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 H2O−H2O pair interaction. Absorption due to the foreign continuum (i.e. caused mostly by H2O−N2 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.

Global radiative and climate effect of the water vapour continuum at visible and near-infrared wavelengths

Recent laboratory measurements show that absorption by the water vapour continuum in near-infrared windows may be about an order of magnitude higher than assumed in many radiation codes. The radiative impact of the continuum at visible and near-infrared wavelengths is examined for the present day and for a possible future warmer climate (with a global-mean total column water increase of 33%). The calculations use a continuum model frequently used in climate models (‘CKD’) and a continuum model where absorption is enhanced at wavelengths greater than 1 µm based on recent measurements (‘CAVIAR’). The continuum predominantly changes the partitioning between solar radiation absorbed by the surface and the atmosphere; changes in top-of-atmosphere net irradiances are smaller. The global-mean clear-sky atmospheric absorption is enhanced by 1.5 W m−2 (about 2%) and 2.8 W m−2 (about 3.5%) for CKD and CAVIAR respectively, relative to a hypothetical no-continuum case, with all-sky enhancements about 80% of these values. The continuum is, in relative terms, more important for radiation budget changes between the present day and a possible future climate. Relative to the no-continuum case, the increase in global-mean clear-sky absorption is 8% higher using CKD and almost 20% higher using CAVIAR; all-sky enhancements are about half these values. The effect of the continuum is estimated for the solar component of the water vapour feedback, the reduction in downward surface irradiance and precipitation change in a warmer world. For CKD and CAVIAR respectively, and relative to the no-continuum case, the solar component of the water vapour feedback is enhanced by about 4 and 9%, the change in clear-sky downward surface irradiance is 7 and 18% more negative, and the global-mean precipitation response decreases by 1 and 4%. There is a continued need for improved continuum measurements, especially at atmospheric temperatures and at wavelengths below 2 µm.

Separating heart and brain: on the reduction of physiological noise from multichannel functional near-infrared spectroscopy (fNIRS) signals

Objective. Functional near-infrared spectroscopy (fNIRS) is an emerging technique for the in vivo assessment of functional activity of the cerebral cortex as well as in the field of brain–computer interface (BCI) research. A common challenge for the utilization of fNIRS in these areas is a stable and reliable investigation of the spatio-temporal hemodynamic patterns. However, the recorded patterns may be influenced and superimposed by signals generated from physiological processes, resulting in an inaccurate estimation of the cortical activity. Up to now only a few studies have investigated these influences, and still less has been attempted to remove/reduce these influences. The present study aims to gain insights into the reduction of physiological rhythms in hemodynamic signals (oxygenated hemoglobin (oxy-Hb), deoxygenated hemoglobin (deoxy-Hb)). Approach. We introduce the use of three different signal processing approaches (spatial filtering, a common average reference (CAR) method; independent component analysis (ICA); and transfer function (TF) models) to reduce the influence of respiratory and blood pressure (BP) rhythms on the hemodynamic responses. Main results. All approaches produce large reductions in BP and respiration influences on the oxy-Hb signals and, therefore, improve the contrast-to-noise ratio (CNR). In contrast, for deoxy-Hb signals CAR and ICA did not improve the CNR. However, for the TF approach, a CNR-improvement in deoxy-Hb can also be found. Significance. The present study investigates the application of different signal processing approaches to reduce the influences of physiological rhythms on the hemodynamic responses. In addition to the identification of the best signal processing method, we also show the importance of noise reduction in fNIRS data.

The water vapour continuum: brief history and recent developments

The water vapour continuum is characterised by absorption that varies smoothly with wavelength, from the visible to the microwave. It is present within the rotational and vibrational–rotational bands of water vapour, which consist of large numbers of narrow spectral lines, and in the many ‘windows’ between these bands. The continuum absorption in the window regions is of particular importance for the Earth’s radiation budget and for remote-sensing techniques that exploit these windows. Historically, most attention has focused on the 8–12 μm (mid-infrared) atmospheric window, where the continuum is relatively well-characterised, but there have been many fewer measurements within bands and in other window regions. In addition, the causes of the continuum remain a subject of controversy. This paper provides a brief historical overview of the development of understanding of the continuum and then reviews recent developments, with a focus on the near-infrared spectral region. Recent laboratory measurements in near-infrared windows, which reveal absorption typically an order of magnitude stronger than in widely used continuum models, are shown to have important consequences for remote-sensing techniques that use these windows for retrieving cloud properties.

RAMI4PILPS: An intercomparison of formulations for the partitioning of solar radiation in land surface models

[1] Remotely sensed, multiannual data sets of shortwave radiative surface fluxes are now available for assimilation into land surface schemes (LSSs) of climate and/or numerical weather prediction models. The RAMI4PILPS suite of virtual experiments assesses the accuracy and consistency of the radiative transfer formulations that provide the magnitudes of absorbed, reflected, and transmitted shortwave radiative fluxes in LSSs. RAMI4PILPS evaluates models under perfectly controlled experimental conditions in order to eliminate uncertainties arising from an incomplete or erroneous knowledge of the structural, spectral and illumination related canopy characteristics typical for model comparison with in situ observations. More specifically, the shortwave radiation is separated into a visible and near-infrared spectral region, and the quality of the simulated radiative fluxes is evaluated by direct comparison with a 3-D Monte Carlo reference model identified during the third phase of the Radiation transfer Model Intercomparison (RAMI) exercise. The RAMI4PILPS setup thus allows to focus in particular on the numerical accuracy of shortwave radiative transfer formulations and to pinpoint to areas where future model improvements should concentrate. The impact of increasing degrees of structural and spectral subgrid variability on the simulated fluxes is documented and the relevance of any thus emerging biases with respect to gross primary production estimates and shortwave radiative forcings due to snow and fire events are investigated.

Evaluating mid-infrared spectroscopy as a new technique for predicting sensory texture attributes of processed cheese

The objective of this study was to investigate the potential application of mid-infrared spectroscopy for determination of selected sensory attributes in a range of experimentally manufactured processed cheese samples. This study also evaluates mid-infrared spectroscopy against other recently proposed techniques for predicting sensory texture attributes. Processed cheeses (n = 32) of varying compositions were manufactured on a pilot scale. After 2 and 4 wk of storage at 4 degrees C, mid-infrared spectra ( 640 to 4,000 cm(-1)) were recorded and samples were scored on a scale of 0 to 100 for 9 attributes using descriptive sensory analysis. Models were developed by partial least squares regression using raw and pretreated spectra. The mouth-coating and mass-forming models were improved by using a reduced spectral range ( 930 to 1,767 cm(-1)). The remaining attributes were most successfully modeled using a combined range ( 930 to 1,767 cm(-1) and 2,839 to 4,000 cm(-1)). The root mean square errors of cross-validation for the models were 7.4(firmness; range 65.3), 4.6 ( rubbery; range 41.7), 7.1 ( creamy; range 60.9), 5.1(chewy; range 43.3), 5.2(mouth-coating; range 37.4), 5.3 (fragmentable; range 51.0), 7.4 ( melting; range 69.3), and 3.1 (mass-forming; range 23.6). These models had a good practical utility. Model accuracy ranged from approximate quantitative predictions to excellent predictions ( range error ratio = 9.6). In general, the models compared favorably with previously reported instrumental texture models and near-infrared models, although the creamy, chewy, and melting models were slightly weaker than the previously reported near-infrared models. We concluded that mid-infrared spectroscopy could be successfully used for the nondestructive and objective assessment of processed cheese sensory quality..

Application of near and mid-infrared spectroscopy to determine cheese quality and authenticity

This paper reviews the current state of development of both near-infrared (NIR) and mid-infrared (MIR) spectroscopic techniques for process monitoring, quality control, and authenticity determination in cheese processing. Infrared spectroscopy has been identified as an ideal process analytical technology tool, and recent publications have demonstrated the potential of both NIR and MIR spectroscopy, coupled with chemometric techniques, for monitoring coagulation, syneresis, and ripening as well as determination of authenticity, composition, sensory, and rheological parameters. Recent research is reviewed and compared on the basis of experimental design, spectroscopic and chemometric methods employed to assess the potential of infrared spectroscopy as a technology for improving process control and quality in cheese manufacture. Emerging research areas for these technologies, such as cheese authenticity and food chain traceability, are also discussed.

Modelling spectral reflectance of open cork oak woodland: a simulation analysis of the effects of vegetation structure and background

This study analyses the influence of vegetation structure (i.e. leaf area index and canopy cover) and seasonal background changes on moderate-resolution imaging spectrometer (MODIS)-simulated reflectance data in open woodland. Approximately monthly spectral reflectance and transmittance field measurements (May 2011 to October 2013) of cork oak tree leaves (Quercus suber) and of the herbaceous understorey were recorded in the region of Ribatejo, Portugal. The geometric-optical and radiative transfer (GORT) model was used to simulate MODIS response (red, near-infrared) and to calculate vegetation indices, investigating their response to changes in the structure of the overstorey vegetation and to seasonal changes in the understorey using scenarios corresponding to contrasting phenological status (dry season vs. wet season). The performance of normalized difference vegetation index (NDVI), soil-adjusted vegetation index (SAVI), and enhanced vegetation index (EVI) is discussed. Results showed that SAVI and EVI were very sensitive to the emergence of background vegetation in the wet season compared to NDVI and that shading effects lead to an opposing trend in the vegetation indices. The information provided by this research can be useful to improve our understanding of the temporal dynamic of vegetation, monitored by vegetation indices.

First CRDS-measurements of water vapour continuum in the 940nm absorption band

Measurements of near-infrared water vapour continuum using continuous wave cavity ring down spectroscopy (cw- CRDS) have been performed at around 10611.6 and 10685:2 cm1. The continuum absorption coefficients for N2- broadening have been determined for two temperatures and wavenumbers. These results represent the first near-IR continuum laboratory data determined within the complex spectral environment in the 940nm water vapour band and are in reasonable agreement with simulations using the semiempirical CKD formulation.

Infrared actuation in aligned polymer-nanotube composites

Rubber composites containing multiwalled carbon nanotubes have been irradiated with near-infrared light to study their reversible photomechanical actuation response. We demonstrate that the actuation is reproducible across differing polymer systems. The response is directly related to the degree of uniaxial alignment of the nanotubes in the matrix, contracting the samples along the alignment axis. The actuation stroke depends on the specific polymer being tested; however, the general response is universal for all composites tested. We conduct a detailed study of tube alignment induced by stress and propose a model for the reversible actuation behavior based on the orientational averaging of the local response. The single phenomenological parameter of this model describes the response of an individual tube to adsorption of low-energy photons; its experimentally determined value may suggest some ideas about such a response.

Water vapour self-continuum and water dimers: 1. Analysis of recent work

Recent laboratory observations and advances in theoretical quantum chemistry allow a reappraisal of the fundamental mechanisms that determine the water vapour self-continuum absorption throughout the infrared and millimetre wave spectral regions. By starting from a framework that partitions bimolecular interactions between water molecules into free-pair states, true bound and quasi-bound dimers, we present a critical review of recent observations, continuum models and theoretical predictions. In the near-infrared bands of the water monomer, we propose that spectral features in recent laboratory-derived self-continuum can be well explained as being due to a combination of true bound and quasi-bound dimers, when the spectrum of quasi-bound dimers is approximated as being double the broadened spectrum of the water monomer. Such a representation can explain both the wavenumber variation and the temperature dependence. Recent observations of the self-continuum absorption in the windows between these near-infrared bands indicate that widely used continuum models can underestimate the true strength by around an order of magnitude. An existing far-wing model does not appear able to explain the discrepancy, and although a dimer explanation is possible, currently available observations do not allow a compelling case to be made. In the 8–12 micron window, recent observations indicate that the modern continuum models either do not properly represent the temperature dependence, the wavelength variation, or both. The temperature dependence is suggestive of a transition from the dominance of true bound dimers at lower temperatures to quasibound dimers at higher temperatures. In the mid- and far-infrared spectral region, recent theoretical calculations indicate that true bound dimers may explain at least between 20% and 40% of the observed self-continuum. The possibility that quasi-bound dimers could cause an additional contribution of the same size is discussed. Most recent theoretical considerations agree that water dimers are likely to be the dominant contributor to the self-continuum in the mm-wave spectral range.

Vibrational overtone spectra of monofluoroacetylene: a preliminary report

High-resolution infrared and near-infrared spectra have been observed for more than 80 overtone bands of the HCCF molecule, including two CH stretching overtones in the visible region. Many of these have been analysed, and many more are in the course of analysis and will be reported later. All fundamentals have now been rotationally analysed and the equilibrium rotational constant determined. These data provide a testing ground for anharmonic force-field analyses, and they are discussed briefly in this connection.

Understanding spectra of highly excited vibrational states

Some of the characteristics of high overtone spectra observed in the near infrared are discussed, particularly in relation to local mode effects, the increasing density of states, and the effect of inter-state resonances and intramolecular vibrational redistribution.