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X-ray Absorption Spectroscopy of Dilute Metalloenzymes at X-ray Free-Electron Lasers in a Shot-by-Shot Mode

X-ray absorption spectroscopy (XAS) of 3d transition metals provides important electronic structure information for many fields. However, X-ray-induced radiation damage under physiological temperature has prevented using this method to study dilute aqueous systems, such as metalloenzymes, as the catalytic reaction proceeds. Here we present a new approach to enable operando XAS of dilute biological samples and demonstrate its feasibility with K-edge XAS spectra from the Mn cluster in photosystem II and the Fe–S centers in photosystem I. This approach combines highly efficient sample delivery strategies and a robust signal normalization method with high-transmission Bragg diffraction-based spectrometers at X-ray free-electron lasers (XFELs) in a damage-free, shot-by-shot mode. These photon-out spectrometers have been optimized for discriminating the metal Mn/Fe Kα fluorescence signals from the overwhelming scattering background present on currently available detectors for XFELs that lack suitable energy discrimination. We quantify the enhanced performance metrics of the spectrometer and discuss its potential applications for acquiring time-resolved XAS spectra of biological samples during their reactions at XFELs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calibrating Laser Gas Measurements by Use of Natural CO2

An improved method of calibration has been devised for instruments that utilize tunable lasers to measure the absorption spectra of atmospheric gases in order to determine the relative abundances of the gases. In this method, CO2 in the atmosphere is used as a natural calibration standard. Unlike in one prior calibration method, it is not necessary to perform calibration measurements in advance of use of the instrument and to risk deterioration of accuracy with time during use. Unlike in another prior calibration method, it is not necessary to include a calibration gas standard (and the attendant additional hardware) in the instrument and to interrupt the acquisition of atmospheric data to perform calibration measurements. In the operation of an instrument of this type, the beam from a tunable diode laser or a tunable quantum-cascade laser is directed along a path through the atmosphere, the laser is made to scan in wavelength over an infrared spectral region that contains one or two absorption spectral lines of a gas of interest, and the transmission (and, thereby, the absorption) of the beam is measured. The concentration of the gas of interest can then be calculated from the observed depth of the absorption line(s), given the temperature, pressure, and path length. CO2 is nearly ideal as a natural calibration gas for the following reasons: CO2 has numerous rotation/vibration infrared spectral lines, many of which are near absorption lines of other gases. The concentration of CO2 relative to the concentrations of the major constituents of the atmosphere is well known and varies slowly and by a small enough amount to be considered constant for calibration in the present context. Hence, absorption-spectral measurements of the concentrations of gases of interest can be normalized to the concentrations of CO2. Because at least one CO2 calibration line is present in every spectral scan of the laser during absorption measurements, the atmospheric CO2 serves continuously as a calibration standard for every measurement point. Figure 1 depicts simulated spectral transmission measurements in a wavenumber range that contains two absorption lines of N2O and one of CO2. The simulations were performed for two different upper-atmospheric pressures for an airborne instrument that has a path length of 80 m. The relative abundance of CO2 in air was assumed to be 360 parts per million by volume (approximately its natural level in terrestrial air). In applying the present method to measurements like these, one could average the signals from the two N2O absorption lines and normalize their magnitudes to that of the CO2 absorption line. Other gases with which this calibration method can be used include H2O, CH4, CO, NO, NO2, HOCl, C2H2, NH3, O3, and HCN. One can also take advantage of this method to eliminate an atmospheric-pressure gauge and thereby reduce the mass of the instrument: The atmospheric pressure can be calculated from the temperature, the known relative abundance of CO2, and the concentration of CO2 as measured by spectral absorption. Natural CO2 levels on Mars provide an ideal calibration standard. Figure 2 shows a second example of the application of this method to Mars atmospheric gas measurements. For sticky gases like H2O, the method is particularly powerful, since water is notoriously difficult to handle at low concentrations in pre-flight calibration procedures.

Webster, Chris↗

Laser Sounder for Global Measurement of CO2 Concentrations in the Troposphere from Space

Measurements of tropospheric CO2 abundance with global-coverage, a few hundred km spatial and monthly temporal resolution are needed to quantify processes that regulate CO2 storage by the land and oceans. The Orbiting Carbon Observatory (OCO) is the first space mission focused on atmospheric CO2 for measuring total column CO, and O2 by detecting the spectral absorption in reflected sunlight. The OCO mission is an essential step, and will yield important new information about atmospheric CO2 distributions. However there are unavoidable limitations imposed by its measurement approach. These include best accuracy only during daytime at moderate to high sun angles, interference by cloud and aerosol scattering, and limited signal from CO2 variability in the lower tropospheric CO2 column. We have been developing a new laser-based technique for the remote measurement of the tropospheric CO2 concentrations from orbit. Our initial goal is to demonstrate a lidar technique and instrument technology that will permit measurements of the CO2 column abundance in the lower troposphere from aircraft. Our final goal is to develop a space instrument and mission approach for active measurements of the CO2 mixing ratio at the 1-2 ppmv level. Our technique is much less sensitive to cloud and atmospheric scattering conditions and would allow continuous measurements of CO2 mixing ratio in the lower troposphere from orbit over land and ocean surfaces during day and night. Our approach is to use the 1570nm CO2 band and a 3-channel laser absorption spectrometer (i.e. lidar used an altimeter mode), which continuously measures at nadir from a near polar circular orbit. The approach directs the narrow co-aligned laser beams from the instrument's lasers toward nadir, and measures the energy of the laser echoes reflected from land and water surfaces. It uses several tunable fiber laser transmitters which allowing measurement of the extinction from a single selected CO2 absorption line in the 1570 nm band. This band is free from interference from other gases and has temperature insensitive absorption lines. During the measurement the lasers are tuned on- and off- a selected CO2 line near 1572 nm and a selected O2 line near 768 nm in the Oxygen A band at kHz rates. The lasers use tunable diode seed lasers followed by fiber amplifiers, and have spectral widths much narrower than the gas absorption lines. The receiver uses a 1-m diameter telescope and photon counting detectors and measures the background light and energies of the laser echoes from the surface. The extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on and offline surface echo via the differential optical absorption technique. Our technique rapidly alternates between several on-line wavelengths set to the sides of the selected gas absorption lines. It exploits the atmospheric pressure broadening of the lines to weight the measurement sensitivity to the atmospheric column below 5 km. This maximizes sensitivity to CO2 in the boundary layer, where variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column will use an identical approach with an O2 line. Thee laser frequencies are tunable and have narrow (MHz) line widths. In combination with sensitive photon counting detectors these enables much higher spectral resolution and precision than is possible with passive spectrometer. 1aser backscatter profiles are also measured, which permits identifying measurements made to cloud tops and through aerosol layers. The measurement approach using lasers in common-nadir-zenith path allows retrieving CO2 column mixing ratios in the lower troposphere irrespective of sun angle. Pulsed laser signals, time gated receiver and a narrow receiver field-of-view are used to isolate the surface laser echo signals and to exclude photons scattered from clouds and aerosols. Nonetheless, the optical absorption change due to a change of a few ppO2 is small, <1 % which makes achieving the needed measurement sensitivities and stabilities quite challenging. Measurement SNRs and stabilities of >600:1 are needed to estimate CO2 mixing ratio at the 1-2 ppm level. We have calculated characteristics of the technique and have demonstrated aspects of the laser, detector and receiver approaches in th e laboratory We have also measured O2 in an absorption cell, and made C02 measurements over a 400 m long (one way) horizontal path using a sensor breadboard. We will describe these and more details of our approach in the paper.

Abshire, James B.↗

Analytical studies of ultrashort optical pulse propagation in a resonant absorbing medium

Resonant absorption in a laser pulse can be reduced to zero if the trailing part induces stimulated emission and returns the absorbed energy back to the pulse. This kind of effect is called Self-Induced Transparency (SIT). Analytic descriptions of short pulse propagation in a resonant medium, based on Slowly Varying Envelope Approximation (SVEA) and in linear media, have been extended in studies of SIT along two principal directions: First, to improve the SVEA by introducing Short Pulse Approximation (SPA); and second, to consider the effect of nonlinear refractive index.

Lee, C. T.↗

Uniformity of Ludwieg tube flows

Pressure and speed of sound measurements are used to obtain averaged gas properties in a Ludwieg combustion tube in which the gas is burned just prior to use. Absorption of a laser beam in the exit flow is used to check the predicted temperature uniformity. The burning process and the heat transfer to the cold walls are modeled. Interferograms of Ludwieg tube boundary layers are utilized to develop a new semiempirical boundary layer expression referred to as the integral density thickness, which is then applied to a recently developed linearized analysis of the effects of this layer. Pressure-time histories are determined for a wide range of tube flow Mach number and aspect ratio. Viscous and nonviscous effects are considered. It is shown that although the influence of the integral density thickness on the flow can be large, a modified linear theory can be used to estimate the effects for arbitrary tube flow Mach number and values of the aspect ratio that include cases where the boundary layers have merged.

Russell, D. A.↗

Direct observation of interface instability during crystal growth

The general aim of this investigation was to study interface stability and solute segregation phenomena during crystallization of a model system. Emphasis was to be placed on direct observational studies partly because this offered the possibility at a later stage of performing related experiments under substantially convection-free conditions in the space shuttle. The major achievements described in this report are: (1) the development of a new model system for fundamental studies of crystal growth from the melt and the measurement of a range of material parameters necessary for comparison of experiment with theory. (2) The introduction of a new method of measuring segregation coefficient using absorption of a laser beam by the liquid phase. (3) The comparison of segregation in crystals grown by gradient freezing and by pulling from the melt. (4) The introduction into the theory of solute segregation of an interface field term and comparison with experiment. (5) The introduction of the interface field term into the theories of constitutional supercooling and morphological stability and assessment of its importance.

Tiller, W. A.↗

Advanced smoke meter development survey and analysis

Ideal smoke meter characteristics are determined to provide a basis for evaluation of candidate systems. Five promising techniques are analyzed in detail to evaluate compilance with the practical smoke meter requirements. Four of the smoke measurement concepts are optical methods: Modulated Transmission (MODTRAN), Cross Beam Absorption Counter (CBAC), Laser Induced Incandescence (LIN), and Photoacoustic Spectroscopy (PAS). A rapid response filter instrument called a Taper Element Oscillating Microbalance (TEOM) is also evaluated. For each technique, the theoretical principles are described, the expected performance is determined, and the advantages and disadvantages are discussed The expected performance is evaluated against each of the smoke meter specifications, and the key questions for further study are given. The most promising smoke meter technique analyzed was MODTRAN, which is a variation on a direct transmission measurement. The soot-laden gas is passed through a transmission cell, and the gas pressure is modulated by a speaker.

Pitz, R. W.↗

Mobile lidar system for measurement of water vapor mixing ratio and ozone number density

The Water Vapor Lidar was modified and extended to make differential absorption measurements of ozone. Water vapor measurements make use of a weak molecular scattering process known as Raman scattering. It is characterized by a shift in wavelength of the scattered beam of light relative to the incident one. Some of the energy of the incident photon is converted to vibrational or rotational energy within the molecule leaving the scattered photon shifted to a slightly longer wavelength. When performing water vapor measurements, profiles are acquired of water vapor mixing ratio from near the ground to beyond 7 km every 2 minutes. By forming a color composite image of the individual profiles, the spatial and temporal evolution of water vapor is visible with vertical resolution of 75 to 150m and temporal resolution of 2 minutes. The ozone lidar is intended for use as a cross calibration facility for other stationary ozone lidar systems. The ozone measurement employs the technique known as differential absorption. The backscattered laser radiation from two different wavelengths is measured. Successful measurements of 308 nm returns were made from 80 km with an averaging period of 6 hours. Using these data and a standard atmosphere density curve, an ozone number density profile was made which agrees very well with the standard ozone curve between 20 and 40 km.

Whiteman, D.↗

A conceptual design study for the EOS Lidar Atmospheric Sounder and Altimeter facility

A preliminary design study is presented for the Lidar Atmospheric Sounder and Altimeter (LASA), an active remote sensor for the Earth Observing System. LASA is designed to measure the global vertical distributions of aerosols, cloud top heights, atmospheric trace gases, atmospheric temperature and pressure, and the height of the PBL. The measurements are made using optical radar, differential absorption lidar, and laser altimetry. An experiment proposed for the LASA facility, the EOS Atmospheric Global Lidar Experiment (EAGLE) is described in detail. The EAGLE program is planned to determine aerosol and cloud distributions, water vapor concentrations, and temperature profiles over the troposphere and aerosol distribution over the stratosphere. The measurement techniques, receiver system, and transmitter for the EAGLE program are examined and the conceptual design of the EAGLE experiment and the LASA/EAGLE interface is outlined.

Mauldin, Lemuel E., III↗

JPL Fourier transform ultraviolet spectrometer

The Fourier Transform Ultraviolet Spectrometer (FTUVS) is a new high resolution interferometric spectrometer for multiple-species detection in the UV, visible and near-IR. As an OH sensor, measurements can be carried out by remote sensing (limb emission and column absorption), or in-situ sensing (long-path absorption or laser-induced fluorescence). As a high resolution detector in a high repetition rate (greater than 10 kHz) LIF system, OH fluorescence can be discriminated against non-resonant background emission and laser scatter, permitting (0, 0) excitation.

Cageao, R. P.↗

Local fluctuations of ozone from 16 km to 45 km deduced from in situ vertical ozone profile

A vertical ozone profile obtained by an in situ ozone sonde from 16 km to 45 km, has allowed to observe local ozone concentration variations. These variations can be observed, thanks to a fast measurement system based on a UV absorption KrF excimer laser beam in a multipass cell. Ozone standard deviation versus altitude calculated from the mean is derived. Ozone variations or fluctuations are correlated with the different dynamic zones of the stratosphere.

Moreau, G.↗

Soot Optical Property Study

Recent past studies of soot reaction processes in laminar premixed and nonpremixed flames generally have used the intrusive technique of thermophoretic sampling and analysis by transmission electron microscopy (TEM) to observe soot structure and obtain important fundamental information about soot particle properties, such as soot primary particle diameters, the rate of change of soot primary particle diameter as a function of time (or rate of soot surface growth or oxidation), the amount of soot particle reactive surface area per unit volume, the number of primary soot particles per unit volume, and the rate of formation of primary soot particles (or the rate of soot primary particle nucleation). Given the soot volume per unit volume of the flame (or the soot volume fraction), all these properties are readily found from a measurement of the soot primary particle diameter (which usually is nearly a constant for each location within a laminar flame). This approach is not possible within freely propagating flames, however, because soot properties at given positions in such flames vary relatively rapidly as a function of time in the soot formation and oxidation regions compared to the relatively lengthy sampling times needed to accumulate adequate soot samples and to minimize effects of soot collected on the sampling grid as it moves to and from the sampling position through other portions of the flame. Thus, nonintrusive optical methods must be used to find the soot primary particle diameters needed to define the soot surface reaction properties mentioned earlier. Unfortunately, approximate nonintrusive methods used during early studies of soot reaction properties in flames, found from laser scattering and absorption measurements analyzed assuming either Rayleigh scattering or Mie scattering from polydisperse effective soot particles having the same mass of soot as individual soot aggregates, have not been found to be an effective way to estimate the soot surface reaction area per unit volume. Thus, alternative nonintrusive optical methods of finding these properties must be sought, which was the objective of this phase of the investigation. The alternative method used here involves use of the Rayleigh-Debye-Gans-Polydisperse-Fractal-Aggregate (RDG-PFA) scattering approximation for soot aggregates in flames. Thus, the development of this method will be discussed next before describing its evaluation as a means of nonintrusively measuring soot primary particle diameters in soot-containing flames.

Aung, K. T.↗

Aircraft(ER-2) and Balloon In-Situ Measurements of HC1, NO(sub 2), HNO(sub 3), N(sub 2)o, and CH(sub 4) for Testing Heterogeneous Chemistry on PSC's and Sulfate Aerosols in the 1991/92 Arctic Winter

Concentrations of HC1 measured in the 1991/3 northern hemisphere lower stratosphere from the ER-2 aircraft are significantly lower than model predictions using both gas phase and heterogeneous chemistry, but are in much better agreement with model predictions for the 1994 southern hemisphere.

In-Situ Sensor (BLISS)↗

Application of STARFLEET Velocimetry in the NASA Langley 0.3-Meter Transonic Cryogenic Tunnel

Selective two-photon absorptive resonance femtosecond laser electronic excitation tagging (STARFLEET) velocimetry is demonstrated for the first time in a NASA Langley wind tunnel with high repetition-rate and single-shot imaging. Experiments performed in the 0.3-meter Transonic Cryogenic Tunnel (TCT) allowed for testing at 300 K over a range of pressures (124 to 517 kPa) and Mach numbers (0.2-0.8) for freestream conditions and flow behind a cylindrical model. Measurement precision and accuracy are determined for the current set of experiments, as are signal intensity and lifetime. Precisions of 3-5 m/s (based on one standard deviation) were typical in the experiment; precisions better than 2% of the mean velocity were obtained for some of the highest velocity conditions. Agreement within a mean error of 3 m/s between STARFLEET freestream velocity measurements and facility DAS readings is demonstrated. STARFLEET is also shown to return spatially-resolved velocity profiles, though some binning of the signal is required.

STARFLEET↗

Method of and apparatus for measuring temperature and pressure

Laser beams are transmitted through gas to a reflecting target, which may be either a solid surface or particulate matter in gas or the gas molecules. The return beams are measured to determine the amount of energy absorbed by the gas. For temperature measurements, the laser beam has a wavelength at which the gas exhibits a relatively temperature sensitive and pressure insensitive absorption characteristic for pressure measurements, the laser beam has a wavelength at which the gas has a relatively pressure sensitive and temperature insensitive absorption characteristic. To reduce the effects of scattering on the absorption measurements a reference laser beam with a weak absorption characteristic is transmitted colinearly with the data beam having a strong absorption characteristic. The two signals are processed as a ratio to eliminate back scattering. Embodiments of transmitters and receivers described include a sequential laser pulse transmitter and receiver, a simultaneous laser pulse transmitter and receiver.

Korb, C. L.↗

Compact Laser-Based Sensors for Monitoring and Control of Gas Turbine Combustors

Research is reported on the development of sensors for gas turbine combustor applications that measure real-time gas temperature using near-infrared water vapor absorption and concentration in the combustor exhaust of trace quantities of pollutant NO and CO using mid-infrared absorption. Gas temperature is extracted from the relative absorption strength of two near-infrared transitions of water vapor. From a survey of the water vapor absorption spectrum, two overtone transitions near 1800 nm were selected that can be rapidly scanned in wavelength by injection current tuning a single DFB diode laser. From the ratio of the absorbances on these selected transitions, a path-integrated gas temperature can be extracted in near-real time. Demonstration measurements with this new temperature sensor showed that combustor instabilities could be identified in the power spectrum of the temperature versus time record. These results suggest that this strategy is extremely promising for gas turbine combustor control applications. Measurements of the concentration of NO and CO in the combustor exhaust are demonstrated with mid-infrared transitions using thermo-electrically cooled, quantum cascade lasers operating near 5.26 and 4.62 microns respectively. Measurements of NO are performed in an insulated exhaust duct of a C2H4-air flame at temperatures of approximately 600 K. CO measurements are performed above a rich H2-air flame seeded with CO2 and cooled with excess N2 to 1150 K. Using a balanced ratiometric detection technique a sensitivity of 0.36 ppm-m was achieved for NO and 0.21 ppm-m for CO. Comparisons between measured and predicted water-vapor and CO2 interference are discussed. The mid-infrared laser quantum cascade laser technology is in its infancy; however, these measurements demonstrate the potential for pollutant monitoring in exhaust gases with mid-IR laser absorption.

Hanson, Ronald K.↗

Development in tunable solid state lasers with high spectral purity, high efficiency and long lifetime for differential absorption lidar

The paper presents a review of tunable vibronic solid state lasers for DIAL measurements and provides new experimental results for tunable Ti:sapphire lasers, materials development, and spectral bandwidth narrowing through injection control. Pulsed injection control of a Ti:sapphire laser with a 2.5-pm narrow band pulsed dye laser and with another Ti:sapphire laser is demonstrated with nearly complete energy extraction, indicating homogeneous line broadening. The status of tunable solid state lasers in the 1.6-2.3 micron range for DIAL measurements of trace gases, and development trends for lasers with reduced cryogenic cooling needs, are included. The effects of laser gain on optical damage, energy extraction, and amplified spontaneous emission are indicated for several tunable lasers.

Hess, R. V.↗

A Comparison of NO Laser-Induced Fluorescence Models at Conditions Relevant to Supersonic and Hypersonic Flows

Planar laser-induced fluorescence (PLIF) of the nitric oxide (NO) molecule has been widely used in wind tunnel facilities for flow visualization, velocity, and temperature measurements. The experimental PLIF measurements are often compared with synthetic PLIF images using computationally derived temperatures, pressures, velocities, and species mole fractions. This approach is commonly referred to as computational flow imaging (CFI). In the present work, we compare signal intensity from PLIF models with experimental PLIF measurements obtained within a low pressure gas cell system at pressures and NO mole fractions relevant to supersonic and hypersonic flowfields. Experimental measurements were compared to several different laser induced-fluorescence models reported in the literature including LIFBASE, LINUS, and a NASA two-level model. The experimental measurements agreed well with all of the models at lower pressures and lower NO mole fractions; the fluorescence there is linear with both of these parameters. However, at higher pressures and mole fractions, the signal becomes nonlinear with respect to these parameters as self-quenching limits the signal and absorption further limits the signal. In fact, for the experimental path length of the experiment, the combination of high pressure and high NO mole fraction causes the experimental results to deviate significantly from the predicted results that neglect absorption of the incident laser sheet. The LINUS model, which allows absorption to be calculated, provided results that agreed better with the experimental measurements. Since supersonic and hypersonic flowfields may contain a region of the flow with high pressures and measurements in large-scale facilities often include a long path length, neglecting absorption may have a significantly negative effect on the CFI comparison to experimental PLIF images. As a result, PLIF models that account for absorption should be included in computational flow imaging approaches for laser induced fluorescence.

laser-induced fluorescence↗