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Optical spectroscopy is widely used for quantitative detection of small molecules in complex gas matrices. Employing a laser as a light source enables highly sensitive, selective, and accurate trace gas analysis in exhaled breath without the need for frequent calibration. Many volatile species with direct physiological relevance, especially small molecules such as CO2, CO, NO, CH4, NH3, HCN, C2H4, and their isotopoloques, can be measured with high time resolution using compact optical analyzers. Thus, laser-based sensors are an important complement to other analytical platforms and contribute to establishing breath gas analysis in the clinical practice. This chapter introduces the basics of optical spectroscopy and describes the most relevant techniques currently used in the field, such as nondispersive, laser absorption, and photoacoustic spectroscopy. Successful applications of optical methods are presented, and the future prospects are discussed. Owing to the advent of novel light sources, such as quantum cascade lasers and optical frequency combs, spectroscopy will continue to play a significant role in breath gas analysis.

We report a setup for high-resolution two-photon spectroscopy using a mid-infrared continuous wave optical parametric oscillator (CW-OPO) and a near-infrared diode laser as the excitation sources, both of which are locked to fully stabilized optical frequency combs. The diode laser is directly locked to a commercial near-infrared optical frequency comb using an optical phase-locked loop. The near-infrared frequency comb is also used to synchronously pump a degenerate femtosecond optical parametric oscillator to produce a fully stabilized mid-infrared frequency comb. The beat frequency between the mid-infrared comb and the CW-OPO is then stabilized through frequency locking. We used the setup to measure a double resonant two-photon transition to a symmetric vibrational state of acetylene with a sub-Doppler resolution and high signal-to-noise ratio. (C) 2017 Optical Society of America

Ammonia concentrations in exhaled breath (eNH(3)) and skin gas of 20 healthy subjects were measured on-line with a commercial cavity ring-down spectrometer and compared to saliva pH and plasma ammonium ion (NH4+), urea and creatinine concentrations. Special attention was given to mouth, nose and skin sampling procedures and the accurate quantification of ammonia in humid gas samples. The obtained median concentrations were 688 parts per billion by volume (ppbv) for mouth-eNH(3), 34 ppbv for nose-eNH3, and 21 ppbv for both mouth-and nose-eNH(3) after an acidic mouth wash (MW). The median ammonia emission rate from the lower forearm was 0.3 ng cm(-2) min(-1). Statistically significant (p < 0.05) correlations between the breath, skin and plasma ammonia/ammonium concentrations were not found. However, mouth-eNH(3) strongly (p < 0.001) correlated with saliva pH. This dependence was also observed in detailed measurements of the diurnal variation and the response of eNH(3) to the acidic MW. It is concluded that eNH(3) as such does not reflect plasma but saliva and airway mucus NH4+ concentrations and is affected by saliva and airway mucus pH. After normalization with saliva pH using the Henderson-Hasselbalch equation, mouth-eNH(3) correlated with plasma NH4+, which points to saliva and plasma NH4+ being linked via hydrolysis of salivary urea.

Biological monitoring usually relies on the collection of blood and urine samples. Although being non-invasive and providing an inextinguishable sampling pool, the analysis of exhaled breath is not well established. A gas phase measurement is, however, inherently simpler than the analysis of complex biological fluids, and modern methods have identified hundreds of volatile compounds in the breath of persons exposed to normal environmental concentrations. The most commonly deployed analytical techniques in breath analysis are gas chromatography combined with mass spectrometry (GC/MS) and other MS-based methods. Lately, also laser-based optical methods, such as cavity ring-down spectroscopy (CRDS), have emerged in the field. With such instruments, it is possible to accurately quantify the concentrations of volatiles in exhaled breath down to below part-per-billion (ppb) levels with sub-second time resolution. Laser spectroscopy thereby enables real-time investigations during and after exposure to exogenous chemicals. In general, depending on the sampling approach used, the measured levels of the breath compounds may vary significantly. It is therefore of importance to systematically study and account for the phenomena affecting the recorded concentrations, and subsequently select an appropriate sampling and measurement strategy. In Helsinki, we have used CRDS to study the background levels of hydrogen cyanide (HCN), ammonia (NH3) and acetylene (C2H2) in the exhaled breath of healthy volunteers. Different sampling techniques have been employed in an effort to standardize the breath sampling event. The realtime elimination kinetics of breath C2H2 after smoking has also been studied.

The hydrogen cyanide (HCN) concentration in exhaled human breath and skin gas samples collected with different sampling techniques was measured using near-infrared cavity ring-down spectroscopy. The median baseline HCN concentrations in samples provided by 19 healthy volunteers 2-4 h after the last meal depended on the employed sampling technique: 6.5 parts per billion by volume (ppbv) in mixed (dead space and end-tidal) mouth-exhaled breath collected to a gas sampling bag, 3.9 ppbv in end-tidal mouth-exhaled breath, 1.3 ppbv in end-tidal nose-exhaled breath, 1.0 ppbv in unwashed skin and 0.6 ppbv in washed skin samples. Diurnal measurements showed that elevated HCN levels are to be expected in mouth-exhaled breath samples after food and drink intake, which suggests HCN generation in the oral cavity. The HCN concentrations in end-tidal nose-exhaled breath and skin gas samples were correlated, and it is concluded that these concentrations best reflect systemic HCN levels., 863QS Times Cited:2 Cited References Count:39

We have measured the acetylene concentration in the exhaled breath of 40 volunteers (31 non-smokers, nine smokers) using near-infrared cavity ring-down spectroscopy. The acetylene levels were found to be the same as in ambient air for non-smokers, whereas elevated levels were observed for smokers. Real-time measurements with sub-second time resolution have been applied to measure the elimination kinetics of acetylene in breath after exposure to tobacco smoke. Three exponential time constants can be distinguished from the data and these can be used to define the residence times for different compartments, according to the multi-compartment model of the human body., 687DS Times Cited:2 Cited References Count:29

This thesis contains five experimental spectroscopic studies that probe the vibration-rotation energy level structure of acetylene and some of its isotopologues. The emphasis is on the development of laser spectroscopic methods for high-resolution molecular spectroscopy. Three of the experiments use cavity ringdown spectroscopy. One is a standard setup that employs a non-frequency stabilised continuous wave laser as a source. In the other two experiments, the same laser is actively frequency stabilised to the ringdown cavity. This development allows for increased repetition rate of the experimental signal and thus the spectroscopic sensitivity of the method is improved. These setups are applied to the recording of several vibration-rotation overtone bands of both H(12)C(12)CH and H(13)C(13)CH. An intra-cavity laser absorption spectroscopy setup that uses a commercial continuous wave ring laser and a Fourier transform interferometer is presented. The configuration of the laser is found to be sub-optimal for high-sensitivity work but the spectroscopic results are good and show the viability of this type of approach. Several ro-vibrational bands of carbon-13 substituted acetylenes are recorded and analysed. Compared with earlier work, the signal-to-noise ratio of a laser-induced dispersed infrared fluorescence experiment is enhanced by more than one order of magnitude by exploiting the geometric characteristics of the setup. The higher sensitivity of the spectrometer leads to the observation of two new symmetric vibrational states of H(12)C(12)CH. The precision of the spectroscopic parameters of some previously published symmetric states is also improved. An interesting collisional energy transfer process is observed for the excited vibrational states and this phenomenon is explained by a simple step-down model., Väitöskirja käsittelee kokeellista korkean erotuskyvyn molekyylispektroskopiaa. Neljä erilaista lasereihin perustuvaa koejärjestelyä on rakennettu ja näitä kaikkia on sovellettu kaasumaisen asetyleenin (HCCH) ja sen eri hiili-13 isotooppivaihdettujen isotopomeerien värähtelyspektrien mittaamiseen. Värähtelyspektrit on mitattu lähi-infrapuna-alueella, missä säteilykentän energia riittää virittämään molekyyliä useamman värähtelykvantin verran. Spektrit koostuvat siirtymistä molekyylin pyörimiseen ja värähtelyyn liittyvien energiatilojen välillä. Tutkimuksessa on käytetty sekä absorptiospektroskopiaa että emissiospektroskopiaa. Emissiokoe on ainutlaatuinen, siinä tutkitaan asetyleenin fluoresenssia elektronisen perustilan sisällä, eri värähtelytilojen välillä. Absorptiokokeet perustuvat ontelovaimenemisspektroskopiaan ja laserontelon sisäiseen absorptiospektroskopiaan. Kaikki koejärjestelyt käyttävät hyväkseen peileistä muodostettujen optisten onteloiden ominaisuuksia. Joko koe on suoritettu laserontelon sisällä tai laserin säde on kytketty erilliseen ulkoiseen onteloon. Etuna on onteloiden sisälle saatava suuri optinen teho ja tietyissä tapauksissa niiden kautta saatava suuri absorptiomatka. Nämä tekijät auttavat parantamaan kokeiden herkkyyttä, eli kokeellisen signaalin voimakkuutta suhteessa kohinaan. Erilaisten uusien koejärjestelyjen lisäksi tutkimus on tuottanut uutta tietoa asetyleenin värähtelyyn ja pyörimiseen liittyvistä energiatiloista. Erityisesti ns. symmetrisiä värähtelytiloja on päästy tutkimaan ainutlaatuisen värähtelyfluoresenssilaitteiston avulla. Kaikki kokeissa mitatut spektrit on tulkittu käyttäen sopivia kvanttimekaanisia malleja, ja tuloksena on joukko malliin littyviä molekyyliparametrejä. Nämä mittaustulokset ovat potentiaalisesti hyödyllisiä sekä kemian perustutkimuksessa että myös soveltavassa tutkimuksessa mm. tähtitieteen alalla.