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In this study, a Eulerian–Lagrangian model is used to study biomass gasification and release of potassium species in a 140 kW atmospheric entrained flow gasifier (EFG). Experimental measurements of water concentration and temperature inside the reactor, together with the gas composition at the gasifier outlet, are used to validate the model. For the first time, a detailed K-release model is used to predict the concentrations of gas-phase K species inside the gasifier, and the results are compared with experimental measurements from an optical port in the EFG. The prediction errors for atomic potassium (K), potassium chloride (KCl), potassium hydroxide (KOH), and total potassium are 1.4%, 9.8%, 5.5%, and 5.7%, respectively, which are within the uncertainty limits of the measurements. The numerical model is used to identify and study the main phenomena that occur in different zones of the gasifier. Five zones are identified in which drying, pyrolysis, combustion, recirculation, and gasification are active. The model was then used to study the transformation and release of different K species from biomass particles. It was found that, for the forest residue fuel that was used in the present study, the organic part of K is released at the shortest residence time, followed by the release of inorganic K at higher residence times. The release of inorganic salts starts by evaporation of KCl and continues by dissociation of K2CO3 and K2SO4, which forms gas-phase KOH. The major fraction of K is released around the combustion zone (around 0.7–1.3 m downstream of the inlet) due to the high H2O concentration and temperature. These conditions lead to rapid dissociation of K2CO3 and K2SO4, which increases the total K concentration from 336 to 510 ppm in the combustion zone. The dissociation of the inorganic salts and KOH formation continues in the gasification zone at a lower rate; hence, the total K concentration slowly increases from 510 ppm at 1.3 m to 561 ppm at the outlet.

Photofragmentation tunable diode laser absorption spectroscopy (PF-TDLAS) was used to simultaneously measure the concentrations of gas phase atomic potassium (K), potassium hydroxide (KOH) and potassium chloride (KCl) in the reactor core of a 140 kWth atmospheric entrained-flow gasifier (EFG). In two gasification experiments at air-to-fuel equivalence ratio of 0.5, the EFG was first run on forest residues (FR) and then on an 80/20 mixture of FR and wheat straw (FR/WS). Combustion at air-to-fuel equivalence ratio of 1.3 was investigated for comparison. A high K(g) absorbance was observed in gasification, requiring the photofragmentation signals from KOH(g) and KCl(g) to be recorded at a fixed detuning of 7.3 cm−1 from the center of the K(g) absorption profile. In combustion, the fragments recombined instantly after the UV pulse within around 10 µs, whereas in gasification, the K(g) fragment concentration first increased further for 30 µs after the UV pulse, before slowly decaying for up to hundreds of µs. According to 0D reaction kinetics simulations, this could be explained by a difference in recombination kinetics, which is dominated by oxygen reactions in combustion and by hydrogen reactions in gasification. The K species concentrations in the EFG were stable on average, but periodic short-term variations due to fuel feeding were observed, as well as a gradual increase in KOH(g) over the day as the reactor approached global equilibrium. A comparison of the average K species concentrations towards the end of each experiment showed a higher total K in the gas phase for FR/WS, with higher K(g) and KCl(g), but lower KOH(g), compared to the FR fuel. The measured values were in reasonable agreement with predictions by thermodynamic equilibrium calculations.

Methane is one of the main gas species produced during biomass gasification and may be a desired or undesired product. Syngas CH4 concentrations are typically >5 vol-% (when desired) and 1–3 vol-% even when efforts are made to minimize it, while thermochemical equilibrium calculations (TEC) predict complete CH4 decomposition. How CH4 is generated and sustained in the reactor core is not well understood. To investigate this, accurate quantification of the CH4 concentration during the process is a necessary first step. We present results from rapid in situ measurements of CH4, soot volume fraction, H2O and gas temperature in the reactor core of an atmospheric entrained-flow biomass gasifier, obtained using tunable diode laser absorption spectroscopy (TDLAS) in the near-infrared (1.4 µm) and mid-infrared (3.1 µm) region. An 80/20 wt% mixture of forest residues and wheat straw was converted using oxygen-enriched air (O2>21 vol%) as oxidizer, while the global air-fuel equivalence ratio (AFR) was set to values between 0.3 and 0.7. Combustion at AFR 1.3 was performed as a reference. The results show that the CH4 concentration increased from 1 to 3 vol-% with decreasing AFR, and strongly correlated with soot production. In general, the TDLAS measurements are in good agreement with extractive diagnostics at the reactor outlet and TEC under fuel-lean conditions, but deviate significantly for lower AFR. Detailed 0D chemical reaction kinetics simulations suggest that the CH4 produced in the upper part of the reactor at temperatures >1700 K was fully decomposed, while the CH4 in the final syngas originated from the pyrolysis of fuel particles at temperatures below 1400 K in the lower section of the reactor core. It is shown that the process efficiency was significantly reduced due to the C and H atoms bound in methane and soot.

Potassium (K) is one of the main and most hazardous trace species released to the gas-phase during thermochemical conversion of biomass. Accurate experimental data and models of K release are needed to better understand the chemistry involved. Tunable diode laser absorption spectroscopy (TDLAS) is used for simultaneous real-time in situ measurements of gas-phase atomic K, water (H2O) and gas temperature in the vicinity (boundary layer) of biomass particles during combustion in a laboratory single-particle reactor. Atomic K is detected in a wide dynamic range, including optically thick conditions, using direct absorption spectroscopy at the wavelength of 770 nm, while H2O and temperature are determined by calibration-free scanned wavelength modulation spectroscopy at 1398 nm. The high accuracy and repeatability of the setup allows to distinguish measurements with varying initial particle mass, laser beam height above the particle and fuel type. Four types of biomass with different ash composition are investigated: softwood, Salix, Miscanthus and wheat straw. For Salix and wheat straw, the K release behaviour is, for the first time, compared to a detailed numerical particle model taking into account the interaction between K/S/Cl composition in the particle ash. A good agreement is achieved between the measured and calculated time-resolved atomic K concentrations for the devolatilization phase of the biomass particles.

Combustion facilities run on pulverized biomass often exhibit fluctuations in fuel feeding and, thus, equivalence ratio and would benefit from fast process control based on optical λ sensors instal ...

The influence of breath sampling on exhaled carbon monoxide (eCO) and related pulmonary gas exchange parameters is investigated in a study with 32 healthy non-smokers. Mid-infrared tunable diode laser absorption spectroscopy and well-controlled online sampling is used to precisely measure mouth- and nose-exhaled CO expirograms at exhalation flow rates (EFRs) of 250, 120 and 60 ml s−1, and for 10 s of breath-holding followed by exhalation at 120 ml s−1. A trumpet model with axial diffusion is employed to fit simulated exhalation profiles to the experimental expirograms, which provides equilibrium airway and alveolar CO concentrations and the average lung diffusing capacity in addition to end-tidal concentrations. For all breathing maneuvers, excellent agreement is found between mouth- and nose-exhaled end-tidal CO (ETCO), and the individual values for ETCO and alveolar diffusing capacity are consistent across maneuvers. The eCO parameters clearly show a dependence on EFR, where the lung diffusing capacity increases with EFR, while ETCO slightly decreases. End-tidal CO is largely independent of ambient air CO and alveolar diffusing capacity. While airway CO is slightly higher than, and correlates strongly with, ambient air CO, and there is a weak correlation with ETCO, the results point to negligible endogenous airway CO production in healthy subjects. An EFR of around 120 ml s−1 can be recommended for clinical eCO measurements. The employed method provides means to measure variations in endogenous CO, which can improve the interpretation of exhaled CO concentrations and the diagnostic value of eCO tests in clinical studies. Clinical trial registration number: 2017/306-31

Photofragmentation spectroscopy is combined with tunable diode laser absorption spectroscopy to measure the line shape of the fragment species. This provides flexibility in choosing the UV pulse location within the line shape and accurate quantification of both target species and background fragment concentrations, even under optically thick conditions. The technique is demonstrated by detection of potassium hydroxide (KOH) and atomic potassium K(g) above solid KOH converted in a premixed methane-air flat flame. Time series of KOH(g) and K(g) concentrations are recorded as a function of solid KOH mass and flame stoichiometry. The total substance released during the conversion is in good agreement with the initial solid KOH mass. Under fuel-rich conditions, increased K(g) concentrations at the expense of KOH(g) are observed compared to thermodynamic equilibrium.

Blood flow and ventilatory flow strongly influence the concentrations of volatile organic compounds (VOCs) in exhaled breath. The physicochemical properties of a compound (e.g., water solubility) additionally determine if the concentration of the compound in breath reflects the alveolar concentration, the concentration in the upper airways, or a mixture of both. Mathematical modeling based on mass balance equations helps to understand how measured breath concentrations are related to their corresponding blood concentrations and physiological parameters, such as metabolic rates and endogenous production rates. In addition, the influence of inhaled compounds on their exhaled concentrations can be quantified and appropriate correction formulas can be derived. Isoprene and acetone, two endogenous VOCs with very different water solubility, have been modeled to explain the essential features of their behavior in breath. This chapter introduces the theory of physiological modeling of exhaled VOCs, with examples of isoprene and acetone.

A numerical and experimental study on the devolatilization of a large biomass particle is carried out to quantify the effect of homogeneous volatile combustion on the conversion of the particle and ...

Optical and intrusive measurement techniques for temperature and soot concentration in hot reacting flows were tested on a small-scale burner in fuel-rich, oxygen-enriched atmospheric flat flames produced to simulate the environment inside an entrained flow reactor. The optical techniques comprised two-color pyrometry (2C-PYR), laser extinction (LE), and tunable diode laser absorption spectroscopy (TDLAS), and the intrusive methods included fine-wire thermocouple thermometry (TC) and electrical low pressure impactor (ELPI) particle analysis. Vertical profiles of temperature and soot concentration were recorded in flames with different equivalence and O2/N2 ratios. The 2C-PYR and LE data were derived assuming mature soot. Gas temperatures up to 2200 K and soot concentrations up to 3 ppmv were measured. Close to the burner surface, the temperatures obtained with the pyrometer were up to 300 K higher than those measured by TDLAS. Further away from the burner, the difference was within 100 K. The TC-derived t...

Tunable diode laser absorption spectroscopy (TDLAS) was used to measure several important process parameters at two different locations inside the reactor of an atmospheric, air-blown 0.1 MWth biomass gasifier. Direct TDLAS at 2298 nm was employed for carbon monoxide (CO) and water vapor (H2O), calibration-free scanned wavelength modulation spectroscopy at 1398 nm for H2O and gas temperature, and direct TDLAS at 770 nm for gaseous elemental potassium, K(g), under optically thick conditions. These constitute the first in situ measurements of K(g) and temperature in a reactor core and in biomass gasification, respectively. In addition, soot volume fractions were determined at all TDLAS wavelengths, and employing fixed-wavelength laser extinction at 639 nm. Issues concerning the determination of the actual optical path length, as well as temperature and species non-uniformities along the line-of-sight are addressed. During a 2-day measurement campaign, peat and stem wood powder were first combusted at an air equivalence ratio (lambda) of 1.2 and then gasified at lambdas of 0.7, 0.6, 0.5, 0.4 and 0.35. Compared to uncorrected thermocouple measurements in the gas stream, actual average temperatures in the reactor core were significantly higher. The CO concentrations at the lower optical access port were comparable to those obtained by gas chromatography at the exhaust. In gasification mode, similar H2O values were obtained by the two different TDLAS instruments. The measured K(g) concentrations were compared to equilibrium calculations. Overall, the reaction time was found to be faster for peat than for stem wood. All sensors showed good performance even in the presence of high soot concentrations, and real-time detection was useful in resolving fast, transient behaviors, such as changes in stoichiometry. Practical implications of in-situ TDLAS monitoring on the understanding and control of gasification processes are discussed.

We use broadband near-infrared continuous-filtering Vernier spectroscopy (CF-VS) for time-resolved detection of H

A sensitive high-resolution sub-Doppler detecting spectrometer, based on noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS), for trace gas detection of species whose transitions have severe spectral overlap with abundant concomitant species is presented. It is designed around a NICE-OHMS instrumentation utilizing balanced detection that provides shot-noise limited Doppler-broadened (Db) detection. By synchronous dithering the positions of the two cavity mirrors, the effect of residual etalons between the cavity and other surfaces in the system could be reduced. An Allan deviation of the absorption coefficient of 2.2 × 10−13 cm−1 at 60 s, which, for the targeted transition in C2H2, corresponds to a 3σ detection sensitivity of 130 ppt, is demonstrated. It is shown that despite significant spectral interference from CO2 at the targeted transition, which precludes Db detection of C2H2, acetylene could be detected in exhaled breath of healthy smokers.

The need for fast and simultaneous detection of multiple combustion-related chemical species in various industrial environments has motivated the use of comb-based spectroscopic techniques in these applications. Dual comb spectroscopy has been employed to simultaneously measure CO2 and H2O concentrations in a gas turbine exhaust with 1% precision [1], and cavity-enhanced optical frequency comb Fourier transform spectroscopy has been used to detect H2O and OH radical in a flame [2,3]. However, the time resolution of these measurements has so far been of the order of seconds. Here, we present a cavity-enhanced continuous-filtering Vernier spectrometer (CF-VS) that allows detection of H2O and OH in a flame with a time resolution of 25 ms.

A continuous-filtering Vernier spectrometer based on an Er:fiber femtosecond laser was developed to acquire broadband H2O and OH spectra in a premixed CH4/air flame with 25 ms time resolution and percent precision on concentrations retrieval.

We use broadband near-infrared continuous-filtering Vernier spectroscopy (CF-VS) for time-resolved detection of H2O and OH radical in a premixed CH4/air flat flame. The CF-VS spectrometer is based on a femtosecond Er:fiber laser, an external cavity that contains the flame, and a detection system comprising a rotating diffraction grating and photodetectors. Spectra of H2O and OH radical around 1570 nm are continuously recorded with 6.6 GHz spectral resolution, 4.0 × 10−7 cm−1 absorption sensitivity, and 25 ms time resolution, while the fuel-air equivalence ratio is periodically modulated with a square wave. The concentrations of the two analytes are retrieved with percent level precision by a fit of a Vernier model to each spectrum spanning 13 nm. The temporal profiles of both concentrations in each modulation cycle are repeatable and the steady-state concentration levels are in good agreement with predictions based on one-dimensional simulations of a static flat flame. The robust CF-VS spectrometer opens up for quantitative monitoring of multiple products of time-varying combustion processes with relatively simple data acquisition procedures.

Potassium (K) is an important element related to ash and fine-particle formation in biomass combustion processes. In situ measurements of gaseous atomic potassium, K(g), using robust optical absorption techniques can provide valuable insight into the K chemistry. However, for typical parts per billion K(g) concentrations in biomass flames and reactor gases, the product of atomic line strength and absorption path length can give rise to such high absorbance that the sample becomes opaque around the transition line center. We present a tunable diode laser atomic absorption spectroscopy (TDLAAS) methodology that enables accurate, calibration-free species quantification even under optically thick conditions, given that Beer−Lambert’s law is valid. Analyte concentration and collisional line shape broadening are simultaneously determined by a least-squares fit of simulated to measured absorption profiles. Method validation measurements of K(g) concentrations in saturated potassium hydroxide vapor in the temperature range 950−1200 K showed excellent agreement with equilibrium calculations, and a dynamic range from 40 pptv cm to 40 ppmv cm. The applicability of the compact TDLAAS sensor is demonstrated by real-time detection of K(g) concentrations close to biomass pellets during atmospheric combustion in a laboratory reactor.

The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the “Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources”. The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.

Exhaled breath carbon monoxide (eCO) is a candidate biomarker for non-invasive assessment of oxidative stress and respiratory diseases. Standard end-tidal CO analysis, however, cannot distinguish, whether eCO reflects endogenous CO production, lung diffusion properties or exogenous sources, and is unable to resolve a potential airway contribution. Coupling real-time breath gas analysis to pulmonary gas exchange modeling holds promise to improve the diagnostic value of eCO. A trumpet model with axial diffusion (TMAD) is used to simulate the dynamics of CO gas exchange in the respiratory system and corresponding eCO concentrations for the first time. The mass balance equation is numerically solved employing a computationally inexpensive routine implementing the method of lines, which provides the distribution of CO in the respiratory tract during inhalation, breath-holding and exhalation with 1 mm spatial and 0.01 s temporal resolution. Initial estimates of the main TMAD parameters, the maximum CO fluxes and diffusing capacities in alveoli and airways, are obtained using healthy population tissue, blood and anatomical data. To verify the model, mouth-exhaled expirograms from two healthy subjects, measured with a novel, home-built laser-based CO sensor, are compared to single-exhalation profiles simulated using actual breath sampling data, such as exhalation flow rate (EFR) and volume. A very good agreement is obtained in exhalation phases I and III for EFRs between 55 and 220 ml/s and after 10 s and 20 s of breath-holding, yielding a unique set of TMAD parameters. The results confirm the recently observed EFR dependence of CO expirograms and suggest that measured end-tidal eCO is always lower than alveolar and capillary CO. Breath-holding allows the observation of close-to-alveolar CO concentrations and increases the sensitivity to the airway TMAD parameters in exhalation phase I. A parametric simulation study shows that a small increase in airway flux can be distinguished from an increase in alveolar flux, and that slight changes in alveolar flux and diffusing capacity have a significantly different effect on phase III of the eCO profiles.

Detection and analysis of volatile compounds in exhaled breath represents an attractive tool for monitoring the metabolic status of a patient and disease diagnosis, since it is non-invasive and fast. Numerous studies have already demonstrated the benefit of breath analysis in clinical settings/applications and encouraged multidisciplinary research to reveal new insights regarding the origins, pathways, and pathophysiological roles of breath components. Many breath analysis methods are currently available to help explore these directions, ranging from mass spectrometry to laser-based spectroscopy and sensor arrays. This review presents an update of the current status of optical methods, using near and mid-infrared sources, for clinical breath gas analysis over the last decade and describes recent technological developments and their applications. The review includes: tunable diode laser absorption spectroscopy, cavity ring-down spectroscopy, integrated cavity output spectroscopy, cavity-enhanced absorption spectroscopy, photoacoustic spectroscopy, quartz-enhanced photoacoustic spectroscopy, and optical frequency comb spectroscopy. A SWOT analysis (strengths, weaknesses, opportunities, and threats) is presented that describes the laser-based techniques within the clinical framework of breath research and their appealing features for clinical use.

We demonstrate a high-temperature water absorption spectrum measured in a flame using cavity-enhanced frequency comb-based Fourier transform spectroscopy. The retrieved transition intensities and frequencies are assigned using the POKAZATEL line list.

Tunable diode laser absorption spectroscopy (TDLAS) is employed for simultaneous detection of gas temperature, water vapor (H2O) and gas-phase atomic potassium, K(g), in an atmospheric, research-scale entrained flow reactor (EFR). In situ measurements are conducted at four different locations in the EFR core to study the progress of thermochemical conversion of softwood and Miscanthus powders with focus on the primary potassium reactions. In an initial validation step during propane flame operation, the measured axial EFR profiles of H2O density-weighted, path-averaged temperature, path-averaged H2O concentration and H2O column density are found in good agreement with 2D CFD simulations and standard flue gas analysis. During biomass conversion, temperature and H2O are significantly higher than for the propane flame, up to 1500 K and 9%, respectively, and K(g) concentrations between 0.2 and 270 ppbv are observed. Despite the large difference in initial potassium content between the fuels, the K(g) concentrations obtained at each EFR location are comparable, which highlights the importance of considering all major ash-forming elements in the fuel matrix. For both fuels, temperature and K(g) decrease with residence time, and in the lower part of the EFR, K(g) is in excellent agreement with thermodynamic equilibrium calculations evaluated at the TDLAS-measured temperatures and H2O concentrations. However, in the upper part of the EFR, where the measured H2O suggested a global equivalence ratio smaller than unity, K(g) is far below the predicted equilibrium values. This indicates that, in contrast to the organic compounds, potassium species rapidly undergo primary ash transformation reactions even if the fuel particles reside in an oxygen-deficient environment. Bio4Energy

The design and application of an H2O/temperature sensor based on scanned calibration-free wavelength modulation spectroscopy (CF-WMS) and a single tunable diode laser at 1.4 μm is presented. The sensor probes two H2O absorption peaks in a single scan and simultaneously retrieves H2O concentration and temperature by least-squares fitting simulated 1f-normalized 2f-WMS spectra to measured 2f/1f-WMS signals, with temperature, concentration and nonlinear modulation amplitude as fitting parameters. Given a minimum detectable absorbance of 1.7×10-5 cm-1 Hz-1/2, the system is applicable down to an H2O concentration of 0.1 % at 1000 K and 20 cm path length (200 ppm·m). The temperature in a water-seeded lab-scale reactor (670-1220 K at 4 % H2O) was determined within an accuracy of 1 % by comparison with the reactor thermocouple. The CF-WMS sensor was applied to real- time in situ measurements of H2O concentration and temperature time histories (0.25 s time resolution) in the hot gases 2 to 11 mm above biomass pellets during atmospheric combustion in the reactor. Temperatures between 1200 and 1600 K and H2O concentrations up to 40 % were detected above the biofuels. 

Absorption spectroscopy is attractive for combustion diagnostics because it allows in-situ and calibration-free quantification of reactants/products and thermometry. However, spectra measured at atmospheric pressure in the near-infrared telecom range, where laser sources and optical components are readily available, suffer from strong water interference. Cavity-enhanced optical frequency comb spectroscopy (CE-OFCS) is well suited for detection of other species, as it provides broad bandwidth with high signal-to-noise ratio and resolution, and allows de-convolving the spectra hidden among water transitions. Here we report detection of OH in the presence of H2O in an atmospheric premixed methane/air flat flame by CE-OFCS at 1.57 μm. We demonstrate a new water line list that is more accurate than HITEMP [1] and we isolate the OH lines by dividing spectra taken at different heights above the burner (HABs) to retrieve OH concentration and flame temperature.

We present a compact sensor for carbon monoxide (CO) in air and exhaled breath based on a room temperature interband cascade laser (ICL) operating at 4.69 µm, a low-volume circular multipass cell and wavelength modulation absorption spectroscopy. A fringe-limited (1σ) sensitivity of 6.5 × 10−8 cm−1Hz-1/2 and a detection limit of 9 ± 5 ppbv at 0.07 s acquisition time are achieved, which constitutes a 25-fold improvement compared to direct absorption spectroscopy. Integration over 10 s increases the precision to 0.6 ppbv. The setup also allows measuring the stable isotope 13CO in breath. We demonstrate quantification of indoor air CO and real-time detection of CO expirograms from healthy non-smokers and a healthy smoker before and after smoking. Isotope ratio analysis indicates depletion of 13CO in breath compared to natural abundance.

Real-time breath gas analysis is a promising, non-invasive tool in medical diagnostics, and well-suited to investigate the physiology of carbon monoxide (CO), a potential biomarker for oxidative stress and respiratory diseases. A sensor for precise, breath-cycle resolved, simultaneous detection of exhaled CO (eCO) and carbon dioxide (eCO2) was developed based on a continuous wave, external-cavity quantum cascade laser (EC-QCL), a low-volume multi-pass cell and wavelength modulation spectroscopy. The system achieves a noise-equivalent (1σ) sensitivity of 8.5 × 10−8 cm−1 Hz−1/2 and (2σ) detection limits of 9 ± 2 ppbv and 650 ± 7 ppmv at 0.14 s spectrum acquisition time for CO and CO2, respectively. Integration over 15 s yields a precision of 0.6 ppbv for CO. The fact that the eCO2 expirograms measured by capnography and laser spectroscopy have essentially identical shape confirms true real-time detection. It is found that the individual eCO exhalation profiles from healthy non-smokers have a slightly different shape than the eCO2 profiles and exhibit a clear dependence on exhalation flow rate and breath-holding time. Detection of indoor air CO and broadband breath profiling across the 93 cm−1 mode-hop-free tuning range of the EC-QCL are also demonstrated.

A numerical and experimental study on the conversion of a biomass particle is carried out to quantify the effect of homogeneous volatile combustion on the biomass pyrolysis. The numerical domain consists of a particle and its surrounding and the model considers detailed chemical kinetic mechanism for reaction of pyrolysis products. A detailed pyrolysis model is employed which provides the composition of pyrolysis products. The effect of gas phase reaction on the conversion time and temperature of the particle is analyzed and it was shown that the gas phase reactions results in shorter pyrolysis time. H2O mole fraction and temperature above a biomass pellet from wheat straw (WS) and stem wood (SW) were experimentally measured using tunable diode laser absorption spectroscopy (TDLAS) while recording the particle mass loss. The TDLAS data were used to validate the numerical model developed for biomass conversion. The results showed that by considering the gas phase reactions a good agreement between the measurement and the model prediction for mass loss and temperature can be achieved. For H2O mole fraction on top of the particle, on the other hand, some discrepancy between the model prediction and the experimental data was observed. Nevertheless, the difference in H2O mole fraction would be much larger by neglecting the gas phase reaction at the particle boundary.

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 ...

We report broadband detection of OH in a premixed CH4/air flat flame at atmospheric pressure using cavity-enhanced absorption spectroscopy based on an Er:fiber femtosecond laserand a Fourier transform spectrometer.By taking ratios of spectra measured at different heights above the burner we separate twenty OH transitions from the largely overlapping water background. Weretrieve from fits to the OH lines the relative variation of the OH concentration and flame temperature with height above the burner and compare them with 1-D simulations of the flamestructure. Full Text: PDF ReferencesG. Meijer, M. G. Boogaarts, R. T. Jongma, D. H. Parker and A. M. Wodtke, "Coherent cavity ring down spectroscopy", Chem. Phys. Lett. 217, 1, 112 (1994). CrossRef S. Cheskis, I. Derzy, V. A. Lozovsky, A. Kachanov and D. Romanini, "Cavity ring-down spectroscopy of OH radicals in low pressure flame", Appl. Phys. B 66, 3, 377 (1998). CrossRef X. Mercier, E. Therssen, J. F. Pauwels and P. Desgroux, "Cavity ring-down measurements of OH radical in atmospheric premixed and diffusion flames.: A comparison with laser-induced fluorescence and direct laser absorption", Chem. Phys. Lett. 299, 1, 75 (1999). CrossRef J. Scherer, D. Voelkel and D. Rakestraw, "Infrared cavity ringdown laser absorption spectroscopy (IR-CRLAS) in low pressure flames", Appl. Phys. B 64, 6, 699 (1997). CrossRef R. Peeters, G. Berden and G. Meijer, "Near-infrared cavity enhanced absorption spectroscopy of hot water and OH in an oven and in flames", Appl. Phys. B 73, 1, 65 (2001). CrossRef T. Aizawa, "Diode-laser wavelength-modulation absorption spectroscopy for quantitative in situ measurements of temperature and OH radical concentration in combustion gases", Appl. Opt. 40, 27, 4894 (2001). CrossRef B. Löhden, S. Kuznetsova, K. Sengstock, V. M. Baev, et al., "Fiber laser intracavity absorption spectroscopy for in situ multicomponent gas analysis in the atmosphere and combustion environments", Appl. Phys. B 102, 2, 331 (2011). CrossRef A. Matynia, M. Idir, J. Molet, C. Roche, et al., "Absolute OH concentration profiles measurements in high pressure counterflow flames by coupling LIF, PLIF, and absorption techniques", Appl. Phys. B 108, 2, 393 (2012). CrossRef R. S. Watt, T. Laurila, C. F. Kaminski and J. Hult, "Cavity Enhanced Spectroscopy of High-Temperature H2O in the Near-Infrared Using a Supercontinuum Light Source", Appl. Spectrosc. 63, 12, 1389 (2009). CrossRef C. Abd Alrahman, A. Khodabakhsh, F. M. Schmidt, Z. Qu and A. Foltynowicz, "Cavity-enhanced optical frequency comb spectroscopy of high-temperature H2O in a flame", Opt. Express 22, 11, 13889 (2014). CrossRef A. Foltynowicz, P. Maslowski, A. J. Fleisher, B. J. Bjork and J. Ye, "Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide", Appl. Phys. B 110, 2, 163 (2013). CrossRef Z. Qu, R. Ghorbani, D. Valiev and F. M. Schmidt, "Calibration-free scanned wavelength modulation spectroscopy ? application to H2O and temperature sensing in flames", Opt. Express 23, 12, 16492 (2015). CrossRef L. Rutkowski, A. Khodabakhsh, A. C. Johansson, D. M. Valiev, et al., "Measurement of H2O and OH in a Flame by Optical Frequency Comb Spectroscopy", CLEO: Science and Innovations SW4H.8 (2016). CrossRef L. S. Rothman, I. E. Gordon, Y. Babikov, A. Barbe, et al., "The HITRAN2012 molecular spectroscopic database", J. Quant. Spectrosc. Radiat. Transf. 130, 4 (2013). CrossRef

Using Fourier transform-based cavity-enhanced optical frequency comb spectroscopy around 1.57 µm we measure high precision low pressure spectra of the 3ν1+ ν3 band of CO2 and high temperature H2O and OH spectra in a premixed methane/air flat flame.

We measure broadband H 2 O and OH spectra in a flame using near-infrared cavity-enhanced Fourier transform optical frequency comb spectroscopy, we retrieve temperature and OH concentration, and compare water spectra to an improved line list.

Dual-frequency modulation (DFM) has been used to continuously track the frequency shifts of optical cavity modes in the vicinity of an optical transition of a gas inside the cavity for assessment o ...

A theoretical investigation of the influence of optical pumping on wavelength modulation absorption spectrometry (WMAS) signals from collision broadened atoms and molecules is presented. General ex ...

We demonstrate detection of broadband high-temperature water spectra in a laminar, premixed methane/air flat flame using high-resolution near-infrared cavity-enhanced optical frequency comb spectroscopy incorporating a fast-scanning Fourier transform spectrometer.

This work examines absorption spectrometry by narrowband light in gaseous media with arbitrary optical thickness when the light induces optical saturation or optical pumping. Two quantities are defined: the observed absorbance, Aobs, and the true absorbance, Atrue. The former is the absorbance that is measured under the existing conditions, whereas the latter represents the absorbance one would measure if the light acted solely as a probe of the populations of the various levels, and it is therefore directly proportional to the concentration or density of absorbers. A general integral equation for the propagation of light in media of arbitrary optical thickness in which the light influences the populations of the levels involved is derived. This expression is transcendental in the observed absorbance and cannot be solved analytically. It is shown that an analytical expression can be derived by investigating the inverse relationship, i.e., Atrue = f ( Aobs). Inasmuch as collision and Doppler broadened media react differently to optical saturation, they are considered separately. It is shown that a nonlinear response results if the medium is optically saturated (or pumped) and not optically thin. Expressions for the error introduced if the technique of standard additions is uncritically applied to such a system are derived.

A theoretical investigation of the influence of optical saturation on wavelength modulation absorption spectrometry (WMAS) signals from collision-broadened transitions is presented. Expressions are ...

A new diode laser-based double modulation absorption spectrometry (DMAS) technique for detection of species in trace amounts/concentrations is presented. The new technique makes use of a simultaneo ...

A discussion about the significance of Absorbance and sample optical thickness in conventional absorption spectrometry and wavelength-modulated laser absorption spectrometry

Calibration-free wavelength modulation spectroscopy was employed for measuring temperature and H2O concentration in combustion environments with a near-infrared DFB-laser, and for detection of CO in human breath using a quantum cascade laser.

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.

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

Diode laser-based continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared region has been used to measure the mixing ratio of acetylene (C(2)H(2)) in ambient air. Detection limits of 120 parts per trillion by volume (pptv) for 20 min and 340 pptv for 70 s acquisition time were achieved without sample pre-concentration, measuring on a C(2)H(2) absorption line at 6565.620 cm(-1) (similar to 1523 nm). Several indoor and outdoor air samples were collected at different locations in the Helsinki metropolitan area and analyzed using static-cell measurements. In addition, flow measurements of indoor and outdoor air have been performed continuously over several days with a time resolution of down to one minute. Baseline acetylene levels in the range of 0.4 to 3 parts per billion by volume (ppbv), with a maximum around midday and a minimum during the night, were measured. Sudden high mixing ratios of up to 60 ppbv were observed in outdoor air during daytime on a minute time scale. In general, the indoor mixing ratios were found to be higher than those in outdoor air. The acetylene levels correlated with the ambient CO levels and with outdoor temperature. 678VQ Times Cited:4 Cited References Count:36

As a result of a combination of an external cavity and modulation techniques, noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is one of the most sensitive absorpt ...

A compact NICE-OHMS spectrometer based on a narrowband fiber laser has been used for detection of C2H2down to an integrated absorption of 5×10-11cm-1in Doppler-broadened and 3×10-10cm-1in Doppler-free mode of operation.

We demonstrate near-infrared cavity-enhanced optical frequency comb spectroscopy of water in a premixed methane/air flat flame. The detection system is based on an Er:fiber femtosecond laser, a high finesse optical cavity containing the flame, and a fast-scanning Fourier transform spectrometer (FTS). High absorption sensitivity is obtained by the combination of a high-bandwidth two-point comb-cavity lock and auto-balanced detection in the FTS. The system allows recording high-temperature water absorption spectra with a resolution of 1 GHz and a bandwidth of 50 nm in an acquisition time of 0.4 s, with absorption sensitivity of 4.2 × 10(-9) cm(-1) Hz(-1/2) per spectral element.