Position-Specific Isotope Analysis of Propane by Mid-IR Laser Absorption Spectroscopy.

Intramolecular or position-specific carbon isotope analysis of propane (13CH3-12CH2-12CH3 and 12CH3-13CH2-12CH3) provides unique insights into its formation mechanism and temperature history. The unambiguous detection of such carbon isotopic distributions with currently established methods is challenging due to the complexity of the technique and the tedious sample preparation. We present a direct and nondestructive analytical technique to quantify the two singly substituted, terminal (13Ct) and central (13Cc), propane isotopomers, based on quantum cascade laser absorption spectroscopy. The required spectral information on the propane isotopomers was first obtained using a high-resolution Fourier-transform infrared (FTIR) spectrometer and then used to select suitable mid-infrared regions with minimal spectral interference to obtain the optimum sensitivity and selectivity. We then measured high-resolution spectra around 1384 cm-1 of both singly substituted isotopomers by mid-IR quantum cascade laser absorption spectroscopy using a Stirling-cooled segmented circular multipass cell (SC-MPC). The spectra of the pure propane isotopomers were acquired at both 300 and 155 K and served as spectral templates to quantify samples with different levels of 13C at the central (c) and terminal (t) positions. A prerequisite for the precision using this reference template fitting method is a good match of amount fraction and pressure between the sample and templates. For samples at natural abundance, we achieved a precision of 0.33 ‰ for δ13Ct and 0.73 ‰ for δ13Cc values within 100 s integration time. This is the first demonstration of site-specific high-precision measurements of isotopically substituted non-methane hydrocarbons using laser absorption spectroscopy. The versatility of this analytical approach may open up new opportunities for the study of isotopic distribution of other organic compounds.

Quantum cascade laser absorption spectrometer with a low temperature multipass cell for precision clumped CO2 measurement.

We present a quantum cascade laser-based absorption spectrometer deploying a compact (145 mL volume) segmented circular multipass cell (SC-MPC) with 6 m optical path length. This SC-MPC is embedded into an effective cooling system to facilitate operation at cryogenic temperatures. For CO2, the sample is cooled to 153 K, i.e. close to the sublimation point at 10 mbar. This enables efficient suppression of interfering hot-band transitions of the more abundant isotopic species and thereby enhances analytical precision. As a demonstration, the amount fractions of all three CO2 isotopologues involved in the kinetic isotope exchange reaction of 12C16O2 + 12C18O2⇌ 2·12C16O18O are measured. The precision in the ratios [12C18O2]/[12C16O2] and [12C16O18O]/[12C16O2] is 0.05 ‰ with 25 s integration time. In addition, we determine the variation of the equilibrium constant, K, of the above exchange reaction for carbon-dioxide samples equilibrated at 300 K and 1273 K, respectively.

Synchronization of frequency combs by optical injection.

Optical frequency combs based on semiconductor lasers are a promising technology for monolithic integration of dual-comb spectrometers. However, the stabilization of offset frequency fceo remains a challenging feat due the lack of octave-spanning spectra. In a dual-comb configuration, the uncorrelated jitter of the offset frequencies leads to a non-periodic signal resulting in broadened beatnotes with a limited signal-to-noise ratio (SNR). Hence, expensive data acquisition schemes and complex signal processing are currently required. Here, we show that the offset frequencies of two frequency combs can be synchronized by optical injection locking, which allows full phase-stabilization when combined with electrical injection locking of both repetition frequencies frep. A single comb line isolated via an optical Vernier filter serves as Master oscillator for injection locking. The resulting dual-comb signal is periodic and stable over thousands of periods. This enables coherent averaging using analog electronics, which increases the SNR and reduces the data size by one and three orders of magnitude, respectively. The presented method will enable fully phase-stabilized dual-comb spectrometers by leveraging on integrated optical filters and provides access for comparing and stabilizing fceo to narrow-linewidth optical references.

Frequency axis for swept dual-comb spectroscopy with quantum cascade lasers.

In dual-comb spectroscopy, there is a one-to-one map between the frequencies of the measured beat notes and the frequencies of the optical comb lines. Its determination usually involves the use of one or more reference lasers with known frequencies. Quantum cascade laser frequency combs, however, are often operated in a free-running mode, and without a reference, the determination of the RF-to-optical frequency map is not trivial. Here, we propose a method by which the comb shift is measured with an unbalanced Mach-Zehnder interferometer, and the spectral point spacing is determined through the intermode beat measured on the laser electrodes. The frequency axis is accurate within ∼ 0.001 cm-1.

High-resolution and gapless dual comb spectroscopy with current-tuned quantum cascade lasers.

We present gapless, high-resolution absorption and dispersion spectra obtained with quantum cascade laser frequency combs covering 55 cm-1. Using phase-sensitive dual comb design, the comb lines are gradually swept over 10 GHz, corresponding to the free spectral range of the laser devices, by applying a current modulation. We show that with interleaving the spectral point spacing is reduced by more than four orders of magnitude over the full spectral span of the frequency comb. The potential of this technique for high-precision gas sensing is illustrated by measuring the low pressure (107 hPa) absorption and dispersion spectra of methane spanning the range of 1170 cm-1 - 1225 cm-1 with a resolution of 0.001 cm-1.

Sensitive detection of HO radicals produced in an atmospheric pressure plasma using Faraday rotation cavity ring-down spectroscopy.

Cavity ring-down spectroscopy (CRDS) is a well-established, highly sensitive absorption technique whose sensitivity and selectivity for trace radical sensing can be further enhanced by measuring the polarization rotation of the intracavity light by the paramagnetic samples in the presence of a magnetic field. In this paper, we highlight the use of this Faraday rotation cavity ring-down spectroscopy (FR-CRDS) for the detection of HO2 radicals. In particular, we use a cold atmospheric pressure plasma jet as a highly efficient source of HO2 radicals and show that FR-CRDS in the near-infrared spectral region (1506 nm) has the potential to be a useful tool for studying radical chemistry. By simultaneously measuring ring-down times of orthogonal linearly polarized light, measurements of Faraday effect-induced rotation angles (θ) and absorption coefficients (α) are retrieved from the same data set. The Faraday rotation measurement exhibits better long-term stability and enhanced sensitivity due to its differential nature, whereby highly correlated noise between the two channels and slow drifts cancel out. The bandwidth-normalized sensitivities are αmin=2.2×10-11 cm-1 Hz-1/2 and θmin=0.62 nrad Hz-1/2. The latter corresponds to a minimum detectable (circular) birefringence of Δnmin=5×10-16 Hz-1/2. Using the overlapping qQ3(N = 4-9) transitions of HO2, we estimate limits of detection of 3.1 × 108 cm-3 based on traditional (absorption) CRDS methods and 6.7 × 107 cm-3 using FR-CRDS detection, where each point of the spectrum was acquired during 2 s. In addition, Verdet constants for pertinent carrier (He, Ar) and bulk (N2, O2) gases were recorded in this spectral region for the first time. These show good agreement with recent measurements of air and values extrapolated from reported Verdet constants at shorter wavelengths, demonstrating the potential of FR-CRDS for measurements of very weak Faraday effects and providing a quantitative validation to the computed rotation angles.

Optical saturation effects in intracavity Faraday modulation spectroscopy (INFAMOS).

We report on the observation of saturation effects in Intracavity Faraday Modulation Spectroscopy (INFAMOS). A quantum cascade laser operating at ∼5.3 µm is used to probe the 2Π3/2 and 2Π1/2 R(3.5) transitions in the fundamental band of nitric oxide. With average intracavity intensities up to 450 W cm-2, the saturation of these molecular transitions is observed up to a total pressure of ∼240 Torr. The experimental data are interpreted by incorporating saturation into a model for the INFAMOS line shape in the homogeneously broadened limit.

Intracavity Faraday modulation spectroscopy (INFAMOS): A tool for radical detection.

We present the intra-cavity Faraday modulation spectroscopy technique, whereby optical feedback cavity-enhanced spectroscopy is coupled with Faraday modulation spectroscopy to greatly enhance the interaction path length of a laser beam with a paramagnetic sample in a magnetic field. We describe a first prototype based upon a cw quantum cascade laser targeting a selection of fundamental rovibrational R-branch transitions of nitric oxide (1890 cm-1), consisting of a linear cavity (finesse F=6300) and a water-cooled solenoid. We demonstrate a minimum detectable Verdet constant of Vmin=4.7×10-14 rad cm-1 G-1 Hz-1/2 (at SNR = 1), corresponding to a single-pass rotation angle of 1.6×10-10 rad Hz-1/2 and a limit of detection of 0.21 ppbv Hz-1/2 NO.

Cavity-Enhanced Near-Infrared Laser Absorption Spectrometer for the Measurement of Acetonitrile in Breath.

Elevated concentrations of acetonitrile have been found in the exhaled breath of patients with cystic fibrosis1 and may indicate the severity of their condition or the presence of an accompanying bacterial infection of the airways. There is therefore interest in detecting acetonitrile in exhaled breath. For this purpose, a cavity-enhanced laser absorption spectrometer (λ = 1.65 µm) with a preconcentration stage was built and is described here. The spectrometer has a limit of detection of 72 ppbv and 114 ppbv of acetonitrile in nitrogen and breath, respectively, with a measurement duration of just under 5 min. The preconcentration stage, which employs a carbon molecular sieve and an adsorption/thermal desorption cycle, can increase the acetonitrile concentration by up to a factor 93, thus, lowering the overall limit of detection to approximately 1 ppbv. The suitability of the system for acetonitrile measurements in breath is demonstrated with breath samples taken from the authors, which yielded acetonitrile concentrations of 23 ± 3 ppbv and 29 ± 3 ppbv, respectively.

Quantitative chemical analysis of surgical smoke generated during laparoscopic surgery with a vessel-sealing device.

BACKGROUND: Exposure to surgical smoke in the operation room has been a long-standing concern. Smoke generated by the interaction between lasers or electrocautery devices with biological tissue contains several toxic and carcinogenic substances, but only a few studies so far have provided quantitative data necessary for risk assessment. METHODS: With laser and Fourier-transform infrared spectroscopy, we investigated the chemical composition of smoke produced with a vessel-sealing device in an anoxic environment during laparoscopic surgery. RESULTS: Harmless concentrations of methane (<34 ppm), ethane (<2 ppm), and ethylene (<10 ppm) were detected. Traces of carbon monoxide (<3.2 ppm) and of the anesthetic sevoflurane (<450 ppm) were also found. CONCLUSIONS. Gas leaking or gas being released from the pneumoperitoneum could therefore increase pollution by waste anesthetic gas in the operating room. Most toxic compounds found in earlier studies remained undetected. Adverse health effects for operating room personnel due to some of those substances (e.g., toluene, styrene, xylene) can be excluded, assuming no significant losses or changes in the chemical composition of the samples occurred between our sampling and measurements.

Automated broad tuning of difference frequency sources for spectroscopic studies.

Transmission spectroscopy over large spectral ranges (>100 cm(-1)) generally requires a reference measurement to be taken separately from the sample scan. The ratio of the two measurements (i.e., the transmittance) is therefore susceptible to baseline changes that occur between the recording of the two spectra. The origins of relatively strong baseline changes (≫1%) of a difference-frequency-generation-based laser spectrometer (tuning range 2900-3144 cm(-1), 150 µW average power) were investigated and a method for minimizing them by improving reproducibility and reducing measurement time is presented. The new method was tested for a gas mixture and the sensitivity for broad absorption features was determined as 5×10(-3) minimum measurable absorbance for a total scan duration of 70 min.

Infrared spectroscopy on smoke produced by cauterization of animal tissue.

In view of in vivo surgical smoke studies a difference-frequency-generation (DFG) laser spectrometer (spectral range 2900-3144 cm(-1)) and a Fourier-transform infrared (FTIR) spectrometer were employed for infrared absorption spectroscopy. The chemical composition of smoke produced in vitro with an electroknife by cauterization of different animal tissues in different atmospheres was investigated. Average concentrations derived are: water vapor (0.87%), methane (20 ppm), ethane (4.8 ppm), ethene (17 ppm), carbon monoxide (190 ppm), nitric oxide (25 ppm), nitrous oxide (40 ppm), ethyne (50 ppm) and hydrogen cyanide (25 ppm). No correlation between smoke composition and the atmosphere or the kind of cauterized tissue was found.

Improved algorithm for quantitative analyses of infrared spectra of multicomponent gas mixtures with unknown compositions.

We present a major improvement of an algorithm based on a spectral library search for the quantitative analysis of multicomponent gas samples with unknown compositions. A quantitative spectral database of infrared spectra is used as a training set to compute regression coefficients. Concentrations are computed in the principal component space via principal component regression (PCR). In addition to previous algorithms, we introduce a rating for each candidate substance depending on the concentration found with PCR and a filter that removes candidates that are predicted with negative concentrations if their rating is below a certain threshold. Negative concentrations arise when the measured spectrum contains components that are not contained in the database. The PCR is recomputed until all candidates have a rating above the threshold. Then an adaptive filter "subtracts" the substance with the highest rating from both the measured spectrum and the library and appends it to a hit list. The iteration of this procedure directly produces a list of substances in order of descending importance (i.e., contribution to the measured absorbance) with their corresponding concentrations. The algorithm is tested on spectra of multicomponent surgical smoke samples. The four main components (water, methane, ethane, and ethene) are identified correctly (within the top 5 of the hit list) for an appropriate choice of the rating threshold. The algorithm describes the composition of the smoke sample correctly despite the presence of features in the spectrum that cannot be explained by the spectrum of any single substance present in the database.

Gas emission during laparoscopic colorectal surgery using a bipolar vessel sealing device: A pilot study on four patients.

BACKGROUND: Dissection during laparoscopic surgery produces smoke containing potentially toxic substances. The aim of the present study was to analyze smoke samples produced during laparoscopic colon surgery using a bipolar vessel sealing device (LigaSuretrade mark). METHODS: Four consecutive patients undergoing left-sided colectomy were enrolled in this pilot study. Smoke was produced by the use of LigaSuretrade mark. Samples (5,5l) were evacuated from the pneumoperitoneum in a closed system into a reservoir. Analysis was performed with CO2-laser-based photoacoustic spectroscopy and confirmed by a Fourier-transform infrared spectrum. The detected spectra were compared to the available spectra of known toxins. RESULTS: Samples from four laparoscopic sigmoid resections were analyzed. No relevant differences were noted regarding patient and operation characteristics. The gas samples were stable over time proven by congruent control measurements as late as 24 h after sampling. The absorption spectra differed considerably between the patients. One broad absorption line at 100 ppm indicating H2O and several unknown molecules were detected. With a sensitivity of alpha min ca 10-5 cm-1 no known toxic substances like phenol or indole were identified. CONCLUSION: The use of a vessel sealing device during laparoscopic surgery does not produce known toxic substances in relevant quantity. Further studies are needed to identify unknown molecules and to analyze gas emission under various conditions.