R. Peverall

4 Cavity ring-down and cavity enhanced spectroscopy using diode lasers

Continuous wave (cw) diode lasers are increasingly being used as light sources in the visible and near-IR regions of the spectrum for cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS); the latter technique is also widely known as integrated cavity output spectroscopy (ICOS). The very high sensitivities to weak absorptions that are possible with cw CRDS and CEAS, coupled with the quantitative nature of the absorption measurements, are enabling a rapidly expanding range of applications. We review the benefits and practical implementation of these techniques; methods of data analysis for extraction of quantitative absorption data; the sensitivities of cw CRDS and CEAS, and how they might be optimised; and applications of cw CRDS and CEAS in molecular spectroscopy, atmospheric chemistry, plasma and flame chemistry, analytical science, and medical diagnosis via breath analysis. The development of CRDS and CEAS techniques exploiting cw diode lasers and, very recently, high luminosity light-emitting diodes, has stimulated a wealth of high-sensitivity measurements. Highlights include quantitative measurement of various ultra-trace gases such as: NO3, NO2 and ethene in ambient air samples; CO2 isotopologues, ethane and other organic compounds in human breath samples; and excited electronic states of N2 and O2 in plasmas and discharges. Exciting developments include wavelength extension into the mid-IR and UV regions, and use of novel locked-cavity techniques to increase data acquisition rates and sensitivities.

Direct and wavelength modulation spectroscopy using a cw external cavity quantum cascade laser

A continuous wave external cavity quantum cascade laser (EC-QCL) operating between 1872 and 1958 cm−1 has been used to make rotationally resolved measurements in the fundamental band of nitric oxide at 140 mTorr, and the ν2 band of water at atmospheric pressure. These measurements demonstrate the advantages of wide tunability and high resolution of the EC-QCL system. From direct absorption spectroscopy on nitric oxide a laser bandwidth of 20 MHz has been deduced and a sensitivity of 8.4×10−4 cm−1 Hz−1/2 was achieved. Wavelength modulation spectroscopy using current modulation enhances the sensitivity by a factor of 23 to 3.7×10−5 cm−1 Hz−1/2.

Following interfacial kinetics in real time using broadband evanescent wave cavity-enhanced absorption spectroscopy: a comparison of light-emitting diodes and supercontinuum sources

A white light-emitting diode (LED) with emission between 420 and 700 nm and a supercontinuum (SC) source with emission between 450 and 2500 nm have been compared for use in evanescent wave broadband cavity-enhanced absorption spectroscopy (EW-BB-CEAS). The method is calibrated using a dye with known absorbance. While the LED is more economic as an excitation source, the SC source is superior both in terms of baseline noise (noise equivalent absorbances lower than 10(-5) compared to 10(-4) absorbance units (a.u.)) and accuracy of the measurement; these baseline noise levels are comparable to evanescent wave cavity ringdown spectroscopy (EW-CRDS) studies while the accessible spectral region of EW-BB-CEAS is much larger (420-750 nm in this study, compared to several tens of nanometres for EW-CRDS). The improvements afforded by the use of an SC source in combination with a high sensitivity detector are demonstrated in the broadband detection of electrogenerated Ir(IV) complexes in a thin-layer electrochemical cell arrangement. Excellent signal to noise is achieved with 10 micros signal accumulation times at a repetition rate of 600 Hz, easily fast enough to follow, in real time, solution kinetics and interfacial processes.

Cavity-enhanced absorption spectroscopy of methane at 1.73 μm

Abstract The integrated cavity output spectroscopy technique has been applied to the study of methane near 1.73 μm using a tunable diode laser. We have shown that this simple approach produces accurate high resolution spectra and have achieved a detection sensitivity of 1.8×10 −7 cm −1 for mirror reflectivities of 99.84%.

Demonstration of a mid-infrared cavity enhanced absorption spectrometer for breath acetone detection.

A high-resolution absorption spectrum of gaseous acetone near 8.2 μm has been taken using both Fourier transform and quantum cascade laser (QCL)-based infrared spectrometers. Absolute absorption cross sections within the 1215-1222 cm(-1) range have been determined, and the spectral window around 1216.5 cm(-1) (σ = 3.4 × 10(-19) cm(2) molecule(-1)) has been chosen for monitoring trace acetone in exhaled breath. Acetone at sub parts-per-million (ppm) levels has been measured in a breath sample with a precision of 0.17 ppm (1σ) by utilizing a cavity enhanced absorption spectrometer constructed from the QCL source and a linear, low-volume, optical cavity. The use of a water vapor trap ensured the accuracy of the results, which have been corroborated by mass spectrometric measurements.

Laser spectroscopy on volatile sulfur compounds: possibilities for breath analysis

There is an emerging interest in the detection of volatile sulfur compounds (VSCs) in the breath environment, given their biological relevance as potential signatures of several pathological conditions. Particularly, laser-based spectroscopic sensors are candidates for conducting accurate breath diagnostics in clinical settings. With these aims in mind, the current status of VSC sensing via laser absorption spectroscopy is reviewed in this paper. Attention has been focused on the most promising exhaled markers of pathological conditions, namely hydrogen sulfide, carbonyl sulfide, methanethiol, carbon disulfide and dimethyl sulfide. Details of the most relevant spectroscopic studies conducted on such molecules are presented, together with suggestions on the future direction of this challenging analytical field.

A chemometric study on human breath mass spectra for biomarker identification in cystic fibrosis

Alveolar breath samples from a small case-control study population have been collected and measured via ion-molecule reaction mass spectrometry, and a constructive statistical approach to the identification of volatile biomarkers has been formulated by applying multivariate statistical methods on the mass spectra. The nature of the data is such that the number of variables largely exceeds the observations, representing a typical experimental scenario when breath analysis is conducted using mass spectrometry. Principal components analysis has been performed on the high dimensional dataset of molecular abundances, providing evidence of case separation and reducing the number of functional discriminators by almost 90%. Afterwards, a deductive approach based on a binary regression was conducted on the reduced dataset, providing an entirely reliable case discrimination model exclusively depending on the concentrations in the breath mixture of 3 out of a total of 97 metabolites.

Characterization of an inductively coupled N2 plasma using sensitive diode laser spectroscopy

In this paper, we present an optical study of the state of N2 produced in an inductively coupled plasma. The operation of the discharge was characterized using ion flux measurements and broadband optical emission, and a clear change from capacitively to inductively coupled behaviour was observed with increasing applied power. The typical ion flux at 100 W and 10 mTorr was found to be 1.8 × 1018 m2 s−1, from which a ion density of ~1.5 × 109 cm−3 was inferred. Diode laser cavity enhanced absorption spectroscopy (CEAS) was used to probe the state via the band at 686 nm. P33 band head spectra were used to determine both the translational (Ttr) and rotational (Trot) temperatures of the molecules at the v = 0 level. These were found to be in equilibrium but dependent on plasma parameters; in a 10 mTorr discharge, Trot ≈ Ttr, varying from ~300 K at 5 W to ~450 K at 400 W applied power. Absolute number densities in individual spin–rotation states were determined by calibrating the CEAS technique using the cavity ringdown time to measure the mirror reflectivity. The overall population in the v = 0 level was found to be (1.19 ± 0.07) × 1010 cm−3 under typical conditions of 100 W radio frequency power and 10 mTorr pressure, corresponding to a discharge efficiency for the production of this level of ~10−5. A kinetic scheme is presented to account for the pressure and power dependence of the A-state concentration in the v = 0 level.

OH detection by absorption of frequency-doubled diode laser radiation at 308 nm

Radiation at 308 nm has been obtained by frequency doubling the output of a commercial diode laser cooled to 165 K. A single pass through a crystal of LiIO3 converted 1 mW of 616 nm radiation to 50 pW of UV, and this was used to detect the OH radical in absorption in a flow tube. Possible extensions of the method for detection of OH in the atmosphere are discussed.

Characterization of an external cavity diode laser based ring cavity NICE-OHMS system

The performance of an external cavity diode laser based noise immune cavity enhanced optical heterodyne molecular spectrometer is presented. To reduce the noise on the signal a ring cavity and a circuit to remove residual amplitude modulation on the pre-cavity laser radiation was implemented. We demonstrate a sensitivity of 4 x 10(-11) cm(-1) Hz(-1/2) using a cavity with a finesse of 2600 on a Doppler-broadened transition of CH(4) at 6610.063 cm(-1).