Micro-drilled anti-resonant fiber is demonstrated as a practicable tool for laser-based spectroscopic acetylene sensing, overcoming the slow fiber-filling time usually associated with hollow-core fiber-based methods. Microchannels were drilled through the side of the fiber, periodically along its length, using image processing to accurately target the gap between the capillaries for minimal loss. A 0.3% acetylene / 0.3% methane gas mixture balanced in air was tested in the near-infrared on two micro-machined fiber samples. Wavelength modulation spectroscopy was used to enhance the sensitivity of the detection. A 1 m anti-resonant fiber with microchannels every 5 cm was found to have a minimum detection limit of 380 parts per billion at atmospheric pressure and 100 s acquisition time with a 22 s fiber filling time without the use of a pressure differential. The filling time was 4.2 s for a 30 cm fiber with a closer microchannel separation of 2 cm.

This paper presents a unique study of the bulk plasma characteristics in a low pressure inductively coupled nitrogen plasma. Saturated cavity ringdown spectroscopy (sat-CRDS) has been used to determine the absolute number densities and translational temperatures of N-2(+)(X, nu = 0). The effect of saturation is readily accounted for by using an effective saturation parameter, S-eff, and determined by a simple method employing measurements at two different gain settings of the detection system. The appropriateness of this method is confirmed by comparison with fitting individual ringdown data using a time-dependent saturation parameter, S(t), within the local approximation model for sat-CRDS; the two methods are in excellent agreement in returning absolute number densities and translational temperatures. N-2(+)(X, nu = 0) number densities are determined across a matrix of pressure (10-100 mTorr) and radio-frequency power (200-400 W) conditions with maximum number densities of ca. 1.3 x 10(10 )cm(-3) while translational temperatures range from 600-1500 K.

Cavity ringdown spectroscopy has been used to investigate the translational and rotational temperatures of the v = 0 and 1 vibrational levels of O2(X) in an inductively coupled plasma at 100 mTorr (13.332 Pa) pressure. All rotational states probed display a clear increase in temperature as plasma power increases: at fixed power, the translational temperature appears largest for rotational states in v = 1 (J= 7, 16, 17, 22) and lowest in the low energy states (J = 1, 18, 19) in v = 0; highly excited rotational states (J = 28, 30, 31) of v = 0 show intermediate behaviour. The rotational temperature values behave similarly. These observations are consistent with the effects of plasma inhomogeneity and can be interpreted with a simple one-dimensional model whereby the pressure, temperature and mole fractions of the various species across the chamber (and arms) are approximated with rational profiles and the corresponding line-of-sight averaged densities and temperatures calculated. This basic model is reasonably successful at reproducing the observations for O2(X, v = 0) and O(3P) densities. The fact that resolving several rotational transitions allows spatial variations within the plasma to be inferred from line-of-sight averaged measurements is an extremely powerful result that could be of great utility in future work.

We report the development of a novel variant of cavity ring-down polarimetry using a continuous-wave laser operating at 532 nm for highly precise chiroptical activity and magnetometry measurements. The key methodology of the apparatus relies upon the external modulation of the laser frequency at the frequency splitting between non-degenerate left- and right-circularly polarised cavity modes. The method is demonstrated by evaluation of the Verdet constants of crystalline CeF3 and fused silica, in addition to the observation of gas- and solution-phase optical rotations of selected chiral molecules. Specifically, optical rotations of (i) vapours of alpha-pinene and R-(+)-limonene, (ii) mutarotating D-glucose in water, and (iii) acidified L-histidine solutions, are determined. The detection sensitivities for the gas- and solution phase chiral activity measurements are ~30 microdeg and ~120 microdeg over a 30 s detection period per cavity roundtrip pass, respectively. Furthermore, the measured optical rotations for R-(+)-limonene are compared with computations performed using the Turbomole quantum chemistry package. The experimentally observed optically rotatory dispersion of this cyclic monoterpene was thus rationalised via consideration of its room temperature conformer distribution as determined by the aforementioned single-point energy calculations.

Enchanced understanding of the drying kinetics of building materials is important to explain durability and improve conservation. Cavity ring-down spectroscopy has been demonstrated to be an effective method to investigate drying kinetics, and is here applied to investigate the drying behaviour of five commonly used building limestones, and one sandstone. Although the time period for phase I drying increases with increasing porosity, the constant mass flux remains essentially unchanged. This is not so for phase II drying diffusivities which are reported for Portland Whit Bed limestone, Portland Base Bed limestone, Clipsham limestone, Bath limestone, Savonnieres limestone and Stoke Hall sandstone, and are found to be in the range 3.0 - 6.5 x 10-9 m2 s-1 at 25 celcius. Differences in the phase II diffusivity do not appear to be solely controlled by porosity. Activation energies associated with phase II drying for Clipsham limestone, Portland Base Bed limestone and Stoke Hall sandstone, are determined to be 31.9 +/- 1.8, 29.4 +/- 1.4 and 27.1 +/- 2.2 kJ mol-1, respectively.

Remote gas detection is often a compromise between high sensitivity and response time. Micro-drilled anti-resonant fiber is used for 0.3% acetylene detection to simultaneously achieve both of these characteristics.

Climate change poses an ever-increasing risk to our stone built heritage. Among conservation actions, the use of consolidant products is considered a possible response to this challenge, and the adoption of nanolimes has been widely studied showing promising results. However, while the effectiveness and method of application has been assessed, few studies have probed the changes in drying kinetics following treatment. In fact, a drastic alteration of the water transport might lead to further anomalies. This study investigates the influence of nanolimes dispersed in ethanol on the drying kinetics of Clipsham limestone using cavity ring-down spectroscopy. The degree of treatment was assessed by gravimetry, Raman spectroscopy, optical microscopy, colorimetry, optical profilometry and thin section analysis. Results showed an increase in the dry mass, observable colour changes and decrease in surface roughness. Small but reproducible increases were observed in the evaporation flux for phase I behaviour following treatment, however, no changes were observed in the total mass of water released or the phase II diffusivity. Determination of the activation energy associated with phase II drying was unchanged following treatment . These results indicate that following treatment there has been little-to-no change in the internal surfaces and structure of the stone to affect vapour transport.

Water plays a major role in the deterioration of porous building materials such as those widely found in built heritage, influencing many physical, chemical, and biological decay processes. This article details a proof-of-principle study using near-infrared cavity ring-down spectroscopy (CRDS) to monitor the release of water and its artificially enriched isotopologues from small (ca. 25 × 25 × 5 mm) samples of limestone subject to drying by a fixed flow of nitrogen with varying levels of humidity and at room temperature and atmospheric pressure. Under low-humidity conditions, the drying kinetics are consistent with the well-established two-phase drying process exhibited by porous materials, namely, an initial constant drying rate period (phase I) followed by a falling drying rate period (phase II). The water diffusivity during phase II, DII, was measured (for Clipsham limestone) to be 3.0 × 10–9 ± 1 × 10–10 m2 s–1. The CRDS measurements allow spectroscopic determination of the total mass of water released by the sample, and the calculated values are in excellent agreement with gravimetric analysis. Importantly, the selectivity and sensitivity afforded by CRDS allows isotope analysis to be carried out, such that the flux of isotopically labeled water out of the sample can be determined under conditions of humidified flow where there may be a simultaneous ingress of water from the environment. Dual-wavelength CRDS distinguishes isotopic species, and it is demonstrated that the drying kinetics and physical properties of the samples are self-consistent when monitoring both HDO and H2O (for HDO, DII was 3.2 × 10–9 ± 4 × 10–10 m2 s–1). As the humidity levels in the flow increase, a departure from the distinct two-phase behavior is observed in the HDO drying curves. These new measurements of isotopically resolved mass fluxes will help refine models for drying mechanisms in porous media.

The absolute number density of ground state oxygen atoms, O( 3 P), present in a 100 mTorr oxygen plasma has been determined as a function of operating power using cavity ringdown spectroscopy (CRDS). The dissociation fraction increases by an order of magnitude from ∼0.8% at 50 W to 8% at 250 W and reflects a similar increase in the electron density over this power range. Emission spectra show that the E–H switchover is accompanied by increased rotational heating of O 2 and this behaviour is also observed in the translational temperatures determined by fitting the Doppler limited O( 3 P) CRDS data. The measurements are contextualised via a volume averaged kinetic model that uses the measured absolute densities of O( 3 P) and O 2 ( a 1 Δ g , v = 0) as a function of power as its benchmarks. Despite the inherent spatial inhomogeneity of the plasma, the volume averaged model, which uses a minimal set of reactions, is able to both reproduce previous measurements on the absolute density of O − and to infer physically reasonable values for both the electron temperature and number density as the E–H switch over is traversed. Time-resolved emission measurements return a value of 0.2 for the wall loss coefficient for O 2 ( b 1 Σ g + ); as a consequence, the number density of O 2 ( b 1 Σ g + ) is (at least) one order of magnitude less than O 2 ( a 1 Δ g ).

Precise optical rotation measurements play an important role in the analysis of chiral molecules in various fields, especially in biological chemistry and pharmacology. In this paper, we demonstrate a new variant of continuous-wave cavity-enhanced polarimetry for detecting the optical activity of two enantiomers of a chiral molecule at 730 nm. It is based on a signal-reversing technique for which the chiral specific rotation is directly determined by the cavity ring-down signal from two counter-propagating beams in a bow-tie cavity. In particular, we ensure reproducible excitation of both modes by broadening the linewidth of a diode laser source by application of a radio frequency perturbation to its injection current. The performance of the polarimeter is demonstrated for the specific rotation of (+)- and (-)-α-pinene in different environments, including the pure vapor, open air, and the liquid phase; the detection precision ranges between 10-5 and 10-4 degrees per cavity pass depending on the environment. The apparatus is a robust and practical tool for quantifying chirality and can be developed for the entire visible and near-infrared spectral regions.

We present measurements of the densities and temperatures (rotational and translational) of the metastable a 1 Δ g ( v = 0) state of O 2 in a cylindrically symmetric RF driven plasma operating in inductive mode at 100 mTorr total pressure and 300 W applied power. Line-of-sight absorption across the plasma region was determined by diode laser cavity ringdown spectroscopy on the (0, 0) vibrational band of the O 2 (b 1 Σ g + ) ← O 2 (a 1 Δ g ) transition near 1.9 μ m. Four rotational quantum states were studied, with a population distribution corresponding to a rotational temperature of 346 ± 38 K. The translational temperature was determined to be 359 ± 16 K from the width of the strongest absorption line, Q (12), and in equilibrium with the rotational distribution. The absolute concentration of O 2 (a 1 Δ g , v = 0) was measured as (9.5 ± 1.3) × 10 13 cm −3 , and corresponds to an apparent (3.5 ± 0.45)% contribution to the total number density. Time-resolved CRDS measurements following plasma extinction were used to deduce a wall loss coefficient, γ , of (2.8 ± 0.3) × 10 −3 on predominantly Al surfaces. Surmising reasonable concentrations for O 2 (b 1 Σ g + ) and an upper limit for the vibrational temperature places the total contribution of O 2 (a 1 Δ g ) at between 3.6% and 5.85%. The variation of the O 2 (a 1 Δ g , v = 0) state concentration with RF power shows a clear transition from the E to H mode excitation near an applied power of 150 W. Allan variance analysis yields a minimum measurable concentration of O 2 (a 1 Δ g , v = 0) of 1.1 × 10 12 cm −3 over 100 ringdown events, an order of magnitude more sensitive than previously reported.

We present precise optical rotation measurements of gaseous chiral samples using near-IR continuous-wave cavity-enhanced polarimetry. Optical rotation is determined by comparing cavity ring-down signals for two counter-propagating beams of orthogonal polarisation which are subject to polarisation rotation by the presence of both an optically active sample and a magneto-optic crystal. A broadband RF noise source applied to the laser drive current is used to tune the laser linewidth and optimise the polarimeter, and this noise-induced laser linewidth is quantified using self-heterodyne beat-note detection. We demonstrate the optical rotation measurement of gas phase samples of enantiomers of α-pinene and limonene with an optimum detection precision of 10 µdeg per cavity pass and an uncertainty in the specific rotation of ∼0.1 deg dm-1 (g/ml)-1 and determine the specific rotation parameters at 730 nm, for (+)- and (-)-α-pinene to be 32.10 ± 0.13 and -32.21 ± 0.11 deg dm-1 (g/ml)-1, respectively. Measurements of both a pure R-(+)-limonene sample and a non-racemic mixture of limonene of unknown enantiomeric excess are also presented, illustrating the utility of the technique.

In this paper we report measurements of the absolute concentration of ground state oxygen atoms produced in a low pressure (≤100 mTorr) inductively coupled oxygen plasma. These experiments have utilised cavity ringdown spectroscopy, allowing line of sight absorption to be measured on the optically forbidden 1D ← 3P transition around 630 nm. Both the translational temperature and the absolute concentrations of the two most populated spin–orbit levels (J = 1 and 2) have been determined as a function of plasma pressure at a fixed operating power of 300 W, allowing accurate determination of dissociation fraction; in all cases, the dissociation fraction is considerable, ≥10%, maximising at 15% for 20 mTorr. Time-resolved measurements of the rate of loss of the oxygen atoms when the plasma is extinguished have allowed the probability for wall-loss in the plasma chamber, γ, to be determined; in this case, for an aluminium surface, γ is determined to be ca. a few ×10−3, with the exact value depending on pressure. In addition, the O− number density is shown to be an inverse function of pressure, showing a maximum of 1.6 × 1010 cm−3 at 10 mTorr, falling to 2 × 109 cm−3 at 100 mTorr, and characteristic of a discharge operating in the detachment regime. The measured number densities are interpreted using calculated electron energy distribution functions and yield physically reasonable values for the electron number density.

In the current pilot study we aimed to determine whether breath analysis could be used to help recognise intra-abdominal infection, using acute appendicitis as an exemplar condition. Our study included 53 patients (aged 18-88 years) divided into three groups: appendix group, 26 (13 male) patients suffering from acute appendicitis; control group 20 (seven male) patients undergoing elective abdominal surgery; normal group, seven patients who were clinically diagnosed with appendicitis, but whose appendix was normal on histological examination. Samples of breath were analysed using ion molecule reaction mass spectroscopy measuring the concentration of volatile compounds (VCs) with molecular masses 27-123. Intraperitoneal gas samples were collected from a subset of 23 patients (nine diagnosed with acute appendicitis). Statistically significant differences in the concentration of VCs in breath were found between the three groups. Acetone, isopropanol, propanol, butyric acid, and further unassigned VCs with molecular mass/charge ratio (m/z) 56, 61 and 87 were all identified with significant endogenous contributions. Principle component analysis was able to separate the control and appendicitis groups for seven variables: m/z = 56, 58, 59, 60, 61, 87 and 88. Comparing breath and intraperitoneal samples showed significant relationships for acetone and the VC with m/z = 61. Our data suggest that it may be possible to help diagnose acute appendicitis by breath analysis; however, factors such as length of starvation remain to be properly accounted for and the management or mitigation of background levels needs to be properly addressed, and larger studies relating breath VCs to the causative organisms may help to highlight the relative importance of individual VCs.

Cold atmospheric pressure plasmas (CAPs) are finding an increasing number of applications in diverse fields such as sterilization, medicine and dentistry, because they induce chemical reactivity at near-ambient temperature. These plasmas are usually generated in noble gas flows which propagate into air, resulting in the production of a wide variety of species which can cause primary and secondary chemistry in both the gas and liquid phases. Detailed understanding of this low temperature reactivity requires selective and sensitive measurements of radical species. In this review we focus upon several techniques from a methodological point of view that are suitable for the sensitive detection of reactive species, or show promise for this purpose. A range of traditional and contemporary spectroscopic methods for measuring across different phases is highlighted in an attempt to present a 'detection landscape' for CAP-borne radicals.

Breath acetone concentrations were measured in 141 subjects (aged 19–91 years, mean = 59.11 years, standard deviation = 12.99 years), male and female, undergoing an oral glucose tolerance test (OGTT), having been referred to clinic on suspicion of type 2 diabetes. Breath samples were measured using an ion-molecule-reaction mass spectrometer, at the commencement of the OGTT, and after 1 and 2 h. Subjects were asked to observe the normal routine before and during the OGTT, which includes an overnight fast and ingestion of 75 g glucose at the beginning of the routine. Several groups of diagnosis were identified: type 2 diabetes mellitus positive (T2DM), n = 22; impaired glucose intolerance (IGT), n = 33; impaired fasting glucose, n = 14; and reactive hypoglycaemia, n = 5. The subjects with no diagnosis (i.e. normoglycaemia) were used as a control group, n = 67. Distributions of breath acetone are presented for the different groups. There was no evidence of a direct relationship between blood glucose (BG) and acetone measurements at any time during the study (0 h: p = 0.4482; 1 h: p = 0.6854; and 2 h: p = 0.1858). Nor were there significant differences between the measurements of breath acetone for the control group and the T2DM group (0 h: p = 0.1759; 1 h: p = 0.4521; and 2 h: p = 0.7343). However, the ratio of breath acetone at 1 h to the initial breath acetone was found to be significantly different for the T2DM group compared to both the control and IGT groups (p = 0.0189 and 0.011, respectively). The T2DM group was also found to be different in terms of ratio of breath acetone after 1 h to that at 2 h during the OGTT. And was distinctive in that it showed a significant dependence upon the level of BG at 2 h (p = 0.0146). We conclude that single measurements of the concentrations of breath acetone cannot be used as a potential screening diagnostic for T2DM diabetes in this cohort, but monitoring the evolution of breath acetone could open a non-invasive window to aid in the diagnosis of metabolic conditions.

A portable and compact device is demonstrated for measuring acetone in breath samples. The device features a 7 cm long high finesse optical cavity as an optical sensor that is coupled to a miniature adsorption preconcentrator containing 0.5 g of polymer material. Acetone is trapped out of breath and released into the optical cavity where it is probed by a near-infrared diode laser operating at ∼1670 nm. With an optical cavity mirror reflectivity of 99.994%, a limit of detection of 159 ppbv (1σ) is demonstrated on samples from breath bags. Initial results on direct breath sampling are presented with a precision of 100 ppbv. The method is validated with measurements made using an ion-molecule reaction mass spectrometer. Data are presented on elevated breath acetone from two individuals following an overnight fast and exercise, and from a third individual during several days of routine behavior.

Hypoglycemia and/or fear of hypoglycemia are major challenges for many with type 1 diabetes (T1D), limiting ability to lower glycemia. Given anecdotal reports of domestic pets alerting owners to blood glucose changes, especially hypoglycemia (1), we hypothesized that volatile organic compounds (VOCs) in exhaled breath might change at low glucose. We studied eight female nonsmoking participants with T1D (aged 46 ± 5 years, diabetes duration 23 ± 7 years, none treated with statins) twice using a single-blinded, computer code–randomized crossover design. An independent research ethics committee approved studies in advance, and subjects provided written consent. Using a stepped insulin clamp (Actrapid; Novo Nordisk, Crawley, U.K.; 0.3 mU/kg/min increasing to 1.5 mU/kg/min), on one occasion (STEP), arterialized plasma glucose (Yellow Springs Instrument 2300 STAT Plus Analyzer) was raised sequentially (7.1 ± 0.8, 8.7 ± 0.4, and 10.7 ± 0.1 mmol/L) then lowered with higher insulin infusion to 4.3 ± 0.3 and 2.8 ± …

The sensitivity of mid-IR quantum cascade laser (QCL) off-axis cavity-enhanced absorption spectroscopy (CEAS), often limited by cavity mode structure and diffraction losses, was enhanced by applying a broadband RF noise to the laser current. A pump-probe measurement demonstrated that the addition of bandwidth-limited white noise effectively increased the laser linewidth, thereby reducing mode structure associated with CEAS. The broadband noise source offers a more sensitive, more robust alternative to applying single-frequency noise to the laser. Analysis of CEAS measurements of a CO(2) absorption feature at 1890  cm(-1) averaged over 100 ms yielded a minimum detectable absorption of 5.5×10(-3)  Hz(-1/2) in the presence of broadband RF perturbation, nearly a tenfold improvement over the unperturbed regime. The short acquisition time makes this technique suitable for breath applications requiring breath-by-breath gas concentration information.