Árpád Mohácsi

Near-infrared diode laser based spectroscopic detection of ammonia: a comparative study of photoacoustic and direct optical absorption methods

A photoacoustic spectroscopic (PAS) and a direct optical absorption spectroscopic (OAS) gas sensor, both using continuous-wave room-temperature diode lasers operating at 1531.8 nm, were compared on the basis of ammonia detection. Excellent linear correlation between the detector signals of the two systems was found. Although the physical properties and the mode of operation of both sensors were significantly different, their performances were found to be remarkably similar, with a sub-ppm level minimum detectable concentration of ammonia and a fast response time in the range of a few minutes.

Diode laser based photoacoustic humidity sensors

Abstract Various diode laser based photoacoustic (PA) systems applied in water vapour detection are presented. The dependence of the systems’ performance on the physical and chemical properties of the measured gas is discussed. It was found that the pressure dependence of the measured PA signal is different for amplitude and wavelength modulated lasers. This difference is explained. Linearity in a concentration range of more than four orders of magnitude in combination with typical accuracy of a few percentages was proved.

Methane biogenesis during sodium azide-induced chemical hypoxia in rats.

Previous studies demonstrated methane generation in aerobic cells. Our aims were to investigate the methanogenic features of sodium azide (NaN(3))-induced chemical hypoxia in the whole animal and to study the effects of l-α-glycerylphosphorylcholine (GPC) on endogenous methane production and inflammatory events as indicators of a NaN(3)-elicited mitochondrial dysfunction. Group 1 of Sprague-Dawley rats served as the sham-operated control; in group 2, the animals were treated with NaN(3) (14 mg·kg(-1)·day(-1) sc) for 8 days. In group 3, the chronic NaN(3) administration was supplemented with daily oral GPC treatment. Group 4 served as an oral antibiotic-treated control (rifaximin, 10 mg·kg(-1)·day(-1)) targeting the intestinal bacterial flora, while group 5 received this antibiotic in parallel with NaN(3) treatment. The whole body methane production of the rats was measured by means of a newly developed method based on photoacoustic spectroscopy, the microcirculation of the liver was observed by intravital videomicroscopy, and structural changes were assessed via in vivo fluorescent confocal laser-scanning microscopy. NaN(3) administration induced a significant inflammatory reaction and methane generation independently of the methanogenic flora. After 8 days, the hepatic microcirculation was disturbed and the ATP content was decreased, without major structural damage. Methane generation, the hepatic microcirculatory changes, and the increased tissue myeloperoxidase and xanthine oxidoreductase activities were reduced by GPC treatment. In conclusion, the results suggest that methane production in mammals is connected with hypoxic events associated with a mitochondrial dysfunction. GPC is protective against the inflammatory consequences of a hypoxic reaction that might involve cellular or mitochondrial methane generation.

External Cavity Diode Laser Based Photoacoustic Detection of CO2 at 1.43 μm: The Effect of Molecular Relaxation

Photoacoustic spectroscopy, based on an external cavity diode laser operating at 1431 nm, was used for measuring CO2 concentration as a minority component in a gas mixture. By using N2 as a buffer gas, a molecular relaxation effect was observed, which influenced both the amplitude and the phase of the measured photoacoustic signal and consequently reduced the sensitivity of the PA system. This molecular relaxation effect could be suppressed by adding water vapor of a constant and relatively high (∼4%) concentration to the gas sample. In parallel with this, the arising spectral interference between H2O and CO2 necessitated the development of a simple yet efficient signal analysis method, which increased the sensitivity of the system by more than one order of magnitude and accordingly reduced the minimum detectable CO2 concentration down to ∼1000 ppm.

A high-sensitivity, near-infrared tunable-diode-laser-based photoacoustic water-vapour-detection system for automated operation

A photoacoustic sensor system for automatic detection of low concentrations of water vapour is described in this paper. A Littman-configuration external-cavity diode laser operating at 1125 nm was used as a light source in combination with a high-sensitivity measuring photoacoustic cell, a reference photoacoustic cell and PC-controlled electronics. The system was calibrated with synthetic gas samples and a detection limit of 13 µmol per mol of water vapour was determined. Adsorption/desorption phenomena at the walls of the measuring photoacoustic cell were found to be an important limiting factor for the sensitivity of the system.

Diode laser based photoacoustic water vapor detection system for atmospheric research.

A wavelength modulated, distributed feedback diode laser based photoacoustic water vapor mixing ratio measuring system for atmospheric research applications is presented. Laser modulation parameters were optimized either at 180 or 500 mbar total pressure to enhance the systems sensitivity for low or high pressures (upper troposphere/lower stratosphere or biosphere exchange layer), respectively. A wavelength locking method was developed that ensured sub-picometer absolute (5 × 10−7 relative) wavelength stability of the laser while consuming minimum additional measurement time. At the calibration of the system, correction factors for the pressure- and temperature-dependence of the photoacoustic signal were determined, which were in turn applied to the calculation of the water vapor mixing ratio from the measured signal during the test operation of the system. The introduced features resulted in reliable, sub-ppm-level water vapor detection even under abrupt gas pressure or temperature variations typical in open atmospheric applications.

Exhaled methane concentration profiles during exercise on an ergometer

Exhaled methane concentration measurements are extensively used in medical investigation of certain gastrointestinal conditions. However, the dynamics of endogenous methane release is largely unknown. Breath methane profiles during ergometer tests were measured by means of a photoacoustic spectroscopy based sensor. Five methane-producing volunteers (with exhaled methane level being at least 1 ppm higher than room air) were measured. The experimental protocol consisted of 5 min rest--15 min pedalling (at a workload of 75 W)--5 min rest. In addition, hemodynamic and respiratory parameters were determined and compared to the estimated alveolar methane concentration. The alveolar breath methane level decreased considerably, by a factor of 3-4 within 1.5 min, while the estimated ventilation-perfusion ratio increased by a factor of 2-3. Mean pre-exercise and exercise methane concentrations were 11.4 ppm (SD:7.3) and 2.8 ppm (SD:1.9), respectively. The changes can be described by the high sensitivity of exhaled methane to ventilation-perfusion ratio and are in line with the Farhi equation.

Photoacoustic spectroscopy-based detector for measuring benzene and toluene concentration in gas and liquid samples

Here we present a novel instrument for on-line, automatic measurement of benzene and toluene concentration in gas and liquid samples produced in the natural gas industry. Operation of the instrument is based on the collection of analytes on an adsorbent, separation using a chromatographic column and detection by near-infrared diode laser-based photoacoustic spectroscopy. Sample handling, measurement and data evaluation are carried out fully automatically, using an integrated, programmable electronic unit. The instrument was calibrated in the laboratory for natural gas, nitrogen and liquid glycol samples, and tested under field conditions at a natural gas dehydration unit of the MOL Hungarian Oil and Gas Company. Minimum detectable concentrations (3σm−1) were found to be 2.5 µg l−1 for benzene and 4 µg l−1 for toluene in gas samples, while 1.5 mg l−1 for benzene and 3 mg l−1 for toluene in liquid samples, which is suitable for measuring benzene and toluene concentration in natural gas and glycol samples occurring at natural gas dehydration plants.

Diode laser based photoacoustic gas measuring instruments intended for medical research

Analysis of breath and gases emanated from skin can be used for early and non-invasive diagnosis of various kinds of diseases. Two portable, compact, photoacoustic spectroscopy based trace gas sensors were developed for the detection of methane emanated from skin and ammonia emanated from oral cavity. The light sources were distributed feedback diode lasers emitting at the absorption lines of ammonia and methane, at 1.53 μm and 1.65 μm, respectively. Photoacoustic method ensures high selectivity, therefore cross-sensitivity was negligible even with large amount of water vapor and carbon dioxide in the gas sample. In case of ammonia a preconcentration unit was used to achieve lower minimum detectable concentration. Gas sample from the oral cavity was drawn through a glass tube to the preconcentration unit that chemically bonded ammonia and released it when heated. The minimum detectable concentration of ammonia was 10 ppb for 15 s gas sampling time (gas sample of 250 cm3). For methane minimum detectable concentration of 0.25 ppm was found with 12 s integration time, and it was proved to be adequate for the detection of methane emanated from human skin and from mice. Instruments measuring methane and ammonia are currently installed at two medical research laboratories at University of Szeged and tested as instruments for non-invasive clinical trials. The aim of the measurements is to determine correlations between diseases or metabolic processes and emanated gases.

Volatile sulphur compound measurement with OralChromaTM: a methodological improvement

The instrumental measurement of volatile sulphur compounds is a common practice to assess halitosis. One of the most widespread devices for that purpose is OralChroma(TM), a combination of a semiconductor gas sensor and a compact gas chromatograph (GC) system. Several lines of evidence indicate that although the hardware of OralChroma(TM) is fit for the precise measurement of volatile sulphur compounds (VSCs), its software needs revision to allow that precision. In this study we sought to develop software to solve this problem, and to test the utility of the new software in a population of patients and controls. The results were also compared with VSC measurements performed with Halimeter(®), another widespread device, so as to assess the correlation. A set of measurements involving volunteers (21 controls and 14 oral cancer patients) were conducted. The analysis of the chromatograms recorded by OralChroma(TM) indicated that the majority of the studied breath samples contained significant amounts of isoprene (the peak was around 100 s) and acetaldehyde (the peak was around 350 s), therefore OralChroma(TM) was also calibrated for both isoprene and acetaldehyde. A linear relationship was found between the concentration (in the range of 80-1400 ppbv for acetaldehyde and 40-560 ppbv for isoprene) and the area under the corresponding peak. In numerous cases the concentrations of VSCs calculated by the software of OralChroma(TM) required revision. In the new software, the concentrations of the VSCs, isoprene and acetaldehyde were determined by fitting the chromatograms with the sum of six Gaussian functions. Based on the findings of the present study we conclude that our new software allows an improved and instantaneous evaluation of OralChroma(TM) chromatograms with the additional possibility of determining the isoprene and acetaldehyde concentrations from breath samples.