic x-ray beam illumination.

  15. Total Absorption Spectroscopy Study of (92)Rb Decay: A Major Contributor to Reactor Antineutrino Spectrum Shape.

    PubMed

    Zakari-Issoufou, A-A; Fallot, M; Porta, A; Algora, A; Tain, J L; Valencia, E; Rice, S; Bui, V M; Cormon, S; Estienne, M; Agramunt, J; Äystö, J; Bowry, M; Briz, J A; Caballero-Folch, R; Cano-Ott, D; Cucoanes, A; Elomaa, V-V; Eronen, T; Estévez, E; Farrelly, G F; Garcia, A R; Gelletly, W; Gomez-Hornillos, M B; Gorlychev, V; Hakala, J; Jokinen, A; Jordan, M D; Kankainen, A; Karvonen, P; Kolhinen, V S; Kondev, F G; Martinez, T; Mendoza, E; Molina, F; Moore, I; Perez-Cerdán, A B; Podolyák, Zs; Penttilä, H; Regan, P H; Reponen, M; Rissanen, J; Rubio, B; Shiba, T; Sonzogni, A A; Weber, C

    2015-09-01

    The antineutrino spectra measured in recent experiments at reactors are inconsistent with calculations based on the conversion of integral beta spectra recorded at the ILL reactor. (92)Rb makes the dominant contribution to the reactor antineutrino spectrum in the 5-8 MeV range but its decay properties are in question. We have studied (92)Rb decay with total absorption spectroscopy. Previously unobserved beta feeding was seen in the 4.5-5.5 region and the GS to GS feeding was found to be 87.5(25)%. The impact on the reactor antineutrino spectra calculated with the summation method is shown and discussed. PMID:26382674

  16. Iron location in O-carboxymethyl chitosans determined by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Klepka, Marcin T.; Lawniczak-Jablonska, Krystyna; Wolska, Anna; Slawska-Waniewska, Anna; Rodrigues, Clóvis A.; Lorini, Josiane; Cruz, Karianne Araujo da

    2011-01-01

    Chitosans represent a class of functional natural polymers. Their unique attribute is the capability to bind metal ions into their structure. This property can be exploited in many biomedical applications, but before that, some questions about metal binding mechanism must be answered. O-carboxymethyl chitosans with accumulated Fe atoms were studied by X-ray absorption spectroscopy. It was shown that iron bonding depends on the technological processes used in chitosan production. The applied technology allows for the selective introduction of either oxygen alone or of nitrogen and oxygen into the nearest neighbourhood of Fe. Therefore, it is possible to control the surroundings of a metal atom depending on requirements.

  17. [Real-time forecasting model for monitoring pollutant with differential optical absorption spectroscopy].

    PubMed

    Li, Su-Wen; Liu, Wen-Qing; Xie, Pin-Hua; Wang, Feng-Sui; Yang, Yi-Jun

    2009-11-01

    For real-time and on-line monitoring DOAS (differential optical absorption spectroscopy) system, a model based on an improved Elman network for monitoring pollutant concentrations was proposed. In order to reduce the systematical complexity, the forecasting factors have been obtained based on the step-wise regression method. The forecasting factors were current concentrations, temperature and relative humidity, and wind speed and wind direction. The dynamic back propagation (BP) algorithm was used for creating training set. The experiment results show that the predicted value follows the real well. So the modified Elman network can meet the demand of DOAS system's real time forecasting.

  18. Quantum cascade laser absorption spectroscopy as a plasma diagnostic tool: an overview.

    PubMed

    Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B; Röpcke, Jürgen

    2010-01-01

    The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry.

  19. An x-ray absorption spectroscopy study of Cd binding onto a halophilic archaeon

    NASA Astrophysics Data System (ADS)

    Showalter, Allison R.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Bunker, Bruce A.

    2016-05-01

    X-ray absorption spectroscopy (XAS) and cadmium (Cd) isotherm experiments determine how Cd adsorbs to the surface of halophilic archaeon Halobacterium noricense. This archaeon, isolated from the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico could be involved with the transport of toxic metals stored in the transuranic waste in the salt mine. The isotherm experiments show that adsorption is relatively constant across the tolerable pH range for H. noricense. The XAS results indicate that Cd adsorption occurs predominately via a sulfur site, most likely sulfhydryl, with the same site dominating all measured pH values.

  20. Thermal Expansion Behaviour of Silver Examined by Extended X-Ray Absorption Fine Structure Spectroscopy

    SciTech Connect

    Dubiel, M.; Chasse, A.; Haug, J.; Schneider, R.; Kruth, H.

    2007-02-02

    EXAFS (extended X-ray absorption fine structure) investigations are reported concerning the thermal expansion behaviour of silver in an extended range of temperature from 10 K to about 950 K measured in transmission mode. Both the ratio method and an EXAFS fitting procedure were applied to reveal the temperature dependence of EXAFS parameters. Models based on quantum and classical thermodynamic perturbation theory have been used to interpret experimental data and compared to XRD (X-ray diffraction) results of bulk silver material. The description of thermodynamic data of thermal expansion of silver in the complete range of temperature by EXAFS Spectroscopy was successful by first calculations using third order quantum perturbation theory.

  1. Direct MD Simulations of Terahertz Absorption and 2D Spectroscopy Applied to Explosive Crystals.

    PubMed

    Katz, G; Zybin, S; Goddard, W A; Zeiri, Y; Kosloff, R

    2014-03-01

    A direct molecular dynamics simulation of the THz spectrum of a molecular crystal is presented. A time-dependent electric field is added to a molecular dynamics simulation of a crystal slab. The absorption spectrum is composed from the energy dissipated calculated from a series of applied pulses characterized by a carrier frequency. The spectrum of crystalline cyclotrimethylenetrinitramine (RDX) and triacetone triperoxide (TATP) were simulated with the ReaxFF force field. The proposed direct method avoids the linear response and harmonic approximations. A multidimensional extension of the spectroscopy is suggested and simulated based on the nonlinear response to a single polarized pulse of radiation in the perpendicular polarization direction. PMID:26274066

  2. Total Absorption Spectroscopy Study of 92Rb Decay: A Major Contributor to Reactor Antineutrino Spectrum Shape

    NASA Astrophysics Data System (ADS)

    Zakari-Issoufou, A.-A.; Fallot, M.; Porta, A.; Algora, A.; Tain, J. L.; Valencia, E.; Rice, S.; Bui, V. M.; Cormon, S.; Estienne, M.; Agramunt, J.; ńystö, J.; Bowry, M.; Briz, J. A.; Caballero-Folch, R.; Cano-Ott, D.; Cucoanes, A.; Elomaa, V.-V.; Eronen, T.; Estévez, E.; Farrelly, G. F.; Garcia, A. R.; Gelletly, W.; Gomez-Hornillos, M. B.; Gorlychev, V.; Hakala, J.; Jokinen, A.; Jordan, M. D.; Kankainen, A.; Karvonen, P.; Kolhinen, V. S.; Kondev, F. G.; Martinez, T.; Mendoza, E.; Molina, F.; Moore, I.; Perez-Cerdán, A. B.; Podolyák, Zs.; Penttilä, H.; Regan, P. H.; Reponen, M.; Rissanen, J.; Rubio, B.; Shiba, T.; Sonzogni, A. A.; Weber, C.

    2015-09-01

    The antineutrino spectra measured in recent experiments at reactors are inconsistent with calculations based on the conversion of integral beta spectra recorded at the ILL reactor. 92Rb makes the dominant contribution to the reactor antineutrino spectrum in the 5-8 MeV range but its decay properties are in question. We have studied 92Rb decay with total absorption spectroscopy. Previously unobserved beta feeding was seen in the 4.5-5.5 region and the GS to GS feeding was found to be 87.5(25)%. The impact on the reactor antineutrino spectra calculated with the summation method is shown and discussed.

  3. Quantum Cascade Laser Absorption Spectroscopy as a Plasma Diagnostic Tool: An Overview

    PubMed Central

    Welzel, Stefan; Hempel, Frank; Hübner, Marko; Lang, Norbert; Davies, Paul B.; Röpcke, Jürgen

    2010-01-01

    The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry. PMID:22163581

  4. Logarithmic conversion of absorption detection in wavelength modulation spectroscopy with a current-modulated diode laser.

    PubMed

    Wang, Yuntao; Cai, Haiwen; Geng, Jianxin; Fang, Zujie

    2009-07-20

    Logarithmic-conversion data processing used in wavelength modulation spectroscopy (WMS) with a current-modulated diode laser as its source is analyzed and compared with second-to-first ratio detection. Analytic Fourier coefficients of logarithmic-converted residual amplitude modulation (RAM) of a light source are given. An experimental setup for methane absorption detection at 1650 nm is described. It is shown theoretically and experimentally that logarithmic-converted WMS cannot only eliminate the fluctuation of received light power, but also improve the signal-to-noise ratio significantly. PMID:19623220

  5. Infrared laser absorption spectroscopy of the ν7 band of jet-cooled iron pentacarbonyl

    NASA Astrophysics Data System (ADS)

    Loroño, M.; Cruse, H. A.; Davies, P. B.

    2000-02-01

    The ν7 parallel band of Fe(CO) 5 has been measured in the 620 cm -1 region using high-resolution diode laser absorption spectroscopy in a free jet expansion. A comparison with simulated band profiles indicated a rotational temperature of between 2 and 3 K in the jet. At these temperatures the K-structure of the Q-branch is partly resolved. The following molecular parameters were obtained: ν0=619.95747(12) cm -1, B7=0.026743(2) cm -1, A7=0.030721(1) cm -1. Approximate values of the quartic centrifugal distortion constants were also obtained from fitting the spectra.

  6. Tunable Diode Laser Absorption Spectroscopy of Metastable Atoms in Dusty Plasmas

    SciTech Connect

    Hoang Tung Do; Hippler, Rainer

    2008-09-07

    Spatial density profile of neon metastable produced in dusty plasma was investigated by means of tunable diode laser absorption spectroscopy. The line averaged measured density drops about 30% with the presence of dust particles. The observations provide evidence for a significant interaction between atoms and powder particles which are important for energy transfer from plasma to particles. The power per unit area absorbed by dust particles due to the collision of metastable atoms with dust particle surface is about some tens of mW/m{sup 2}.

  7. X-Ray Absorption Spectroscopy of Cuprous-Thiolate Clusters in Saccharomyces Cerevisiae Metallothionein

    SciTech Connect

    Zhang, L.; Pickering, I.J.; Winge, D.R.; George, G.N.

    2009-05-28

    Copper (Cu) metallothioneins are cuprous-thiolate proteins that contain multimetallic clusters, and are thought to have dual functions of Cu storage and Cu detoxification. We have used a combination of X-ray absorption spectroscopy (XAS) and density-functional theory (DFT) to investigate the nature of Cu binding to Saccharomyces cerevisiae metallothionein. We found that the XAS of metallothionein prepared, containing a full complement of Cu, was quantitatively consistent with the crystal structure, and that reconstitution of the apo-metallothionein with stoichiometric Cu results in the formation of a tetracopper cluster, indicating cooperative binding of the Cu ions by the metallothionein.

  8. Two attosecond pulse transient absorption spectroscopy and extraction of the instantaneous AC Stark shift in helium

    NASA Astrophysics Data System (ADS)

    Bækhøj, Jens E.; Bojer Madsen, Lars

    2016-07-01

    In two attosecond pulse absorption spectroscopy (TAPAS) the use of two attosecond XUV pulses allows the extraction of atomic and molecular quantum mechanical dipole phases from spectroscopic measurements. TAPAS relies on interference between processes that individually only include a single XUV photon, and therefore does not rely on high intensity attosecond pulses. To show the usefulness and limitations of the TAPAS method we investigate its capability of capturing the instantaneous AC Stark shift induced by a midinfrared 3200 nm pulse in the | 1{{s}}2{{p}}> state of helium.

  9. [Real-time forecasting model for monitoring pollutant with differential optical absorption spectroscopy].

    PubMed

    Li, Su-Wen; Liu, Wen-Qing; Xie, Pin-Hua; Wang, Feng-Sui; Yang, Yi-Jun

    2009-11-01

    For real-time and on-line monitoring DOAS (differential optical absorption spectroscopy) system, a model based on an improved Elman network for monitoring pollutant concentrations was proposed. In order to reduce the systematical complexity, the forecasting factors have been obtained based on the step-wise regression method. The forecasting factors were current concentrations, temperature and relative humidity, and wind speed and wind direction. The dynamic back propagation (BP) algorithm was used for creating training set. The experiment results show that the predicted value follows the real well. So the modified Elman network can meet the demand of DOAS system's real time forecasting. PMID:20101985

  10. Transient absorption spectroscopy detection of sensitized delayed fluorescence in chiral benzophenone/naphthalene systems

    NASA Astrophysics Data System (ADS)

    Bonancía, Paula; Jiménez, M. Consuelo; Miranda, Miguel A.

    2011-10-01

    Transient absorption spectroscopy has proven to be a powerful tool to investigate the formation and decay of excited singlet states upon triplet-triplet annihilation, following T-T energy transfer from a selectively excited sensitizer. Thus, upon selective excitation of benzophenone (BZP) by laser flash photolysis (LFP) at λ = 355 nm in the presence of naphthalene (NPT), a negative band centered at 340 nm has been detected, with growth and decay in the microsecond timescale. It has been assigned to the P-type NPT delayed-fluorescence. In the case of chiral BZP/NPT systems, stereodifferentiation has been observed in the kinetics of the involved photophysical processes.

  11. Determination of heavy metals in solid emission and immission samples using atomic absorption spectroscopy

    SciTech Connect

    Fara, M.; Novak, F.

    1995-12-01

    Both flame and electrothermal methods of atomic absorption spectroscopy (AAS) have been applied to the determination of Al, As, Be, Ca, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, TI, Se, V and Zn in emission and emission (deposition) samples decomposed in open PTFE test-tubes by individual fuming-off hydrofluoric, perchloroic and nitric acid. An alternative hydride technique was also used for As and Se determination and Hg was determined using a self-contained AAS analyzer. A graphite platform proved good to overcome non-spectral interferences in AAS-ETA. Methods developed were verified by reference materials (inc. NBS 1633a).

  12. Automated system for x-ray absorption spectroscopy of nanoparticle nucleation and growth

    SciTech Connect

    Calvin, S.; Carpenter, E.E.; Cestone, V.; Kurihara, L.K.; Harris, V.G.; Brown, E.C.

    2005-01-01

    X-ray absorption spectroscopy (XAS) is a useful tool for studying nanoparticle synthesis and growth. Described here is a system for automating synthesis and data collection, allowing time-resolved XAS measurements at a synchrotron to be accurately combined with measurements made under identical conditions elsewhere, and promising the ability to use XAS with experiments in combinatorial chemistry. The primary components of this system are a commercial parallel processor and a custom flow cell. The system has been used to collect data on the synthesis of iron oxides from iron(II) acetylacetonate.

  13. Sensing atmospheric reactive species using light emitting diode by incoherent broadband cavity enhanced absorption spectroscopy.

    PubMed

    Yi, Hongming; Wu, Tao; Wang, Guishi; Zhao, Weixiong; Fertein, Eric; Coeur, Cécile; Gao, Xiaoming; Zhang, Weijun; Chen, Weidong

    2016-05-16

    We overview our recent progress in the developments and applications of light emitting diode-based incoherent broadband cavity enhanced absorption spectroscopy (LED-IBBCEAS) techniques for real-time optical sensing chemically reactive atmospheric species (HONO, NO3, NO2) in intensive campaigns and in atmospheric simulation chamber. New application of optical monitoring of NO3 concentration-time profile for study of the NO3-initiated oxidation process of isoprene in a smog chamber is reported. PMID:27409951

  14. Combination of optical emission and broadband absorption spectroscopy for diagnostics of HID lamps

    NASA Astrophysics Data System (ADS)

    Ruhrmann, Cornelia; Bergner, Andre; Hoebing, Thomas; Mentel, Juergen; Awakowicz, Peter

    2011-11-01

    HID lamps are used in several fields of application e.g. in street or automotive lighting as well as in video projection systems. Most of these lamps contain mercury to generate a high pressure buffer gas filling and thereby an appropriate power input into the arc. Due to its toxicity, the replacement of mercury is of particular interest in recent research of HID lamps. Currently, the emission coefficient of a mercury double line is used to determine the plasma temperature and thereby particle densities inside an HID lamp. A combination of optical emission and broadband absorption spectroscopy allows evaluating the plasma temperature without the need of mercury emission lines. It offers in combination with emission spectroscopy the possibility to calculate the total density of atoms and ions of elements also inside a mercury-free HID lamp. In this paper the measuring method is applied to a mercury-containing special research HID lamp (YAG lamp), seeded with rare earth iodines.

  15. In situ characterization of few-cycle laser pulses in transient absorption spectroscopy.

    PubMed

    Blättermann, Alexander; Ott, Christian; Kaldun, Andreas; Ding, Thomas; Stooß, Veit; Laux, Martin; Rebholz, Marc; Pfeifer, Thomas

    2015-08-01

    Attosecond transient absorption spectroscopy has thus far been lacking the capability to simultaneously characterize the intense laser pulses at work within a time-resolved quantum-dynamics experiment. However, precise knowledge of these pulses is key to extracting quantitative information in strong-field highly nonlinear light-matter interactions. Here, we introduce and experimentally demonstrate an ultrafast metrology tool based on the time-delay-dependent phase shift imprinted on a strong-field-driven resonance. Since we analyze the signature of the laser pulse interacting with the absorbing spectroscopy target, the laser pulse duration and intensity are determined in situ. As we also show, this approach allows for the quantification of time-dependent bound-state dynamics in one and the same experiment. In the future, such experimental data will facilitate more precise tests of strong-field dynamics theories.

  16. Wavelet transform based on the optimal wavelet pairs for tunable diode laser absorption spectroscopy signal processing.

    PubMed

    Li, Jingsong; Yu, Benli; Fischer, Horst

    2015-04-01

    This paper presents a novel methodology-based discrete wavelet transform (DWT) and the choice of the optimal wavelet pairs to adaptively process tunable diode laser absorption spectroscopy (TDLAS) spectra for quantitative analysis, such as molecular spectroscopy and trace gas detection. The proposed methodology aims to construct an optimal calibration model for a TDLAS spectrum, regardless of its background structural characteristics, thus facilitating the application of TDLAS as a powerful tool for analytical chemistry. The performance of the proposed method is verified using analysis of both synthetic and observed signals, characterized with different noise levels and baseline drift. In terms of fitting precision and signal-to-noise ratio, both have been improved significantly using the proposed method.

  17. A Complete Overhaul of the Electron Energy-Loss Spectroscopy and X-Ray Absorption Spectroscopy Database: eelsdb.eu.

    PubMed

    Ewels, Philip; Sikora, Thierry; Serin, Virginie; Ewels, Chris P; Lajaunie, Luc

    2016-06-01

    The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration. The submission process has been streamlined to encourage spectrum submissions and the new design gives greater emphasis on contributors' original work by highlighting their papers. With numerous new filters and a powerful search function, it is now simple to explore the database of several hundred EELS and XAS spectra. Interactive plots allow spectra to be overlaid, facilitating online comparison. An application-programming interface has been created, allowing external tools and software to easily access the information held within the database. In addition to the database itself, users can post and manage job adverts and read the latest news and events regarding the EELS and XAS communities. In accordance with the ongoing drive toward open access data increasingly demanded by funding bodies, the database will facilitate open access data sharing of EELS and XAS spectra. PMID:26899024

  18. A Complete Overhaul of the Electron Energy-Loss Spectroscopy and X-Ray Absorption Spectroscopy Database: eelsdb.eu.

    PubMed

    Ewels, Philip; Sikora, Thierry; Serin, Virginie; Ewels, Chris P; Lajaunie, Luc

    2016-06-01

    The electron energy-loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) database has been completely rewritten, with an improved design, user interface, and a number of new tools. The database is accessible at https://eelsdb.eu/ and can now be used without registration. The submission process has been streamlined to encourage spectrum submissions and the new design gives greater emphasis on contributors' original work by highlighting their papers. With numerous new filters and a powerful search function, it is now simple to explore the database of several hundred EELS and XAS spectra. Interactive plots allow spectra to be overlaid, facilitating online comparison. An application-programming interface has been created, allowing external tools and software to easily access the information held within the database. In addition to the database itself, users can post and manage job adverts and read the latest news and events regarding the EELS and XAS communities. In accordance with the ongoing drive toward open access data increasingly demanded by funding bodies, the database will facilitate open access data sharing of EELS and XAS spectra.

  19. X-ray absorption spectroscopy on magnetic nanoscale systems for modern applications

    NASA Astrophysics Data System (ADS)

    Schmitz-Antoniak, Carolin

    2015-06-01

    X-ray absorption spectroscopy facilitated by state-of-the-art synchrotron radiation technology is presented as a powerful tool to study nanoscale systems, in particular revealing their static element-specific magnetic and electronic properties on a microscopic level. A survey is given on the properties of nanoparticles, nanocomposites and thin films covering a broad range of possible applications. It ranges from the ageing effects of iron oxide nanoparticles in dispersion for biomedical applications to the characterisation on a microscopic level of nanoscale systems for data storage devices. In this respect, new concepts for electrically addressable magnetic data storage devices are highlighted by characterising the coupling in a BaTiO3/CoFe2O4 nanocomposite as prototypical model system. But classical magnetically addressable devices are also discussed on the basis of tailoring the magnetic properties of self-assembled ensembles of FePt nanoparticles for data storage and the high-moment material Fe/Cr/Gd for write heads. For the latter cases, the importance is emphasised of combining experimental approaches in x-ray absorption spectroscopy with density functional theory to gain a more fundamental understanding.

  20. Glucose sensing by waveguide-based absorption spectroscopy on a silicon chip

    PubMed Central

    Ryckeboer, E.; Bockstaele, R.; Vanslembrouck, M.; Baets, R.

    2014-01-01

    In this work, we demonstrate in vitro detection of glucose by means of a lab-on-chip absorption spectroscopy approach. This optical method allows label-free and specific detection of glucose. We show glucose detection in aqueous glucose solutions in the clinically relevant concentration range with a silicon-based optofluidic chip. The sample interface is a spiral-shaped rib waveguide integrated on a silicon-on-insulator (SOI) photonic chip. This SOI chip is combined with micro-fluidics in poly(dimethylsiloxane) (PDMS). We apply aqueous glucose solutions with different concentrations and monitor continuously how the transmission spectrum changes due to glucose. Based on these measurements, we derived a linear regression model, to relate the measured glucose spectra with concentration with an error-of-fitting of only 1.14 mM. This paper explains the challenges involved and discusses the optimal configuration for on-chip evanescent absorption spectroscopy. In addition, the prospects for using this sensor for glucose detection in complex physiological media (e.g. serum) is briefly discussed. PMID:24877021

  1. Novel focal point multipass cell for absorption spectroscopy on small sized atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Winter, Jörn; Hänel, Mattis; Reuter, Stephan

    2016-04-01

    A novel focal point multipass cell (FPMPC) was developed, in which all laser beams propagate through a common focal point. It is exclusively constructed from standard optical elements. Main functional elements are two 90∘ off-axis parabolic mirrors and two retroreflectors. Up to 17 laser passes are demonstrated with a near-infrared laser beam. The number of laser passes is precisely adjustable by changing the retroreflector distance. At the focal point beams are constricted to fit through an aperture of 0.8 mm. This is shown for 11 beam passes. Moreover, the fast temporal response of the cell permits investigation of transient processes with frequencies up to 10 MHz. In order to demonstrate the applicability of the FPMPC for atmospheric pressure plasma jets, laser absorption spectroscopy on the lowest excited argon state (1s5) was performed on a 1 MHz argon atmospheric pressure plasma jet. From the obtained optical depth profiles, the signal-to-noise ratio was deduced. It is shown that an elevation of the laser pass number results in an proportional increase of the signal-to-noise ratio making the FPMPC an appropriate tool for absorption spectroscopy on plasmas of small dimensions.

  2. Total Absorption Spectroscopy of the 137Xe, 137I, and 92Rb β-Decays

    NASA Astrophysics Data System (ADS)

    Rasco, B. C.; Fijałkowska, A.; Karny, M.; Rykaczewski, K. P.; Wolińska-Cichocka, M.; Goetz, K. C.; Grzywacz, R. K.; Gross, C. J.; Miernik, K.; Stracener, D.

    2015-10-01

    The NaI(Tl) based Modular Total Absorption Spectrometer (MTAS) was constructed to measure improved β-decay feeding patterns from neutron-rich nuclei. It is difficult to measure β-decay feeding intensities with high precision γ-ray measurements due to the low efficiency of high precision detectors. There are several important applications of improved measurements of β-decay feeding patterns by total absorption spectroscopy; improve understanding of elemental abundances in the universe, help with stockpile stewardship, contribute to understanding of underlying nuclear structure, and improve β-decay feeding measurements to calculate accurately the νe spectra needed to evaluate precisely reactor neutrino measurements. We present β-decay feeding results for two ``priority one'' measurements, 137Xe and 137I, and for 92Rb, which is a large individual contributor to the νe uncertainty of the reactor anomaly. In addition to β- γ decays, 137I has a β-neutron decay channel which is measurable in MTAS. We will demonstrate techniques for analyzing MTAS γ-decay data. We will also describe β and neutron spectroscopy in MTAS. This work was supported by the US DOE by Award No. DE-FG02- 96ER40978 and by US DOE, Office of Nuclear Physics.

  3. Evolution of Silver Nanoparticles in the Rat Lung Investigated by X-ray Absorption Spectroscopy

    PubMed Central

    2015-01-01

    Following a 6-h inhalation exposure to aerosolized 20 and 110 nm diameter silver nanoparticles, lung tissues from rats were investigated with X-ray absorption spectroscopy, which can identify the chemical state of silver species. Lung tissues were processed immediately after sacrifice of the animals at 0, 1, 3, and 7 days post exposure and the samples were stored in an inert and low-temperature environment until measured. We found that it is critical to follow a proper processing, storage and measurement protocol; otherwise only silver oxides are detected after inhalation even for the larger nanoparticles. The results of X-ray absorption spectroscopy measurements taken in air at 85 K suggest that the dominating silver species in all the postexposure lung tissues were metallic silver, not silver oxide, or solvated silver cations. The results further indicate that the silver nanoparticles in the tissues were transformed from the original nanoparticles to other forms of metallic silver nanomaterials and the rate of this transformation depended on the size of the original nanoparticles. We found that 20 nm diameter silver nanoparticles were significantly modified after aerosolization and 6-h inhalation/deposition, whereas larger, 110 nm diameter nanoparticles were largely unchanged. Over the seven-day postexposure period the smaller 20 nm silver nanoparticles underwent less change in the lung tissue than the larger 110 nm silver nanoparticles. In contrast, silica-coated gold nanoparticles did not undergo any modification processes and remained as the initial nanoparticles throughout the 7-day study period. PMID:25517690

  4. Time-resolved postdischarge absolute silicon monoxide density measurement by resonant absorption spectroscopy in a nonthermal atmospheric plasma

    SciTech Connect

    Motret, Olivier; Coursimault, Fabien; Pouvesle, Jean-Michel

    2006-11-01

    In this study we present the technique of resonant absorption spectroscopy diagnostic developed to estimate the density of silicon monoxide (SiO) molecules during the postdischarge of an atmospheric dielectric barrier discharge plasma. The ultraviolet (0,0) rovibrational band of the SiO(A {sup 1}{pi}-X {sup 1}{sigma}{sup +}) electronic transition was investigated. Effective values of absorption coefficient and absorption cross section for the rotational transitions under consideration were calculated. The SiO concentration was estimated by comparison between experimental and computed spectra. The self-absorption in the probe reactor was taken into account in the computed spectra.

  5. Exhaust gas monitoring based on absorption spectroscopy in the process industry

    NASA Astrophysics Data System (ADS)

    Zhang, Shuai; Liu, Wen-qing; Zhang, Yu-jun; Shu, Xiao-wen; Kan, Rui-feng; Cui, Yi-ben; He, Ying; Xu, Zhen-yu; Geng, Hui; Liu, Jian-guo

    2009-07-01

    This non-invasive gas monitor for exhaust gas monitoring must has high reliability and requires little maintenance. Monitor for in-situ measurements using tunable diode laser absorption spectroscopy (TDLAS) in the near infrared, can meet these requirements. TDLAS has evolved over the past decade from a laboratory especially to an accepted, robust and reliable technology for trace gas sensing. With the features of tunability and narrow linewidth of the distributed feedback (DFB) diode laser and by precisely tuning the laser output wavelength to a single isolated absorption line of the gas, TDLAS technique can be utilized to measure gas concentration with high sensitivity. Typical applications for monitoring of H2S, NH3, HC1 and HF are described here together by wavelength modulation spectroscopy with second-harmonic(WMS-2F) detection. This paper will illustrate the problems related to on-line applications, in particular, the overfall effects, automatic light intensity correction, temperature correction, which impacted on absorption coefficient and give details of how effect of automatic correction is necessary. The system mainly includes optics and electronics, optical system mainly composed of fiber, fiber coupler and beam expander, the electron part has been placed in safe analysis room not together with the optical part. Laser merely passes through one-meter-long pipes by the fiber coupling technology, so the system itself has anti-explosion. The results of the system are also presented in the end, the system's response time is only 0.5s, and can be achieved below 1×10-5 the detection limit at the volume fraction, it can entirely replace the traditional methods of detection exhaust gas in the process industry.

  6. Electronic structure measurements of metal-organic solar cell dyes using x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, Phillip S.

    The focus of this thesis is twofold: to report the results of X-ray absorption studies of metal-organic dye molecules for dye-sensitized solar cells and to provide a basic training manual on X-ray absorption spectroscopy techniques and data analysis. The purpose of our research on solar cell dyes is to work toward an understanding of the factors influencing the electronic structure of the dye: the choice of the metal, its oxidation state, ligands, and cage structure. First we study the effect of replacing Ru in several common dye structures by Fe. First-principles calculations and X-ray absorption spectroscopy at the C 1s and N 1s edges are combined to investigate transition metal dyes in octahedral and square planar N cages. Octahedral molecules are found to have a downward shift in the N 1s-to-pi* transition energy and an upward shift in C 1s-to-pi* transition energy when Ru is replaced by Fe, explained by an extra transfer of negative charge from Fe to the N ligands compared to Ru. For the square planar molecules, the behavior is more complex because of the influence of axial ligands and oxidation state. Next the crystal field parameters for a series of phthalocyanine and porphyrins dyes are systematically determined using density functional calculations and atomic multiplet calculations with polarization-dependent X-ray absorption spectra. The polarization dependence of the spectra provides information on orbital symmetries which ensures the determination of the crystal field parameters is unique. A uniform downward scaling of the calculated crystal field parameters by 5-30% is found to be necessary to best fit the spectra. This work is a part of the ongoing effort to design and test new solar cell dyes. Replacing the rare metal Ru with abundant metals like Fe would be a significant advance for dye-sensitized solar cells. Understanding the effects of changing the metal centers in these dyes in terms of optical absorption, charge transfer, and electronic

  7. Saturation dynamics and working limits of saturated absorption cavity ringdown spectroscopy.

    PubMed

    Sadiek, Ibrahim; Friedrichs, Gernot

    2016-08-17

    Cavity ringdown spectroscopy (CRDS) in the linear absorption regime is a well-established method for sensitive trace gas detection, but only a few studies have addressed quantitative measurements in the presence of a saturated sample. In fact, saturation is usually avoided in order to escape from the required complex modeling of the saturation process that depends on the characteristics of the absorbing species, its interaction with the surrounding gas as well as on the temporal and spectral characteristics of the cavity excitation. Conversely, the novel saturated-absorption cavity ringdown spectroscopy approach (SCAR/Sat-CRDS) takes advantage of sample saturation in order to allow one to extract both the gas absorption and the empty cavity loss rates from a single ringdown event. Using a new continuous-wave infrared CRD spectrometer equipped with a tunable narrow-bandwidth high-power OPO laser system and a 18 bit digitizer, the transient dynamics of absorption saturation and the working limits of the Sat-CRDS approach in terms of its ability to extract reliable trace gas concentrations have been experimentally studied in this work. Using a strong methane transition as a test case, the excitation power P0 and saturation power PS have been systematically varied to explore a wide range of saturation regimes. At pressures 5 μbar < p < 2 mbar, the saturation intensity revealed a nearly linear pressure dependence showing that non-collisional processes contribute to the overall relaxation. A ratio of P0/PS ≈ 15 turned out to be optimal with working limits of 5 < P0/PS < 300. Moreover, the ratio of the absorption and empty cavity loss rates, γg/γc, has been varied to test the dynamic range of the method. At γg > γc, a pronounced coupling between the two parameters has been observed. Finally, a standard error analysis was performed revealing that the Sat-CRDS approach holds its advantages over conventional CRDS implementations in particular when the attainable

  8. Soft X-Ray Absorption Spectroscopy at an X-ray Free Electron Laser

    NASA Astrophysics Data System (ADS)

    Higley, Daniel; Schlotter, William; Turner, Joshua; Moeller, Stefan; Mitra, Ankush; Tsukamoto, Arata; Marvel, Robert; Haglund, Richard; Durr, Hermann; Stohr, Joachim; Dakovski, Georgi

    2015-03-01

    X-ray free electron lasers, providing coherent, ultrafast, high intensity x-ray pulses, have enabled groundbreaking scattering experiments to probe the atomic structure of materials on femtosecond timescales. Nonetheless, x-ray absorption spectroscopy (XAS), one of the most fundamental and common x-ray techniques practiced at synchrotron light sources, has proven challenging to conduct with satisfactory signal-to-noise levels at soft x-ray energies using free electron laser sources. The ability to routinely collect high quality XAS spectra, especially in a time-resolved manner, will open many new scientific possibilities in the areas of ultrafast demagnetization, phase transitions and chemical dynamics to highlight a few. Here, we report how XAS using total fluorescence yield detection yields high signal-to-noise x-ray absorption spectra at an x-ray free electron laser source. Data were collected over multiple absorption edges on technologically relevant materials. These measurements were recorded on the Soft X-Ray Materials Science instrument at the Linac Coherent Light Source. The results are easily extendable to time-resolved measurements.

  9. Vacuum-UV absorption spectroscopy of interstellar ice analogues. III. Isotopic effects

    NASA Astrophysics Data System (ADS)

    Cruz-Diaz, G. A.; Caro, G. M. Muñoz; Chen, Y.-J.

    2014-04-01

    This paper reports the first measurements of solid-phase vacuum-ultraviolet (VUV) absorption cross-sections of heavy isotopologues present in icy dust grain mantles of dense interstellar clouds and cold circumstellar environments. Pure ices composed of D2O, CD3OD, 13CO2, and 15N15N were deposited at 8 K, a value similar to the coldest dust temperatures in space. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave discharged hydrogen flow lamp as the VUV source. Prior to this work, we have recently submitted a similar study of the light isotopologues (Cruz-Diaz, Muñoz Caro & Chen). The VUV spectra are compared to those of the light isotopologues in the solid phase, and to the gas phase spectra of the same molecules. Our study is expected to improve very significantly the models that estimate the VUV absorption of ice mantles in space, which have often used the available gas phase data as an approximation of the absorption cross sections of the molecular ice components. We will show that this work has also important implications for the estimation of the photodesorption rates per absorbed photon in the ice.

  10. Supercontinuum high-speed cavity-enhanced absorption spectroscopy for sensitive multispecies detection.

    PubMed

    Werblinski, Thomas; Lämmlein, Bastian; Huber, Franz J T; Zigan, Lars; Will, Stefan

    2016-05-15

    Cavity-enhanced absorption spectroscopy is promising for many applications requiring a very high concentration sensitivity but often accompanied by low temporal resolution. In this Letter, we demonstrate a broadband cavity-enhanced absorption spectrometer capable of detection rates of up to 50 kHz, based on a spatially coherent supercontinuum (SC) light source and an in-house-built, high-speed near-infrared spectrograph. The SC spectrometer allows for the simultaneous quantitative detection of CO2, C2H2, and H2O within a spectral range from 1420 to 1570 nm. Using cavity mirrors with a specified reflectivity of R=98.0±0.3% a minimal spectrally averaged absorption coefficient of αmin=1·10-5  cm-1 can be detected at a repetition rate of 50 kHz. PMID:27176993

  11. Probing the Inner Regions of Protoplanetary Disks with CO Absorption Line Spectroscopy

    NASA Astrophysics Data System (ADS)

    McJunkin, Matthew; France, Kevin; Burgh, Eric B.; Herczeg, Gregory J.; Schindhelm, Eric; Brown, Joanna M.; Brown, Alexander

    2013-03-01

    Carbon monoxide (CO) is the most commonly used tracer of molecular gas in the inner regions of protoplanetary disks. CO can be used to constrain the excitation and structure of the circumstellar environment. Absorption line spectroscopy provides an accurate assessment of a single line of sight through the protoplanetary disk system, giving more straightforward estimates of column densities and temperatures than CO and molecular hydrogen (H2) emission line studies. We analyze new observations of ultraviolet CO absorption from the Hubble Space Telescope along the sightlines to six classical T Tauri stars. Gas velocities consistent with the stellar velocities, combined with the moderate-to-high disk inclinations, argue against the absorbing CO gas originating in a fast-moving disk wind. We conclude that the far-ultraviolet observations provide a direct measure of the disk atmosphere or possibly a slow disk wind. The CO absorption lines are reproduced by model spectra with column densities in the range N(12CO) ~ 1016-1018 cm-2 and N(13CO) ~ 1015-1017 cm-2, rotational temperatures T rot(CO) ~ 300-700 K, and Doppler b-values, b ~ 0.5-1.5 km s-1. We use these results to constrain the line-of-sight density of the warm molecular gas (n CO ~ 70-4000 cm-3) and put these observations in context with protoplanetary disk models.

  12. Direct single-mode fibre-coupled miniature White cell for laser absorption spectroscopy.

    PubMed

    Kühnreich, Benjamin; Höh, Matthias; Wagner, Steven; Ebert, Volker

    2016-02-01

    We present the design, setup, and characterization of a new lens-free fibre-coupled miniature White cell for extractive gas analysis using direct tunable diode laser absorption spectroscopy (dTDLAS). The construction of this cell is based on a modified White cell design and allows for an easy variation of the absorption length in the range from 29 cm to 146 cm. The design avoids parasitic absorption paths outside the cell by using direct, lensless fibre coupling and allows small physical cell dimensions and cell volumes. To characterize the cell performance, different H2O and CH4 concentration levels were measured using dTDLAS. Detection limits of 2.5 ppm ⋅ m for CH4 (at 1.65 μm) and 1.3 ppm ⋅ m for H2O (at 1.37 μm) were achieved. In addition, the gas exchange time and its flow-rate dependence were determined for both species and found to be less than 15 s for CH4 and up to a factor of thirteen longer for H2O. PMID:26931838

  13. Direct single-mode fibre-coupled miniature White cell for laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kühnreich, Benjamin; Höh, Matthias; Wagner, Steven; Ebert, Volker

    2016-02-01

    We present the design, setup, and characterization of a new lens-free fibre-coupled miniature White cell for extractive gas analysis using direct tunable diode laser absorption spectroscopy (dTDLAS). The construction of this cell is based on a modified White cell design and allows for an easy variation of the absorption length in the range from 29 cm to 146 cm. The design avoids parasitic absorption paths outside the cell by using direct, lensless fibre coupling and allows small physical cell dimensions and cell volumes. To characterize the cell performance, different H2O and CH4 concentration levels were measured using dTDLAS. Detection limits of 2.5 ppm ṡ m for CH4 (at 1.65 μm) and 1.3 ppm ṡ m for H2O (at 1.37 μm) were achieved. In addition, the gas exchange time and its flow-rate dependence were determined for both species and found to be less than 15 s for CH4 and up to a factor of thirteen longer for H2O.

  14. Initial Results of Optical Vortex Laser Absorption Spectroscopy in the HYPER-I Device

    NASA Astrophysics Data System (ADS)

    Yoshimura, Shinji; Asai, Shoma; Aramaki, Mitsutoshi; Terasaka, Kenichiro; Ozawa, Naoya; Tanaka, Masayoshi; Morisaki, Tomohiro

    2015-11-01

    Optical vortex beams have a potential to make a new Doppler measurement, because not only parallel but perpendicular movement of atoms against the beam axis causes the Doppler shift of their resonant absorption frequency. As the first step of a proof-of-principle experiment, we have performed the optical vortex laser absorption spectroscopy for metastable argon neutrals in an ECR plasma produced in the HYPER-I device at the National Institute for Fusion Science, Japan. An external cavity diode laser (TOPTICA, DL100) of which center wavelength was 696.735 nm in vacuum was used for the light source. The Hermite-Gaussian (HG) beam was converted into the Laguerre-Gaussian (LG) beam (optical vortex) by a computer-generated hologram displayed on the spatial light modulator (Hamamatsu, LCOS-SLM X10468-07). In order to make fast neutral flow across the LG beam, a high speed solenoid valve system was installed on the HYPER-I device. Initial results including the comparison of absorption spectra for HG and LG beams will be presented. This study was supported by NINS young scientists collaboration program for cross-disciplinary study, NIFS collaboration research program (NIFS13KOAP026), and JSPS KAKENHI grant number 15K05365.

  15. Microplasmas as vacuum ultraviolet source for Cl-atom density measurements by resonance absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Martin, Virginie; Bauville, Gérard; Sadeghi, Nader; Puech, Vincent

    2011-11-01

    A micro-hollow cathode discharge was used to generate radiation on the chlorine atom resonance lines. Such radiation could be used to measure, by resonance absorption spectroscopy, the density of chlorine atoms in either ground state (3p5 2P3/2) or in the fine structure metastable state (3p5 2P1/2), which is located at 882.35 cm-1. Among the nine analysed lines in the 132-142 nm spectral region, only those at 137.953 and 139.653 nm, which are strong enough and are not affected by the self-absorption, can be used for the resonance absorption diagnostic of the ground state and the metastable state, respectively. The best operating conditions of the lamp source are 0.5% of Cl2 in argon at 150 mbar and 4 mA discharge current. The measured 800 ± 30 K gas temperature of the microplasma, indicates that under these specific conditions, these two lines are dominantly Doppler broadened. So their profile is Gaussian shaped with full widths at half maximum of (4.7 ± 0.1) × 10-4 nm.

  16. Diagnostics of O Atoms in Inductively Coupled O2 Plasma Employing Vacuum Ultraviolet Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Nagai, Hisao; Hori, Masaru; Goto, Toshio; Hiramatsu, Mineo; Takashima, Seigou

    2002-10-01

    The compact measurement system for absolute densities of oxygen (O) atom has been developed employing a vacuum ultraviolet absorption spectroscopy (VUVAS) technique with a high-pressure micro-discharge hollow cathode lamp (MHCL) as a light source. The influences of self-absorption, emission line profiles of the MHCL, and the background absorption on determination of absolute O atom density were investigated. This system has been applied for measuring of absolute O atom densities in an inductively coupled O2 plasma. O atom densities were estimated to be on the order of 4 x 10^11 -4 x 10^12 cm-3, at an O2 pressure ranging from 1.3 to 26.7 Pa. The behavior of O atom density measured using VUVAS technique was consistent with that obtained by actinometry technique using 844.6 nm and 777.2 nm. Moreover, the lifetime of O atom in the afterglow plasma has been investigated. The decay curves of the O atom density were fitted with exponential functions. The extinction process of O atom in the inductively coupled O2 plasma is discussed.

  17. The Optical Absorption Coefficient of Bean Seeds Investigated Using Photoacoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sanchez-Hernandez, G.; Hernandez-Aguilar, C.; Dominguez-Pacheco, A.; Cruz-Orea, A.; Perez-Reyes, M. C. J.; Martinez, E. Moreno

    2015-06-01

    A knowledge about seed optical parameters is of great relevance in seed technology practice. Such parameters provide information about its absorption and reflectance, which could be useful for biostimulation processes, by light sources, in early stages of seed germination. In the present research photoacoustic spectroscopy (PAS) and the Rosencwaig and Gersho model were used to determine the optical absorption coefficient () of five varieties of bean seeds ( Phaseolus vulgaris L.), of different productive cycles; the seeds were biostimulated by laser treatment to evaluate the effects of biostimulation pre-sowing. It was found that the bean varieties V1, V2, V4, and V5 were optically opaque in the visible spectrum; in the case of the V3 variety, this sample was optically transparent from 680 nm. The varieties of the studied bean seeds showed significant statistical differences in sizes and also in their optical absorption spectra. The biostimulation effects showed that the seed samples with a higher optical penetration length had a positive biostimulation, in the percentage of germination, obtaining an enhancement of 47 % compared to the control sample. The utility of PAS for the optical characterization of seeds has been demonstrated in this study of the laser biostimulation process of this kind of samples.

  18. Laser-induced micro-plasmas in air for incoherent broadband cavity-enhanced absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Ruth, Albert; Dixneuf, Sophie; Orphal, Johannes

    2016-04-01

    Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) is an experimentally straightforward absorption method where the intensity of light transmitted by an optically stable (high finesse) cavity is measured. The technique is realized using broadband incoherent sources of radiation and therefore the amount of light transmitted by a cavity consisting of high reflectance mirrors (typically R > 99.9%) can be low. In order to find an alternative to having an incoherent light source outside the cavity, an experiment was devised, where a laser-induced plasma in ambient air was generated inside a quasi-confocal cavity by a high-power femtosecond laser. The emission from the laser-induced plasma was utilized as pulsed broadband light source. The time-dependent spectra of the light leaking from the cavity were compared with those of the laser-induced plasma emission without the cavity. It was found that the light emission was sustained by the cavity despite the initially large optical losses caused by the laser-induced plasma in the cavity. The light sustained by the cavity was used to measure part of the S1 ← S0 absorption spectrum of gaseous azulene at its vapour pressure at room temperature in ambient air, as well as the strongly forbidden γ-band in molecular oxygen (b1Σ(2,0) ← X3Σ(0,0)).

  19. Impact of atmospheric state uncertainties on retrieved XCO2 columns from laser differential absorption spectroscopy measurements

    NASA Astrophysics Data System (ADS)

    Zaccheo, T. Scott; Pernini, Timothy; Snell, Hilary E.; Browell, Edward V.

    2014-01-01

    This work assesses the impact of uncertainties in atmospheric state knowledge on retrievals of carbon dioxide column amounts (XCO2) from laser differential absorption spectroscopy (LAS) measurements. LAS estimates of XCO2 columns are normally derived not only from differential absorption observations but also from measured or prior knowledge of atmospheric state that includes temperature, moisture, and pressure along the viewing path. In the case of global space-based monitoring systems, it is often difficult if not impossible to provide collocated in situ measurements of atmospheric state for all observations, so retrievals often rely on collocated remote-sensed data or values derived from numerical weather prediction (NWP) models to describe the atmospheric state. A radiative transfer-based simulation framework, combined with representative global upper-air observations and matched NWP profiles, was used to assess the impact of model differences on estimates of column CO2 and O2 concentrations. These analyses focus on characterizing these errors for LAS measurements of CO2 in the 1.57-μm region and of O2 in the 1.27-μm region. The results provide a set of signal-to-noise metrics that characterize the errors in retrieved values associated with uncertainties in atmospheric state and provide a method for selecting optimal differential absorption line pairs to minimize the impact of these noise terms.

  20. Improvement of differential optical absorption spectroscopy with a multichannel scanning technique.

    PubMed

    Brauers, T; Hausmann, M; Brandenburger, U; Dorn, H P

    1995-07-20

    Differential optical absorption spectroscopy (DOAS) of atmospheric trace gases requires the detection of optical densities below 0.1%. Photodiode arrays are used more and more as detectors for DOAS because they allow one to record larger spectral intervals simultaneously. This type of optical multichannel analyzer (OMA), however, shows sensitivity differences among the individual photodiodes (pixels), which are of the order of 1%. To correct for this a sensitivity reference spectrum is usually recorded separately from the trace-gas measurements. Because of atmospheric turbulence the illumination of the detector while an atmospheric absorption spectrum is being recorded is different from the conditions during the reference measurement. As a result the sensitivity patterns do not exactly match, and the corrected spectra still show a residual structure that is due to the sensitivity difference. This effect usually limits the detection of optical densities to approximately 3 × 10(-4). A new method for the removal of the sensitivity pattern is presented in this paper: Scanning the spectrometer by small wavelength increments after each readout of the OMA allows one to separate the OMA-fixed pattern and the wavelength-fixed structures (absorption lines). The properties of the new method and its applicability are demonstrated with simulated spectra. Finally, first atmospheric measurements with a laser long-path instrument demonstrate a detection limit of 3 × 10(-5) of a DOAS experiment. PMID:21052280

  1. Doppler-Free Two-Photon Absorption Spectroscopy of Naphthalene Assisted by AN Optical Frequency Comb

    NASA Astrophysics Data System (ADS)

    Nishiyama, Akiko; Matsuba, Ayumi; Misono, Masatoshi

    2014-06-01

    Optical frequency combs are powerful tools for precise frequency measurements in various wavelength regions. The combs have been applied not only to metrology, but also to molecular spectroscopy. Recently, we studied high resolution spectroscopy of iodine molecule assisted by an optical frequency comb. In the study, the comb was used for frequency calibration of a scanning dye laser. In this study, we developed a frequency calibration scheme with a comb and an acousto-optic modulator to realize more precise frequency measurement in a wide frequency range. And the frequency calibration scheme was applied to Doppler-free two-photon absorption (DFTPA) spectroscopy of naphthalene. Naphthalene is one of the prototypical aromatic molecules, and its detailed structure and dynamics in excited states have been reported. We measured DFTPA spectra of A^1B1u(v4=1) ← X^1A_g(v=0) transition around 298 nm. A part of obtained spectra is shown in the figure. The spectral lines are rotationally resolved and the resolution is about 100 kHz. The horizontal axis was calibrated by the developed frequency calibration system employing the comb. The uncertainties of the calibrated frequencies were determined by the fluctuations of the comb modes which were stabilized to a GPS-disciplined clock. A. Nishiyama, D. Ishikawa, and M. Misono, J. Opt. Soc. Am. B 30, 2107 (2013).

  2. Absorption spectroscopy characterization measurements of a laser-produced Na atomic beam

    SciTech Connect

    Ching, C.H.; Bailey, J.E.; Lake, P.W.; Filuk, A.B.; Adams, R.G.; McKenney, J.

    1996-06-01

    This work describes a pulsed Na atomic beam source developed for spectroscopic diagnosis of a high-power ion diode on the Particle Beam Fusion Accelerator II. The goal is to produce a {approximately} 10{sup 12}-cm{sup {minus}3}-density Na atomic beam that can be injected into the diode acceleration gap to measure electric and magnetic fields from the Stark and Zeeman effects through laser-induced-fluorescence or absorption spectroscopy. A {approximately} 10 ns fwhm, 1.06 {micro}m, 0.6 J/cm{sup 2} laser incident through a glass slide heats a Na-bearing thin film, creating a plasma that generates a sodium vapor plume. A {approximately} 1 {micro}sec fwhm dye laser beam tuned to 5,890 {angstrom} is used for absorption measurement of the Na I resonant doublet by viewing parallel to the film surface. The dye laser light is coupled through a fiber to a spectrograph with a time-integrated CCD camera. A two-dimensional mapping of the Na vapor density is obtained through absorption measurements at different spatial locations. Time-of-flight and Doppler broadening of the absorption with {approximately} 0.1 {angstrom} spectral resolution indicate that the Na neutral vapor temperature is about 0.5 to 2 eV. Laser-induced-fluorescence from {approximately} 1 {times} 10{sup 12}-cm{sup {minus}3} Na I 3s-3p lines observed with a streaked spectrograph provides a signal level sufficient for {approximately} 0.06 {angstrom} wavelength shift measurements in a mock-up of an ion diode experiment.

  3. Quantitative treatment of coarsely binned low-resolution recordings in molecular absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Spietz, Peter; Martín, Juan Carlos Gómez; Burrows, John P.

    2006-06-01

    Optical multichannel detectors like photodiode arrays or CCD cameras combined with grating spectrometers are commonly used as detection systems in quantitative absorption spectroscopy. As a trade-off to broad spectral coverage, banded spectral features are sometimes recorded with insufficient spectral resolution and/or insufficiently fine detector binning. This renders the true physical spectrum of recorded intensities changed by instrumental and spectrum specific artefacts thus impeding comparability between results from different set-ups. In this work, it is demonstrated that in the case of a "well-behaved" - i.e. free of ro-vibronic structure - absorption band like the iodine monoxide IO(4 ← 0) transition, these effects can easily change the apparent peak absorption by up to 50%. Also deviations from the strict linearity (Beer-Lambert's law) between absorber concentration and apparent, i.e. pixelwise optical density occur. This can be critical in studies of chemical kinetics. It is shown that the observed non-linearity can cause errors of up to 50% in the determination of a second order rate coefficient for the IO self reaction. To overcome the problem, a consistent and rigorous integral approach for the treatment of intensity recordings is developed. Linearity between optical density and absorber concentration thereby is re-established. The method is validated using artificial test data as well as experimental data of the IO(4 ← 0) absorption transition, obtained in the context of I 2/O 3 photochemistry studies. The agreement is accurate to within ±2% (test data) and ±3% (experimental data) supporting the validity of the approach. Possible consequences for other spectroscopic work are indicated.

  4. INTEGRAL FIELD SPECTROSCOPY OF AGN ABSORPTION OUTFLOWS: MRK 509 AND IRAS F04250–5718

    SciTech Connect

    Liu, Guilin; Arav, Nahum; Rupke, David S. N.

    2015-11-15

    Ultraviolet (UV) absorption lines provide abundant spectroscopic information enabling the probe of the physical conditions in active galactic nucleus (AGN) outflows, but the outflow radii (and the energetics consequently) can only be determined indirectly. We present the first direct test of these determinations using integral field unit (IFU) spectroscopy. We have conducted Gemini IFU mapping of the ionized gas nebulae surrounding two AGNs, whose outflow radii have been constrained by UV absorption line analyses. In Mrk 509, we find a quasi-spherical outflow with a radius of 1.2 kpc and a velocity of ∼290 km s{sup −1}, while IRAS F04250–5718 is driving a biconical outflow extending out to 2.9 kpc, with a velocity of ∼580 km s{sup −1} and an opening angle of ∼70°. The derived mass flow rate ∼5 and >1 M{sub ⊙} yr{sup −1}, respectively, and the kinetic luminosity ≳1 × 10{sup 41} erg s{sup −1} for both. Adopting the outflow radii and geometric parameters measured from IFU, absorption line analyses would yield mass flow rates and kinetic luminosities in agreement with the above results within a factor of ∼2. We conclude that the spatial locations, kinematics, and energetics revealed by this IFU emission-line study are consistent with pre-existing UV absorption line analyses, providing a long-awaited direct confirmation of the latter as an effective approach for characterizing outflow properties.

  5. A X-Ray Absorption Spectroscopy Study of Manganese Containing Compounds and Photosynthetic Spinach Chloroplasts.

    NASA Astrophysics Data System (ADS)

    Kirby, Jon Allan

    The manganese sites in chloroplasts, long thought to be involved in photosynthetic oxygen evolution have been examined and partially characterized by X-ray Absorption Spectroscopy (XAS) using synchrotron radiation. The local environment about the manganese atoms is estimated from an analysis of the extended X-ray Absorption Fine Structure (EXAFS). Comparisons with and simulations of the manganese EXAFS for several reference compounds leads to a model in which the chloroplast manganese atoms are contained in a binuclear complex similar to di-u-oxo -tetrakis-(2,2'-bipyridine) dimanganese. It is suggested that the partner metal is another manganese. The bridging ligands are most probably oxygen. The remaining manganese ligands are carbon, oxygen, or nitrogen. A roughly linear correlation between the X-ray K edge onset energy and the "coordination charge" of a large number of manganese coordination complexes and compounds has been developed. Entry of the chloroplast manganese edge energy onto this correlation diagram establishes that the active pool of manganese is in an oxidation state greater than +2. If the manganese is in a dimeric form the oxidation states are most probably (II,III). Underlying these results is an extensive data analysis methodology. The method developed involves the use of many different background removal techniques, Fourier transforms and ultimately curve fitting to the modulations in the x-ray absorption cross sections. A large number of model compounds were used to evaluate the analysis method. These analyses are used to show that the two major curve fitting models available are essentially equivalent. Due to its greater versatility, the theoretical model of Teo and Lee is preferred (J. Am. Chem. Soc. (1979), 101, 2815). The results are also used to determine the informational limitations of XAS within the limits of the present understanding of X-ray absorption phenomena by inner shell electrons for atoms with atomic number greater than that

  6. Laser absorption spectroscopy using lead salt and quantum cascade tunable lasers

    NASA Astrophysics Data System (ADS)

    Namjou-Khales, Khosrow

    A new class of analytic instruments based on the detection of chemical species through their spectroscopic absorption 'fingerprint' is emerging based on the use of tunable semiconductor lasers as the excitation source. Advantages of this approach include compact device size, in-line measurement capability, and large signal-bandwidth product. To realize these advantages will require the marriage of laser devices with broad tunability in the infrared spectral range with sophisticated signal processing techniques. Currently, commercial devices based on short wavelength telecommunications type lasers exist but there is potential for much more versatile instruments based on longer wavelength operation. This thesis is divided into two parts. In the first part I present a theoretical analysis and experimental characterization of frequency and wavelength modulation spectroscopy using long wavelength infrared tunable lasers. The experimental measurements were carried out using commercially available lead salt lasers and excellent agreement is found between theoretically predicted performance and experimental verification. The lead salt laser has several important drawbacks as a source in practical instrumentation. In the second part of the thesis I report on the use of the quantum cascade (QC) laser for use in sensitive absorption spectroscopy. The QC laser is a new type of tunable device developed at Bell Laboratories. It features broad infrared tunability, single mode distributed feedback operation, and near room temperature lasing. Using the modulation techniques developed originally for the lead salt lasers, the QC laser was used to detect Nsb2O and other small molecules with absorption features near 8 mum wavelength. The noise equivalent absorption for our measurements was 5× 10sp{-5}/sqrt{Hz} which corresponds to a detection limit of ˜0.25 ppm-m/sqrt{Hz} for Nsb2O. The QC laser sensitivity was found to be limited by excess amplitude modulation in the detection

  7. Understanding the sensitivity of cavity-enhanced absorption spectroscopy: pathlength enhancement versus noise suppression

    NASA Astrophysics Data System (ADS)

    Ouyang, B.; Jones, R. L.

    2012-12-01

    Cavity-enhanced absorption spectroscopy is now widely used as an ultrasensitive technique in observing weak spectroscopic absorptions. Photons inside the cavity are reflected back and forth between the mirrors with reflectivities R close to one and thus (on average) exploit an absorption pathlength L that is 1/(1 - R) longer than a single pass measurement. As suggested by the Beer-Lambert law, this increase in L results in enhanced absorbance A (given by αL with α being the absorption coefficient) which in turn favours the detection of weak absorptions. At the same time, however, only (1 - R) of the incident light can enter the cavity [assuming that mirror transmission T is equal to (1 - R)], so that the reduction in transmitted light intensity Δ I caused by molecular absorption equates to that would be obtained if in fact no cavity were present. The enhancement in A = Δ I/ I, where I is the total transmitted light intensity, achievable from CEAS therefore comes not from an increase in Δ I, but a sharp decrease in I. In this paper, we calculate the magnitudes of these two terms before and after a cavity is introduced, and aim at interpreting the sensitivity improvement offered by cavity-enhanced absorption spectroscopy from this observable-oriented (i.e. Δ I and I) perspective. It is first shown that photon energy stored in the cavity is at best as intense as the input light source, implying that any absorbing sample within the cavity is exposed to the same or even lower light intensity after the cavity is formed. As a consequence, the intensity of the light absorbed or scattered by the sample, which corresponds to the Δ I term aforementioned, is never greater than would be the case in a single pass measurement. It is then shown that while this "numerator" term is not improved, the "denominator" term, I, is reduced considerably; therefore, the increase in contrast ratio Δ I/ I is solely contributed by the attenuation of transmitted background light I and is

  8. In-situ ultra-sensitive infrared absorption spectroscopy of biomolecule interactions in real time with plasmonic nanoantennas

    PubMed Central

    Adato, Ronen; Altug, Hatice

    2013-01-01

    Infrared absorption spectroscopy is a powerful biochemical analysis tool as it extracts detailed molecular structural information in a label-free fashion. Its molecular specificity renders the technique sensitive to the subtle conformational changes exhibited by proteins in response to a variety of stimuli. Yet, sensitivity limitations and the extremely strong absorption bands of liquid water severely limit infrared spectroscopy in performing kinetic measurements in biomolecules’ native, aqueous environments. Here we demonstrate a plasmonic chip-based technology that overcomes these challenges, enabling the in-situ monitoring of protein and nanoparticle interactions at high sensitivity in real time, even allowing the observation of minute volumes of water displacement during binding events. Our approach leverages the plasmonic enhancement of absorption bands in conjunction with a non-classical form of internal reflection. These features not only expand the reach of infrared spectroscopy to a new class of biological interactions but also additionally enable a unique chip-based technology. PMID:23877168

  9. Total fluxes of sulfur dioxide from the Italian volcanoes Etna, Stromboli, and Vulcano measured by differential absorption lidar and passive differential optical absorption spectroscopy

    SciTech Connect

    Edner, H.; Ragnarson, P.; Svanberg, S.; Wallinder, E.; Ferrara, R.; Cioni, R.; Raco, B.; Taddeucci, G.

    1994-09-20

    The authors present measurements of the total flux of sulfur dioxide from three Italian volcanoes Etna, Stromboli, and Vulcano, measured in a three day period in Sept, 1992. The fluxes were measured from shipboard by means of an active differential absorption lidar technique, and a passive differential optical absorption spectroscopy technique. Corrections had to be applied to the passive optical technique because the light source paths were not well defined. The total fluxes were found to be roughly 25, 180, and 1300 tons/day for Vulcano, Stromboli, and Etna, respectively. 43 refs., 10 figs., 6 tabs.

  10. Inside and Outside: X-ray Absorption Spectroscopy Mapping of Chemical Domains in Graphene Oxide.

    PubMed

    De Jesus, Luis R; Dennis, Robert V; Depner, Sean W; Jaye, Cherno; Fischer, Daniel A; Banerjee, Sarbajit

    2013-09-19

    The oxidative chemistry of graphite has been investigated for over 150 years and has attracted renewed interest given the importance of exfoliated graphene oxide as a precursor to chemically derived graphene. However, the bond connectivities, steric orientations, and spatial distribution of functional groups remain to be unequivocally determined for this highly inhomogeneous nonstoichiometric material. Here, we demonstrate the application of principal component analysis to scanning transmission X-ray microscopy data for the construction of detailed real space chemical maps of graphene oxide. These chemical maps indicate very distinct functionalization motifs at the edges and interiors and, in conjunction with angle-resolved near-edge X-ray absorption fine structure spectroscopy, enable determination of the spatial location and orientations of functional groups. Chemical imaging of graphene oxide provides experimental validation of the modified Lerf-Klinowski structural model. Specifically, we note increased contributions from carboxylic acid moieties at edge sites with epoxide and hydroxyl species dominant within the interior domains.

  11. NO binding kinetics in myoglobin investigated by picosecond Fe K-edge absorption spectroscopy

    PubMed Central

    Silatani, Mahsa; Lima, Frederico A.; Penfold, Thomas J.; Rittmann, Jochen; Reinhard, Marco E.; Rittmann-Frank, Hannelore M.; Borca, Camelia; Grolimund, Daniel; Milne, Christopher J.; Chergui, Majed

    2015-01-01

    Diatomic ligands in hemoproteins and the way they bind to the active center are central to the protein’s function. Using picosecond Fe K-edge X-ray absorption spectroscopy, we probe the NO-heme recombination kinetics with direct sensitivity to the Fe-NO binding after 532-nm photoexcitation of nitrosylmyoglobin (MbNO) in physiological solutions. The transients at 70 and 300 ps are identical, but they deviate from the difference between the static spectra of deoxymyoglobin and MbNO, showing the formation of an intermediate species. We propose the latter to be a six-coordinated domed species that is populated on a timescale of ∼200 ps by recombination with NO ligands. This work shows the feasibility of ultrafast pump–probe X-ray spectroscopic studies of proteins in physiological media, delivering insight into the electronic and geometric structure of the active center. PMID:26438842

  12. X-ray absorption spectroscopy study in the BaFe2As2 family

    NASA Astrophysics Data System (ADS)

    Koh, Yoonyoung; Kim, Yeongkwan; Yang, Wanli; Kim, Changyoung

    2012-02-01

    One of the representative Fe-based superconductor families, BaFe2As2 (Tc =38K) is a semimetal with the same number of hole and electron carriers, and is in a spin density wave state below 139K. It has been reported that various types of ``doped'' BaFe2As2 systems can obtained by substitution of Ba, Fe, and As atoms. However, an important issue has been recently raised regarding whether each type of substitution indeed induces effective charge doping or not. It is essential to clarify whether each type of substitution indeed induce an effective doping in BaFe2As2 system. To clarify the carrier doping issue, we performed high resolution X-ray absorption spectroscopy experiment on Ba(Fe,Co)2As2, Ba(Fe,Ru)2As2, BaFe2(As,P)2 which are representative ``doped'' BaFe2As2 systems.

  13. Electronic topological transition in zinc under pressure: An x-ray absorption spectroscopy study

    NASA Astrophysics Data System (ADS)

    Aquilanti, G.; Trapananti, A.; Minicucci, M.; Liscio, F.; Twaróg, A.; Principi, E.; Pascarelli, S.

    2007-10-01

    Zinc metal has been studied at high pressure using x-ray absorption spectroscopy. In order to investigate the role of the different degrees of hydrostaticity on the occurrence of structural anomalies following the electronic topological transition, two pressure transmitting media have been used. Results show that the electronic topological transition, if it exists, does not induce an anomaly in the local environment of compressed Zn as a function of hydrostatic pressure and any anomaly must be related to a loss of hydrostaticity of the pressure transmitting medium. The near-edge structures of the spectra, sensitive to variations in the electronic density of states above the Fermi level, do not show any evidence of electronic transition whatever pressure transmitting medium is used.

  14. X-ray absorption spectroscopy to probe interfacial issues in photolithography.

    SciTech Connect

    Angelopoulos, Marie (IBM, T.J. Watson Research Center, Yorktown Heights, NY); Lenhart, Joseph Ludlow; Wu, Wen-li (National Institute of Standards and Technology, Gaithersburg, MD); Sambasivan, Sharadha (National Institute of Standards and Technology, Gaithersburg, MD); Fischer, Daniel A. (National Institute of Standards and Technology, Gaithersburg, MD); Jones, Ronald L. (National Institute of Standards and Technology, Gaithersburg, MD); Soles, Christopher L. (National Institute of Standards and Technology, Gaithersburg, MD); Lin, Eric K. (National Institute of Standards and Technology, Gaithersburg, MD); Goldfarb, Dario L. (IBM, T.J. Watson Research Center, Yorktown Heights, NY)

    2003-03-01

    We utilize near edge X-ray absorption fine structure spectroscopy (NEXASFS) to provide detailed chemical insight into two interfacial problems facing sub-100 nm patterning. First, chemically amplified photo-resists are sensitive to surface phenomenon, which causes deviations in the pattern profile near the interface. Striking examples include T-topping, closure, footing, and undercutting. NEXAFS was used to examine surface segregation of a photo-acid generator at the resist/air interface and to illustrate that the surface extent of deprotection in a model resist film can be different than the bulk extent of deprotection. Second, line edge roughness becomes increasingly critical with shrinking patterns, and may be intimately related to the line edge deprotection profile. A NEXAFS technique to surface depth profile for compositional gradients is described with the potential to provide chemical information about the resist line edge.

  15. Zinc ligands in the metal hyperaccumulator Thlaspi caerulescens as determined using X-ray absorption spectroscopy

    SciTech Connect

    Salt, D.E.; Prince, R.C.; Baker, A.J.M.; Raskin, I.; Pickering, I.J.

    1999-03-01

    Using the noninvasive technique of X-ray absorption spectroscopy (XAS), the authors have been able to determine the ligand environment of Zn in different tissues of the Zn-hyperaccumulator Thlaspi caerulescens. The majority of intracellular Zn in roots of T. caerulescens was found to be coordinated with histidine. In the xylem sap Zn was found to be transported mainly as the free hydrated Zn{sup 2+} cation with a smaller proportion coordinated with organic acids. In the shoots, Zn coordination occurred mainly via organic acids, with a smaller proportion present as the hydrated cation and coordinated with histidine and the cell wall. Their data suggest that histidine plays an important role in Zn homeostasis in the roots, whereas organic acids are involved in xylem transport and Zn storage in shoots.

  16. Studies of Y-Ba-Cu-O single crystals by x-ray absorption spectroscopy

    SciTech Connect

    Krol, A.; Ming, Z.H.; Kao, Y.H.; Nuecker, N.; Roth, G.; Fink, J.; Smith, G.C.; Erband, A.; Mueller-Vogt, G.; Karpinski, J.; Kaldis, E.; Schoenmann, K.

    1992-02-01

    The symmetry and density of unoccupied states of YBa{sub 2}Cu{sub 3}O{sub 7} YBa{sub 2}Cu{sub 4}O{sub 8} have been investigated by orientation dependent x-ray absorption spectroscopy on the O 1s edge using a bulk-sensitive fluorescence-yield-detection method. It has been found that the O 2p holes are distributed equally between the CuO{sub 2} planes and CuO chains and that the partial density of unoccupied O 2p states in the CuO{sub 2} planes are identical in both systems investigated. The upper Hubbard band has been observed in the planes but not in the chains in both systems. 18 refs.

  17. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-09-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms.

  18. Elemental characterisation of melanin in feathers via synchrotron X-ray imaging and absorption spectroscopy

    PubMed Central

    Edwards, Nicholas P.; van Veelen, Arjen; Anné, Jennifer; Manning, Phillip L.; Bergmann, Uwe; Sellers, William I.; Egerton, Victoria M.; Sokaras, Dimosthenis; Alonso-Mori, Roberto; Wakamatsu, Kazumasa; Ito, Shosuke; Wogelius, Roy A.

    2016-01-01

    Melanin is a critical component of biological systems, but the exact chemistry of melanin is still imprecisely known. This is partly due to melanin’s complex heterogeneous nature and partly because many studies use synthetic analogues and/or pigments extracted from their natural biological setting, which may display important differences from endogenous pigments. Here we demonstrate how synchrotron X-ray analyses can non-destructively characterise the elements associated with melanin pigment in situ within extant feathers. Elemental imaging shows that the distributions of Ca, Cu and Zn are almost exclusively controlled by melanin pigment distribution. X-ray absorption spectroscopy demonstrates that the atomic coordination of zinc and sulfur is different within eumelanised regions compared to pheomelanised regions. This not only impacts our fundamental understanding of pigmentation in extant organisms but also provides a significant contribution to the evidence-based colour palette available for reconstructing the appearance of fossil organisms. PMID:27658854

  19. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals, Final Technical Report

    DOE R&D Accomplishments Database

    Curl, Robert F.; Glass, Graham P.

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  20. High resolution electron energy loss spectroscopy: A new probe of subgap absorption in amorphous solids

    SciTech Connect

    Lopinski, G.P.; Lannin, J.S.

    1996-10-01

    The use of high resolution electron energy spectroscopy (HREELS) as a new method for studies of subgap absorption in thin films of amorphous semiconductors is demonstrated. For a-Si films, the {alpha}({omega}) values extracted from the measured loss spectra are in quantitative agreement with previous optical measurements. The method is also applied to both threefold and diamond-like amorphous carbon films, yielding {alpha}({omega}) down to considerably lower energies ({approximately}50 meV) than previously reported. The HREELS method is shown to be complementary to existing techniques in that it can access the regime of low energies and ultrathin films which is difficult to investigate with the conventional methods. {copyright} {ital 1996 American Institute of Physics.}

  1. Studies of fluorine in catalysts with ultrasoft X-ray absorption spectroscopy

    SciTech Connect

    Davis, S.M. ); Meitzner, G.D. ); Fischer, D.A. ); Gland, J. )

    1993-08-01

    The structures of fluorine-doped alumina catalyst powders have been studied by fluorescence yield ultrasoft X-ray absorption spectroscopy. The results presented here demonstrate that important local structural information can be obtained by the technique. It is established that fluoride ions are substituted for oxygen in alumina at low concentration of adsorbed fluorine. For doping levels larger than those required for saturation of the monolayer, the authors observed AlF[sub 3]-like features in the radial structure function. These results are in agreement with previous observations of bulk AlF[sub 3] in aluminas with high levels of fluorine doping. The fluorescence yield method is well suited for determining structures of a wide range of ceramic materials. 22 refs., 4 figs.

  2. Infrared reflection-absorption spectroscopy: principles and applications to lipid-protein interaction in Langmuir films.

    PubMed

    Mendelsohn, Richard; Mao, Guangru; Flach, Carol R

    2010-04-01

    Infrared reflection-absorption spectroscopy (IRRAS) of lipid/protein monolayer films in situ at the air/water interface provides unique molecular structure and orientation information from the film constituents. The technique is thus well suited for studies of lipid/protein interaction in a physiologically relevant environment. Initially, the nature of the IRRAS experiment is described and the molecular structure information that may be obtained is recapitulated. Subsequently, several types of applications, including the determination of lipid chain conformation and tilt as well as elucidation of protein secondary structure are reviewed. The current article attempts to provide the reader with an understanding of the current capabilities of IRRAS instrumentation and the type of results that have been achieved to date from IRRAS studies of lipids, proteins, and lipid/protein films of progressively increasing complexity. Finally, possible extensions of the technology are briefly considered. PMID:20004639

  3. Axial segregation in high intensity discharge lamps measured by laser absorption spectroscopy

    SciTech Connect

    Flikweert, A.J.; Nimalasuriya, T.; Groothuis, C.H.J.M.; Kroesen, G.M.W.; Stoffels, W.W.

    2005-10-01

    High intensity discharge lamps have a high efficiency. These lamps contain rare-earth additives (in our case dysprosium iodide) which radiate very efficiently. A problem is color separation in the lamp because of axial segregation of the rare-earth additives, caused by diffusion and convection. Here two-dimensional atomic dysprosium density profiles are measured by means of laser absorption spectroscopy; the order of magnitude of the density is 10{sup 22} m{sup -3}. The radially resolved atomic density measurements show a hollow density profile. In the outer parts of the lamp molecules dominate, while the center is depleted of dysprosium atoms due to ionization. From the axial profiles the segregation parameter is determined. It is shown that the lamp operates on the right-hand side of the Fischer curve [J. Appl. Phys. 47, 2954 (1976)], i.e., a larger convection leads to less segregation.

  4. Performance improvements in temperature reconstructions of 2-D tunable diode laser absorption spectroscopy (TDLAS)

    NASA Astrophysics Data System (ADS)

    Choi, Doo-Won; Jeon, Min-Gyu; Cho, Gyeong-Rae; Kamimoto, Takahiro; Deguchi, Yoshihiro; Doh, Deog-Hee

    2016-02-01

    Performance improvement was attained in data reconstructions of 2-dimensional tunable diode laser absorption spectroscopy (TDLAS). Multiplicative Algebraic Reconstruction Technique (MART) algorithm was adopted for data reconstruction. The data obtained in an experiment for the measurement of temperature and concentration fields of gas flows were used. The measurement theory is based upon the Beer-Lambert law, and the measurement system consists of a tunable laser, collimators, detectors, and an analyzer. Methane was used as a fuel for combustion with air in the Bunsen-type burner. The data used for the reconstruction are from the optical signals of 8-laser beams passed on a cross-section of the methane flame. The performances of MART algorithm in data reconstruction were validated and compared with those obtained by Algebraic Reconstruction Technique (ART) algorithm.

  5. X-Ray absorption spectroscopy investigation of 1-alkyl-3-methylimidazolium bromide salts

    SciTech Connect

    D'Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina; Bodo, Enrico; Caminiti, Ruggero; Aquilanti, Giuliana; Hazemann, Jean Louis; Testemale, Denis; Mancini, Giordano

    2011-08-21

    X-ray absorption spectroscopy (XAS) has been used to unveil the bromide ion local coordination structure in 1-alkyl-3-methylimidazolium bromide [C{sub n}mim]Br ionic liquids (ILs) with different alkyl chains. The XAS spectrum of 1-ethyl-3-methylimidazolium bromide has been found to be different from those of the other members of the series, from the butyl to the decyl derivatives, that have all identical XAS spectra. This result indicates that starting from 1-buthyl-3-methylimidazolium bromide the local molecular arrangement around the bromide anion is the same independently from the length of the alkyl chain, and that the imidazolium head groups in the liquid ILs with long alkyl chains assume locally the same orientation as in the [C{sub 4}mim]Br crystal. With this study we show that the XAS technique is an effective direct tool for unveiling the local structural arrangements around selected atoms in ILs.

  6. Xe nanocrystals in Si studied by x-ray absorption fine structure spectroscopy

    SciTech Connect

    Faraci, Giuseppe; Pennisi, Agata R.; Zontone, Federico

    2007-07-15

    The structural configuration of Xe clusters, obtained by ion implantation in a Si matrix, has been investigated as a function of the temperature by x-ray absorption fine structure spectroscopy. In contrast with previous results, we demonstrate that an accurate analysis of the data, using high order cumulants, gives evidence of Xe fcc nanocrystals at low temperature, even in the as-implanted Si; expansion of the Xe lattice is always found as a function of the temperature, with no appreciable overpressure. We point out that a dramatic modification of these conclusions can be induced by an incorrect analysis using standard symmetrical pair distribution function G(r); for this reason, all the results were checked by x-ray diffraction measurements.

  7. [Air pollutants study by differential optical absorption spectroscopy with transmit-receive fibers].

    PubMed

    Wei, Yong-Jie; Geng, Xiao-Juan; Chen, Bo; Liu, Cui-Cui; Chen, Wen-Liang

    2013-10-01

    The differential optical absorption spectroscopy system is presented to monitor air pollutants, such as SO2, NO2, etc. The system employs a reflective telescope to collimate light source and focus absorbed light. A combined transmitting and receiving fiber bundle is set to the focus of a concave mirror. A Xenon lamp works as the light source. The light is coupled into the transmitting fiber, and then collimated by the reflective telescope system. After absorbed by the pollutants, the light is reflected by a pyramid mirror far away the telescope. Then the absorbed light is incident on the concave mirror the second time, and focused on the focal plane again. The receiving fiber induces the light which carries the information of the measured gas into a spectrometer. We can get the concentration of the pollutants by DOAS algorithm. Experimental results show that the proposed method can be adopted to measure some pollutants in air quality monitoring.

  8. Laser absorption spectroscopy diagnostics of helium metastable atoms generated in dielectric barrier discharge cryoplasmas

    NASA Astrophysics Data System (ADS)

    Urabe, Keiichiro; Muneoka, Hitoshi; Stauss, Sven; Sakai, Osamu; Terashima, Kazuo

    2015-10-01

    Cryoplasmas, which are plasmas whose gas temperatures are below room temperature (RT), have shown dynamic changes in their physical and chemical characteristics when the gas temperature in the plasmas (Tgp) was decreased from RT. In this study, we measured the temporal behavior of helium metastable (Hem) atoms generated in a parallel-plate dielectric barrier discharge at ambient gas temperatures (Tga) of 300, 100, and 14 K and with a gas density similar to atmospheric conditions by laser absorption spectroscopy. The increments of Tgp to Tga were less than 20 K. We found from the results that the Hem lifetime and maximum density become longer and larger over one order of magnitude for lower Tga. The reasons for the long Hem lifetime at low Tga are decreases in the rate coefficients of three-body Hem quenching reactions and in the amounts of molecular impurities with boiling points higher than that of He.

  9. Structural analysis of sulfur in natural rubber using X-ray absorption near-edge spectroscopy.

    PubMed

    Pattanasiriwisawa, Wanwisa; Siritapetawee, Jaruwan; Patarapaiboolchai, Orasa; Klysubun, Wantana

    2008-09-01

    X-ray absorption near-edge spectroscopy (XANES) has been applied to natural rubber in order to study the local environment of sulfur atoms in sulfur crosslinking structures introduced in the vulcanization process. Different types of chemical accelerators in conventional, semi-efficient and efficient vulcanization systems were investigated. The experimental results show the good sensitivity and reproducibility of XANES to characterize the local geometry and electronic environment of the sulfur K-shell under various conditions of vulcanization and non-vulcanization of natural rubber. Several applications of XANES in this study demonstrate an alternative way of identifying sulfur crosslinks in treated natural rubber based on differences in their spectra and oxidation states. PMID:18728323

  10. High resolution absorption coefficients for Freon-12. [by using tunable diode laser spectroscopy

    NASA Technical Reports Server (NTRS)

    Hoell, J. M.; Bair, C. H.; Williams, B.; Harward, C.

    1979-01-01

    The ultra high resolution absorption coefficients of the Q-branch of Freon-12 obtained with tunable diode laser spectroscopy are presented. Continuous spectra are presented from 1155/cm to 1163/cm, and absolute wavelength calibration was obtained using SO2 spectra as a standard and a 5 cm Ge etalon for relative calibration between SO2 lines. The Freon-12 data obtained at a pressure of 0.05 torr showed a rich and highly structured spectra, but with the exception of three isolated features, collisional broadening reduces the spectra to a structureless continuum for nitrogen pressures greater than 20 torr. The spectra at 1161/cm continue to exhibit structure at atmospheric pressure.

  11. Absolute 1* quantum yields for the ICN A state by diode laser gain versus absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Hess, Wayne P.; Leone, Stephen R.

    1987-01-01

    Absolute I* quantum yields were measured as a function of wavelength for room temperature photodissociation of the ICN A state continuum. The temperature yields are obtained by the technique of time-resolved diode laser gain-versus-absorption spectroscopy. Quantum yields are evaluated at seven wavelengths from 248 to 284 nm. The yield at 266 nm is 66.0 +/- 2% and it falls off to 53.4 +/- 2% and 44.0 +/- 4% at 284 and 248 respectively. The latter values are significantly higher than those obtained by previous workers using infrared fluorescence. Estimates of I* quantum yields obtained from analysis of CN photofragment rotational distributions, as discussed by other workers, are in good agreement with the I* yields. The results are considered in conjunction with recent theoretical and experimental work on the CN rotational distributions and with previous I* yield results.

  12. Ge doped HfO{sub 2} thin films investigated by x-ray absorption spectroscopy

    SciTech Connect

    Miotti, Leonardo; Bastos, Karen P.; Lucovsky, Gerald; Radtke, Claudio; Nordlund, Dennis

    2010-07-15

    The stability of the tetragonal phase of Ge doped HfO{sub 2} thin films on Si(100) was investigated. Hf(Ge)O{sub 2} films with Ge atomic concentrations varying from 0% to 15% were deposited by remote plasma chemical vapor deposition. The atomic structure on the oxide after rapid thermal annealing was investigated by x-ray absorption spectroscopy of the O and Ge K edges and by Rutherford backscattering spectrometry. The authors found that Ge concentrations as low as 5 at. % effectively stabilize the tetragonal phase of 5 nm thick Hf(Ge)O{sub 2} on Si and that higher concentrations are not stable to rapid thermal annealing at temperatures above 750 deg. C.

  13. [Genetic programming used for the measurement of CO concentration based on nondispersive infrared absorption spectroscopy].

    PubMed

    Chen, Jin; Duan, Fa-jie; Tong, Ying; Gao, Qiang

    2011-07-01

    Nondispersive infrared absorption spectroscopy(NDIR) is an important method to measure CO concentration in the air. In the present study, an open-path measurement system and continuous measuring device was developed, and genetic programming was used to establish the calibration model of subjects' light intensity sampling values. Continuous measurements were carried out in 10 different concentration of CO, and 40 sampled data were acquired and analyzed. For validation set, the correlation coefficient was 0.9997. The biggest relative error of validation was 4.00%, and the average relative error was 1.11%. Results show that genetic programming can be a good method for the modeling of gas concentration measurements equipped with NDIR systems.

  14. Fast transient absorption spectroscopy of the early events in photoexcited chiral benzophenone naphthalene dyads

    NASA Astrophysics Data System (ADS)

    Perez-Ruiz, Raul; Groeneveld, Michiel; van Stokkum, Ivo H. M.; Tormos, Rosa; Williams, René M.; Miranda, Miguel A.

    2006-09-01

    Photoinduced intra-molecular energy transfer in two ketoprofen(KP)-naproxol(NPX) diastereomers proceeds via two pathways. Very fast singlet-triplet energy transfer ( k = 1.2 × 10 11 s -1) from KP to NPX occurs for a small percentage (6%) and the major pathway is triplet-triplet energy transfer ( k ˜ 3 × 10 9 s -1). This was shown with femtosecond transient absorption spectroscopy and global and target analysis. Whereas the NPX triplet decay is strongly stereospecific (ratio of 1.6), the NPX triplet state formation for both dyads is very similar (ratio of 1 for the fast process and 1.2 for the slower process).

  15. X-ray absorption/emission line spectroscopy of the Galactic hot gaseous halo

    NASA Astrophysics Data System (ADS)

    Wang, Daniel

    2016-04-01

    There is an ongoing debate as to whether or not the Milky Way is surrounded by a large-scale, massive corona. Vastly different conclusions as to its extent and mass have been drawn from existing studies based on X-ray absorption and/or emission line spectroscopy. I will discuss my assessment of this issue, focusing on various uncertainties and potential problems in the present data, analyses, results, and interpretations.In particular, I will examine how different assumptions about the temperature distribution of the corona affect the inference of its physical scale. I will also discuss the external perspectives of galactic coronae obtained form observing nearby highly-inclined disk galaxies.

  16. Note: Sample chamber for in situ x-ray absorption spectroscopy studies of battery materials

    SciTech Connect

    Pelliccione, CJ; Timofeeva, EV; Katsoudas, JP; Segre, CU

    2014-12-01

    In situ x-ray absorption spectroscopy (XAS) provides element-specific characterization of both crystalline and amorphous phases and enables direct correlations between electrochemical performance and structural characteristics of cathode and anode materials. In situ XAS measurements are very demanding to the design of the experimental setup. We have developed a sample chamber that provides electrical connectivity and inert atmosphere for operating electrochemical cells and also accounts for x-ray interactions with the chamber and cell materials. The design of the sample chamber for in situ measurements is presented along with example XAS spectra from anode materials in operating pouch cells at the Zn and Sn K-edges measured in fluorescence and transmission modes, respectively. (C) 2014 AIP Publishing LLC.

  17. [Air pollutants study by differential optical absorption spectroscopy with transmit-receive fibers].

    PubMed

    Wei, Yong-Jie; Geng, Xiao-Juan; Chen, Bo; Liu, Cui-Cui; Chen, Wen-Liang

    2013-10-01

    The differential optical absorption spectroscopy system is presented to monitor air pollutants, such as SO2, NO2, etc. The system employs a reflective telescope to collimate light source and focus absorbed light. A combined transmitting and receiving fiber bundle is set to the focus of a concave mirror. A Xenon lamp works as the light source. The light is coupled into the transmitting fiber, and then collimated by the reflective telescope system. After absorbed by the pollutants, the light is reflected by a pyramid mirror far away the telescope. Then the absorbed light is incident on the concave mirror the second time, and focused on the focal plane again. The receiving fiber induces the light which carries the information of the measured gas into a spectrometer. We can get the concentration of the pollutants by DOAS algorithm. Experimental results show that the proposed method can be adopted to measure some pollutants in air quality monitoring. PMID:24409736

  18. Broadband femtosecond transient absorption spectroscopy for a CVD Mo S2 monolayer

    NASA Astrophysics Data System (ADS)

    Aleithan, Shrouq H.; Livshits, Maksim Y.; Khadka, Sudiksha; Rack, Jeffrey J.; Kordesch, Martin E.; Stinaff, Eric

    2016-07-01

    Carrier dynamics in monolayer Mo S2 have been investigated using broadband femtosecond transient absorption spectroscopy (FTAS). A tunable pump pulse was used while a broadband probe pulse revealed ground and excited state carrier dynamics. Interestingly, for pump wavelengths both resonant and nonresonant with the A and B excitons, we observe a broad ground state bleach around 2.9 eV, with decay components similar to A and B. Associating this bleach with the band nesting region between K and Γ in the band structure indicates significant k-space delocalization and overlap among excitonic wave functions identified as A, B, C, and D. Comparison of time dynamics for all features in resonance and nonresonance excitation is consistent with this finding.

  19. Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

    SciTech Connect

    Sheps, Leonid; Chandler, David W.

    2013-04-01

    Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transient reaction intermediates in a simple, inexpensive, and robust experimental package.

  20. High resolution laser induced fluorescence Doppler velocimetry utilizing saturated absorption spectroscopy

    SciTech Connect

    Aramaki, Mitsutoshi; Ogiwara, Kohei; Etoh, Shuzo; Yoshimura, Shinji; Tanaka, Masayoshi Y.

    2009-05-15

    A high resolution laser induced fluorescence (LIF) system has been developed to measure the flow velocity field of neutral particles in an electron-cyclotron-resonance argon plasma. The flow velocity has been determined by the Doppler shift of the LIF spectrum, which is proportional to the velocity distribution function. Very high accuracy in velocity determination has been achieved by installing a saturated absorption spectroscopy unit into the LIF system, where the absolute value and scale of laser wavelength are determined by using the Lamb dip and the fringes of a Fabry-Perot interferometer. The minimum detectable flow velocity of a newly developed LIF system is {+-}2 m/s, and this performance remains unchanged in a long-time experiment. From the radial measurements of LIF spectra of argon metastable atoms, it is found that there exists an inward flow of neutral particles associated with neutral depletion.

  1. The irradiation of ammonia ice studied by near edge x-ray absorption spectroscopy

    SciTech Connect

    Parent, Ph.; Bournel, F.; Lasne, J.; Laffon, C.; Carniato, S.; Lacombe, S.; Strazzulla, G.; Gardonio, S.; Lizzit, S.; Kappler, J.-P.; Joly, L.

    2009-10-21

    A vapor-deposited NH{sub 3} ice film irradiated at 20 K with 150 eV photons has been studied with near-edge x-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen K-edge. Irradiation leads to the formation of high amounts (12%) of molecular nitrogen N{sub 2}, whose concentration as a function of the absorbed energy has been quantified to 0.13 molecule/eV. The stability of N{sub 2} in solid NH{sub 3} has been also studied, showing that N{sub 2} continuously desorbs between 20 and 95 K from the irradiated ammonia ice film. Weak concentrations (<1%) of other photoproducts are also detected. Our NEXAFS simulations show that these features own to NH{sub 2}, N{sub 2}H{sub 2}, and N{sub 3}{sup -}.

  2. Detection, identification and mapping of iron anomalies in brain tissue using X-ray absorption spectroscopy

    SciTech Connect

    Mikhaylova, A.; Davidson, M.; Toastmann, H.; Channell, J.E.T.; Guyodo, Y.; Batich, C.; Dobson, J.

    2008-06-16

    This work describes a novel method for the detection, identification and mapping of anomalous iron compounds in mammalian brain tissue using X-ray absorption spectroscopy. We have located and identified individual iron anomalies in an avian tissue model associated with ferritin, biogenic magnetite and haemoglobin with a pixel resolution of less than 5 {micro}m. This technique represents a breakthrough in the study of both intra- and extra-cellular iron compounds in brain tissue. The potential for high-resolution iron mapping using microfocused X-ray beams has direct application to investigations of the location and structural form of iron compounds associated with human neurodegenerative disorders - a problem which has vexed researchers for 50 years.

  3. Relaxation dynamics of photoexcited excitons in rubrene single crystals using femtosecond absorption spectroscopy.

    PubMed

    Tao, S; Ohtani, N; Uchida, R; Miyamoto, T; Matsui, Y; Yada, H; Uemura, H; Matsuzaki, H; Uemura, T; Takeya, J; Okamoto, H

    2012-08-31

    The relaxation dynamics of an exciton in rubrene was investigated by femtosecond absorption spectroscopy. Exciton relaxation to a self-trapped state occurs via the coherent oscillation with 78 cm(-1) due to a coupled mode of molecular deformations with phenyl-side-group motions and molecular displacements. From the temperature dependence of the decay time of excitons, the energy necessary for an exciton to escape from a self-trapped state is evaluated to be ~35 meV (~400 K). As a result, a self-trapped exciton is stable at low temperatures. At room temperature, excitons can escape from a self-trapped state and, subsequently, they are dissociated to charged species. The exciton dissociation mechanism is discussed on the basis of the results. PMID:23002882

  4. Determination of cadmium, copper, and lead in sodium chloride food salts by flame atomic absorption spectroscopy.

    PubMed

    Alvarez De Eulate, M J; Montoro, R; Ybañez, N; De La Guardia, M

    1986-01-01

    A method for determination of Cd, Cu, and Pb in sodium chloride food salt samples has been developed. It consists of extraction in 4-methyl-2-pentanone of the complexes formed with ammonium pyrrolidine dithiocarbamate and further analysis of the extracts by flame atomic absorption spectroscopy. Detection limits in ng/g salt were 0.2 for Cd, 0.7 for Cu, and 10.0 for Pb. The coefficients of variation of 12 independent analyses were 13% for Cd (at a level of 0.4 ppb), 18% for Cu (1.6 ppb), and 5% for Pb (40 ppb). The recoveries were 100 +/- 0% for Cd, 115 +/- 14% for Cu, and 100 +/- 13% for Pb. PMID:3771460

  5. Gas cell for in situ soft X-ray transmission-absorption spectroscopy of materials

    SciTech Connect

    Drisdell, W. S.; Kortright, J. B.

    2014-07-15

    A simple gas cell design, constructed primarily from commercially available components, enables in situ soft X-ray transmission-absorption spectroscopy of materials in contact with gas at ambient temperature. The cell has a minimum X-ray path length of 1 mm and can hold gas pressures up to ∼300 Torr, and could support higher pressures with simple modifications. The design enables cycling between vacuum and gas environments without interrupting the X-ray beam, and can be fully sealed to allow for measurements of air-sensitive samples. The cell can attach to the downstream port of any appropriate synchrotron beamline, and offers a robust and versatile method for in situ measurements of certain materials. The construction and operation of the cell are discussed, as well as sample preparation and proper spectral analysis, illustrated by examples of spectral measurements. Potential areas for improvement and modification for specialized applications are also mentioned.

  6. Electronic absorption spectroscopy of polycyclic aromatic hydrocarbons (PAHs) radical cations generated in oleum: a superacid medium.

    PubMed

    Cataldo, Franco; Iglesias-Groth, Susana; Manchado, Arturo

    2010-12-01

    Oleum (fuming sulphuric acid), a well known superacid, was used as medium for the generation of the radical cation of a series of selected PAHs. The resulting radical cation spectra were studied by electronic absorption spectroscopy. Not only common PAHs like naphthalene, anthracene, tetracene, pentacene, perylene, pyrene, benzo[a]pyrene, phenanthrene and picene were studied but also the less common and very large PAHs relevant also for the astrochemical research, like coronene, hexabenzocoronene, quaterrylene, dicoronylene and a coronene oligomer. A correlation between the first ionization potential (IP1) of the PAHs studied and the energy to the so-called A-type band of the radical cations observed in oleum has led to the equation IP1=1.30EA+4.39 (in eV) which permits to estimate the energy of the PAHs radical cation transition (EA) in the VIS-NIR knowing the relative ionization potential or vice versa. PMID:20863743

  7. X-ray absorption spectroscopy in electrical fields: An element-selective probe of atomic polarization

    NASA Astrophysics Data System (ADS)

    Ney, V.; Wilhelm, F.; Ollefs, K.; Rogalev, A.; Ney, A.

    2016-01-01

    We have studied a range of polar and nonpolar materials using x-ray absorption near-edge spectroscopy (XANES) in external electric fields. An energy shift of the XANES by a few meV/kV is found which scales linearly with the applied voltage, thus being reminiscent of the linear Stark effect. This is corroborated by the consistent presence of this energy shift in polar thin films and bulk crystals and its absence in nonpolar materials as well as in conducting films. The observed energy shift of the XANES is different between two atomic species in one specimen and appears to scale linearly with the atomic number of the studied element. Therefore, XANES in electrical fields opens the perspective to study atomic polarization with element specificity in a range of functional materials.

  8. Understanding the collapse mechanism in Langmuir monolayers through polarization modulation-infrared reflection absorption spectroscopy.

    PubMed

    Goto, Thiago Eichi; Caseli, Luciano

    2013-07-23

    The collapse of films at the air-water interface is related to a type of 2D-to-3D transition that occurs when a Langmuir monolayer is compressed beyond its stability limit. Studies on this issue are extremely important because defects in ultrathin solid films can be better understood if the molecular mechanisms related to collapse processes are elucidated. This paper explores how the changes of vibration of specific groups of lipid molecules, as revealed by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS), are affected by the monolayer collapse. Different mechanisms of collapse were studied, for those lipids that undergo constant-area collapse (such as stearic acid) and for those that undergo constant-pressure collapse (such as DPPC, DPPG, and DODAB). Lipid charges also affect the mechanism of collapse, as demonstrated for two oppositely charged lipids.

  9. Orientation of a monolayer of dipolar molecules on graphene from X-ray absorption spectroscopy.

    PubMed

    Johnson, Phillip S; Huang, Changshui; Kim, Myungwoong; Safron, Nathaniel S; Arnold, Michael S; Wong, Bryan M; Gopalan, Padma; Himpsel, F J

    2014-03-11

    Recently, single-walled carbon nanotubes as well as graphene functionalized with azobenzene chromophores have drawn attention for applications in optoelectronics due to their ability to undergo cis-trans isomerization when exposed to light. The electronic properties of the nanocarbon materials at these unconventional interfaces can be tailored by gaining structural insight into the organic monolayers at the molecular level. In this work, we use polarization-dependent X-ray absorption spectroscopy to probe the orientation of three chromophores on graphene, all identical except for their terminal groups. All three terminal groups (methyl, nitro, and nitrile) are well-oriented, with a tilt angle of about 30° from the substrate for the shared azobenzene group. Density functional theory calculations are in good agreement with experimental results and give two similar, stable configurations for the orientation of these molecules on graphene.

  10. Determination of scandium in sea-water by atomic-absorption spectroscopy.

    PubMed

    Chau, Y K; Wong, P Y

    1968-08-01

    A method for the determination of scandium in sea-water at the sub-microgram level has been developed. Scandium is coprecipitated with iron(III) hydroxide at pH 8-9, and then separated from the iron by ion-exchange. The final concentration is achieved by extracting the scandium into a solution of oxine in butanol. A nitrous oxide-acetylene flame is used for the determination by atomic-absorption spectroscopy. Recoveries of 99-100% are obtained. The storage of the solutions before analysis has been investigated by radiometric techniques with (46)Sc. The scandium concentration in surface waters of the South China Sea was found to be 0.01 +/- 0.005 microg/l .

  11. Active differential optical absorption spectroscopy for NO2 gas pollution using blue light emitting diodes

    NASA Astrophysics Data System (ADS)

    Aljalal, Abdulaziz; Gasmi, Khaled; Al-Basheer, Watheq

    2015-05-01

    Availability of high intensity light emitting diodes in the blue region offer excellent opportunity for using them in active Differential Optical Absorption Spectroscopy (DOAS) to detect air pollution. Their smooth and relatively broad spectral emissions as well as their long life make them almost ideal light sources for active DOAS. In this study, we report the usage of a blue light emitting diode in an active DOAS setup to measure traces of NO2 gas and achieving few parts per billion detection limit for a path length of 300 m. Details of the setup will be presented along with the effects on measurement accuracy due to shifts in the measured spectra calibration and due to using theoretical instrument Gaussian function instead of the measured instrument function.

  12. [Studies on the remote measurement of the emission of formaldehyde by mobile differential optical absorption spectroscopy].

    PubMed

    Wu, Feng-Cheng; Xie, Pin-Hua; Li, Ang; Si, Fu-Qi; Dou, Ke; Liu, Yu; Xu, Jin; Wang, Jie

    2011-11-01

    Formaldehyde (HCHO) is the most abundant carbonyl compounds that play an important role in atmospheric chemistry and photochemical reactions. Formaldehyde is an important indicator of atmospheric reactivity and urban atmospheric aerosol precursors. In the present paper, the emission of formaldehyde from chemical area was measured using the mobile differential optical absorption spectroscopy (DOAS). This instrument uses the zenith scattered sunlight as the light source with successful sampling in the area loop. Vertical column density was retrieved by this system, combined with the meteorological wind field and car speed information, the emission of formaldehyde in the area was estimated. The authors carried out the measuring experiment in one chemical plant in Beijing using this technology. The result showed that the average value of the flux of formaldehyde in this area was 605 kg x h(-1) during the measuring period. PMID:22242505

  13. Diffuse-light absorption spectroscopy by fiber optics for detecting and quantifying the adulteration of extra virgin olive oil

    NASA Astrophysics Data System (ADS)

    Mignani, A. G.; Ciaccheri, L.; Ottevaere, H.; Thienpont, H.; Conte, L.; Marega, M.; Cichelli, A.; Attilio, C.; Cimato, A.

    2010-09-01

    A fiber optic setup for diffuse-light absorption spectroscopy in the wide 400-1700 nm spectral range is experimented for detecting and quantifying the adulteration of extra virgin olive oil caused by lower-grade olive oils. Absorption measurements provide spectral fingerprints of authentic and adulterated oils. A multivariate processing of spectroscopic data is applied for discriminating the type of adulterant and for predicting its fraction.

  14. Optical analysis of trapped Gas—Gas in Scattering Media Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Svanberg, S.

    2010-01-01

    An overview of the new field of Gas in Scattering Media Absorption Spectroscopy (GASMAS) is presented. The technique investigates sharp gas spectral signatures, typically 10000 times sharper than those of the host material, in which the gas is trapped in pores or cavities. The presence of pores causes strong multiple scattering. GASMAS combines narrow-band diode-laser spectroscopy, developed for atmospheric gas monitoring, with diffuse media optical propagation, well-known from biomedical optics. Several applications in materials science, food packaging, pharmaceutics and medicine have been demonstrated. So far molecular oxygen and water vapour have been studied around 760 and 935 nm, respectively. Liquid water, an important constituent in many natural materials, such as tissue, has a low absorption at such wavelengths, and this is also true for haemoglobin, making propagation possible in many natural materials. Polystyrene foam, wood, fruits, food-stuffs, pharmaceutical tablets, and human sinus cavities (frontal, maxillary and mastoideal) have been studied, demonstrating new possibilities for characterization and diagnostics. Transport of gas in porous media (diffusion) can be studied by first subjecting the material to, e.g., pure nitrogen, and then observing the rate at which normal, oxygen-containing air, reinvades the material. The conductance of the passages connecting a sinus with the nasal cavity can be objectively assessed by observing the oxygen gas dynamics when flushing the nose with nitrogen. Drying of materials, when liquid water is replaced by air and water vapour, is another example of dynamic processes which can be studied. The technique has also been extended to remote-sensing applications (LIDAR-GASMAS or Multiple-Scattering LIDAR).

  15. Quantum cascade laser absorption spectroscopy of UF6 at 7.74 μm for analytical uranium enrichment measurements

    NASA Astrophysics Data System (ADS)

    Lewicki, Rafal; Kosterev, Anatoliy A.; Toor, Fatima; Yao, Yu; Gmachl, Claire; Tsai, Tracy; Wysocki, Gerard; Wang, Xiaojun; Troccoli, Mariano; Fong, Mary; Tittel, Frank K.

    2010-01-01

    The ν1+ν3 combination band of uranium hexafluoride (UF6) is targeted to perform analytical enrichment measurements using laser absorption spectroscopy. A high performance widely tunable EC-QCL sources emitting radiation at 7.74 μm (1291 cm-1) is employed as an UF6-LAS optical source to measure the unresolved rotational-vibrational spectral structure of several tens of wavenumbers (cm-1). A preliminary spectroscopic measurement based on a direct laser absorption spectroscopy of methane (CH4) as an appropriate UF6 analyte simulant, was demonstrated.

  16. Resonant excited state absorption and relaxation mechanisms in Tb3+-doped calcium aluminosilicate glasses: an investigation by thermal mirror spectroscopy.

    PubMed

    Bianchi, G S; Zanuto, V S; Astrath, F B G; Malacarne, L C; Terra, I A A; Catunda, T; Nunes, L A O; Jacinto, C; Andrade, L H C; Lima, S M; Baesso, M L; Astrath, N G C

    2013-11-15

    Resonant excited state absorption (ESA) and relaxation processes in Tb(3+)-doped aluminosilicate glasses are quantitatively evaluated. A model describing the excitation steps and upconversion emission is developed and applied to interpret the results from laser-induced surface deformation using thermal mirror spectroscopy. The fluorescence quantum efficiency of level (5)D(4) was found to be close to unity and concentration independent while, for the level (5)D(3), it decreases with Tb(3+) concentration. Emission spectroscopy measurements supported these results. ESA cross sections are found to be more than three orders of magnitude higher than the ground state absorption cross section. PMID:24322101

  17. X-ray absorption spectroscopy and EPR studies of oriented spinach thylakoid preparations

    SciTech Connect

    Andrews, J.C. |

    1995-08-01

    In this study, oriented Photosystem II (PS II) particles from spinach chloroplasts are studied with electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) to determine more details of the structure of the oxygen evolving complex (OEC). The nature of halide binding to Mn is also studied with Cl K-edge and Mn EXAFS (extended x-ray absorption fine structure) of Mn-Cl model compounds, and with Mn EXAFS of oriented PS II in which Br has replaced Cl. Attention is focused on the following: photosynthesis and the oxygen evolving complex; determination of mosaic spread in oriented photosystem II particles from signal II EPR measurement; oriented EXAFS--studies of PS II in the S{sub 2} state; structural changes in PS II as a result of treatment with ammonia: EPR and XAS studies; studies of halide binding to Mn: Cl K-edge and Mn EXAFS of Mn-Cl model compounds and Mn EXAFS of oriented Br-treated photosystem II.

  18. β-Carotene Revisited by Transient Absorption and Stimulated Raman Spectroscopy.

    PubMed

    Quick, Martin; Kasper, Marc-André; Richter, Celin; Mahrwald, Rainer; Dobryakov, Alexander L; Kovalenko, Sergey A; Ernsting, Nikolaus P

    2015-12-21

    β-Carotene in n-hexane was examined by femtosecond transient absorption and stimulated Raman spectroscopy. Electronic change is separated from vibrational relaxation with the help of band integrals. Overlaid on the decay of S1 excited-state absorption, a picosecond process is found that is absent when the C9 -methyl group is replaced by ethyl or isopropyl. It is attributed to reorganization on the S1 potential energy surface, involving dihedral angles between C6 and C9 . In Raman studies, electronic states S2 or S1 were selected through resonance conditions. We observe a broad vibrational band at 1770 cm(-1) in S2 already. With 200 fs it decays and transforms into the well-known S1 Raman line for an asymmetric C=C stretching mode. Low-frequency activity (<800 cm(-1) ) in S2 and S1 is also seen. A dependence of solvent lines on solute dynamics implies intermolecular coupling between β-carotene and nearby n-hexane molecules. PMID:26433210

  19. In Situ X-Ray Absorption Spectroscopy Study of the LiNiO2 Electrode

    NASA Astrophysics Data System (ADS)

    Mansour, A. N.; McBreen, J.; Melendres, C. A.

    1997-03-01

    LiNiO2 is one of the most promising active material for the development of novel 4V rechargeable lithium batteries. Recent x-ray diffraction studies showed that the electrochemical reactivity of this electrode is sensitive to the structure of the starting material as well as the charged products. To further examine this material, we have conducted an x-ray absorption spectroscopy (XAS) study to determine the structure of this electrode as a function of its charge state. Specifically, the x-ray absorption Ni K-edge energy, the pre-edge structure, and local structure parameters such as bond lengths, coordination numbers and disorders were investigated at various states of charge corresponding to Li_(1-x)NiO2 for x values of 0.0, 0.11, 0.23, 0.34, 0.45, 0.82, and 0.99. The charging which proceeds via lithium de-intercalation was conducted using constant current anodization at 0.5 mA in a non aqueous electrolyte consisting of 1M LiPF6 in 1:1:3 propylene ! carbonate, ethylene carbonate and dimethyl carbonate. The XAS results for this electrode will be compared with those of γ-NiOOH and KNiIO_6, the latter being used as a reference for quadrivalent nickel.

  20. Photo-induced dynamics in heterocyclic aromatic molecules probed by femtosecond XUV transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lackner, Florian; Chatterley, Adam S.; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.; Gessner, Oliver

    2016-05-01

    We report on the ring-opening and dissociation dynamics of strong-field ionized selenophene (C4 H4 Se), studied by transient XUV absorption spectroscopy at the Se 3d edge. The table-top experiments are facilitated by high-order harmonic generation coupled with a gas phase transient XUV absorption setup that is optimized for the study of organic compounds. Employing element-specific core-to-valence transitions, the ultrafast molecular dynamics are monitored from the perspective of the well-localized Se atoms. Spectral features are assigned based on first principles TDDFT calculations for a large manifold of electronic states. We observe signatures of rapidly (~ 35 fs) decaying highly excited molecular cations, the formation of ring-opened products on a 100 fs time scale and, most notably, the elimination of bare Se+ ions in a very rapid multi-step process. A delayed onset of the Se+ ions provides direct evidence that both selenium-carbon bonds are broken within only ~ 130 fs and that a sequential mechanism, presumably an initial ring-opening followed by a subsequent breaking of the second bond, is required to eliminate the atomic fragments.

  1. Strontium localization in bone tissue studied by X-ray absorption spectroscopy.

    PubMed

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Stahl, Kenny

    2014-02-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X-ray absorption spectra resulted in a compositional model and allowed the relative distribution of strontium in the different bone components to be estimated. Approximately 35-45% of the strontium present is incorporated into calcium hydroxyapatite (CaHA) by substitution of some of the calcium ions occupying highly ordered sites, and at least 30% is located at less ordered sites where only the first solvation shell is resolved, suggesting that strontium is surrounded by only oxygen atoms similar to Sr(2+) in solution. Strontium was furthermore shown to be absorbed in collagen in which it obtains a higher structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas the relative distribution of strontium among the different components appears to be independent of treatment period and dose level.

  2. X-ray absorption spectroscopy as a probe of dissolved polysulfides in lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2015-03-01

    There has been enormous interest lately in lithium sulfur batteries, since they have 5 times the theoretical capacity of lithium ion batteries. Large-scale adoption of this technology has been hampered by numerous shortcomings, chiefly the poor utilization of the active cathode material and rapid capacity fading during cycling. Overcoming these limitations requires methods capable of identifying and quantifying the products of the poorly understood electrochemical reactions. One recent advance has been the use of X-ray absorption spectroscopy (XAS), an element-specific probe of the unoccupied energy levels around an excited atom upon absorption of an X-ray photon, to identify the reaction products and intermediates. In this talk, we'll present first principles molecular dynamics and spectral simulations of dissolved lithium polysulfide species, showing how finite temperature dynamics, molecular geometry, molecular charge state and solvent environment conspire to determine the peak positions and intensity of the XAS. We'll present a spectral analysis of the radical (-1e charge) species, and reveal a unique low energy feature that can be used to identify these species from their more common dianion (-2e charge) counterparts.

  3. Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 2. Closure study.

    PubMed

    Müller, Thomas; Müller, Detlef; Dubois, René

    2006-04-01

    Spectral particle extinction coefficients of atmospheric aerosols were measured with, to the best of our knowledge, a newly designed differential optical absorption spectroscopy (DOAS) instrument. A closure study was carried out on the basis of optical and microphysical aerosol properties obtained from nephelometer, particle soot/absorption photometer, hygroscopic tandem differential mobility analyzer, twin differential mobility particle sizer, aerodynamic particle sizer, and Berner impactors. The data were collected at the urban site of Leipzig during a period of 10 days in March 2000. The performance test also includes a comparison of the optical properties measured with DOAS to particle optical properties calculated with a Mie-scattering code. The computations take into account dry and ambient particle conditions. Under dry particle conditions the linear regression and the correlation coefficient for particle extinction are 0.95 and 0.90, respectively. At ambient conditions these parameters are 0.89 and 0.97, respectively. An inversion algorithm was used to retrieve microphysical particle properties from the extinction coefficients measured with DOAS. We found excellent agreement within the retrieval uncertainties.

  4. [Study on Differential Optical Absorption Spectroscopy Data Processing Based on Chirp-Z Transformation].

    PubMed

    Zheng, Hai-ming; Li, Guang-jie; Wu, Hao

    2015-06-01

    Differential optical absorption spectroscopy (DOAS) is a commonly used atmospheric pollution monitoring method. Denoising of monitoring spectral data will improve the inversion accuracy. Fourier transform filtering method is effectively capable of filtering out the noise in the spectral data. But the algorithm itself can introduce errors. In this paper, a chirp-z transform method is put forward. By means of the local thinning of Fourier transform spectrum, it can retain the denoising effect of Fourier transform and compensate the error of the algorithm, which will further improve the inversion accuracy. The paper study on the concentration retrieving of SO2 and NO2. The results show that simple division causes bigger error and is not very stable. Chirp-z transform is proved to be more accurate than Fourier transform. Results of the frequency spectrum analysis show that Fourier transform cannot solve the distortion and weakening problems of characteristic absorption spectrum. Chirp-z transform shows ability in fine refactoring of specific frequency spectrum.

  5. Cavity-enhanced absorption spectroscopy with a red LED source for NOx trace analysis

    NASA Astrophysics Data System (ADS)

    Triki, M.; Cermak, P.; Méjean, G.; Romanini, D.

    2008-04-01

    Incoherent broad-band cavity-enhanced absorption spectroscopy (IBB-CEAS) based on arc lamps has been around for a few years, but only two reports exist using light-emitting diodes (LEDs). We present a setup based on a 643-nm LED which is of interest for the simultaneous detection of NO3 and NO2. The latter is chosen for testing as it is stable and available in calibrated diluted samples. A detection limit in the ppbv range is obtained with 2-min averaging (5×10-9 /cm rms baseline noise level), comparable to the best performance of chemiluminescence devices used for pollution monitoring. At 1-s acquisition time, the detection limit is below 10 ppbv. Extrapolation to NO3 yields a detection limit of a few pptv for a few minutes averaging. We also test the retrieval of absolute sample absorption (and concentration) using the cavity mirror reflectivity obtained with a commercial spectrophotometer, and we conclude that a calibration based on a reference sample of known concentration is preferable for accurate concentration measurements with IBB-CEAS. Finally, we present a rigorous frequency-domain derivation of cavity transmission as a function of wavelength for a broad-band spectrally smooth source, which complements the time-domain derivation by Fiedler et al. This derivation exposes an issue with multiple transverse mode excitation inherent to this technique, which may result in slightly distorted spectral profiles.

  6. Metamaterial-enhanced vibrational absorption spectroscopy for the detection of protein molecules

    NASA Astrophysics Data System (ADS)

    Bui, Tung S.; Dao, Thang D.; Dang, Luu H.; Vu, Lam D.; Ohi, Akihiko; Nabatame, Toshihide; Lee, Youngpak; Nagao, Tadaaki; Hoang, Chung V.

    2016-08-01

    From visible to mid-infrared frequencies, molecular sensing has been a major successful application of plasmonics because of the enormous enhancement of the surface electromagnetic nearfield associated with the induced collective motion of surface free carriers excited by the probe light. However, in the lower-energy terahertz (THz) region, sensing by detecting molecular vibrations is still challenging because of low sensitivity, complicated spectral features, and relatively little accumulated knowledge of molecules. Here, we report the use of a micron-scale thin-slab metamaterial (MM) architecture, which functions as an amplifier for enhancing the absorption signal of the THz vibration of an ultrathin adsorbed layer of large organic molecules. We examined bovine serum albumin (BSA) as a prototype large protein molecule and Rhodamine 6G (Rh6G) and 3,3‧-diethylthiatricarbocyanine iodide (DTTCI) as examples of small molecules. Among them, our MM significantly magnified only the signal strength of bulky BSA. On the other hand, DTTCI and Rh6G are inactive, as they lack low-frequency vibrational modes in this frequency region. The results obtained here clearly demonstrate the promise of MM-enhanced absorption spectroscopy in the THz region for detection and structural monitoring of large biomolecules such as proteins or pathogenic enzymes.

  7. Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS) in low pressure flames

    SciTech Connect

    Scherer, J.J.; Rakestraw, D.J.

    1996-12-31

    The authors have employed Infrared Cavity Ringdown Laser Absorption Spectroscopy (IR-CRLAS) as a diagnostic tool for combustion chemistry studies. High resolution rovibrational absorption spectra have been obtained in low pressure laminar flames in the mid-infrared employing a pulsed single mode optical parametric oscillator (OPO) laser system. The high sensitivity and generality of IR-CRLAS for combustion studies is demonstrated in a variety of flames and is shown to be robust even in sooting environments with high temperature gradients. The ability to obtain spatially resolved data is also demonstrated in one dimensional laminar flame studies. These preliminary results indicate the potential of IR-CRLAS as a combustion diagnostic which is capable of obtaining absolute concentrations of reactants, intermediates, and products simultaneously within a narrow spectral region. In this demonstration, two information rich mid-infrared spectral regions (1.6 and 3-4 microns) have been probed at Doppler-limited resolution with an effective laser bandwidth of < 0.007 cm{sup -1}.

  8. Time-resolved tunable diode laser absorption spectroscopy of pulsed plasma.

    PubMed

    Adámek, P; Olejníček, J; Čada, M; Kment, Š; Hubička, Z

    2013-07-15

    A method for time-resolved tunable diode laser absorption spectroscopy (LAS) has been developed. In this Letter, we describe in detail a developed electronic module that controls the time resolution of the LAS system. The transistor-transistor logic signal triggering the plasma pulse is used for generation of two signals: the first one triggers fine tuning of the laser wavelength and the second one controls time-defined signal sampling from the absorption detector. The described method and electronic system enable investigation of the temporal evolution of the density and temperature of selected particles in technological plasma systems. The high-power impulse magnetron sputtering system with a period of 10 ms and a duty cycle of 1% has been used to verify this method. The temporal evolution of argon metastable density was measured in the active part of the pulse and in the afterglow. The resulting density of Ar* displays a double-peak structure with a first peak in the plasma "ON" phase and a second peak in the afterglow approximately 1 ms after the end of the pulse.

  9. Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

    NASA Astrophysics Data System (ADS)

    Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

    2015-11-01

    The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

  10. Millisecond Kinetics of Nanocrystal Cation Exchange UsingMicrofluidic X-ray Absorption Spectroscopy

    SciTech Connect

    Chan, Emory M.; Marcus, Matthew A.; Fakra, Sirine; Elnaggar,Mariam S.; Mathies, Richard A.; Alivisatos, A. Paul

    2007-05-07

    We describe the use of a flow-focusing microfluidic reactorto measure the kinetics of theCdSe-to-Ag2Se nanocrystal cation exchangereaction using micro-X-ray absorption spectroscopy (mu XAS). The smallmicroreactor dimensions facilitate the millisecond mixing of CdSenanocrystal and Ag+ reactant solutions, and the transposition of thereaction time onto spatial coordinates enables the in situ observation ofthe millisecond reaction with mu XAS. XAS spectra show the progression ofCdSe nanocrystals to Ag2Se over the course of 100 ms without the presenceof long-lived intermediates. These results, along with supporting stoppedflow absorption experiments, suggest that this nanocrystal cationexchange reaction is highly efficient and provide insight into how thereaction progresses in individual particles. This experiment illustratesthe value and potential of in situ microfluidic X-ray synchrotrontechniques for detailed studies of the millisecond structuraltransformations of nanoparticles and other solution-phase reactions inwhich diffusive mixing initiates changes in local bond structures oroxidation states.

  11. Calculation of the spatial resolution in two-photon absorption spectroscopy applied to plasma diagnosis

    SciTech Connect

    Garcia-Lechuga, M.; Fuentes, L. M.; Grützmacher, K.; Pérez, C. Rosa, M. I. de la

    2014-10-07

    We report a detailed characterization of the spatial resolution provided by two-photon absorption spectroscopy suited for plasma diagnosis via the 1S-2S transition of atomic hydrogen for optogalvanic detection and laser induced fluorescence (LIF). A precise knowledge of the spatial resolution is crucial for a correct interpretation of measurements, if the plasma parameters to be analysed undergo strong spatial variations. The present study is based on a novel approach which provides a reliable and realistic determination of the spatial resolution. Measured irradiance distribution of laser beam waists in the overlap volume, provided by a high resolution UV camera, are employed to resolve coupled rate equations accounting for two-photon excitation, fluorescence decay and ionization. The resulting three-dimensional yield distributions reveal in detail the spatial resolution for optogalvanic and LIF detection and related saturation due to depletion. Two-photon absorption profiles broader than the Fourier transform-limited laser bandwidth are also incorporated in the calculations. The approach allows an accurate analysis of the spatial resolution present in recent and future measurements.

  12. [Study on Differential Optical Absorption Spectroscopy Data Processing Based on Chirp-Z Transformation].

    PubMed

    Zheng, Hai-ming; Li, Guang-jie; Wu, Hao

    2015-06-01

    Differential optical absorption spectroscopy (DOAS) is a commonly used atmospheric pollution monitoring method. Denoising of monitoring spectral data will improve the inversion accuracy. Fourier transform filtering method is effectively capable of filtering out the noise in the spectral data. But the algorithm itself can introduce errors. In this paper, a chirp-z transform method is put forward. By means of the local thinning of Fourier transform spectrum, it can retain the denoising effect of Fourier transform and compensate the error of the algorithm, which will further improve the inversion accuracy. The paper study on the concentration retrieving of SO2 and NO2. The results show that simple division causes bigger error and is not very stable. Chirp-z transform is proved to be more accurate than Fourier transform. Results of the frequency spectrum analysis show that Fourier transform cannot solve the distortion and weakening problems of characteristic absorption spectrum. Chirp-z transform shows ability in fine refactoring of specific frequency spectrum. PMID:26601381

  13. NO2 measurements in Hong Kong using LED based long path differential optical absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Chan, K. L.; Pöhler, D.; Kuhlmann, G.; Hartl, A.; Platt, U.; Wenig, M. O.

    2012-05-01

    In this study we present the first long term measurements of atmospheric nitrogen dioxide (NO2) using a LED based Long Path Differential Optical Absorption Spectroscopy (LP-DOAS) instrument. This instrument is measuring continuously in Hong Kong since December 2009, first in a setup with a 550 m absorption path and then with a 3820 m path at about 30 m to 50 m above street level. The instrument is using a high power blue light LED with peak intensity at 450 nm coupled into the telescope using a Y-fibre bundle. The LP-DOAS instrument measures NO2 levels in the Kowloon Tong and Mongkok district of Hong Kong and we compare the measurement results to mixing ratios reported by monitoring stations operated by the Hong Kong Environmental Protection Department in that area. Hourly averages of coinciding measurements are in reasonable agreement (R = 0.74). Furthermore, we used the long-term data set to validate the Ozone Monitoring Instrument (OMI) NO2 data product. Monthly averaged LP-DOAS and OMI measurements correlate well (R = 0.84) when comparing the data for the OMI overpass time. We analyzed weekly patterns in both data sets and found that the LP-DOAS detects a clear weekly cycle with a reduction on weekends during rush hour peaks, whereas OMI is not able to observe this weekly cycle due to its fix overpass time (13:30-14:30 LT - local time).

  14. Metamaterial-enhanced vibrational absorption spectroscopy for the detection of protein molecules.

    PubMed

    Bui, Tung S; Dao, Thang D; Dang, Luu H; Vu, Lam D; Ohi, Akihiko; Nabatame, Toshihide; Lee, YoungPak; Nagao, Tadaaki; Hoang, Chung V

    2016-01-01

    From visible to mid-infrared frequencies, molecular sensing has been a major successful application of plasmonics because of the enormous enhancement of the surface electromagnetic nearfield associated with the induced collective motion of surface free carriers excited by the probe light. However, in the lower-energy terahertz (THz) region, sensing by detecting molecular vibrations is still challenging because of low sensitivity, complicated spectral features, and relatively little accumulated knowledge of molecules. Here, we report the use of a micron-scale thin-slab metamaterial (MM) architecture, which functions as an amplifier for enhancing the absorption signal of the THz vibration of an ultrathin adsorbed layer of large organic molecules. We examined bovine serum albumin (BSA) as a prototype large protein molecule and Rhodamine 6G (Rh6G) and 3,3'-diethylthiatricarbocyanine iodide (DTTCI) as examples of small molecules. Among them, our MM significantly magnified only the signal strength of bulky BSA. On the other hand, DTTCI and Rh6G are inactive, as they lack low-frequency vibrational modes in this frequency region. The results obtained here clearly demonstrate the promise of MM-enhanced absorption spectroscopy in the THz region for detection and structural monitoring of large biomolecules such as proteins or pathogenic enzymes. PMID:27555217

  15. Strontium localization in bone tissue studied by X-ray absorption spectroscopy.

    PubMed

    Frankær, Christian Grundahl; Raffalt, Anders Christer; Stahl, Kenny

    2014-02-01

    Strontium has recently been introduced as a pharmacological agent for the treatment and prevention of osteoporosis. We determined the localization of strontium incorporated into bone matrix from dogs treated with Sr malonate by X-ray absorption spectroscopy. A new approach for analyzing the X-ray absorption spectra resulted in a compositional model and allowed the relative distribution of strontium in the different bone components to be estimated. Approximately 35-45% of the strontium present is incorporated into calcium hydroxyapatite (CaHA) by substitution of some of the calcium ions occupying highly ordered sites, and at least 30% is located at less ordered sites where only the first solvation shell is resolved, suggesting that strontium is surrounded by only oxygen atoms similar to Sr(2+) in solution. Strontium was furthermore shown to be absorbed in collagen in which it obtains a higher structural order than when present in serum but less order than when it is incorporated into CaHA. The total amount of strontium in the samples was determined by inductively coupled plasma mass spectrometry, and the amount of Sr was found to increase with increasing dose levels and treatment periods, whereas the relative distribution of strontium among the different components appears to be independent of treatment period and dose level. PMID:24101232

  16. X-ray-absorption-spectroscopy study of manganese-containing compounds and photosynthetic spinach chloroplasts

    SciTech Connect

    Kirby, J.A.

    1981-05-01

    The manganese sites in chloroplasts, long thought to be involved in photosynthetic oxygen evolution have been examined and partially characterized by x-ray Absorption Spectroscopy (XAS) using synchrotron radiation. The local environment about the manganese atoms is estimated from an analysis of the extended X-ray Absorption Fine Structure (EXAFS). Comparisons with and simulations of the manganese EXAFS for several reference compounds leads to a model in which the chloroplast manganese atoms are contained in a binuclear complex similar to di-u-oxo-tetrakis-(2,2'-bipyridine) dimanganese. It is suggested that the partner metal is another manganese. The bridging ligands are most probably oxygen. The remaining manganese ligands are carbon, oxygen, or nitrogen. A roughly linear correlation between the X-ray K edge onset energy and the coordination charge of a large number of manganese coordination complexes and compounds has been developed. Entry of the chloroplast manganese edge energy onto this correlation diagram establishes that the active pool of manganese is in an oxidation state greater than +2.

  17. Metamaterial-enhanced vibrational absorption spectroscopy for the detection of protein molecules

    PubMed Central

    Bui, Tung S.; Dao, Thang D.; Dang, Luu H.; Vu, Lam D.; Ohi, Akihiko; Nabatame, Toshihide; Lee, YoungPak; Nagao, Tadaaki; Hoang, Chung V.

    2016-01-01

    From visible to mid-infrared frequencies, molecular sensing has been a major successful application of plasmonics because of the enormous enhancement of the surface electromagnetic nearfield associated with the induced collective motion of surface free carriers excited by the probe light. However, in the lower-energy terahertz (THz) region, sensing by detecting molecular vibrations is still challenging because of low sensitivity, complicated spectral features, and relatively little accumulated knowledge of molecules. Here, we report the use of a micron-scale thin-slab metamaterial (MM) architecture, which functions as an amplifier for enhancing the absorption signal of the THz vibration of an ultrathin adsorbed layer of large organic molecules. We examined bovine serum albumin (BSA) as a prototype large protein molecule and Rhodamine 6G (Rh6G) and 3,3′-diethylthiatricarbocyanine iodide (DTTCI) as examples of small molecules. Among them, our MM significantly magnified only the signal strength of bulky BSA. On the other hand, DTTCI and Rh6G are inactive, as they lack low-frequency vibrational modes in this frequency region. The results obtained here clearly demonstrate the promise of MM-enhanced absorption spectroscopy in the THz region for detection and structural monitoring of large biomolecules such as proteins or pathogenic enzymes. PMID:27555217

  18. Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 2. Closure study.

    PubMed

    Müller, Thomas; Müller, Detlef; Dubois, René

    2006-04-01

    Spectral particle extinction coefficients of atmospheric aerosols were measured with, to the best of our knowledge, a newly designed differential optical absorption spectroscopy (DOAS) instrument. A closure study was carried out on the basis of optical and microphysical aerosol properties obtained from nephelometer, particle soot/absorption photometer, hygroscopic tandem differential mobility analyzer, twin differential mobility particle sizer, aerodynamic particle sizer, and Berner impactors. The data were collected at the urban site of Leipzig during a period of 10 days in March 2000. The performance test also includes a comparison of the optical properties measured with DOAS to particle optical properties calculated with a Mie-scattering code. The computations take into account dry and ambient particle conditions. Under dry particle conditions the linear regression and the correlation coefficient for particle extinction are 0.95 and 0.90, respectively. At ambient conditions these parameters are 0.89 and 0.97, respectively. An inversion algorithm was used to retrieve microphysical particle properties from the extinction coefficients measured with DOAS. We found excellent agreement within the retrieval uncertainties. PMID:16607998

  19. Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 1. system setup and characterization.

    PubMed

    Müller, Thomas; Müller, Detlef; Dubois, René

    2005-03-20

    We describe an instrument for measuring the particle extinction coefficient at ambient conditions in the spectral range from 270 to 1000 nm. It is based on a differential optical absorption spectroscopy (DOAS) system, which was originally used for measuring trace-gas concentrations of atmospheric absorbers in the ultraviolet-visible wavelength range. One obtains the particle extinction spectrum by measuring the total atmospheric extinction and subtracting trace-gas absorption and Rayleigh scattering. The instrument consists of two nested Newton-type telescopes, which are simultaneously used for emitting and detecting light, and two arrays of retroreflectors at the ends of the two light paths. The design of this new instrument solves crucial problems usually encountered in the design of such instruments. The telescope is actively repositioned during the measurement cycle. Particle extinction is simultaneously measured at several wavelengths by the use of two grating spectrometers. Optical turbulence causes lateral movement of the spot of light in the receiver telescope. Monitoring of the return signals with a diode permits correction for this effect. Phase-sensitive detection efficiently suppresses background signals from the atmosphere as well as from the instrument itself. The performance of the instrument was tested during a measurement period of 3 months from January to March 2000. The instrument ran without significant interruption during that period. A mean accuracy of 0.032 km(-1) was found for the extinction coefficient for an 11-day period in March. PMID:15813269

  20. Measurement of tropospheric OH by laser long-path absorption spectroscopy

    NASA Technical Reports Server (NTRS)

    Kraft, Michael; Perner, D.

    1994-01-01

    OH-radicals are measured by laser long-path absorption spectroscopy. A tunable Nd:YAG/dye laser system provides broadbanded light at 308 nm. The beam is expanded to 0.3 m and pointed to an array of retroreflectors placed at a distance of 2800 m. The returning beam is separated from the outgoing beam and focused into a spectrometer of 0.3 pm resolution. A 1024 element diode array is used as a detector. The signal is digitized by a 14 bit analog to digital converter. The ultimate aim is a detection limit of 10(exp 5) molecules cm(exp -3) of OH. However the measurements in 1991 allowed only the recognition of OH absorptions corresponding to 3 x 10(exp 6) OH cm(exp -3) with a signal to noise ratio of two. Improvements of the instrument are under way. The advantages of the DOAS method are: the accuracy of detection is guaranteed because loss of OH radicals within the device is avoided, the rate of OH production by the device is negligible, and absorptions of other trace gases could be corrected for; and the calibration procedure for the device is fast and easy. The disadvantages of the system are: time resolution is about minutes because about ten spectra had to be added to keep the noise level down, the OH concentration is averaged along the whole light path, weight (500 kg) and size (4x4 m) of the device; and approximately 10 l/min of coolant and supply of 8 kW electrical power are necessary.

  1. Multipitched Diffraction Gratings for Surface Plasmon Resonance-Enhanced Infrared Reflection Absorption Spectroscopy.

    PubMed

    Petefish, Joseph W; Hillier, Andrew C

    2015-11-01

    We demonstrate the application of metal-coated diffraction gratings possessing multiple simultaneous pitch values for surface enhanced infrared absorption (SEIRA) spectroscopy. SEIRA increases the magnitude of vibrational signals in infrared measurements by one of several mechanisms, most frequently involving the enhanced electric field associated with surface plasmon resonance (SPR). While the majority of SEIRA applications to date have employed nanoparticle-based plasmonic systems, recent advances have shown how various metals and structures lead to similar signal enhancement. Recently, diffraction grating couplers have been demonstrated as a highly tunable platform for SEIRA. Indeed, gratings are an experimentally advantageous platform due to the inherently tunable nature of surface plasmon excitation at these surfaces since both the grating pitch and incident angle can be used to modify the spectral location of the plasmon resonance. In this work, we use laser interference lithography (LIL) to fabricate gratings possessing multiple pitch values by subjecting photoresist-coated glass slides to repetitive exposures at varying orientations. After metal coating, these gratings produced multiple, simultaneous plasmon peaks associated with the multipitched surface, as identified by infrared reflectance measurements. These plasmon peaks could then be coupled to vibrational modes in thin films to provide localized enhancement of infrared signals. We demonstrate the flexibility and tunability of this platform for signal enhancement. It is anticipated that, with further refinement, this approach might be used as a general platform for broadband enhancement of infrared spectroscopy. PMID:26458177

  2. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

  3. Characterising legacy spent nuclear fuel pond materials using microfocus X-ray absorption spectroscopy.

    PubMed

    Bower, W R; Morris, K; Mosselmans, J F W; Thompson, O R; Banford, A W; Law, K; Pattrick, R A D

    2016-11-01

    Analysis of a radioactive, coated concrete core from the decommissioned, spent nuclear fuel cooling pond at the Hunterston-A nuclear site (UK) has provided a unique opportunity to study radionuclides within a real-world system. The core, obtained from a dividing wall and sampled at the fill level of the pond, exhibited radioactivity (dominantly (137)Cs and (90)Sr) heterogeneously distributed across both painted faces. Chemical analysis of the core was undertaken using microfocus spectroscopy at Diamond Light Source, UK. Mapping of Sr across the surface coatings using microfocus X-ray fluorescence (μXRF) combined with X-ray absorption spectroscopy showed that Sr was bound to TiO2 particles in the paint layers, suggesting an association between TiO2 and radiostrontium. Stable Sr and Cs sorption experiments using concrete coupons were also undertaken to assess their interactions with the bulk concrete in case of a breach in the coating layers. μXRF and scanning electron microscopy showed that Sr was immobilized by the cement phases, whilst at the elevated experimental concentrations, Cs was associated with clay minerals in the aggregates. This study provides a crucial insight into poorly understood infrastructural contamination in complex systems and is directly applicable to the UK's nuclear decommissioning efforts. PMID:27262277

  4. Multipitched Diffraction Gratings for Surface Plasmon Resonance-Enhanced Infrared Reflection Absorption Spectroscopy.

    PubMed

    Petefish, Joseph W; Hillier, Andrew C

    2015-11-01

    We demonstrate the application of metal-coated diffraction gratings possessing multiple simultaneous pitch values for surface enhanced infrared absorption (SEIRA) spectroscopy. SEIRA increases the magnitude of vibrational signals in infrared measurements by one of several mechanisms, most frequently involving the enhanced electric field associated with surface plasmon resonance (SPR). While the majority of SEIRA applications to date have employed nanoparticle-based plasmonic systems, recent advances have shown how various metals and structures lead to similar signal enhancement. Recently, diffraction grating couplers have been demonstrated as a highly tunable platform for SEIRA. Indeed, gratings are an experimentally advantageous platform due to the inherently tunable nature of surface plasmon excitation at these surfaces since both the grating pitch and incident angle can be used to modify the spectral location of the plasmon resonance. In this work, we use laser interference lithography (LIL) to fabricate gratings possessing multiple pitch values by subjecting photoresist-coated glass slides to repetitive exposures at varying orientations. After metal coating, these gratings produced multiple, simultaneous plasmon peaks associated with the multipitched surface, as identified by infrared reflectance measurements. These plasmon peaks could then be coupled to vibrational modes in thin films to provide localized enhancement of infrared signals. We demonstrate the flexibility and tunability of this platform for signal enhancement. It is anticipated that, with further refinement, this approach might be used as a general platform for broadband enhancement of infrared spectroscopy.

  5. Interactions of Polyvinylpyrrolidone with Chlorin e6-Based Photosensitizers Studied by NMR and Electronic Absorption Spectroscopy.

    PubMed

    Hädener, Marianne; Gjuroski, Ilche; Furrer, Julien; Vermathen, Martina

    2015-09-10

    Polyvinylpyrrolidone (PVP) can act as potential drug delivery vehicle for porphyrin-based photosensitizers in photodynamic therapy (PDT) to enhance their stability and prevent porphyrin self-association. In the present study the interactions of PVP (MW 10 kDa) were probed with five different derivatives of chlorin e6 (CE6) bearing either one of the amino acids serine, lysine, tyrosine or arginine, or monoamino-hexanoic acid as substituent. All derivatives of CE6 (xCE) formed aggregates of a similar structure in aqueous buffer in the millimolar range. In the presence of PVP monomerization of all xCE aggregates could be proved by (1)H NMR spectroscopy. xCE-PVP complex formation was confirmed by (1)H NMR T2 relaxation and diffusion ordered spectroscopy (DOSY). (1)H(1)H-NOESY data suggested that the xCE uptake into the PVP polymer matrix is governed by hydrophobic interactions. UV-vis absorption and fluorescence emission bands of xCE in the micromolar range revealed characteristic PVP-induced bathochromic shifts. The presented data point out the potential of PVP as carrier system for amphiphilic derivatives of chlorin e6. The capacity of PVP to monomerize xCE aggregates may enhance their efficiency as possible photosensitizers in PDT.

  6. Towards a standard for the dynamic measurement of pressure based on laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Douglass, K. O.; Olson, D. A.

    2016-06-01

    We describe an approach for creating a standard for the dynamic measurement of pressure based on the measurement of fundamental quantum properties of molecular systems. From the linewidth and intensities of ro-vibrational transitions we plan on making an accurate determination of pressure and temperature. The goal is to achieve an absolute uncertainty for time-varying pressure of 5% with a measurement rate of 100 kHz, which will in the future serve as a method for the traceable calibration of pressure sensors used in transient processes. To illustrate this concept we have used wavelength modulation spectroscopy (WMS), due to inherent advantages over direct absorption spectroscopy, to perform rapid measurements of carbon dioxide in order to determine the pressure. The system records the full lineshape profile of a single ro-vibrational transition of CO2 at a repetition rate of 4 kHz and with a systematic measurement uncertainty of 12% for the linewidth measurement. A series of pressures were measured at a rate of 400 Hz (10 averages) and from these measurements the linewidth was determined with a relative uncertainty of about 0.5% on average. The pressures measured using WMS have an average difference of 0.6% from the absolute pressure measured with a capacitance diaphragm sensor.

  7. Synchrotron soft X-ray absorption spectroscopy study of carbon and silicon nanostructures for energy applications.

    PubMed

    Zhong, Jun; Zhang, Hui; Sun, Xuhui; Lee, Shuit-Tong

    2014-12-10

    Carbon and silicon materials are two of the most important materials involved in the history of the science and technology development. In the last two decades, C and Si nanoscale materials, e.g., carbon nanotubes, graphene, and silicon nanowires, and quantum dots, have also emerged as the most interesting nanomaterials in nanoscience and nanotechnology for their myriad promising applications such as for electronics, sensors, biotechnology, etc. In particular, carbon and silicon nanostructures are being utilized in energy-related applications such as catalysis, batteries, solar cells, etc., with significant advances. Understanding of the nature of surface and electronic structures of nanostructures plays a key role in the development and improvement of energy conversion and storage nanosystems. Synchrotron soft X-ray absorption spectroscopy (XAS) and related techniques, such as X-ray emission spectroscopy (XES) and scanning transmission X-ray microscopy (STXM), show unique capability in revealing the surface and electronic structures of C and Si nanomaterials. In this review, XAS is demonstrated as a powerful technique for probing chemical bonding, the electronic structure, and the surface chemistry of carbon and silicon nanomaterials, which can greatly enhance the fundamental understanding and also applicability of these nanomaterials in energy applications. The focus is on the unique advantages of XAS as a complementary tool to conventional microscopy and spectroscopy for effectively providing chemical and structural information about carbon and silicon nanostructures. The employment of XAS for in situ, real-time study of property evolution of C and Si nanostructures to elucidate the mechanisms in energy conversion or storage processes is also discussed.

  8. Two-dimensional (2D) infrared (IR) correlation spectroscopy for dynamic absorption behavior of oleic acid (OA) onto silica gel

    NASA Astrophysics Data System (ADS)

    Genkawa, Takuma; Kanematsu, Wataru; Shinzawa, Hideyuki

    2014-07-01

    Dynamic absorption behavior of oleic acid (OA) onto silica gel was probed by infrared (IR) spectroscopy. Once OA is injected into silica gel placed on a horizontal attenuated total reflectance prism, the silica gel starts to absorb the OA molecules due to the molecular-level interaction based on hydrogen bonding between the COOH of OA and the OH of silica gel. The substantial level of variation of spectral feature is readily observed during the absorption of OA onto silica gel. 2D correlation analysis of the time-dependent IR spectra reveals fine details of absorption dynamics of OA molecules depending on the molecular structure. The predominant absorption of the monomers occurs at the onset of the absorption, and it is then quickly followed by the decrease in the dimers. In other words, the dissociation of the liquid crystals occurs via the disuniting of the tightly packed OA dimers.

  9. Time-resolved detection of temperature, concentration, and pressure in a shock tube by intracavity absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Fjodorow, Peter; Fikri, Mustapha; Schulz, Christof; Hellmig, Ortwin; Baev, Valery M.

    2016-06-01

    In this paper, we demonstrate the first application of intracavity absorption spectroscopy (ICAS) for monitoring species concentration, total pressure, and temperature in shock-tube experiments. ICAS with a broadband Er3+-doped fiber laser is applied to time-resolved measurements of absorption spectra of shock-heated C2H2. The measurements are performed in a spectral range between 6512 and 6542 cm-1, including many absorption lines of C2H2, with a time resolution of 100 µs and an effective absorption path length of 15 m. Up to 18-times increase of the total pressure and a temperature rise of up to 1200 K have been monitored. Due to the ability of simultaneously recording many absorption lines in a broad spectral range, the presented technique can also be applied to multi-component analysis of transient single-shot processes in reactive gas mixtures in shock tubes, pulse detonation engines, or explosions.

  10. Retrieval interval mapping, a tool to optimize the spectral retrieval range in differential optical absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vogel, L.; Sihler, H.; Lampel, J.; Wagner, T.; Platt, U.

    2012-06-01

    Remote sensing via differential optical absorption spectroscopy (DOAS) has become a standard technique to identify and quantify trace gases in the atmosphere. The technique is applied in a variety of configurations, commonly classified into active and passive instruments using artificial and natural light sources, respectively. Platforms range from ground based to satellite instruments and trace-gases are studied in all kinds of different environments. Due to the wide range of measurement conditions, atmospheric compositions and instruments used, a specific challenge of a DOAS retrieval is to optimize the parameters for each specific case and particular trace gas of interest. This becomes especially important when measuring close to the detection limit. A well chosen evaluation wavelength range is crucial to the DOAS technique. It should encompass strong absorption bands of the trace gas of interest in order to maximize the sensitivity of the retrieval, while at the same time minimizing absorption structures of other trace gases and thus potential interferences. Also, instrumental limitations and wavelength depending sources of errors (e.g. insufficient corrections for the Ring effect and cross correlations between trace gas cross sections) need to be taken into account. Most often, not all of these requirements can be fulfilled simultaneously and a compromise needs to be found depending on the conditions at hand. Although for many trace gases the overall dependence of common DOAS retrieval on the evaluation wavelength interval is known, a systematic approach to find the optimal retrieval wavelength range and qualitative assessment is missing. Here we present a novel tool to determine the optimal evaluation wavelength range. It is based on mapping retrieved values in the retrieval wavelength space and thus visualize the consequence of different choices of retrieval spectral ranges, e.g. caused by slightly erroneous absorption cross sections, cross correlations and

  11. Revealing electronic structure changes in Chevrel phase cathodes upon Mg insertion using X-ray absorption spectroscopy.

    PubMed

    Wan, Liwen F; Wright, Joshua; Perdue, Brian R; Fister, Timothy T; Kim, Soojeong; Apblett, Christopher A; Prendergast, David

    2016-06-29

    Following previous work predicting the electronic response of the Chevrel phase Mo6S8 upon Mg insertion (Thöle et al., Phys. Chem. Chem. Phys., 2015, 17, 22548), we provide the experimental proof, evident in X-ray absorption spectroscopy, to illustrate the charge compensation mechanism of the Chevrel phase compound during Mg insertion and de-insertion processes. PMID:27314253

  12. A Simplified Digestion Protocol for the Analysis of Hg in Fish by Cold Vapor Atomic Absorption Spectroscopy

    ERIC Educational Resources Information Center

    Kristian, Kathleen E.; Friedbauer, Scott; Kabashi, Donika; Ferencz, Kristen M.; Barajas, Jennifer C.; O'Brien, Kelly

    2015-01-01

    Analysis of mercury in fish is an interesting problem with the potential to motivate students in chemistry laboratory courses. The recommended method for mercury analysis in fish is cold vapor atomic absorption spectroscopy (CVAAS), which requires homogeneous analyte solutions, typically prepared by acid digestion. Previously published digestion…

  13. Electronic absorption spectroscopy of PAHs in supersonic jets and ultracold liquid helium droplets

    NASA Astrophysics Data System (ADS)

    Huisken, Friedrich; Staicu, Angela; Krasnokutski, Serge; Henning, Thomas

    Neutral and cationic polycyclic aromatic hydrocarbons (PAHs) are discussed as possible carriers of the diffuse interstellar bands (DIBs), still unassigned astrophysical absorption features observed in the spectra of reddened stars (Salama et al. 1999). Despite the importance of this class of molecules for astrophysics and nanophysics (PAHs can be regarded as nanoscale fragments of a sheet of graphite), the spectroscopic characterization of PAHs under well-defined conditions (low temperature and collision-free environment) has remained a challenge. Recently we have set up a cavity ring-down spectrometer combined with a pulsed supersonic jet expansion to study neutral and cationic PAHs under astrophysical conditions. PAHs studied so far include the neutral molecules anthracene (Staicu et al. 2004) and pyrene (Rouillé et al. 2004) as well as the cationic species naphthalene+ and anthracene+ (Sukhorukov et al. 2004). Employing another molecular beam apparatus, the same molecules (except of the cationic species) were also studied in liquid helium droplets (Krasnokutski et al. 2005, Rouillé et al. 2004). This novel technique combines several advantages of conventional matrix spectroscopy with those of gas phase spectroscopy. Notable advantages are the possibility to study molecules with low vapor pressure and to use a mass spectrometer facilitating spectral assignments. The most recent studies were devoted to phenanthrene and the more complicated (2,3)-benzofluorene. These molecules were investigated in the gas phase by cavity ring-down spectroscopy and in liquid helium droplets using depletion spectroscopy. For benzofluorene the present studies constitute the first reported measurements both in the gas phase and in helium droplets. The origin of the S1 ← S0 gas phase transition could be located at 29 894.3 cm-1, and a series of vibronic bands was recorded below 31 500 cm-1. In contrast to previously studied PAHs, the shift induced by the helium droplets was very

  14. Investigation of band gap narrowing in nitrogen-doped La2Ti2O7 with transient absorption spectroscopy.

    PubMed

    Yost, Brandon T; Cushing, Scott K; Meng, Fanke; Bright, Joeseph; Bas, Derek A; Wu, Nianqiang; Bristow, Alan D

    2015-12-14

    Doping a semiconductor can extend the light absorption range, however, it usually introduces mid-gap states, reducing the charge carrier lifetime. This report shows that doping lanthanum dititinate (La2Ti2O7) with nitrogen extends the valence band edge by creating a continuum of dopant states, increasing the light absorption edge from 380 nm to 550 nm without adding mid-gap states. The dopant states are experimentally resolved in the excited state by correlating transient absorption spectroscopy with a supercontinuum probe and DFT prediction. The lack of mid-gap states is further confirmed by measuring the excited state lifetimes, which reveal the shifted band edge only increased carrier thermalization rates to the band edge and not interband charge recombination under both ultraviolet and visible excitation. Terahertz (time-domain) spectroscopy also reveals that the conduction mechanism remains unchanged after doping, suggesting the states are delocalized. PMID:26531849

  15. Low-Dimensional Water on Ru(0001); Model System for X-ray Absorption Spectroscopy Studies of Liquid Water

    SciTech Connect

    Nordlund, D.; Ogasawara, H.; Andersson, K.J.; Tatarkhanov, M.; Salmeron, M.; Pettersson, L. G. M.; Nilsson, A.

    2009-05-11

    We present an x-ray absorption spectroscopy results for fully broken to a complete H-bond network of water molecules on Ru(0001) by varying the morphology from isolated water molecules via two-dimensional clusters to a fully covered monolayer as probed by scanning tunneling microscopy. The sensitivity of x-ray absorption to the symmetry of H-bonding is further elucidated for the amino (-NH{sub 2}) group in glycine adsorbed on Cu(110) where the E-vector is parallel either to the NH donating an H-bond or to the non-H-bonded NH. The results give further evidence for the interpretation of the various spectral features of liquid water and for the general applicability of x-ray absorption spectroscopy to analyze H-bonded systems.

  16. Low-Dimensional Water on Ru(0001)Model System for X-ray Absorption Spectroscopy Studies of Liquid Water

    SciTech Connect

    Nordlund, D

    2012-02-14

    We present an x-ray absorption spectroscopy results for fully broken to a complete H-bond network of water molecules on Ru(0001) by varying the morphology from isolated water molecules via two-dimensional clusters to a fully covered monolayer as probed by scanning tunneling microscopy. The sensitivity of x-ray absorption to the symmetry of H-bonding is further elucidated for the amino (-NH{sub 2}) group in glycine adsorbed on Cu(110) where the E-vector is parallel either to the NH donating an H-bond or to the non-H-bonded NH. The results give further evidence for the interpretation of the various spectral features of liquid water and for the general applicability of x-ray absorption spectroscopy to analyze H-bonded systems.

  17. Charge Carrier Dynamics of Quantum Confined Semiconductor Nanoparticles Analyzed via Transient Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Thibert, Arthur Joseph, III

    Semiconductor nanoparticles are tiny crystalline structures (typically range from 1 - 100 nm) whose shape in many cases can be dictated through tailored chemical synthesis with atomic scale precision. The small size of these nanoparticles often results in quantum confinement (spatial confinement of wave functions), which imparts the ability to manipulate band-gap energies thus allowing them to be optimally engineered for different applications (i.e., photovoltaics, photocatalysis, imaging). However, charge carriers excited within these nanoparticles are often involved in many different processes: trapping, trap migration, Auger recombination, non-radiative relaxation, radiative relaxation, oxidation / reduction, or multiple exciton generation. Broadband ultrafast transient absorption laser spectroscopy is used to spectrally resolve the fate of excited charge carriers in both wavelength and time, providing insight as to what synthetic developments or operating conditions will be necessary to optimize their efficiency for certain applications. This thesis outlines the effort of resolving the dynamics of excited charge carriers for several Cd and Si based nanoparticle systems using this experimental technique. The thesis is organized into five chapters and two appendices as indicated below. Chapter 1 provides a brief introduction to the photophysics of semiconductor nanoparticles. It begins by defining what nanoparticles, semiconductors, charge carriers, and quantum confinement are. From there it details how the study of charge carrier dynamics within nanoparticles can lead to increased efficiency in applications such as photocatalysis. Finally, the experimental methodology associated with ultrafast transient absorption spectroscopy is introduced and its power in mapping charge carrier dynamics is established. Chapter 2 (JPCC, 19647, 2011) introduces the first of the studied samples: water-solubilized 2D CdSe nanoribbons (NRs), which were synthesized in the Osterloh

  18. Metastable argon atom density in complex argon/acetylene plasmas determined by means of optical absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Sushkov, Vladimir; Herrendorf, Ann-Pierra; Hippler, Rainer

    2016-10-01

    Optical emission and absorption spectroscopy has been utilized to investigate the instability of acetylene-containing dusty plasmas induced by growing nano-particles. The density of Ar(1s5) metastable atoms was derived by two methods: tunable diode laser absorption spectroscopy and with the help of the branching ratio method of emitted spectral lines. Results of the two techniques agree well with each other. The density of Ar(1s3) metastable atoms was also measured by means of optical emission spectroscopy. The observed growth instability leads to pronounced temporal variations of the metastable and other excited state densities. An analysis of optical line ratios provides evidence for a depletion of free electrons during the growth cycle but no indication for electron temperature variations.

  19. Characterization of metalloproteins by high-throughput X-ray absorption spectroscopy.

    PubMed

    Shi, Wuxian; Punta, Marco; Bohon, Jen; Sauder, J Michael; D'Mello, Rhijuta; Sullivan, Mike; Toomey, John; Abel, Don; Lippi, Marco; Passerini, Andrea; Frasconi, Paolo; Burley, Stephen K; Rost, Burkhard; Chance, Mark R

    2011-06-01

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal- binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  20. Absorption Spectroscopy Study of Acid-Base and Metal-Binding Properties of Flavanones

    NASA Astrophysics Data System (ADS)

    Shubina, V. S.; Shatalina, Yu. V.

    2013-11-01

    We have used absorption spectroscopy to study the acid-base and metal-binding properties of two structurally similar flavanones: taxifolin and naringenin. We have determined the acid dissociation constants for taxifolin (pKa1 = 7.10 ± 0.05, pKa2 = 8.60 ± 0.09, pKa3 = 8.59 ± 0.19, pKa4 = 11.82 ± 0.36) and naringenin (pKa1 = 7.05 ± 0.05, pKa2 = 8.85 ± 0.09, pKa3 = 12.01 ± 0.38). The appearance of new absorption bands in the visible wavelength region let us determine the stoichiometric composition of the iron (II) complexes of the flavanones. We show that at pH 5, in solution there is a mixture of complexes between taxifolin and iron (II) ions in stoichiometric ratio 2:1 and 1:2, while at pH 7.4 and pH 9, we detect a 1:1 taxifolin:Fe(II) complex. We established that at these pH values, naringenin forms a 2:1 complex with iron (II) ions. We propose structures for the complexes formed. Comprehensive study of the acid-base properties and the metal-binding capability of the two structurally similar flavanones let us determine the structure-properties relation and the conditions under which antioxidant activity of the polyphenols appears, via chelation of variable-valence metal ions.

  1. Characterization of Metalloproteins by High-throughput X-ray Absorption Spectroscopy

    SciTech Connect

    W Shi; M Punta; J Bohon; J Sauder; R DMello; M Sullivan; J Toomey; D Abel; M Lippi; et al.

    2011-12-31

    High-throughput X-ray absorption spectroscopy was used to measure transition metal content based on quantitative detection of X-ray fluorescence signals for 3879 purified proteins from several hundred different protein families generated by the New York SGX Research Center for Structural Genomics. Approximately 9% of the proteins analyzed showed the presence of transition metal atoms (Zn, Cu, Ni, Co, Fe, or Mn) in stoichiometric amounts. The method is highly automated and highly reliable based on comparison of the results to crystal structure data derived from the same protein set. To leverage the experimental metalloprotein annotations, we used a sequence-based de novo prediction method, MetalDetector, to identify Cys and His residues that bind to transition metals for the redundancy reduced subset of 2411 sequences sharing <70% sequence identity and having at least one His or Cys. As the HT-XAS identifies metal type and protein binding, while the bioinformatics analysis identifies metal-binding residues, the results were combined to identify putative metal-binding sites in the proteins and their associated families. We explored the combination of this data with homology models to generate detailed structure models of metal-binding sites for representative proteins. Finally, we used extended X-ray absorption fine structure data from two of the purified Zn metalloproteins to validate predicted metalloprotein binding site structures. This combination of experimental and bioinformatics approaches provides comprehensive active site analysis on the genome scale for metalloproteins as a class, revealing new insights into metalloprotein structure and function.

  2. [Study on determination of plume velocity by passive differential optical absorption spectroscopy].

    PubMed

    Li, Ang; Xie, Pin-hua; Liu, Wen-qing; Liu, Jian-guo; Dou, Ke; Lin, Yi-hui

    2008-10-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure various trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range. Passive DOAS using the zenith scattered sunlight as the light source can obtain the continuous column density distribution of air pollutants (such as SO2 and NO2) by scanning the plume emitted from sources on a mobile platform, then with the plume velocity information the total emission value can be ultimately estimated. In practice it is hard to calculate the total emission because there is no efficient way to accurately get the plume velocity which is the most important parameter. Usually the wind speed near ground is used as the actual plume speed, which constitutes the greatest source of uncertainty in the passive DOAS measurements for the total emission calculation. A passive DOAS method for the determination of plume velocity of pollution source was studied in the present paper. Two passive DOAS systems were placed under the plume along the plume transmission direction to observed the scattered sunlight at one fixed sepasation angle, and then the plume velocity was derived from the time delay resulting from the plume moving a certain distance, and also the plume height needed in the plume velocity calculation was measured by the same two passive DOAS systems. Measurement of the plume emitted from a certain power plant was carried out by the two passive DOAS systems and the plume velocities of 3.6 and 5.4 m x s(-1) at two separate moments were derived. The comparison with the wind speed measured at the same time by the single theodolite wind observation method indicates that this optical remote sensing method based on passive DOAS can be used to determine the plume velocity by monitoring the total emission from sources.

  3. Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

    USGS Publications Warehouse

    Kim, C.S.; Brown, Gordon E.; Rytuba, J.J.

    2000-01-01

    Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg-1 (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of ??25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis

  4. Incorporation of arsenic in mammal bone: X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Kretschmer, X.; Pingitore, N. E.; Cruz-Jimenez, G.

    2002-12-01

    X-ray absorption spectroscopy (XAS) of the distal tibia of a modern deer, Odocoileus virginianus, revealed that the energy position of the As K edge matched that of a reference arsenic(V) model compound. Comparison of the x-ray absorption near edge structure (XANES) of the deer spectrum to the spectra of model As compounds indicated a close match to arsenate(V), e.g., zinc orthoarsenate(5). This indicates that the nearest-neighbor shell of the arsenic in the bone consists of four oxygens in the tetrahedral arrangement typical of arsenic(V) oxysalts. The XANES analysis demonstrates that the arsenic in the deer bone is not associated with an organic compound as a result of methylation. This suggests that the arsenic is associated with the mineral fraction of the bone, most likely with As substituting for P at the latter's structural site in the hydroxyapatite. The XAS data for the deer bone were very noisy due to the low level of arsenic present, just over 1 ppm.. A total of 18 scans, taking nearly a full 8-hour beam shift, were averaged to obtain the spectrum studied. It is not clear that the second neighbor shell can be characterized sufficiently from these data to confirm that As substitutes for P in hydroxyapatite. We conducted our XAS experiments on beam line 4-3 at the Stanford Synchrotron Radiation Laboratory. Data were collected in the fluorescence mode, using a solid state, 13-element Ge-detector. The energy reference was As(0) metal foil run parasitically in transmission mode during collection of the bone spectra. The edge shift seen in the experimental and As(V) model compound relative to the energy position of the arsenic(0) foil is consistent with the additional energy required to photoeject the 1-s electron of As(V), relative to that required for As(0). Arsenic content of the deer bone was determined by inductively coupled plasma mass spectrometry.

  5. [Study on determination of plume velocity by passive differential optical absorption spectroscopy].

    PubMed

    Li, Ang; Xie, Pin-hua; Liu, Wen-qing; Liu, Jian-guo; Dou, Ke; Lin, Yi-hui

    2008-10-01

    Differential optical absorption spectroscopy (DOAS) technique has been used to measure various trace gases in the atmosphere by their strongly structured absorption of radiation in the UV and visible spectral range. Passive DOAS using the zenith scattered sunlight as the light source can obtain the continuous column density distribution of air pollutants (such as SO2 and NO2) by scanning the plume emitted from sources on a mobile platform, then with the plume velocity information the total emission value can be ultimately estimated. In practice it is hard to calculate the total emission because there is no efficient way to accurately get the plume velocity which is the most important parameter. Usually the wind speed near ground is used as the actual plume speed, which constitutes the greatest source of uncertainty in the passive DOAS measurements for the total emission calculation. A passive DOAS method for the determination of plume velocity of pollution source was studied in the present paper. Two passive DOAS systems were placed under the plume along the plume transmission direction to observed the scattered sunlight at one fixed sepasation angle, and then the plume velocity was derived from the time delay resulting from the plume moving a certain distance, and also the plume height needed in the plume velocity calculation was measured by the same two passive DOAS systems. Measurement of the plume emitted from a certain power plant was carried out by the two passive DOAS systems and the plume velocities of 3.6 and 5.4 m x s(-1) at two separate moments were derived. The comparison with the wind speed measured at the same time by the single theodolite wind observation method indicates that this optical remote sensing method based on passive DOAS can be used to determine the plume velocity by monitoring the total emission from sources. PMID:19123375

  6. Source X-UV pour la spectroscopie d'absorption en régime femtoseconde

    NASA Astrophysics Data System (ADS)

    Lecherbourg, L.; Fourmaux, S.; Kieffer, J. C.; Martin, F.; Pépin, H.; Chaker, M.; Magnan, S.; Coté, C. Y.

    2006-12-01

    Les processus dynamiques se produisant lors de transitions de phase ultra-rapide peuvent être déduits à partir de mesures de diffraction ou d'absorption de rayonnement X. Les lasers femtosecondes ont récemment été utilisés pour étudier la dynamiques de la matière au moyen d'une pompe optique et d'une sonde X : du rayonnement X K alpha produit par interaction laser plasma. Nous présentons nos plus récents résultats concernant le développement d'un sytème de spectroscopie d'absorption du rayonnement X (XAS) basée sur une source laser-plasma large bande dans la gamme 1-5 nm permettant d'atteindre une résolution temporelle femtoseconde. Le système est conçu pour sonder les dynamiques électroniques ayant lieu durant la transion de phase semiconducteur-métal du dyoxide de vanadium (VO2) lorsque celle-ci est initiée par une impulsion laser femtoseconde. Dans la présente expérience, un spectre large bande proche du seuil L du vanadium (511 eV) et du seuil K de l'oxygène (525 eV) du VO2 a été généré et mesuré avec un haut rapport signal sur bruit (100), une grande résolution spectrale (Δ E/E = 4.2× 10-3), et une résolution temporelle de 1,2 ps.

  7. Ultrafast Excited State Relaxation of a Metalloporphyrin Revealed by Femtosecond X-ray Absorption Spectroscopy.

    PubMed

    Shelby, Megan L; Lestrange, Patrick J; Jackson, Nicholas E; Haldrup, Kristoffer; Mara, Michael W; Stickrath, Andrew B; Zhu, Diling; Lemke, Henrik T; Chollet, Matthieu; Hoffman, Brian M; Li, Xiaosong; Chen, Lin X

    2016-07-20

    Photoexcited Nickel(II) tetramesitylporphyrin (NiTMP), like many open-shell metalloporphyrins, relaxes rapidly through multiple electronic states following an initial porphyrin-based excitation, some involving metal centered electronic configuration changes that could be harnessed catalytically before excited state relaxation. While a NiTMP excited state present at 100 ps was previously identified by X-ray transient absorption (XTA) spectroscopy at a synchrotron source as a relaxed (d,d) state, the lowest energy excited state (J. Am. Chem. Soc., 2007, 129, 9616 and Chem. Sci., 2010, 1, 642), structural dynamics before thermalization were not resolved due to the ∼100 ps duration of the available X-ray probe pulse. Using the femtosecond (fs) X-ray pulses of the Linac Coherent Light Source (LCLS), the Ni center electronic configuration from the initial excited state to the relaxed (d,d) state has been obtained via ultrafast Ni K-edge XANES (X-ray absorption near edge structure) on a time scale from hundreds of femtoseconds to 100 ps. This enabled the identification of a short-lived Ni(I) species aided by time-dependent density functional theory (TDDFT) methods. Computed electronic and nuclear structure for critical excited electronic states in the relaxation pathway characterize the dependence of the complex's geometry on the electron occupation of the 3d orbitals. Calculated XANES transitions for these excited states assign a short-lived transient signal to the spectroscopic signature of the Ni(I) species, resulting from intramolecular charge transfer on a time scale that has eluded previous synchrotron studies. These combined results enable us to examine the excited state structural dynamics of NiTMP prior to thermal relaxation and to capture intermediates of potential photocatalytic significance.

  8. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

  9. NO_2 Trace Measurements by Optical-Feedback Cavity-Enhanced Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ventrillard-Courtillot, I.; Desbois, Th.; Foldes, T.; Romanini, D.

    2009-06-01

    In order to reach the sub-ppb NO_2 detection level required for environmental applications in remote areas, we develop a spectrometer based on a technique introduced a few years ago, named Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) [1]. It allows very sensitive and selective measurements, together with the realization of compact and robust set-ups as was subsequently demonstrated during measurements campaigns in harsh environments [2]. OF-CEAS benefits from the optical feedback to efficiently inject a cw-laser in a V-shaped high finesse cavity (typically 10 000). Cavity-enhanced absorption spectra are acquired on a small spectral region (˜1 cm^{-1}) that enables selective and quantitative measurements at a fast acquisition rate with a detection limit of several 10^{-10} cm^{-1} as reported in this work. Spectra are obtained with high spectral definition (150 MHz highly precisely spaced data points) and are self calibrated by cavity rind-down measurements regularly performed (typically every second). NO_2 measurements are performed with a commercial extended cavity diode laser around 411 nm, spectral region where intense electronic transitions occur. We will describe the set-up developed for in-situ measurements allowing real time concentration measurements at typically 5 Hz; and then report on the measurements performed with calibrated NO_2 reference samples to evaluate the linearity of the apparatus. The minimum detectable absorption loss is estimated by considering the standard deviation of the residual of one spectrum. We achieved 2x10^{-10} cm^{-1} for a single spectrum recorded in less than 100 ms at 100 mbar. It leads to a potential detection limit of 3x10^8 molecules/cm^3, corresponding to about 150 pptv at this pressure. [1] J. Morville, S. Kassi, M. Chenevier, and D. Romanini, Appl. Phys. B, 80, 1027 (2005). [2] D. Romanini, M. Chenevrier, S. Kassi, M. Schmidt, C. Valant, M. Ramonet, J. Lopez, and H.-J. Jost, Appl. Phys. B, 83, 659

  10. Application of X-ray Absorption Spectroscopy to the study of nuclear structural materials

    NASA Astrophysics Data System (ADS)

    Liu, Shanshan

    One of key technologies for the next generation nuclear systems are advanced materials, including high temperature structural materials, fast neutron resistance core materials and so on. Local structure determination in these systems, which often are crystallographically intractable, is critical to gaining an understanding of their properties. In this thesis, X-ray Absorption Spectroscopy (XAS), including Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES), is used to examine the geometric and electronic structure of nuclear structural materials under varying conditions. The thesis is divided into two main sections. The first examines the structural analysis of nanostructured ferritic alloys (NFA) which are dispersion strengthened by an ultra high density of Y-Ti-O enriched nano-features, resulting in remarkable high temperature creep strength and radiation damage resistance. Titanium and Yttrium K-edge XAS shows commercial alloys MA957 and J12YWT more closely resemble the as received Fe-14Cr-3W-0.4Ti (wt. %) powders, and mechanically alloyed (MA) powders with 0.25Y2O3 (wt. %). It shows that a significant fraction of substitutional Ti remains dissolved in the (BCC) ferrite matrix. In contrast, annealed powders and hot isostatic press (HIP) consolidated alloys show high temperature heat treatments shift the Y and Ti to more oxidized states that are consistent with combinations of Y2Ti2O7 and, especially, TiO. The second section describes corrosion studies of Pb with 316L stainless steel, molybdenum and spinet (MgAl2O4) at high temperature by XAS. The corrosion of fuel cladding and structural materials by liquid lead at elevated temperatures is an issue that must be considered when designing advanced nuclear systems and high-power spallation neutron targets. The results of ex-situ studies show that a Mo substrate retained a smooth and less corroded surface than 316L stainless steel sample at elevated temperature. In

  11. Microbeam x-ray absorption spectroscopy study of chromium in large-grain uranium dioxide fuel

    NASA Astrophysics Data System (ADS)

    Mieszczynski, C.; Kuri, G.; Bertsch, J.; Martin, M.; Borca, C. N.; Delafoy, Ch; Simoni, E.

    2014-09-01

    Synchrotron-based microprobe x-ray absorption spectroscopy (XAS) has been used to study the local atomic structure of chromium in chromia-doped uranium dioxide (UO2) grains. The specimens investigated were a commercial grade chromia-doped UO2 fresh fuel pellet, and materials from a spent fuel pellet of the same batch, irradiated with an average burnup of ~40 MW d kg-1. Uranium L3-edge and chromium K-edge XAS have been measured, and the structural environments of central uranium and chromium atoms have been elucidated. The Fourier transform of uranium L3-edge extended x-ray absorption fine structure shows two well-defined peaks of U-O and U-U bonds at average distances of 2.36 and 3.83 Å. Their coordination numbers are determined as 8 and 11, respectively. The chromium Fourier transform extended x-ray absorption fine structure of the pristine UO2 matrix shows similar structural features with the corresponding spectrum of the irradiated spent fuel, indicative of analogous chromium environments in the two samples studied. From the chromium XAS experimental data, detectable next neighbor atoms are oxygen and uranium of the cation-substituted UO2 lattice, and two distinct subshells of chromium and oxygen neighbors, possibly because of undissolved chromia particles present in the doped fuels. Curve-fitting analyses using theoretical amplitude and phase-shift functions of the closest Cr-O shell and calculations with ab initio computer code FEFF and atomic clusters generated from the chromium-dissolved UO2 structure have been carried out. There is a prominent reduction in the length of the adjacent Cr-O bond of about 0.3 Å in chromia-doped UO2 compared with the ideal U-O bond length in standard UO2 that would be expected because of the change in effective Coulomb interactions resulting from replacing U4+ with Cr3+ and their ionic size differences. The contraction of shortest Cr-U bond is ~0.1 Å relative to the U-U bond length in bulk UO2. The difference in the

  12. Diagnosis of a two wire X-pinch by X-ray absorption spectroscopy utilizing a doubly curved ellipsoidal crystal

    SciTech Connect

    Cahill, A. D. Hoyt, C. L. Shelkovenko, T. A. Pikuz, S. A. Hammer, D. A.

    2014-12-15

    X-ray absorption spectroscopy is a powerful tool for the diagnosis of plasmas over a wide range of both temperature and density. However, such a measurement is often limited to probing plasmas with temperatures well below that of the x-ray source in order to avoid object plasma emission lines from obscuring important features of the absorption spectrum. This has excluded many plasmas from being investigated by this technique. We have developed an x-ray spectrometer that provides the ability to record absorption spectra from higher temperature plasmas than the usual approach allows without the risk of data contamination by line radiation emitted by the plasma under study. This is accomplished using a doubly curved mica crystal which is bent both elliptically and cylindrically. We present here initial absorption spectra obtained from an aluminum x-pinch plasma.

  13. X-ray absorption spectroscopy of lithium sulfur battery reaction intermediates

    NASA Astrophysics Data System (ADS)

    Wujcik, Kevin; Pascal, Tod; Prendergast, David; Balsara, Nitash

    2015-03-01

    Lithium sulfur batteries have a theoretical energy density nearly five times greater than current lithium ion battery standards, but questions still remain regarding the reaction pathways through which soluble lithium polysulfide (Li2Sx, ``x'' ranging from 2 to 8) reaction intermediates are formed. Complicating spectroelectrochemical approaches to elucidate redox pathways is the challenge of obtaining spectral standards for individual Li2Sx species. Lithium polysulfides cannot be isolated as individual component and exist only in solution as a distribution of different Li2Sx molecules formed via disproportionation reactions (e.g. 2Li2S4 goes to Li2S3 + Li2S5). X-ray absorption spectroscopy (XAS) at the sulfur K-edge has recently been employed as a technique to study Li-S chemistry. We have recently obtained XAS standards for individual Li2Sx species via first principles DFT simulations and the excited electron and core hole approach. Here, experimental sulfur K-edge XAS of Li2Sx species dissolved in poly(ethylene oxide) are compared to spectra obtained from analogous theoretical calculations. The impact that polysulfide solution concentration and the presence of other lithium salts (e.g. LiNO3) have on X-ray spectra of Li2Sx species is explored via experiment and theory.

  14. Study on the interaction of methylene blue with cyclodextrin derivatives by absorption and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Guomei; Shuang, Shaomin; Dong, Chuan; Pan, Jinghao

    2003-11-01

    The ability of β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), and carboxymethyl-β-cyclodextrin (CM-β-CD) to break the aggregate of the methylene blue (MB) and to form 1:1 inclusion complexes has been studied by absorption and fluorescence spectroscopy. Experimental conditions including concentrations of various cyclodextrins (β-CD, HP-β-CD and CM-β-CD) and media acidity were investigated for the inclusion formation in detail. The formation constants are calculated by using steady-state fluorimetry, from which the inclusion capacity of different cyclodextrins (CDs) is compared. The results suggest that the charged β-cyclodextrin (CM-β-CD) is more suitable for inclusion of the cationic dye MB than the neutral β-cyclodextrins (β-CD, HP-β-CD) at pH>5. A mechanism is proposed which is consistent with the stronger binding of MB with CM-β-CD compared with the other CDs at pH>5.

  15. Acousto-optic differential optical absorption spectroscopy for atmospheric measurement of nitrogen dioxide in Hong Kong.

    PubMed

    Cheng, Andrew Y S; Chan, M H

    2004-12-01

    Measurement of the atmospheric concentration of nitrogen dioxide (NO(2)) pollutant was demonstrated by differential optical absorption spectroscopy (DOAS) using a visible acousto-optic tunable filter. In a traditional spectral scanning DOAS system for atmospheric concentration monitoring, a highly stable light source is required. When the light intensity fluctuates during scanning, the concentration retrieval will be inaccurate. In order to reduce the error due to intensity fluctuations, a modified DOAS system has been developed by introducing a broadband light intensity monitoring channel. Using the measured intensity of the broadband channel as the intensity of the light source, the spectrum can be de-biased and the residual intensity variation will primarily result from atmospheric extinction. In addition, by employing the lock-in detection technique, the background light interference is also removed in the modified DOAS system. The atmospheric NO(2) concentration measurement was performed at the campus of City University of Hong Kong, and the results were compared with the concentration reported from a nearby monitoring station in Sham Shui Po, operated by the Hong Kong Environmental Protection Department.

  16. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    SciTech Connect

    Collingwood, J.F.; Mikhaylova, A.; Davidson, M.R.; Batich, C.; Streit, W.J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R.S.; Dobson, J.

    2008-06-16

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (< 5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterize anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution {approx} 5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  17. Structural models and atomic distribution of bimetallic nanoparticles as investigated by X-ray absorption spectroscopy.

    PubMed

    Hwang, Bing-Joe; Sarma, Loka Subramanyam; Chen, Jiun-Ming; Chen, Ching-Hsiang; Shih, Shou-Chu; Wang, Guo-Rung; Liu, Din-Goa; Lee, Jyh-Fu; Tang, Mau-Tsu

    2005-08-10

    In this report, we describe a general methodology to determine the extent of alloying or atomic distribution quantitatively in bimetallic nanoparticles (NPs) by X-ray absorption spectroscopy (XAS). The structural parameters determined in these studies serve as a quantitative index and provide a general route to determine the structural aspects of the bimetallic NPs. We have derived various types of possible structural models based on the extent of alloying and coordination number parameters of bimetallic NPs. We also discussed the nature of homo- and heterometallic interactions in bimetallic NPs based on the extent of alloying. Herein, we use carbon-supported platinum-ruthenium bimetallic nanoparticles to demonstrate the proposed methodology, and this can be extended further to get more insights into the alloying extent or atomic distribution of other bimetallic systems. The results demonstrated in this paper open up methods to determine the atomic distribution of bimetallic NPs, which is an extremely important parameter that strongly influences the physicochemical properties of NPs and their applications.

  18. High-resolution x-ray absorption spectroscopy studies of metal compounds in neurodegenerative brain tissue

    NASA Astrophysics Data System (ADS)

    Collingwood, J. F.; Mikhaylova, A.; Davidson, M. R.; Batich, C.; Streit, W. J.; Eskin, T.; Terry, J.; Barrea, R.; Underhill, R. S.; Dobson, J.

    2005-01-01

    Fluorescence mapping and microfocus X-ray absorption spectroscopy are used to detect, locate and identify iron biominerals and other inorganic metal accumulations in neurodegenerative brain tissue at sub-cellular resolution (<5 microns). Recent progress in developing the technique is reviewed. Synchrotron X-rays are used to map tissue sections for metals of interest, and XANES and XAFS are used to characterise anomalous concentrations of the metals in-situ so that they can be correlated with tissue structures and disease pathology. Iron anomalies associated with biogenic magnetite, ferritin and haemoglobin are located and identified in an avian tissue model with a pixel resolution ~5 microns. Subsequent studies include brain tissue sections from transgenic Huntington's mice, and the first high-resolution mapping and identification of iron biominerals in human Alzheimer's and control autopsy brain tissue. Technical developments include use of microfocus diffraction to obtain structural information about biominerals in-situ, and depositing sample location grids by lithography for the location of anomalies by conventional microscopy. The combined techniques provide a breakthrough in the study of both intra- and extra-cellular iron compounds and related metals in tissue. The information to be gained from this approach has implications for future diagnosis and treatment of neurodegeneration, and for our understanding of the mechanisms involved.

  19. Using Softer X-ray Absorption Spectroscopy to Probe Biological Systems

    SciTech Connect

    Akabayov,B.; Doonan, C.; Pickering, I.; George, G.; Sagi, I.

    2005-01-01

    Many inorganic species are now recognized as being essential for life, including many forms of sulfur, phosphate and numerous classes of metal ions. For example, recent progress in the fields of biochemistry and biology has pointed out the critical importance of sulfur in the biosynthesis of vital cofactors and active sites in proteins, and in the complex reaction mechanisms often involved. Special attention has also been drawn to the diverse roles of alkaline (Na{sup +}, K{sup +}) and alkaline earth (Mg{sup 2+}, Ca{sup 2+}) metal ions in mediating the activity of RNA, proteins and many processes in living cells. While the general effect of these ions in biology is mostly understood, information on their detailed role is deficient. Here the application of softer X-ray absorption spectroscopy (XAS) to probe the local structural and electronic environment of such ions within their biological complexes and during physiological reactions is discussed. In addition, the required experimental set-up and the difficulties associated with conducting softer XAS experiments on biological samples are presented.

  20. Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy

    SciTech Connect

    Smith, Jacob W.; Lam, Royce K.; Saykally, Richard J.; Shih, Orion; Rizzuto, Anthony M.; Prendergast, David

    2015-08-28

    Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO{sub 3}{sup −} and NO{sub 2}{sup −}. The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.

  1. Ozone monitoring using differential optical absorption spectroscopy (DOAS) and UV photometry instruments in Sohar, Oman.

    PubMed

    Nawahda, Amin

    2015-08-01

    Ground level ozone (O3) concentrations were measured across Sohar highway in Oman during a four-month period from September to December 2014 by using an open-path deferential optical absorption spectroscopy (DOAS) instrument. The monthly average concentrations of O3 varied from 19.6 to 29.4 ppb. The measurements of O3 are compared with the measurements of a non-open-path UV photometry analyzer (UVP). The percent difference (PD) concept and linear regression methods were used to compare the readings of the two instruments. The findings show high correlation coefficients between the measurements of the DOAS and UVP instruments. The DOAS measurements of O3 are found to be less than those measured by the UVP instrument; the correlation coefficients between absolute PD values and meteorological parameters and PM2.5 were very low indicating a minor effect; therefore, titrations of O3 by traffic emissions and difference in elevation could be the reason for the difference in the measurements of the two instruments.

  2. Velocity distribution function of sputtered Cu atoms obtained by time resolved optical absorption spectroscopy

    SciTech Connect

    Kang, Namjun; Gaboriau, Freddy; Ricard, Andre; Oh, Soo-ghee

    2010-01-15

    A new method based on time resolved optical absorption spectroscopy is proposed to determine the velocity distribution function of sputtered Cu atoms in a magnetron plasma discharge. The method consists of applying a short pulse of 1.5 {mu}s and of recording time variations in copper atom density in off pulse at different positions (1, 2, and 3 cm) from target surface under 3-30 mTorr. The time evolution of the density is then converted into velocity distribution. We estimate that only sputtered atoms with radial velocity component lower than 0.5 km/s are detected. The average velocity of Cu atoms is evaluated as the first order moment of the velocity distribution functions. The velocity distribution functions become the more dispersive the farther from target surface. The average velocities vary in the range of 2.5-3 km/s at the vicinity of target surface whereas at 3 cm a decrease from 2.5 to 1.2 km/s is observed at 30 mTorr.

  3. X-ray absorption spectroscopy of iron at multimegabar pressures in laser shock experiments

    NASA Astrophysics Data System (ADS)

    Harmand, M.; Ravasio, A.; Mazevet, S.; Bouchet, J.; Denoeud, A.; Dorchies, F.; Feng, Y.; Fourment, C.; Galtier, E.; Gaudin, J.; Guyot, F.; Kodama, R.; Koenig, M.; Lee, H. J.; Miyanishi, K.; Morard, G.; Musella, R.; Nagler, B.; Nakatsutsumi, M.; Ozaki, N.; Recoules, V.; Toleikis, S.; Vinci, T.; Zastrau, U.; Zhu, D.; Benuzzi-Mounaix, A.

    2015-07-01

    Taking advantage of the new opportunities provided by x-ray free electron laser (FEL) sources when coupled to a long laser pulse as available at the Linear Coherent Light Source (LCLS), we have performed x-ray absorption near-edge spectroscopy (XANES) of laser shock compressed iron up to 420 GPa (±50 ) and 10 800 K (±1390 ). Visible diagnostics coupled with hydrodynamic simulations were used to infer the thermodynamical conditions along the Hugoniot and the release adiabat. A modification of the pre-edge feature at 7.12 keV in the XANES spectra is observed above pressures of 260 GPa along the Hugoniot. Comparing with ab initio calculations and with previous laser-heated diamond cell data, we propose that such changes in the XANES pre-edge could be a signature of molten iron. This interpretation then suggests that iron is molten at pressures and temperatures higher than 260 GPa (±29 ) and 5680 K (±700 ) along the principal Fe Hugoniot.

  4. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy.

    PubMed

    Lam, Royce K; Smith, Jacob W; Saykally, Richard J

    2016-05-21

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

  5. Phase transitions of amorphous solid acetone in confined geometry investigated by reflection absorption infrared spectroscopy.

    PubMed

    Shin, Sunghwan; Kang, Hani; Kim, Jun Soo; Kang, Heon

    2014-11-26

    We investigated the phase transformations of amorphous solid acetone under confined geometry by preparing acetone films trapped in amorphous solid water (ASW) or CCl4. Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to monitor the phase changes of the acetone sample with increasing temperature. An acetone film trapped in ASW shows an abrupt change in the RAIRS features of the acetone vibrational bands during heating from 80 to 100 K, which indicates the transformation of amorphous solid acetone to a molecularly aligned crystalline phase. Further heating of the sample to 140 K produces an isotropic solid phase, and eventually a fluid phase near 157 K, at which the acetone sample is probably trapped in a pressurized, superheated condition inside the ASW matrix. Inside a CCl4 matrix, amorphous solid acetone crystallizes into a different, isotropic structure at ca. 90 K. We propose that the molecularly aligned crystalline phase formed in ASW is created by heterogeneous nucleation at the acetone-water interface, with resultant crystal growth, whereas the isotropic crystalline phase in CCl4 is formed by homogeneous crystal growth starting from the bulk region of the acetone sample.

  6. Cadmium accumulation in the crayfish, Procambarus clarkii, using graphite furnace atomic absorption spectroscopy

    SciTech Connect

    Diaz-Mayans, J.; Hernandez, F.; Medina, J.; Del Ramo, J.; Torreblanca, A.

    1986-11-01

    Lake Albufera and the surrounding rice-field waters are being subject to very heavy loads of sewage and toxic industrial residues (including heavy metals and pesticides) from the many urban and wastewaters in this area. The American red crayfish Procambarus clarkii is native to the Louisiana marshes (USA). In 1978, the crayfish appeared in Lake Albufera near Valencia (Spain), and presently, without adequate sanitary controls, the crayfish is being fished commercially for human consumption. In view of this interest, it is important to have accurate information on concentrations of cadmium in natural waters and cadmium levels of tissues of freshwaters animals used as human food, as well as the accumulation rates of this metal in this animal. In the present study, the authors investigated the accumulation of cadmium in several tissues of the red crayfish, P clarkii (Girard) from Lake Albufera following cadmium exposure. Determinations of cadmium were made by flameless atomic absorption spectroscopy and the standard additions method. Digestion of samples was made by wet ashing in open flasks with concentrated HNO/sub 3/ at 80-90/sup 0/C.

  7. Total Absorption Spectroscopy of Fission Fragments Relevant for Reactor Antineutrino Spectra and Decay Heat Calculations

    NASA Astrophysics Data System (ADS)

    Porta, A.; Zakari-Issoufou, A.-A.; Fallot, M.; Algora, A.; Tain, J. L.; Valencia, E.; Rice, S.; Bui, V. M.; Cormon, S.; Estienne, M.; Agramunt, J.; Äystö, J.; Bowry, M.; Briz, J. A.; Caballero-Folch, R.; Cano-Ott, D.; Cucouanes, A.; Elomaa, V.-V.; Eronen, T.; Estévez, E.; Farrelly, G. F.; Garcia, A. R.; Gelletly, W.; Gomez-Hornillos, M. B.; Gorlychev, V.; Hakala, J.; Jokinen, A.; Jordan, M. D.; Kankainen, A.; Karvonen, P.; Kolhinen, V. S.; Kondev, F. G.; Martinez, T.; Mendoza, E.; Molina, F.; Moore, I.; Perez-Cerdán, A. B.; Podolyák, Zs.; Penttilä, H.; Regan, P. H.; Reponen, M.; Rissanen, J.; Rubio, B.; Shiba, T.; Sonzogni, A. A.; Weber, C.

    2016-03-01

    Beta decay of fission products is at the origin of decay heat and antineutrino emission in nuclear reactors. Decay heat represents about 7% of the reactor power during operation and strongly impacts reactor safety. Reactor antineutrino detection is used in several fundamental neutrino physics experiments and it can also be used for reactor monitoring and non-proliferation purposes. 92,93Rb are two fission products of importance in reactor antineutrino spectra and decay heat, but their β-decay properties are not well known. New measurements of 92,93Rb β-decay properties have been performed at the IGISOL facility (Jyväskylä, Finland) using Total Absorption Spectroscopy (TAS). TAS is complementary to techniques based on Germanium detectors. It implies the use of a calorimeter to measure the total gamma intensity de-exciting each level in the daughter nucleus providing a direct measurement of the beta feeding. In these proceedings we present preliminary results for 93Rb, our measured beta feedings for 92Rb and we show the impact of these results on reactor antineutrino spectra and decay heat calculations.

  8. Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

    USGS Publications Warehouse

    Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

    2006-01-01

    Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

  9. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O2 lattice in an irradiated (60 MW d kg-1) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (˜0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am3+ species within an [AmO8]13- coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix.

  10. Standoff gas leak detectors based on tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Frish, M. B.; Wainner, R. T.; Green, B. D.; Laderer, M. C.; Allen, M. G.

    2005-11-01

    Trace gas sensing and analysis by Tunable Diode Laser Absorption Spectroscopy (TDLAS) has become a robust and reliable technology accepted for industrial process monitoring and control, quality assurance, environmental sensing, plant safety, and infrastructure security. Sensors incorporating well-packaged wavelength-stabilized near-infrared (1.2 to 2.0 μm) laser sources sense over a dozen toxic or industrially-important gases. A large emerging application for TDLAS is standoff sensing of gas leaks, e.g. from natural gas pipelines. The Remote Methane Leak Detector (RMLD), a handheld standoff TDLAS leak survey tool that we developed, is replacing traditional leak detection tools that must be physically immersed within a leak to detect it. Employing a 10 mW 1.6 micron DFB laser, the RMLD illuminates a non-cooperative topographic surface, up to 30 m distant, and analyzes returned scattered light to deduce the presence of excess methane. The eye-safe, battery-powered, 6-pound handheld RMLD enhances walking pipeline survey rates by more than 30%. When combined with a spinning or rastering mirror, the RMLD serves as a platform for mobile leak mapping systems. Also, to enable high-altitude surveying and provide aerial disaster response, we are extending the standoff range to 3000 m by adding an EDFA to the laser transmitter.

  11. Speciation of selenium in stream insects using X-ray absorption spectroscopy

    SciTech Connect

    Ruwandi Andrahennadi; Mark Wayland; Ingrid J. Pickering

    2007-11-15

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  12. The Chemistry os Spent Nuclear Fuel From X-Ray Absorption Spectroscopy

    SciTech Connect

    F.A. Fortner; A.J. Kropf; J.C. Cunnane

    2006-09-21

    Present and future nuclear fuel cycles will require an understanding of the complex chemistry of trace fission products and transuranium actinides in spent nuclear fuel (SNF). Because of the unique analytical challenges presented by SNF to the materials scientist, many of its fundamental physical and chemical properties remain poorly understood, especially on the microscopic scale. Such an understanding of the chemical states of radionuclides in SNF would benefit development of technologies for fuel monitoring, fuel performance improvement and modeling, fuel reprocessing, and spent fuel storage and disposal. We have recently demonstrated the use of synchrotron x-ray absorption spectroscopy (XAS) to examine crystal chemical properties of actinides and fission products in extracted specimens of SNF. Information obtained includes oxidation state, chemical bond coordination, and quantitative elemental concentration and distribution. We have also used XAS in a scanning mode to obtain x-ray spectral micrographs with resolution approaching 1 micron. A brief overview of the technique will be presented, along with findings on uranium, plutonium, neptunium, technetium, and molybdenum in commercial PWR SNF specimens.

  13. X-ray absorption spectroscopy of biomimetic dye molecules for solar cells

    SciTech Connect

    Cook, Peter L.; Liu Xiaosong; Himpsel, F. J.; Yang Wanli

    2009-11-21

    Dye-sensitized solar cells are potentially inexpensive alternatives to traditional semiconductor solar cells. In order to optimize dyes for solar cells we systematically investigate the electronic structure of a variety of porphyrins and phthalocyanines. As a biological model system we use the heme group in cytochrome c which plays a role in biological charge transfer processes. X-ray absorption spectroscopy of the N 1s and C 1s edges reveals the unoccupied molecular orbitals and the orientation of the molecules in thin films. The transition metal 2p edges reflect the oxidation state of the central metal atom, its spin state, and the ligand field of the surrounding N atoms. The latter allows tuning of the energy position of the lowest unoccupied orbital by several tenths of an eV by tailoring the molecules and their deposition. Fe and Mn containing phthalocyanines oxidize easily from +2 to +3 in air and require vacuum deposition for obtaining a reproducible oxidation state. Chlorinated porphyrins, on the other hand, are reduced from +3 to +2 during vacuum deposition at elevated temperatures. These findings stress the importance of controlled thin film deposition for obtaining photovoltaic devices with an optimum match between the energy levels of the dye and those of the donor and acceptor electrodes, together with a molecular orientation for optimal overlap between the {pi} orbitals in the direction of the carrier transport.

  14. DNA interaction probed by evanescent wave cavity ring-down absorption spectroscopy via functionalized gold nanoparticles.

    PubMed

    Yao, Yi-Ju; Lin, King-Chuen

    2014-04-11

    Evanescent wave cavity ring-down absorption spectroscopy (EW-CRDS) is employed to study interaction and binding kinetics of DNA strands by using gold nanoparticles (Au NPs) as sensitive reporters. These Au NPs are connected to target DNA of study that hybridizes with the complementary DNA fixed on the silica surface. By the absorbance of Au NPs, the interaction between two DNA strands may be examined to yield an adsorption equilibrium constant of 2.2×10(10) M(-1) using Langmuir fit. The binding efficiency that is affected by ion concentration, buffer pH and temperature is also examined. This approach is then applied to the label-free detection of the DNA mutation diseases using the sandwich hybridization assay. For monitoring a gene associated with sickle-cell anemia, the detection limit and the adsorption equilibrium constant is determined to be 1.2 pM and (3.7±0.8)×10(10) M(-1), distinct difference from the perfectly matched DNA sequence that yields the corresponding 0.5 pM and (1.1±0.2)×10(11) M(-1). The EW-CRDS method appears to have great potential for the investigation of the kinetics of a wide range of biological reactions.

  15. [Monitoring the change in CO concentration in combustion with tunable diode laser absorption spectroscopy].

    PubMed

    Xia, Hui; Liu, Wen-Qing; Zhang, Yu-Jun; Kan, Rui-Feng; Chen, Dong; Cui, Yi-Ben; He, Ying; Chen, Jiu-Ying; Wang, Min; Wang, Tie-Dong

    2008-11-01

    In the present paper, the technology of tunable diode laser absorption spectroscopy (TDLAS) in conjunction with the open path multi-pass Herriot cell and the new-style detection method of auto-balanced detection combined with wavelength modulation technology were used, and the concentration of CO produced in combustion of alcohol blowtorch was measured. It was found in the measured result that the change in CO concentration in the flame of alcohol blowtorch presented a stated periodicity in the process of combustion and the average concentration of CO was calculated to be 49.4 (10(-6) ratio by volume). The experiment is showed that with the conjunction of auto-balanced detection and the second harmonics detection method, adopting the open path multi-pass Herrriot cell to detect the concentration of CO in the combustion of alcohol blowtorch is accurate and contents the detection requirement. It was proved that the system made for measuring the concentration of CO in the flame of alcohol blowtorch in combustion establishes foundation well for developing on-line combustion monitoring based on TDLAS. PMID:19271470

  16. Atomic-scale roughness of Li metal surface evident in soft X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Prendergast, David; Wan, Liwen; Liang, Yufeng; Chuang, Yi-De; Qiao, Ruimin; Yan, Shishen; Yang, Wanli

    2015-03-01

    Realizing Li metal electrodes depends on fundamental understanding and efficient control of surface properties, which requires reliable characterization of the Li metal surface. Controlled experiments of Li K-edge soft X-ray absorption spectroscopy (XAS) reveal evidence of steady oxidation of the Li metal surface even under ultrahigh vacuum (UHV) conditions. The XAS of the short-lived Li metal surface, prepared by in-situ scratching, exhibits a prominent peak at 55.6 eV, more intense and at a slightly higher energy than the first peak expected for bulk Li metal at 55 eV. First-principles XAS calculations explain the origin of both the increased intensity and energy shift. This required the use of surface structural models with under-coordinated Li atoms and an estimated 4 Åinelastic mean-free-path for Auger electrons, implying extreme surface sensitivity of the measurements to the first 2-3 atomic layers. This work provides a benchmark on both experiment and theory for further studies of Li and other reactive metal surfaces, which are currently under scrutiny for next-generation energy storage devices. DP, LW, and YL acknowledge support from the Joint Center for Energy Storage Research, an Energy Innovation Hub funded by the US Dept. of Energy, Office of Science, Basic Energy Sciences.

  17. Measurement of nickel, cobalt and chromium in toy make-up by atomic absorption spectroscopy.

    PubMed

    Corazza, Monica; Baldo, Federica; Pagnoni, Antonella; Miscioscia, Roberta; Virgili, Annarosa

    2009-01-01

    Cosmetics should not contain more than 5 ppm of nickel, chromium or cobalt and, in order to minimize the risk of sensitization in very sensitive subjects, the target amount should be as low as 1 ppm. However, there are no published reports on the presence of these metals in toy make-up. This study analysed 52 toy make-ups using atomic absorption spectroscopy. More than 5 ppm of nickel was present in 14/52 (26.9%) samples. Chromium exceeded 5 ppm in 28/52 (53.8%) samples, with values over 1000 ppm in 3 eye shadows. Cobalt was present in amounts over 5 ppm in 5/52 (9.6%) samples. Powdery toy make-up (eye shadows) had the highest levels of metals, and "creamy" toy make-up (lip gloss and lipsticks) the lowest. Toy make-ups are potentially sensitizing items, especially for atopic children, who have a damaged skin barrier that may favour penetration of allergens.

  18. Detection of Glucose with Atomic Absorption Spectroscopy by Using Oligonucleotide Functionalized Gold Nanoparticle.

    PubMed

    Zhang, Hong; Yan, Honglian; Ling, Liansheng

    2016-06-01

    A novel method for the detection of glucose was established with atomic absorption spectroscopy by using the label of gold nanoparticle (AuNP). Silver-coated glass assembled with oligonucleotide 5'-SH-T12-AGA CAA GAG AGG-3' (Oligo 1) was acted as separation probe, oligonucleotide 5'-CAA CAG AGA ACG-T12-SH-3' modified gold nanoparticle (AuNP-Oligo 2) was acted as signal-reporting probe. Oligonucleotide 5'-CGT TCT CTG TTG CCT CTC TTG TCT-3' (Oligo 3) could hybridize with Oligo 1 on the surface of silver-coated glass and AuNP-Oligo 2, and free AuNP-Oligo 2 could be removed by rinsing with buffer. Hence the concentration of Oligo 3 was transformed into the concentration of gold element. In addition, Oligo 3 could be cleaved into DNA fragments by glucose, glucose oxidase and Fe(2+)-EDTA through Fenton reaction. Thereby the concentration of glucose could be transformed to the absorbance of gold element. Under the optimum conditions, the integrated absorbance decreased proportionally to the concentration of glucose over the range from 50.0 μM to 1.0 mM with a detection limit of 40.0 μM. Moreover, satisfactory result was obtained when the assay was used to determinate glucose in human serum. PMID:27427698

  19. X-ray absorption spectroscopy studies of reactions of technetium, uranium and neptunium with mackinawite.

    PubMed

    Livens, Francis R; Jones, Mark J; Hynes, Amanda J; Charnock, John M; Mosselmans, J Fred W; Hennig, Christoph; Steele, Helen; Collison, David; Vaughan, David J; Pattrick, Richard A D; Reed, Wendy A; Moyes, Lesley N

    2004-01-01

    Technetium, uranium and neptunium may all occur in the environment in more than one oxidation state (IV or VII, IV or VI and IV or V respectively). The surface of mackinawite, the first-formed iron sulfide phase in anoxic conditions, can promote redox changes so a series of laboratory experiments were carried out to explore the interactions of Tc, U and Np with this mineral. The products of reaction were characterised using X-ray absorption spectroscopy. Technetium, added as TcO4(-), is reduced to oxidation state IV and forms a TcS(2)-like species. On oxidation of the mackinawite in air to form goethite, Tc remains in oxidation state IV but in an oxide, rather than a sulfide environment. At low concentrations, uranium forms uranyl surface complexes on oxidised regions of the mackinawite surface but at higher concentrations, the uranium promotes surface oxidation and forms a mixed oxidation state oxide phase. Neptunium is reduced to oxidation IV and forms a surface complex with surface sulfide ions. The remainder of the Np coordination sphere is filled with water molecules or hydroxide ions.

  20. Detection of Glucose with Atomic Absorption Spectroscopy by Using Oligonucleotide Functionalized Gold Nanoparticle.

    PubMed

    Zhang, Hong; Yan, Honglian; Ling, Liansheng

    2016-06-01

    A novel method for the detection of glucose was established with atomic absorption spectroscopy by using the label of gold nanoparticle (AuNP). Silver-coated glass assembled with oligonucleotide 5'-SH-T12-AGA CAA GAG AGG-3' (Oligo 1) was acted as separation probe, oligonucleotide 5'-CAA CAG AGA ACG-T12-SH-3' modified gold nanoparticle (AuNP-Oligo 2) was acted as signal-reporting probe. Oligonucleotide 5'-CGT TCT CTG TTG CCT CTC TTG TCT-3' (Oligo 3) could hybridize with Oligo 1 on the surface of silver-coated glass and AuNP-Oligo 2, and free AuNP-Oligo 2 could be removed by rinsing with buffer. Hence the concentration of Oligo 3 was transformed into the concentration of gold element. In addition, Oligo 3 could be cleaved into DNA fragments by glucose, glucose oxidase and Fe(2+)-EDTA through Fenton reaction. Thereby the concentration of glucose could be transformed to the absorbance of gold element. Under the optimum conditions, the integrated absorbance decreased proportionally to the concentration of glucose over the range from 50.0 μM to 1.0 mM with a detection limit of 40.0 μM. Moreover, satisfactory result was obtained when the assay was used to determinate glucose in human serum.

  1. X-ray Absorption Spectroscopy Characterization of a Li/S Cell

    DOE PAGES

    Ye, Yifan; Kawase, Ayako; Song, Min-Kyu; Feng, Bingmei; Liu, Yi-Sheng; Marcus, Matthew A.; Feng, Jun; Cairns, Elton J.; Guo, Jinghua; Zhu, Junfa

    2016-01-11

    The X-ray absorption spectroscopy technique has been applied to study different stages of the lithium/sulfur (Li/S) cell life cycle. We investigated how speciation of S in Li/S cathodes changes upon the introduction of CTAB (cetyltrimethylammonium bromide, CH3(CH2)15N+(CH3)3Br₋) and with charge/discharge cycling. The introduction of CTAB changes the synthesis reaction pathway dramatically due to the interaction of CTAB with the terminal S atoms of the polysulfide ions in the Na2Sx solution. For the cycled Li/S cell, the loss of electrochemically active sulfur and the accumulation of a compact blocking insulating layer of unexpected sulfur reaction products on the cathode surface duringmore » the charge/discharge processes make the capacity decay. Lastly, a modified coin cell and a vacuum-compatible three-electrode electro-chemical cell have been introduced for further in-situ/in-operando studies.« less

  2. Atomic Structure of Pt3Ni Nanoframe Electrocatalysts by in Situ X-ray Absorption Spectroscopy.

    PubMed

    Becknell, Nigel; Kang, Yijin; Chen, Chen; Resasco, Joaquin; Kornienko, Nikolay; Guo, Jinghua; Markovic, Nenad M; Somorjai, Gabor A; Stamenkovic, Vojislav R; Yang, Peidong

    2015-12-23

    Understanding the atomic structure of a catalyst is crucial to exposing the source of its performance characteristics. It is highly unlikely that a catalyst remains the same under reaction conditions when compared to as-synthesized. Hence, the ideal experiment to study the catalyst structure should be performed in situ. Here, we use X-ray absorption spectroscopy (XAS) as an in situ technique to study Pt3Ni nanoframe particles which have been proven to be an excellent electrocatalyst for the oxygen reduction reaction (ORR). The surface characteristics of the nanoframes were probed through electrochemical hydrogen underpotential deposition and carbon monoxide electrooxidation, which showed that nanoframe surfaces with different structure exhibit varying levels of binding strength to adsorbate molecules. It is well-known that Pt-skin formation on Pt-Ni catalysts will enhance ORR activity by weakening the binding energy between the surface and adsorbates. Ex situ and in situ XAS results reveal that nanoframes which bind adsorbates more strongly have a rougher Pt surface caused by insufficient segregation of Pt to the surface and consequent Ni dissolution. In contrast, nanoframes which exhibit extremely high ORR activity simultaneously demonstrate more significant segregation of Pt over Ni-rich subsurface layers, allowing better formation of the critical Pt-skin. This work demonstrates that the high ORR activity of the Pt3Ni hollow nanoframes depends on successful formation of the Pt-skin surface structure.

  3. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy.

    PubMed

    Lam, Royce K; Smith, Jacob W; Saykally, Richard J

    2016-05-21

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility. PMID:27208929

  4. A multi-channel monolithic Ge detector system for fluorescence x-ray absorption spectroscopy

    SciTech Connect

    Bucher, J.J.; Allen, P.G.; Edelstein, N.M.; Shuh, D.K.; Madden, N.W.; Cork, C.; Luke, P.; Pehl, D.; Malone, D.

    1995-03-01

    Construction and performance of a monolithic quad-pixel Ge detector for fluorescence x-ray absorption spectroscopy (XAS) at synchrotron radiation sources are described. The detector semiconductor element has an active surface area of 4.0 cm{sup 2} which is electrically separated into four 1.0 cm{sup 2} pixels, with little interfacial dead volume. Spatial response of the array shows that cross-talk between adjacent pixels is < 10% for 5.9 keV photons that fall within 0.5 mm of the pixel boundaries. The detector electronics system uses pre-amplifiers built at LBNL with commercial Tennelec Model TC 244 amplifiers. Using an {sup 55}Fe test source (MnK{sub {alpha}}, 5.9 keV), energy resolution of better than 200 eV is achieved with a 4 {mu}sec peaking time. At 0.5 {mu}sec peaking time, pulse pileup results in a 75% throughput efficiency for an incoming count rate of 100 kHz. Initial XAS fluoresncece measurements at the beamline 4 wiggler end stations at SSRL show that the detector system has several advantages over commercial x-ray spectrometers for low-concentration counting.

  5. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Taga, Raijeli L.; Zheng, Jiajia; Huynh, Trang; Ng, Jack; Harris, Hugh H.; Noller, Barry

    2010-06-01

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe6(SO4)4(OH)12) by lead L3-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM10 particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  6. Identification of lead chemical form in mine waste materials by X-ray absorption spectroscopy

    SciTech Connect

    Taga, Raijeli L.; Ng, Jack; Zheng Jiajia; Huynh, Trang; Noller, Barry; Harris, Hugh H.

    2010-06-23

    X-ray absorption spectroscopy (XAS) provides a direct means for measuring lead chemical forms in complex samples. In this study, XAS was used to identify the presence of plumbojarosite (PbFe{sub 6}(SO{sub 4}){sub 4}(OH){sub 12}) by lead L{sub 3}-edge XANES spectra in mine waste from a small gold mining operation in Fiji. The presence of plumbojarosite in tailings was confirmed by XRD but XANES gave better resolution. The potential for human uptake of Pb from tailings was measured using a physiologically based extract test (PBET), an in-vitro bioaccessibility (BAc) method. The BAc of Pb was 55%. Particle size distribution of tailings indicated that 40% of PM{sub 10} particulates exist which could be a potential risk for respiratory effects via the inhalation route. Food items collected in the proximity of the mine site had lead concentrations which exceed food standard guidelines. Lead within the mining lease exceeded sediment guidelines. The results from this study are used to investigate exposure pathways via ingestion and inhalation for potential risk exposure pathways of Pb in that locality. The highest Pb concentration in soil and tailings was 25,839 mg/kg, exceeding the Australian National Environment Protection Measure (NEPM) soil health investigation levels.

  7. Urban atmospheric formaldehyde concentrations measured by a differential optical absorption spectroscopy method.

    PubMed

    Li, Xiang; Wang, Shangshang; Zhou, Rui; Zhou, Bin

    2014-02-01

    In this study a differential optical absorption spectroscopy (DOAS) method was used to monitor formaldehyde (HCHO) concentrations in Shanghai ambient air at a research station in Fudan University. The measurements were carried out during April 2010-April 2011 and a total of 120 940 recorded data points were obtained. The average HCHO concentration was found to be the highest (10.0 ppbv) during August 2010 and the lowest (2.0 ppbv) during April 2010. The diurnal variation of HCHO and O3 followed very similar trends in all the seasons. This was evident from the fact that HCHO had a strong positive correlation with O3. Both peaked once in the morning (07:00-09:00 local time), and once in the night (16:00-19:00 local time). The peak concentrations varied from season to season, which could be attributed to the seasonal variation in anthropogenic activity, traffic movement and atmospheric boundary layer conditions. The background HCHO concentration in 2011 winter (similar to 12.0 ppbv) was an order of magnitude higher than that observed in 2010 spring (similar to 2.0 ppbv); corresponding with the results of several pollution controls adopted by the Shanghai administrative government before and after the EXPO 2010 period (May 1, 2010-Oct. 31 2010). This study contributed the basic information for understanding the concentration level and the chemical processes of atmospheric HCHO in a major metropolitan area. PMID:24362786

  8. [Studies on the data processing method in chlorine measurement by differential optical absorption spectroscopy technology].

    PubMed

    Ye, Cong-Lei; Xie, Pin-Hua; Qin, Min; Li, Ang; Ling, Liu-Yi; Hu, Ren-Zhi; Yang, Jing-Wen

    2012-07-01

    In this paper, based on Differential Optical Absorption Spectroscopy (DOAS) technique, experimental measurements of chlorine was carried out in the laboratory with a small self-built experimental system. In dealing with the standard cross-section of chlorine, we presented two different methods: triangle filtering and polynomial fitting. Experiments showed that the concentration of chlorine could be accurately retrieved by the latter one. Simulation results showed that the error of retrieval result by fifth-order polynomial fitting was smaller than by other orders and an actual retrieval example shows that the fitting spectrums were nearly coincident with the measured spectrums with a residual delta(peak to peak) below 5 per hundred; The results measured in different sample pools displayed a high linearity of 0.9961 by this method. The main sources of errors during the entire experiment were simply analyzed. According to the experimental result above, it is feasible to detect chlorine using DOAS technology by polynomial fitting. PMID:23016314

  9. Non-invasive gas monitoring in newborn infants using diode laser absorption spectroscopy: a case study

    NASA Astrophysics Data System (ADS)

    Lundin, Patrik; Svanberg, Emilie K.; Cocola, Lorenzo; Lewander, Märta; Andersson-Engels, Stefan; Jahr, John; Fellman, Vineta; Svanberg, Katarina; Svanberg, Sune

    2012-03-01

    Non-invasive diode laser spectroscopy was, for the first time, used to assess gas content in the intestines and the lungs of a new-born, 4 kg, baby. Two gases, water vapor and oxygen, were studied with two low-power tunable diode lasers, illuminating the surface skin tissue and detecting the diffusely emerging light a few centimeters away. The light, having penetrated into the tissue, had experienced absorption by gas located in the lungs and in the intestines. Very distinct water vapor signals were obtained from the intestines while imprint from oxygen was lacking, as expected. Detectable, but minor, signals of water vapor were also obtained from the lungs, illuminating the armpit area and detecting below the collar bone. Water vapor signals were seen but again oxygen signals were lacking, now due to the difficulties of penetration of the oxygen probing light into the lungs of this full-term baby. Ultra-sound images were obtained both from the lungs and from the stomach of the baby. Based on dimensions and our experimental findings, we conclude, that for early pre-term babies, also oxygen should be detectable in the lungs, in addition to intestine and lung detection of water vapor. The present paper focuses on the studies of the intestines while the lung studies will be covered in a forthcoming paper.

  10. Adsorption on carbon nanotubes studied using polarization-modulated infrared reflection-absorption spectroscopy.

    PubMed

    Bermudez, V M

    2005-05-26

    Single-wall carbon nanotubes (SWNTs), deposited onto an Al substrate from a liquid suspension, have been cleaned by annealing in ultrahigh vacuum. The effects of exposing the sample in situ to atomic H (or D) and/or to dimethyl methylphosphonate [DMMP, (CH(3)O)(2)(CH(3))P=O] were then studied using polarization-modulated infrared reflection-absorption spectroscopy. Atomic H reacts preferentially near strained or defective regions in the nanotube wall to produce a spectrum consistent with alkane-like species (>CH(2) and -CH(3)). Only a small fraction of the >C=C< sites in the nanotube wall react with H, and there is no clear evidence for monohydride >C(H)-C(H)< species. For DMMP, data were obtained under steady-state conditions in reagent pressures in excess of half the room-temperature vapor pressure. Adsorption occurs via the P=O group with a coverage that depends on the ambient pressure. Varying the DMMP coverage by changing the pressure causes changes in the spectrum that can be related to the strength of the DMMP/SWNT interaction. Preadsorbed H is seen to have little or no effect on the subsequent adsorption of DMMP. For DMMP, the molecular features are superimposed on a broad, smoothly varying background that can be related to adsorption-induced changes in the Drude parameters characterizing the SWNT free-carrier density and scattering lifetime.

  11. Speciation of Selenium in Stream Insects Using X-Ray Absorption Spectroscopy

    SciTech Connect

    Andrahennadi, R.; Wayland, M.; Pickering, I.J.

    2009-05-28

    Selenium contamination in the environment is a widespread problem affecting insects and other wildlife. Insects occupy a critical middle link and aid in trophic transfer of selenium in many terrestrial and freshwater food chains, but the mechanisms of selenium uptake through the food chain are poorly understood. In particular, biotransformation of selenium by insects into different chemical forms will greatly influence how toxic or benign the selenium is to that organism or to its predators. We have used X-ray absorption spectroscopy (XAS) to identify the chemical form of selenium in insects inhabiting selenium contaminated streams near Hinton, Alberta (Canada). Selenium K near-edge spectra indicate a variability of selenium speciation among the insects that included mayflies (Ephemeroptera), stoneflies (Plecoptera), caddisflies (Trichoptera), and craneflies (Diptera). Higher percentages of inorganic selenium were observed in primary consumers, detritivores, and filter feeders than in predatory insects. Among the organic forms of selenium, organic selenides constituted a major fraction in most organisms. A species modeled as trimethylselenonium was observed during the pupal stage of caddisflies. These results provide insights into how the insects cope with their toxic cargo, including how the selenium is biotransformed into less toxic forms and how it can be eliminated from the insects. More broadly, this study demonstrates the strengths of XAS to probe the effects of heavy elements at trace levels in insects from the field.

  12. Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lam, Royce K.; Smith, Jacob W.; Saykally, Richard J.

    2016-05-01

    While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering. We have investigated mixtures of methanol, ethanol, and isopropanol with water by liquid microjet X-ray absorption spectroscopy on the oxygen K-edge, an atom-specific probe providing details of both inter- and intra-molecular structure. The measured spectra evidence a significant enhancement of hydrogen bonding originating from the methanol and ethanol hydroxyl groups upon the addition of water. These additional hydrogen bonding interactions would strengthen the liquid-liquid interactions, resulting in additional ordering in the liquid structures and leading to a reduction in entropy and a negative enthalpy of mixing, consistent with existing thermodynamic data. In contrast, the spectra of the isopropanol-water mixtures exhibit an increase in the number of broken alcohol hydrogen bonds for mixtures containing up to 0.5 water mole fraction, an observation consistent with existing enthalpy of mixing data, suggesting that the measured negative excess entropy is a result of clustering or micro-immiscibility.

  13. Understanding Sulfur Poisoning and Regeneration of Nickel Biomass Conditioning Catalysts using X-Ray Absorption Spectroscopy

    SciTech Connect

    Yung, M. M.; Cheah, S.; Kuhn, J. N.

    2013-01-01

    The production of biofuels can proceed via a biomass gasification to produce syngas, which can then undergo catalytic conditioning and reforming reactions prior to being sent to a fuel synthesis reactor. Catalysts used for biomass conditioning are plagued by short lifetimes which are a result of, among other things, poisoning. Syngas produced from biomass gasification may contain between 30-300 ppm H2S, depending on the feedstock and gasification conditions, and H2S is a key catalyst poison. In order to overcome catalyst poisoning, either an H2S-tolerant catalyst or an efficient regeneration protocol should be employed. In this study, sulfur K-edge X-ray absorption near edge spectroscopy (XANES) was used to monitor sulfur species on spent catalyst samples and the transformation of these species from sulfides to sulfates during steam and air regeneration on a Ni/Mg/K/Al2O3 catalyst used to condition biomass-derived syngas. Additionally, nickel K-edge EXAFS and XANES are used to examine the state of nickel species on the catalysts. Post-reaction samples showed the presence of sulfides on the H2S-poisoned nickel catalyst and although some gaseous sulfur species were observed to leave the catalyst bed during regeneration, sulfur remained on the catalyst and a transformation from sulfides to sulfates was observed. The subsequent H2 reduction led to a partial reduction of sulfates back to sulfides. A proposed reaction sequence is presented and recommended regeneration strategies are discussed.

  14. Field-rugged sensitive hydrogen peroxide sensor based on tunable diode laser absorption spectroscopy (TDLAS)

    NASA Astrophysics Data System (ADS)

    Frish, M. B.; Morency, J. R.; Laderer, M. C.; Wainner, R. T.; Parameswaran, K. R.; Kessler, W. J.; Druy, M. A.

    2010-04-01

    This paper reports the development and initial testing of a field-portable sensor for monitoring hydrogen peroxide (H2O2) and water (H2O) vapor concentrations during building decontamination after accidental or purposeful exposure to hazardous biological materials. During decontamination, a sterilization system fills ambient air with water and peroxide vapor to near-saturation. The peroxide concentration typically exceeds several hundred ppm for tens of minutes, and subsequently diminishes below 1 ppm. The H2O2/ H2O sensor is an adaptation of a portable gas-sensing platform based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) technology. By capitalizing on its spectral resolution, the TDLAS analyzer isolates H2O2 and H2O spectral lines to measure both vapors using a single laser source. It offers a combination of sensitivity, specificity, fast response, dynamic range, linearity, ease of operation and calibration, ruggedness, and portability not available in alternative H2O2 detectors. The H2O2 range is approximately 0- 5,000 ppm. The autonomous and rugged instrument provides real-time data. It has been tested in a closed-loop liquid/vapor equilibrium apparatus and by comparison against electrochemical sensors.

  15. Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics.

    PubMed

    Merten, André; Tschritter, Jens; Platt, Ulrich

    2011-02-10

    We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments.

  16. Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics.

    PubMed

    Merten, André; Tschritter, Jens; Platt, Ulrich

    2011-02-10

    We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments. PMID:21343997

  17. Ozone monitoring using differential optical absorption spectroscopy (DOAS) and UV photometry instruments in Sohar, Oman.

    PubMed

    Nawahda, Amin

    2015-08-01

    Ground level ozone (O3) concentrations were measured across Sohar highway in Oman during a four-month period from September to December 2014 by using an open-path deferential optical absorption spectroscopy (DOAS) instrument. The monthly average concentrations of O3 varied from 19.6 to 29.4 ppb. The measurements of O3 are compared with the measurements of a non-open-path UV photometry analyzer (UVP). The percent difference (PD) concept and linear regression methods were used to compare the readings of the two instruments. The findings show high correlation coefficients between the measurements of the DOAS and UVP instruments. The DOAS measurements of O3 are found to be less than those measured by the UVP instrument; the correlation coefficients between absolute PD values and meteorological parameters and PM2.5 were very low indicating a minor effect; therefore, titrations of O3 by traffic emissions and difference in elevation could be the reason for the difference in the measurements of the two instruments. PMID:26138853

  18. Ultrafast holography and transient absorption spectroscopy in charge-transfer polymers

    SciTech Connect

    McBranch, D.W.; Maniloff, E.S.; Vacar, D.; Heeger, A.J.

    1997-10-01

    Charge-transfer polymers are a new class of nonlinear optical materials which can be used for generating femtosecond holographic gratings. Using semiconducting polymers sensitized with varying concentrations of C{sub 60}, holographic gratings were recorded by individual ultrafast laser pulses; the diffraction efficiency and time decay of the gratings were measured using non-degenerate four-wave mixing. Using a figure of merit for dynamic data processing, the temporal diffraction efficiency, this new class of materials exhibits between two and 12 orders of magnitude higher response than previous reports. The charge transfer range at polymer/C{sub 60} interfaces was further studied using transient absorption spectroscopy. The fact that charge-transfer occurs in the picosecond-time scale in bilayer structures (thickness 200 {angstrom}) implies that diffusion of localized excitations to the interface is not the dominant mechanism; the charge transfer range is a significant fraction of the film thickness. From analysis of the excited state decay curves, we estimate the charge transfer range to be 80 {angstrom} and interpret that range as resulting from quantum delocalization of the photoexcitations.

  19. A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions.

    PubMed

    Brown, Matthew A; Redondo, Amaia Beloqui; Jordan, Inga; Duyckaerts, Nicolas; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Müächler, Jean-Pierre; Birrer, Mario; Honegger, Juri; Wetter, Reto; Wörner, Hans Jakob; van Bokhoven, Jeroen A

    2013-07-01

    A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented. PMID:23902081

  20. A new endstation at the Swiss Light Source for ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy measurements of liquid solutions

    SciTech Connect

    Brown, Matthew A.; Redondo, Amaia Beloqui; Duyckaerts, Nicolas; Mächler, Jean-Pierre; Jordan, Inga; Wörner, Hans Jakob; Lee, Ming-Tao; Ammann, Markus; Nolting, Frithjof; Kleibert, Armin; Huthwelker, Thomas; Birrer, Mario; Honegger, Juri; Wetter, Reto; Bokhoven, Jeroen A. van

    2013-07-15

    A new liquid microjet endstation designed for ultraviolet (UPS) and X-ray (XPS) photoelectron, and partial electron yield X-ray absorption (XAS) spectroscopies at the Swiss Light Source is presented. The new endstation, which is based on a Scienta HiPP-2 R4000 electron spectrometer, is the first liquid microjet endstation capable of operating in vacuum and in ambient pressures up to the equilibrium vapor pressure of liquid water at room temperature. In addition, the Scienta HiPP-2 R4000 energy analyzer of this new endstation allows for XPS measurements up to 7000 eV electron kinetic energy that will enable electronic structure measurements of bulk solutions and buried interfaces from liquid microjet samples. The endstation is designed to operate at the soft X-ray SIM beamline and at the tender X-ray Phoenix beamline. The endstation can also be operated using a Scienta 5 K ultraviolet helium lamp for dedicated UPS measurements at the vapor-liquid interface using either He I or He II α lines. The design concept, first results from UPS, soft X-ray XPS, and partial electron yield XAS measurements, and an outlook to the potential of this endstation are presented.