The water vapour self- and water-nitrogen continuum absorption in the 1000 and 2500 cm(-1) atmospheric windows

The pure water vapour and water-nitrogen continuum absorption in the 1000 and 2500?cm(-1) atmospheric windows has been studied using a 2?m base-length White-type multi-pass cell coupled with a BOMEM DA3-002 Fourier transform infrared spectrometer. The measurements were carried out at the National Institute of Standards and Technology (NIST, Gaithersburg, MD) over the course of several years (2004, 2006-2007, 2009). New data on the H(2)O:N(2) continuum in the 1000?cm(-1) window are presented and summarized along with the other experimental results and the continuum model. The experimental data reported on the water vapour continuum in these atmospheric windows basically agree with the most reliable laboratory data from the other sources. The MT_CKD (Mlawer-Tobin-Clough-Kneizys-Davies) continuum model significantly departs from the experimental data in both windows. The deviation observed includes the continuum magnitude, spectral behaviour and temperature dependence. In the 2500?cm(-1) region, the model does not allow for the nitrogen fundamental collision-induced absorption (CIA) band intensity enhancement caused by H(2)O:N(2) collisions and underestimates the actual absorption by over two orders of magnitude. The water vapour continuum interpretation as a typical CIA spectrum is reviewed and discussed.     

Airborne and satellite remote sensing of the mid-infrared water vapour continuum

Remote sensing of the atmosphere from space plays an increasingly important role in weather forecasting. Exploiting observations from the latest generation of weather satellites relies on an accurate knowledge of fundamental spectroscopy, including the water vapour continuum absorption. Field campaigns involving the Facility for Airborne Atmospheric Measurements research aircraft have collected a comprehensive dataset, comprising remotely sensed infrared radiance observations collocated with accurate measurements of the temperature and humidity structure of the atmosphere. These field measurements have been used to validate the strength of the infrared water vapour continuum in comparison with the latest laboratory measurements. The recent substantial changes to self-continuum coefficients in the widely used MT_CKD (Mlawer-Tobin-Clough-Kneizys-Davies) model between 2400 and 3200?cm(-1) are shown to be appropriate and in agreement with field measurements. Results for the foreign continuum in the 1300-2000?cm(-1) band suggest a weak temperature dependence that is not currently included in atmospheric models. A one-dimensional variational retrieval experiment is performed that shows a small positive benefit from using new laboratory-derived continuum coefficients for humidity retrievals.     

Development and recent evaluation of the MT_CKD model of continuum absorption

Water vapour continuum absorption is an important contributor to the Earth's radiative cooling and energy balance. Here, we describe the development and status of the MT_CKD (MlawerTobinCloughKneizysDavies) water vapour continuum absorption model. The perspective adopted in developing the MT_CKD model has been to constrain the model so that it is consistent with quality analyses of spectral atmospheric and laboratory measurements of the foreign and self continuum. For field measurements, only cases for which the characterization of the atmospheric state has been highly scrutinized have been used. Continuum coefficients in spectral regions that have not been subject to compelling analyses are determined by a mathematical formulation of the spectral shape associated with each water vapour monomer line. This formulation, which is based on continuum values in spectral regions in which the coefficients are well constrained by measurements, is applied consistently to all water vapour monomer lines from the microwave to the visible. The results are summed-up (separately for the foreign and self) to obtain continuum coefficients from 0?to 20?000?cm(-1). For each water vapour line, the MT_CKD line shape formulation consists of two components: exponentially decaying far wings of the line plus a contribution from a water vapour molecule undergoing a weak interaction with a second molecule. In the MT_CKD model, the first component is the primary agent for the continuum between water vapour bands, while the second component is responsible for the majority of the continuum within water vapour bands. The MT_CKD model should be regarded as a semi-empirical model with strong constraints provided by the known physics. Keeping the MT_CKD continuum consistent with current observational studies necessitates periodic updates to the water vapour continuum coefficients. In addition to providing details on the MT_CKD line shape formulation, we describe the most recent update to the model, MT_CKD_2.5, which is based on an analysis of satellite- and ground-based observations from 2385 to 2600?cm(-1) (approx. 4?μm).     

Absolute high spectral resolution measurements of surface solar radiation for detection of water vapour continuum absorption

Solar-pointing Fourier transform infrared (FTIR) spectroscopy offers the capability to measure both the fine scale and broadband spectral structure of atmospheric transmission simultaneously across wide spectral regions. It is therefore suited to the study of both water vapour monomer and continuum absorption behaviours. However, in order to properly address this issue, it is necessary to radiatively calibrate the FTIR instrument response. A solar-pointing high-resolution FTIR spectrometer was deployed as part of the 'Continuum Absorption by Visible and Infrared radiation and its Atmospheric Relevance' (CAVIAR) consortium project. This paper describes the radiative calibration process using an ultra-high-temperature blackbody and the consideration of the related influence factors. The result is a radiatively calibrated measurement of the solar irradiation at the ground across the IR region from 2000 to 10?000?cm(-1) with an uncertainty of between 3.3 and 5.9 per cent. This measurement is shown to be in good general agreement with a radiative-transfer model. The results from the CAVIAR field measurements are being used in ongoing studies of atmospheric absorbers, in particular the water vapour continuum.     

H(2)O--N(2) collision-induced absorption band intensity in the region of the N(2) fundamental: ab initio investigation of its temperature dependence and comparison with laboratory data

The present paper aims at ab initio and laboratory evaluation of the N(2) collision-induced absorption band intensity arising from interactions between N(2) and H(2)O molecules at wavelengths of around 4?μm. Quantum chemical calculations were performed in the space of five intermolecular coordinates and varying N--N bond length using M?ller-Plesset perturbation and CCSD(T) methods with extrapolation of the electronic energy to the complete basis set. This made it possible to construct the intermolecular potential energy surface and to define the surface of the N--N dipole derivative with respect to internal coordinate. The intensity of the nitrogen fundamental was then calculated as a function of temperature using classical integration. Experimental spectra were recorded with a BOMEM DA3-002 FTIR spectrometer and 2?m base-length multipass White cell. Measurements were conducted at temperatures of 326, 339, 352 and 363?K. The retrieved water-nitrogen continuum significantly deviates from the MT_CKD model because the relatively strong nitrogen absorption induced by H(2)O was not included in this model. Substantial uncertainties in the measurements of the H(2)O-N(2) continuum meant that quantification of any temperature dependence was not possible. The comparison of the integrated N(2) fundamental band intensity with our theoretical estimates shows reasonably good agreement. Theory indicates that the intensity as a function of temperature has a minimum at approximately 500?K.     

Effect of atmospheric radiance errors in radiometric sea-surface skin temperature measurements

Errors in measurements of sea-surface skin temperature (SSST) caused by inappropriate measurements of sky radiance are discussed; both model simulations and in situ data obtained in the Atlantic Ocean are used. These errors are typically caused by incorrect radiometer view geometry (pointing), temporal mismatches between the sea surface and atmospheric views, and the effect of wind on the sea surface. For clear-sky, overcast, or high-humidity atmospheric conditions, SSST is relatively insensitive (<0.1 K) to sky-pointing errors of ?10 degrees and to temporal mismatches between the sea and sky views. In mixed-cloud conditions, SSST errors greater than ?0.25 K are possible as a result either of poor radiometer pointing or of a temporal mismatch between the sea and sky views. Sea-surface emissivity also changes with sea view pointing angle. Sea view pointing errors should remain below 5 degrees for SSST errors of <0.1 K. We conclude that the clear-sky requirement of satellite infrared SSST observations means that sky-pointing errors are small when one is obtaining in situ SSST validation data at zenith angles of <40 degrees . At zenith angles greater than this, large errors are possible in high-wind-speed conditions. We recommend that high-resolution inclinometer measurements always be used, together with regular alternating sea and sky views, and that the temporal mismatch between sea and sky views be as small as possible. These results have important implications for the development of operational autonomous instruments for determining SSST for the long-term validation of satellite SSST.     

Infrared collision-induced absorption by N(2) near 4.3 μm for atmospheric applications: measurements and empirical modeling

Accurate measurements of collision-induced absorption by pure nitrogen in the fundamental band near 4.3 μm have been made in the 0-10 atm and 230-300 K pressure and temperature ranges, respectively. A Fourier-transform spectrometer was used with a resolution of 0.5 cm(-1). The current measurements, which agree well with previous ones but are more precise, reveal that weak features are superimposed on the broad N(2) continuum. These features have negligible temperature dependence, and their origin is not clear at the present time. Available experimental data in the 190-300 K temperature range have been used to build a simple empirical model that is suitable for use to compute atmospheric N(2) absorption. Tests indicate that this model is accurate unlike the estimates produced by widely used atmospheric transmission codes.     

Infrared collision-induced absorption by O2 near 6.4 microm for atmospheric applications: measurements and empirical modeling

Accurate measurements of collision-induced absorption by O(2) and O(2)-N(2) mixtures in the fundamental band near 6.4 mum have been made. A Fourier-transform spectrometer was used with a resolution of 0.5 cm(-1). Absorption has been investigated in the 0-20-atm and 193-293 K pressure and temperature ranges, respectively. The current measurements confirm that the broad O(2) continuum carries small features whose attribution is not yet clear. Available experimental data in the 190-360 K temperature range have been used to build a simple, low cost computer, empirical model that is well adapted for computation of atmospheric O(2) absorption. Tests show that it is accurate, contrary to predictions of widely used atmospheric transmission codes.     

Recent advances in measurement of the water vapour continuum in the far-infrared spectral region

We present a new derivation of the foreign-broadened water vapour continuum in the far-infrared (far-IR) pure rotation band between 24?μm and 120?μm (85-420?cm(-1)) from field data collected in flight campaigns of the Continuum Absorption by Visible and IR radiation and Atmospheric Relevance (CAVIAR) project with Imperial College's Tropospheric Airborne Fourier Transform Spectrometer (TAFTS) far-IR spectro-radiometer instrument onboard the Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft; and compare this new derivation with those recently published in the literature in this spectral band. This new dataset validates the current Mlawer-Tobin-Clough-Kneizys-Davies (MT-CKD) 2.5 model parametrization above 300?cm(-1), but indicates the need to strengthen the parametrization below 300?cm(-1), by up to 50 per cent at 100?cm(-1). Data recorded at a number of flight altitudes have allowed measurements within a wide range of column water vapour environments, greatly increasing the sensitivity of this analysis to the continuum strength.     

Measurements of the foreign-broadened continuum of water vapor in the 6.3 microm band at -30 degrees C

The foreign-broadened continuum of water vapor in the nu2 band (5-7.7 microm, 1300-2000 cm(-1)) is important for satellite-based retrievals of water vapor in the upper troposphere, where temperatures are below -25 degrees C. Continuum coefficients have previously been measured mostly at or above +23 degrees C. We present continuum coefficients in the nu(2) band retrieved from measurements made in Antarctica at temperatures near -30 degrees C: atmospheric transmission at South Pole Station and atmospheric emission at Dome C. The continuum coefficients derived from these measurements are generally in agreement with the widely used Mlawer, Tobin-Clough, Kneizys, Davies continuum. Differences are at most 30%, corresponding to a 6% relative error in retrieved upper-tropospheric humidity.     

Analysis of aircraft exhausts with Fourier-transform infrared emission spectroscopy

Because of the worldwide growth in air traffic and its increasing effects on the atmospheric environment, it is necessary to quantify the direct aircraft emissions at all altitudes. In this study Fourier-transform infrared emission spectroscopy as a remote-sensing multi-component-analyzing technique for aircraft exhausts was investigated at ground level with a double pendulum interferometer and a line-by-line computer algorithm that was applied to a multilayer radiative transfer problem. Initial measurements were made to specify the spectral windows for traceable compounds, to test the sensitivity of the system, and to develop calibration and continuum handling procedures. To obtain information about the radial temperature and concentration profiles, we developed an algorithm for the analysis of an axial-symmetric multilayered plume by use of the CO(2) hot band at approximately 2400 cm(-1). Measurements were made with several in-service engines. Effects that were due to engine aging were detected but have to be analyzed systematically in the near future. Validation measurements were carried out with a conventional propane gas burner to compare the results with those obtained with standard measurement equipment. These measurements showed good agreement to within +/-20% for the CO and NO(x) results. The overall accuracy of the system was found to be +/-30%. The detection limits of the system for a typical engine plume (380 degrees C, ? = 50 cm) are below 0.1% for CO(2), ~0.7% for H(2)O, ~20 ppmv (parts per million by volume) for CO, and ~90 ppmv for NO.     

Measurement and modeling of ozone and nitrogen oxides produced by laser breakdown in oxygen-nitrogen atmospheres

The production of ozone nad nitrogen oxides was studied during multiple laser breakdown in oxygen-nitrogen mixtures at atmospheric pressure. About 2000 laser shots at 10(10) W cm-2 were delivered into a sealed reaction chamber. The chamber with a long capillary was designed to measure absorption of O3, NO, and NO2 as a function of the number of laser shots. The light source for absorption measurements was the continuum radiation emitted by the plasma during the first 0.2 microsecond of its evolution. A kinetic model was developed that encompassed the principal chemical reactions between the major atmospheric components and the products of laser breakdown. In the model, the laser plasma was treated as a source of nitric oxide and atomic oxygen, whose rates of production were calculated using measured absorption by NO, NO2, and O3. The calculated concentration profiles for NO, NO2, and O3 were in good agreement with measured profiles over a time scale of 0-200 s. The steady-state concentration of ozone was measured in a flow cell in air. For a single breakdown in air, the estimated steady-state yield of ozone was 2 x 10(12) molecules, which agreed with the model prediction. This study can be of importance for general understanding of laser plasma chemistry and for elucidating the nature of spectral interferences and matrix effects that may take place in applied spectrochemical analysis.     

Portable Fourier transform infrared spectroradiometer for field measurements of radiance and emissivity

A hand-held, battery-powered Fourier transform infrared spectroradiometer weighing 12.5 kg has been developed for the field measurement of spectral radiance from the Earth's surface and atmosphere in the 3-5-μm and 8-14-μm atmospheric windows, with a 6-cm(-1) spectral resolution. Other versions of this instrument measure spectral radiance between 0.4 and 20 μm, using different optical materials and detectors, with maximum spectral resolutions of 1 cm(-1). The instrument tested here has a measured noise-equivalent delta T of 0.01 °C, and it measures surface emissivities, in the field, with an accuracy of 0.02 or better in the 8-14-μm window (depending on atmospheric conditions), and within 0.04 in accessible regions of the 3-5-μm window. The unique, patented design of the interferometer has permitted operation in weather ranging from 0 to 45 °C and 0 to 100% relative humidity, and in vibration-intensive environments such as moving helicopters. The instrument has made field measurements of radiance and emissivity for 3 yr without loss of optical alignment. We describe the design of the instrument and discuss methods used to calibrate spectral radiance and calculate spectral emissivity from radiance measurements. Examples of emissivity spectra are shown for both the 3-5-μm and 8-14-μm atmospheric windows.     

Development of a Tunable, Narrow-Linewidth, CW 2.066-mum Ho:YLF Laser for Remote Sensing of Atmospheric CO(2) and H(2)O

A smoothly tunable, narrow-linewidth, cw, 32-mW, 2.066-mum Ho:YLF laser was constructed and used for the first time in preliminary spectroscopic measurements of atmospheric CO(2) and H(2)O. The laser was constructed with a 4.5-mm-long, TE-cooled, codoped 5% Tm and 0.5% Ho yttrium lithium fluoride crystal (cut at Brewster's angle) pumped by an Ar(+)-pumped 500-mW Ti:sapphire laser operating at 792 nm. Intracavity etalons were used to reduce the laser linewidth to approximately 0.025 cm(-1) (0.75 GHz), and the laser wavelength was continuously and smoothly tunable over approximately 6 cm(-1) (180 GHz). The Ho:YLF laser was used to perform spectroscopic measurements on molecular CO(2) in a laboratory absorption cell and to measure the concentration of CO(2) and water vapor in the atmosphere with an initial accuracy of approximately 5-10%. The measurement uncertainty was found to be due to several noise sources, including the effect of asymmetric intensity of the laser modes within the laser linewidth, fluctuations caused by atmospheric turbulence and laser beam/target movement, and background spectral shifts.     

Airborne differential absorption lidar system for measurements of atmospheric water vapor and aerosols

An airborne differential absorption lidar (DIAL) system has been developed at the NASA Langley Research Center for remote measurements of atmospheric water vapor (H(2)O) and aerosols. A solid-state alexandrite laser with a 1-pm linewidth and > 99.85% spectral purity was used as the on-line transmitter. Solid-state avalanche photodiode detector technology has replaced photomultiplier tubes in the receiver system, providing an average increase by a factor of 1.5-2.5 in the signal-to-noise ratio of the H(2)O measurement. By incorporating advanced diagnostic and data-acquisition instrumentation into other subsystems, we achieved additional improvements in system operational reliability and measurement accuracy. Laboratory spectroscopic measurements of H(2)O absorption-line parameters were perfo med to reduce the uncertainties in our knowledge of the absorption cross sections. Line-center H(2)O absorption cross sections were determined, with errors of 3-6%, for more than 120 lines in the 720-nm region. Flight tests of the system were conducted during 1989-1991 on the NASA Wallops Flight Facility Electra aircraft, and extensive intercomparison measurements were performed with dew-point hygrometers and H(2)O radiosondes. The H(2)O distributions measured with the DIAL system differed by ≤ 10% from the profiles determined with the in situ probes in a variety of atmospheric conditions.     

Dual quantum cascade laser trace gas instrument with astigmatic Herriott cell at high pass number

We have developed and demonstrated a high-sensitivity trace gas instrument employing two mid-infrared quantum cascade lasers and an astigmatic Herriott sample cell with up to a 240?m path length. Several aspects of astigmatic Herriott cell optics have been addressed to enable operation at a high pass number (up to 554), including aberrations and pattern selection to minimize interference fringes. The new instrument design, based on the 200?m cell, can measure various atmospheric trace gases, depending on the installed lasers, with multiple trace gases measured simultaneously. Demonstrated concentration noise levels (1?s average) are 40?parts per trillion [(ppt) 10(-12)] for formaldehyde, 10?ppt for carbonyl sulfide, 110?ppt for hydrogen peroxide (H2O2), and 180?ppt for nitrous acid (HONO). High-precision measurements of nitrous oxide and methane have been recorded at the same time as high-sensitivity measurements of HONO and H2O2.     

Single diode laser sensor for wide-range H2O temperature measurements

A single diode laser absorption sensor (near 1477 nm) useful for simultaneous temperature and H2O concentration measurements is developed. The diode laser tunes approximately 1.2 cm(-1) over three H2O absorption transitions in each measurement. The line strengths of the transitions are measured over a temperature range from 468 to 977 K, based on high-resolution absorption measurements in a heated static cell. The results indicate that the selected transitions are suitable for sensitive temperature measurements in atmospheric pressure combustion systems using absorption line ratios. Comparing the results with HITRAN 96 data, it appears that these transitions will be sensitive over a wide range of temperatures (450-2000 K), suggesting applicability for combustion measurements.     

Side-line tunable laser transmitter for differential absorption lidar measurements of CO2: design and application to atmospheric measurements

A 2 microm wavelength, 90 mJ, 5 Hz pulsed Ho laser is described with wavelength control to precisely tune and lock the wavelength at a desired offset up to 2.9 GHz from the center of a CO(2) absorption line. Once detuned from the line center the laser wavelength is actively locked to keep the wavelength within 1.9 MHz standard deviation about the setpoint. This wavelength control allows optimization of the optical depth for a differential absorption lidar (DIAL) measuring atmospheric CO(2) concentrations. The laser transmitter has been coupled with a coherent heterodyne receiver for measurements of CO(2) concentration using aerosol backscatter; wind and aerosols are also measured with the same lidar and provide useful additional information on atmospheric structure. Range-resolved CO(2) measurements were made with <2.4% standard deviation using 500 m range bins and 6.7 min? (1000 pulse pairs) integration time. Measurement of a horizontal column showed a precision of the CO(2) concentration to <0.7% standard deviation using a 30 min? (4500 pulse pairs) integration time, and comparison with a collocated in situ sensor showed the DIAL to measure the same trend of a diurnal variation and to detect shorter time scale CO(2) perturbations. For vertical column measurements the lidar was setup at the WLEF tall tower site in Wisconsin to provide meteorological profiles and to compare the DIAL measurements with the in situ sensors distributed on the tower up to 396 m height. Assuming the DIAL column measurement extending from 153 m altitude to 1353 m altitude should agree with the tower in situ sensor at 396 m altitude, there was a 7.9 ppm rms difference between the DIAL and the in situ sensor using a 30 min? rolling average on the DIAL measurement.     

Combination of fiber-guided pulsed erbium and holmium laser radiation for tissue ablation under water

Because of the high absorption of near-infrared laser radiation in biological tissue, erbium lasers and holmium lasers emitting at 3 and 2 μm, respectively, have been proven to have optimal qualities for cutting or welding and coagulating tissue. To combine the advantages of both wavelengths, we realized a multiwavelength laser system by simultaneously guiding erbium and holmium laser radiation by means of a single zirconium fluoride (ZrF(4)) fiber. Laser-induced channel formation in water and poly(acrylamide) gel was investigated by the use of a time-resolved flash-photography setup, while pressure transients were recorded simultaneously with a needle hydrophone. The shapes and depths of vapor channels produced in water and in a submerged gel after single erbium and after combination erbium-holmium radiation delivered by means of a 400-μm ZrF(4) fiber were measured. Transmission measurements were performed to determine the amount of pulse energy available for tissue ablation. The effects of laser wavelength and the delay time between pulses of different wavelengths on the photomechanical and photothermal responses of meniscal tissue were evaluated in vitro by the use of histology. It was observed that the use of a short (200-μs, 100-mJ) holmium laser pulse as a prepulse to generate a vapor bubble through which the ablating erbium laser pulse can be transmitted (delay time, 100 μs) increases the cutting depth in meniscus from 450 to 1120 μm as compared with the depth following a single erbium pulse. The results indicate that a combination of erbium and holmium laser radiation precisely and efficiently cuts tissue under water with 20-50-μm collateral tissue damage.     

Mid-infrared measurements of the atmospheric emission over the South Pole using a radiometrically calibrated Fourier transform spectrometer

We conducted year-round measurements of the downwelling atmospheric infrared emission over the South Pole in 1992. The instrument covered the 550-1600-wave-number region with 1-wave-number resolution. We calculated the water vapor content for clear-sky cases and found a good correlation with the surface temperature, with values ranging from 0.2 to 0.8 mm. Ozone-sonde profiles were compared with total column abundances of O(3) retrieved from the spectra. The experiment is explained in detail, including the instrumentation, calibration, and retrieval methods used. The calibrated spectra contain information about several trace gases, water, clouds, temperature profiles, and aerosols.