Numerical Study and Experimental Verification of Biomass Conversion and Potassium Release in a 140 kW Entrained Flow Gasifier.

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.

Quantitative Tomographic Laser Absorption Imaging of Atomic Potassium during Combustion of Potassium Chloride Salt and Biomass.

Gaseous potassium (K) species play an important role in biomass combustion processes, and imaging techniques are powerful tools to investigate the related gas-phase chemistry. Here, laser absorption imaging of gaseous atomic K in flames is implemented using tunable diode laser absorption spectroscopy at 769.9 nm and a high-speed complementary metal oxide semiconductor (CMOS) camera recording at 30 kfps. Atomic K absorption spectra are acquired for each camera pixel in a field of view of 28 × 28 mm at a rate of 100 Hz. The technique is used to determine the spatial distribution of atomic K concentration during the conversion of potassium chloride (KCl) salt and wheat straw particles in a laminar premixed CH4/air flame with an image pixel resolution of up to 120 µm. Due to axisymmetry in setup geometry and, consequently, atomic K distributions, the radial atomic K concentration fields could be reconstructed by one-dimensional tomography. For the KCl sample, the K concentration field was in excellent agreement with previous point measurements. In the case of wheat straw, atomic K concentrations of around 3 ppm were observed in a cylindrical flame during devolatilization. In the char conversion phase, a spherical layer of atomic K, with concentrations reaching 25 ppm, was found within 5 mm of the particle surface, while the concentration rapidly decreased to sub-ppm levels along the vertical axis. In both cases, a thin (∼1 mm) layer without any atomic K was observed in close vicinity to the particle, suggesting that the potassium was initially not released in its atomic form.

Ultrafast Widefield Mid-Infrared Photothermal Heterodyne Imaging.

Mid-infrared photothermal (MIP) microscopy is a valuable tool for sensitive and fast chemical imaging with high spatial resolution beyond the mid-infrared diffraction limit. The highest sensitivity is usually achieved with heterodyne MIP employing photodetector point-scans and lock-in detection, while the fastest systems use camera-based widefield MIP with pulsed probe light. One challenge is to simultaneously achieve high sensitivity, spatial resolution, and speed in a large field of view. Here, we present widefield mid-infrared photothermal heterodyne (WIPH) imaging, where a digital frequency-domain lock-in (DFdLi) filter is used for simultaneous multiharmonic demodulation of MIP signals recorded by individual camera pixels at frame rates up to 200 kHz. The DFdLi filter enables the use of continuous-wave probe light, which, in turn, eliminates the need for synchronization schemes and allows measuring MIP decay curves. The WIPH approach is characterized by imaging potassium ferricyanide microparticles and applied to detect lipid droplets (alkyne-palmitic acid) in 3T3-L1 fibroblast cells, both in the cell-silent spectral region around 2100 cm-1 using an external-cavity quantum cascade laser. The system achieved up to 4000 WIPH images per second at a signal-to-noise ratio of 5.52 and 1 µm spatial resolution in a 128 × 128 µm field of view. The technique opens up for real-time chemical imaging of fast processes in biology, medicine, and material science.

Impact of breath sampling on exhaled carbon monoxide.

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.

TDLAS-based photofragmentation spectroscopy for detection of K and KOH in flames under optically thick conditions.

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.

Time-resolved continuous-filtering Vernier spectroscopy of H2O and OH radical in a flame.

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.

High-resolution trace gas detection by sub-Doppler noise-immune cavity-enhanced optical heterodyne molecular spectrometry: application to detection of acetylene in human breath.

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.

Fitting of single-exhalation profiles using a pulmonary gas exchange model-application to carbon monoxide.

Real-time breath gas analysis coupled to gas exchange modeling is emerging as promising strategy to enhance the information gained from breath tests. It is shown for exhaled breath carbon monoxide (eCO), a potential biomarker for oxidative stress and respiratory diseases, that a weighted, nonlinear least-squares fit of simulated to measured expirograms can be used to extract physiological parameters, such as airway and alveolar concentrations and diffusing capacities. Experimental CO exhalation profiles are acquired with high time-resolution and precision using mid-infrared tunable diode laser absorption spectroscopy and online breath sampling. A trumpet model with axial diffusion is employed to generate eCO profiles based on measured exhalation flow rates and volumes. The concept is demonstrated on two healthy non-smokers exhaling at a flow rate of 250 ml s-1 during normal breathing and at 120 ml s-1 after 10 s of breath-holding. The obtained gas exchange parameters of the two subjects are in a similar range, but clearly distinguishable. Over a series of twenty consecutive expirograms, the intra-individual variation in the alveolar parameters is less than 6%. After a 2 h exposure to 10 ± 2 ppm CO, end-tidal and alveolar CO concentrations are significantly increased (by factors of 2.7 and 4.9 for the two subjects) and the airway CO concentration is slightly higher, while the alveolar diffusing capacity is unchanged compared to before exposure. Using model simulations, it is found that a three-fold increase in maximum airway CO flux and a reduction in alveolar diffusing capacity by 60% lead to clearly distinguishable changes in the exhalation profile shape. This suggests that extended breath CO analysis has clinical relevance in assessing airway inflammation and chronic obstructive pulmonary disease. Moreover, the novel methodology contributes to the standardization of real-time breath gas analysis.

Modeling Pulmonary Gas Exchange and Single-Exhalation Profiles of Carbon Monoxide.

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 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.

Laser spectroscopy for breath analysis: towards clinical implementation.

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.

ICL-based TDLAS sensor for real-time breath gas analysis of carbon monoxide isotopes.

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.

Tunable Diode Laser Atomic Absorption Spectroscopy for Detection of Potassium under Optically Thick Conditions.

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.

14th congress of combustion by-products and their health effects-origin, fate, and health effects of combustion-related air pollutants in the coming era of bio-based energy sources.

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.

Calibration-free scanned wavelength modulation spectroscopy--application to H(2)O and temperature sensing in flames.

A calibration-free scanned wavelength modulation spectroscopy scheme requiring minimal laser characterization is presented. Species concentration and temperature are retrieved simultaneously from a single fit to a group of 2f/1f-WMS lineshapes acquired in one laser scan. The fitting algorithm includes a novel method to obtain the phase shift between laser intensity and wavelength modulation, and allows for a wavelength-dependent modulation amplitude. The scheme is demonstrated by detection of H(2)O concentration and temperature in atmospheric, premixed CH(4)/air flat flames using a sensor operating near 1.4 µm. The detection sensitivity for H(2)O at 2000 K was 4 × 10(-5) cm(-1) Hz(-1/2), and temperature was determined with a precision of 10 K and absolute accuracy of ~50 K. A parametric study of the dependence of H(2)O and temperature on distance to the burner and total fuel mass flow rate shows good agreement with 1D simulations.

Cavity-enhanced optical frequency comb spectroscopy of high-temperature H2O in a flame.

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.

Doppler-broadened fiber-laser-based NICE-OHMS - Improved detectability.

The performance of fiber-laser-based noise-immune cavity-enhanced optical heterodyne molecular spectrometry (NICE-OHMS) has been improved by elimination of the technical constraints that limited its first demonstration. Doppler-broadened detection of C(2)H(2) and CO(2) at ~1531 nm is demonstrated using a cavity with a finesse of 4800. Frequency and wavelength modulated detection at absorption and dispersion phase are compared and the optimum mode of detection is discussed. A minimum detectable absorption of 8 x 10-(11) cm(-1), which corresponds to a detection limit of 4.5 ppt (2 ppt.m) for C(2)H(2), was obtained for an acquisition time of 0.7 s by lineshape fitting. The linearity of the pressure dependence of the signal strengths is investigated for both C(2)H(2) and CO(2).

Absorption spectrometry by narrowband light in optically saturated and optically pumped collision and Doppler broadened gaseous media under arbitrary optical thickness conditions.

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, A(obs), and the true absorbance, A(true). 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., A(true) = f(A(obs)). 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.