Water vapour foreign-continuum absorption in near-infrared windows from laboratory measurements

For a long time, it has been believed that atmospheric absorption of radiation within wavelength regions of relatively high infrared transmittance (so-called 'windows') was dominated by the water vapour self-continuum, that is, spectrally smooth absorption caused by H(2)O--H(2)O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H(2)O--N(2) bimolecular absorption in the Earth's atmosphere) was considered to be negligible in the windows. We report new retrievals of the water vapour foreign continuum from high-resolution laboratory measurements at temperatures between 350 and 430?K in four near-infrared windows between 1.1 and 5?μm (9000-2000?cm(-1)). Our results indicate that the foreign continuum in these windows has a very weak temperature dependence and is typically between one and two orders of magnitude stronger than that given in representations of the continuum currently used in many climate and weather prediction models. This indicates that absorption owing to the foreign continuum may be comparable to the self-continuum under atmospheric conditions in the investigated windows. The calculated global-average clear-sky atmospheric absorption of solar radiation is increased by approximately 0.46?W?m(-2) (or 0.6% of the total clear-sky absorption) by using these new measurements when compared with calculations applying the widely used MTCKD (Mlawer-Tobin-Clough-Kneizys-Davies) foreign-continuum model.     

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).     

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.     

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.     

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.     

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.     

Rocketborne cryogenic (10 K) high-resolution interferometer spectrometer flight HIRIS: auroral and atmospheric IR emission spectra

A Michelson interferometer spectrometer cooled to 10 degrees by liquid helium was flown into an IBC class III aurora on 1 April 1976 from Poker Flat, Alas. The sensor, HIRIS, covered the spectral range 455-2500 wave numbers (4-22 microm) with a spectral resolution of 1.8 cm(-1) and an NESR of 5 x 10-12 W/cm2 scrm(-1) at 1000 cm(-1). An atmospheric emission spectrum was obtained every 0.7 sec over an altitude range of 70-125 km. Atmospheric spectra were obtained of CO2 (nu3), NO (Deltanu = 1), O3 (nu3) and CO2 (nu2). Auroral produced excitations were observed for each band, this being the first known measurement of auroral enhancements of O3 (nu3), 9.6 microm, and CO2 (nu2), 15 microm, emissions.     

Molar absorptivities of glucose and other biological molecules in aqueous solutions over the first overtone and combination regions of the near-infrared spectrum

Molar absorptivities are measured for water, glucose, alanine, ascorbate, lactate, triacetin, and urea in the near-infrared spectral region at 37 degrees C. Values are based on the Beer-Lambert law and cover the first overtone (1550-1850 nm; 6450-5400 cm(-1)) and combination (2000-2500 nm; 4000-5000 cm(-1)) spectral windows through aqueous media. Accurate calculations demand accounting for the impact of water displacement upon dissolution of solute. In this regard, water displacement coefficients are measured and reported for each solute. First overtone absorptivities range from 2 to 7 x 10(-5) mM(-1)mm(-1) for all solutes except urea, for which absorptivity values are below 0.5 x 10(-5) mM(-1) mm(-1) across this spectral range. Molar absorptivities over the combination spectral region range from 0.8 to 3.2 x 10(-4) mM(-1) mm(-1), which is a factor of four to five greater than the first overtone absorptivities. Accuracy of the measured values is assessed by comparing calculated or modeled spectra with spectra measured from standard solutions. This comparison reveals accurately modeled spectra in terms of magnitude and position of solute absorption bands. Both actual and modeled spectra from glucose solutions reveal positive and negative absorbance values depending on the measurement wavelength. It is shown that the net absorbance of light is controlled by the magnitude of the absorptivity of glucose compared to the product of the absorptivity of water and the water displacement coefficient for glucose.     

Modeling of gas absorption cross sections by use of principal-component-analysis model parameters

Monitoring the amount of gaseous species in the atmosphere and exhaust gases by remote infrared spectroscopic methods calls for the use of a compilation of spectral data, which can be used to match spectra measured in a practical application. Model spectra are based on time-consuming line-by-line calculations of absorption cross sections in databases by use of temperature as input combined with path length and partial and total pressure. It is demonstrated that principal component analysis (PCA) can be used to compress the spectrum of absorption cross sections, which depend strongly on temperature, into a reduced representation of score values and loading vectors. The temperature range from 300 to 1000 K is studied. This range is divided into two subranges (300-650 K and 650-1000K), and separate PCA models are constructed for each. The relationship between the scores and the temperature values is highly nonlinear. It is shown, however, that because the score-temperature relationships are smooth and continuous, they can be modeled by polynomials of varying degrees. The accuracy of the data compression method is validated with line-by-line-calculated absorption data of carbon monoxide and water vapor. Relative deviations between the absorption cross sections reconstructed from the PCA model parameters and the line-by-line-calculated values are found to be smaller than 0.15% for cross sections exceeding 1.27 x 10(-21) cm(-1) atm(-1) (CO) and 0.20% for cross sections exceeding 4.03 x 10(-21) cm(-1) atm(-1) (H2O). The computing time is reduced by a factor of 10(4).     

Intracavity absorption spectroscopy with a tunable multimode traveling-wave ring Ti:sapphire laser

A tunable multimode unidirectional traveling-wave Ti:sapphire laser was developed to measure in situ the atmospheric absorption spectra using intracavity absorption spectroscopy. The effective absorption path length was 2100 km. O2 and H2O vapor lines in atmosphere with absorption coefficients of 10(-6)-10(-8) cm(-1) were measured with uncertainties <5%, and the absorption coefficients were in agreement with those estimated from the HITRAN database. By tuning the wavelength, a weak absorption line with an absorption coefficient of 10(-9) cm(-1) was measured with a sensitivity of 2×10(-10) cm(-1). The sensitivity was limited by the residual parasitic variation that appeared in the spectrum.     

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.     

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.     

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.     

Experimental investigation of the self- and N(2)-broadened continuum within the ν(2) band of water vapor

We present an experimental study of the self- and N(2)-broadened H(2) O continuum in microwindows within the ν(2) fundamental centered at ~1600 cm(-1). The continuum is derived from transmission spectra recorded at room temperature with a BOMEM Fourier transform spectrometer at a resolution of ~0.040 cm(-1). Although we find general agreement with previous studies, our results suggest that there is significant near-wing super-Lorentzian behavior that produces a highly wave-number-dependent structure in the continuum as it is currently defined.     

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.     

Global spectroscopy of the water monomer

Given the large energy required for its electronic excitation, the most important properties of the water molecule are governed by its ground potential energy surface (PES). Novel experiments are now able to probe this surface over a very extended energy range, requiring new theoretical procedures for their interpretation. As part of this study, a new, accurate, global spectroscopic-quality PES and a new, accurate, global dipole moment surface are developed. They are used for the computation of the high-resolution spectrum of water up to the first dissociation limit and beyond as well as for the determination of Stark coefficients for high-lying states. The water PES has been determined by combined ab initio and semi-empirical studies. As a first step, a very accurate, global, ab initio PES was determined using the all-electron, internally contracted multi-reference configuration interaction technique together with a large Gaussian basis set. Scalar relativistic energy corrections are also determined in order to move the energy determinations close to the relativistic complete basis set full configuration interaction limit. The electronic energies were computed for a set of about 2500 geometries, covering carefully selected configurations from equilibrium up to dissociation. Nuclear motion computations using this PES reproduce the observed energy levels up to 39?000?cm(-1) with an accuracy of better than 10?cm(-1). Line positions and widths of resonant states above dissociation show an agreement with experiment of about 50?cm(-1). An improved semi-empirical PES is produced by fitting the ab initio PES to accurate experimental data, resulting in greatly improved accuracy, with a maximum deviation of about 1?cm(-1) for all vibrational band origins. Theoretical results based on this semi-empirical surface are compared with experimental data for energies starting at 27?000?cm(-1), going all the way up to dissociation at about 41?000?cm(-1) and a few hundred wavenumbers beyond it.     

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.     

Stable isotope ratios using cavity ring-down spectroscopy: determination of 13C/12C for carbon dioxide in human breath

We have constructed a cavity ring-down spectrometer employing a near-IR external cavity diode laser capable of measuring 13C/12C isotopic ratios in CO2 in human breath. The system, which has a demonstrated minimum detectable absorption loss of 3.2 x 10(-11) cm(-1) Hz(-1/2), determines the isotopic ratio of 13C16O16O/12C16O16O by measuring the intensities of rotationally resolved absorption features of each species. As in isotope ratio mass spectrometry (IRMS), the isotopic ratio of a sample is compared to that of a standard CO2 sample calibrated to the Pee Dee Belemnite scale and reported as the sample's delta13C value. Measurements of eight replicate CO2 samples standardized by IRMS and consisting of 5% CO2 in N2 at atmospheric pressure demonstrated a precision of 0.22/1000 for the technique. Delta13C values were also obtained for breath samples from individuals testing positive and negative for the presence of Helicobacter pylori, the leading cause of peptic ulcers in humans. This study demonstrates the ability of the instrument to obtain delta13C values in breath samples with sufficient precision to serve as a useful medical diagnostic.     

Temperature measurements in a rapid compression machine using mid-infrared H₂O absorption spectroscopy near 7.6 μm

A method for measuring the temporal temperature and number density in a rapid compression machine (RCM) using quantum cascade laser absorption spectroscopy near 7.6?μm is developed and presented in this paper. The ratios of H₂O absorption peaks at 1316.55 cm^-1 and 1316.97 cm^-1 are used for these measurements. In order to isolate the effects of chemical reactions, an inert mixture of argon with 2.87% water vapor is used for the present investigation. The end of compression pressures and temperatures in the RCM measurements are P_C=10, 15, and 20 bar in the range of T_C=1000 to 1200?K. The measured temperature history is compared with that calculated based on the adiabatic core assumption and is found to be within ±5 K. The measured temporal number density of H₂O to an accuracy of 1%, using the absolute absorption of the two rovibrational lines, show that the mixture is highly uniform in temperature. A six-pass, 5.08?cm Herriott cell is used to calibrate the line strengths in air and broadening in an Ar bath gas.