Laser spectroscopy for breath analysis : towards clinical implementation

Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.Peer reviewe

The water vapour continuum in near-infrared windows – current understanding and prospects for its inclusion in spectroscopic databases

Spectroscopic catalogues, such as GEISA and HITRAN, do not yet include information on the water vapour continuum that pervades visible, infrared and microwave spectral regions. This is partly because, in some spectral regions, there are rather few laboratory measurements in conditions close to those in the Earth’s atmosphere; hence understanding of the characteristics of the continuum absorption is still emerging. This is particularly so in the near-infrared and visible, where there has been renewed interest and activity in recent years. In this paper we present a critical review focusing on recent laboratory measurements in two near-infrared window regions (centred on 4700 and 6300 cm−1) and include reference to the window centred on 2600 cm−1 where more measurements have been reported. The rather few available measurements, have used Fourier transform spectroscopy (FTS), cavity ring down spectroscopy, optical-feedback – cavity enhanced laser spectroscopy and, in very narrow regions, calorimetric interferometry. These systems have different advantages and disadvantages. Fourier Transform Spectroscopy can measure the continuum across both these and neighbouring windows; by contrast, the cavity laser techniques are limited to fewer wavenumbers, but have a much higher inherent sensitivity. The available results present a diverse view of the characteristics of continuum absorption, with differences in continuum strength exceeding a factor of 10 in the cores of these windows. In individual windows, the temperature dependence of the water vapour self-continuum differs significantly in the few sets of measurements that allow an analysis. The available data also indicate that the temperature dependence differs significantly between different near-infrared windows. These pioneering measurements provide an impetus for further measurements. Improvements and/or extensions in existing techniques would aid progress to a full characterisation of the continuum – as an example, we report pilot measurements of the water vapour self-continuum using a supercontinuum laser source coupled to an FTS. Such improvements, as well as additional measurements and analyses in other laboratories, would enable the inclusion of the water vapour continuum in future spectroscopic databases, and therefore allow for a more reliable forward modelling of the radiative properties of the atmosphere. It would also allow a more confident assessment of different theoretical descriptions of the underlying cause or causes of continuum absorption

Simultaneous cavity-enhanced and cavity ringdown absorption spectroscopy using optical feedback

International audienceWe present a scheme of optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) including a fast optical switch to produce cavity ringdown spectra (OF-CRDS) simultaneously. This also works as a dynamically adjustable variable attenuator allowing to compensate for reduced signal levels in correspondence with absorption lines. For this, an acousto-optic deflector is used in a double-pass configuration to eliminate the single-pass frequency shift, which is incompatible with optical feedback. This is probably the most effective device providing the required fast response and the high extinction ratio necessary to perform clean ringdown measurements. The resulting direct comparison of OF-CEAS and OF-CRDS shows that these produce almost equivalent spectral data, with 0.3 % maximal difference at the top of an absorption line having a signal-to-noise ratio (S/N) of 3,300. OF-CEAS is largely winning on the short-term noise level while OF-CRDS appears to be more immune from interference fringes, delivering cleaner spectra after longer averaging

Optical cavity spectroscopy using heterodyne detection with optical feedback laser frequency locking

We demonstrate an accurate high sensitivity method for cavity spectroscopy. We measure the frequency intervals of transverse electromagnetic modes relative to a fundamental mode in a high finesse optical resonator, and attribute their mode numbers unambiguously. A laser is frequency locked to a fundamental TEM 00 cavity mode by optical feedback, and phase modulation is used to obtain frequency side bands, which may come to resonance with other transverse cavity modes as the radio-frequency of the modulation is tuned. At these resonances, transmission of the side bands is sensitively detected by heterodyning with the carrier. We also analyse the transverse spatial profile of the heterodyne signal for identification of mode numbers. The adjustment of the Gaussian cavity model to the measured frequency intervals yields accurate values of cavity length, mirrors radius of curvature and mirrors ellipticity, to the ppm level

Nitric Oxide Analysis Down to ppt Levels by Optical-Feedback Cavity-Enhanced Absorption Spectroscopy

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Relevance of laser spectroscopy OF-CEAS (optical feedback cavity enhanced absorption spectroscopy), for the measurement of carbon monoxide in healthy volunteers.

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NO2 trace measurements by optical feedback cavity-enhanced absorption spectroscopy

In order to reach the sub-ppb NO2 detection level required for environmental applications in remote areas, we are developing a spectrometer that exploits a technique that we introduced several years ago, named Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) [1]. It allows very sensitive and selective measurements, together with the realization of compact and robust set-ups as was subsequently demonstrated during measurements campaigns in harsh environments [2,3]. OF-CEAS benefits from the optical feedback (OF) to efficiently inject a cw-laser in a high finesse cavity (typically F >10 000). Absorption spectra are acquired on a small spectral region (~1 cm-1) that enables selective and quantitative measurements at a fast acquisition rate (~10 Hz) with a detection limit of several 10-10 cm-1 as reported in this paper. Spectra are obtained with high spectral resolution (~150 MHz) and are self calibrated by cavity rind-down measurements regularly performed (typically every second). Therefore, OF-CEAS appears very attractive for NO2 trace detection. This work is performed in the blue spectral region where NO2 has intense electronic transitions. Our setup involves a commercial extended cavity diode laser (ECDL) working at room temperature around 411nm. A first setup was developed [4] to demonstrate that OF sensitivity of ECDL is fully consistent with this technique, initially introduced with distributed feedback diode lasers in the near infrared region. In this paper we will report on a new set-up developed for in-situ measurements with proper mechanical, acoustic and thermal insulation. Additionally, new data processing was implemented allowing real time concentration measurements. It is based on a reference spectra recorded under controlled conditions by OF-CEAS and used later to fit the observed spectra. We will present measurements performed with calibrated NO2 reference samples demonstrating a good linearity of the apparatus. The minimum detectable absorption loss is estimated by considering the standard deviation of the spectra. We achieved better than 2x10-10 cm-1 for a single spectrum recorded in less than 100ms at 100mbar. This limit constitutes an improved of more than one order of magnitude as compare to the previous measurements reported in [4]. It leads to a detection limit of 3x108 molecules/cm3, corresponding to about 150pptv at 100mbar. At atmospheric pressure the same measurement would yield a detection limit of 15pptv assuming we can maintain the same level of sensitivity. But currently, works are under development to transfer the low minimum detectable absorption limit, already obtained for one spectrum, to a set of real time measurements. These are now limited by amplitude fluctuations of a few ppb from one spectrum to another one. [1] J. Morville, S. Kassi, M. Chenevier, and D. Romanini, Appl. Phys. B, 80, 1027 (2005). [2] D. Romanini, M. Chenevrier, S. Kassi, M. Schmidt, C. Valant, M. Ramonet, J. Lopez, and H.-J. Jost, Appl. Phys. B, 83, 659 (2006). [2] E.R.T. Kerstel, R.Q. Iannone, M. Chenevrier, S. Kassi, H.-J. Jost and D. Romanini, Appl. Phys. B, 84, 343 (2006). [4] I. Courtillot, J. Morville, V. Motto-Ros, and D. Romanini, Appl. Phys. B, 85, 407 (2006).info:eu-repo/semantics/nonPublishe

Relevance of laser spectroscopy OF-CEAS (optical feedback cavity enhanced absorption spectroscopy), for the measurement of carbon monoxide in healthy volunteers.

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Part per trillion nitric oxide measurement by optical feedback cavity-enhanced absorption spectroscopy in the mid-infrared

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