Rapid and precise measurement of carbonate clumped isotopes using laser spectroscopy.

Carbonate clumped isotope abundance is an important paleothermometer, but measurement is difficult, slow, and subject to cardinal mass (m/z) interferences using isotope ratio mass spectrometry (IRMS). Here, we describe an optical spectroscopic measurement of carbonate clumped isotopes. We have adapted a tunable infrared laser differential absorption spectrometer (TILDAS) system to measure the abundances of four CO2 isotopologues used for clumped isotope thermometry. TILDAS achieves the same precision (0.01‰ SE) as IRMS measurements rapidly (∼50 min per carbonate analysis) and using small samples (<2 mg of calcite), without making assumptions about 17O abundance in the sample. A temperature calibration based on 406 analyses of CO2 produced by digestion of 51 synthetic carbonates equilibrated at 6° to 1100°C is consistent with results for natural carbonates and previous calibrations. Our system results were indistinguishable from IRMS systems after replicating the InterCarb interlaboratory calibration. Measurement by TILDAS could change the landscape for clumped isotope analysis.

High-Precision Triple Oxygen Isotope Analysis of Carbon Dioxide by Tunable Infrared Laser Absorption Spectroscopy.

Precision measurements of the stable isotope ratios of oxygen (18O/16O and 17O/16O) in CO2 are critical to atmospheric monitoring and terrestrial climate research. High-precision 17O measurements by isotope ratio mass spectrometry (IRMS) are challenging because they require complicated sample preparation procedures, long measurement times, and relatively large samples sizes. Recently, tunable infrared laser direct absorption spectroscopy (TILDAS) has shown significant potential as an alternative technique for triple oxygen isotope analysis of CO2, although the ultimate level of reproducibility is unknown, partly because it is unclear how to relate TILDAS measurements to an internationally accepted isotope abundance scale (e.g., VSMOW2-SLAP2). Here, we present a method for high-precision triple oxygen isotope analysis of CO2 by TILDAS, requiring ∼8-9 µmol of CO2 (or 0.9 mg carbonate) in 50 min, plus ∼1.5 h for sample preparation and dilution of CO2 in N2 to a nominal 400 µmol mol-1. Overall reproducibility of Δ'17O (CO2) was 0.004‰ (4 per meg) for IAEA603 (SE, n = 6) and 10 per meg for NBS18 (SE, n = 4). Values corrected to the VSMOW2-SLAP2 scale are in good agreement with established techniques of high-precision IRMS, with the exception of Δ'17O measured by platinum-catalyzed exchange of CO2 with O2. Compared to high-precision IRMS, TILDAS offers the advantage of ∼10 times less sample, and greater throughput, without loss of reproducibility. The flexibility of the technique should allow for many important applications to global biogeochemical monitoring and investigation of 17O anomalies in a range of geological materials.

First investigation and absolute calibration of clumped isotopes in N2 O by mid-infrared laser spectroscopy.

RATIONALE: Unravelling the biogeochemical cycle of the potent greenhouse gas nitrous oxide (N2 O) is an underdetermined problem in environmental sciences due to the multiple source and sink processes involved, which complicate mitigation of its emissions. Measuring the doubly isotopically substituted molecules (isotopocules) of N2 O can add new opportunities to fingerprint and constrain its cycle. METHODS: We present a laser spectroscopic technique to selectively and simultaneously measure the eight most abundant isotopocules of N2 O, including three doubly substituted species - so called "clumped isotopes". For the absolute quantification of individual isotopocule abundances, we propose a new calibration scheme that combines thermal equilibration of a working standard gas with a direct mole fraction-based approach. RESULTS: The method is validated for a large range of isotopic composition values by comparison with other established methods (laser spectroscopy using conventional isotopic scale and isotope ratio mass spectrometry). Direct intercomparison with recently developed ultrahigh-resolution mass spectrometry shows clearly the advantages of the new laser technique, especially with respect to site specificity of isotopic substitution in the N2 O molecule. CONCLUSIONS: Our study represents a new methodological basis for the measurements of both singly substituted and clumped N2 O isotopes. It has a high potential to stimulate future research in the N2 O community by establishing a new class of reservoir-insensitive tracers and molecular-scale insights.

Rapid and Precise Analysis of Carbon Dioxide Clumped Isotopic Composition by Tunable Infrared Laser Differential Spectroscopy.

The high precision measurement of doubly substituted ("clumped") isotopologues in CO2 is a topic of significant interest in isotope geochemistry. Here we describe the performance of a new isotope ratio laser spectrometer using tunable infrared laser differential absorption spectroscopy (TILDAS). The TILDAS instrument has two continuous-wave lasers to simultaneously measure the four isotopologues involved in the 12C16O2 + 13C16O18O ⇆ 13C16O2 + 12C16O18O exchange reaction. CO2 samples are trapped in a low volume (∼250 mL) optical multipass cell with a path length of 36 m. Each sample is compared to a reference gas, and clumped isotopologue precision of 0.01‰ (SE) is achieved within 20 min for 15 µmol samples. Similar precision is also achieved for bulk isotopic composition. The degree of rare isotope clumping in excess of strictly random distribution (Δ16O13C18O) measured by this TILDAS instrument varies linearly with theoretically calculated values and shows a very weak dependence on bulk isotopic composition.

Precise Measurements of 12CH2D2 by Tunable Infrared Laser Direct Absorption Spectroscopy.

We present precise measurements of doubly deuterated methane (12CH2D2) in natural methane samples using tunable infrared laser direct absorption spectroscopy (TILDAS). Using a 413 m optical path length astigmatic Herriott cell and two quantum cascade lasers (QCLs) scanning the spectral regions of 1090.46 ± 0.1 and 1200.23 ± 0.1 cm-1, the instrument simultaneously measures the five main isotopologues of methane. The ratios 13CH3D/12CH4 and 12CH2D2/12CH4 are measured at 0.01‰ and 0.5‰ (1σ) instrumental precision, respectively. The instrumental accuracy was assessed by measuring a series of methane gases with a range of δ13C and δD values but with the abundances of all isotopologues driven to thermal equilibrium at 250 °C. The estimated accuracy of Δ12CH2D2 is 1‰ (1σ) on the basis of the results of the heated methane samples. This new TILDAS instrument provides a simple and rapid technique to explore the sources of methane in the environment.

Design and performance of a dual-laser instrument for multiple isotopologues of carbon dioxide and water.

A design and results for an instrument with a quantum cascade laser and an antimonide diode laser to measure simultaneously and with high precision seven isotopologues of carbon dioxide and water vapor. Methods and results for determining the effects that limit absorption noise at the level of 5x10(-6) are presented and discussed.

Demonstration of an ethane spectrometer for methane source identification.

Methane is an important greenhouse gas and tropospheric ozone precursor. Simultaneous observation of ethane with methane can help identify specific methane source types. Aerodyne Ethane-Mini spectrometers, employing recently available mid-infrared distributed feedback tunable diode lasers (DFB-TDL), provide 1 s ethane measurements with sub-ppb precision. In this work, an Ethane-Mini spectrometer has been integrated into two mobile sampling platforms, a ground vehicle and a small airplane, and used to measure ethane/methane enhancement ratios downwind of methane sources. Methane emissions with precisely known sources are shown to have ethane/methane enhancement ratios that differ greatly depending on the source type. Large differences between biogenic and thermogenic sources are observed. Variation within thermogenic sources are detected and tabulated. Methane emitters are classified by their expected ethane content. Categories include the following: biogenic (<0.2%), dry gas (1-6%), wet gas (>6%), pipeline grade natural gas (<15%), and processed natural gas liquids (>30%). Regional scale observations in the Dallas/Fort Worth area of Texas show two distinct ethane/methane enhancement ratios bridged by a transitional region. These results demonstrate the usefulness of continuous and fast ethane measurements in experimental studies of methane emissions, particularly in the oil and natural gas sector.

Feasibility and potential utility of multicomponent exhaled breath analysis for predicting development of radiation pneumonitis after stereotactic ablative radiotherapy.

INTRODUCTION: In this prospective pilot study, we evaluated the feasibility and potential utility of measuring multiple exhaled gases as biomarkers of radiation pneumonitis (RP) in patients receiving stereotactic ablative radiotherapy (SABR) for lung tumors. METHODS: Breath analysis was performed for 26 patients receiving SABR for lung tumors. Concentrations of exhaled nitric oxide (eNO), carbon monoxide (eCO), nitrous oxide (eN2O), and carbon dioxide (eCO2) were measured before and immediately after each fraction using real-time, infrared laser spectroscopy. RP development (CTCAE grade ≥2) was correlated with baseline gas concentrations, acute changes in gas concentrations after each SABR fraction, and dosimetric parameters. RESULTS: Exhaled breath analysis was successfully completed in 77% of patients. Five of 20 evaluable patients developed RP at a mean of 5.4 months after SABR. Acute changes in eNO and eCO concentrations, defined as percent changes between each pre-fraction and post-fraction measurement, were significantly smaller in RP versus non-RP cases (p = 0.022 and 0.015, respectively). In an exploratory analysis, a combined predictor of baseline eNO greater than 24 parts per billion and acute decrease in eCO less than 5.5% strongly correlated with RP incidence (p =0.0099). Neither eN2O nor eCO2 concentrations were significantly associated with RP development. Although generally higher in patients destined to develop RP, dosimetric parameters were not significantly associated with RP development. CONCLUSIONS: The majority of SABR patients in this pilot study were able to complete exhaled breath analysis. Baseline concentrations and acute changes in concentrations of exhaled breath components were associated with RP development after SABR. If our findings are validated, exhaled breath analysis may become a useful approach for noninvasive identification of patients at highest risk for developing RP after SABR.

Measurement of a doubly substituted methane isotopologue, ¹³CH3D, by tunable infrared laser direct absorption spectroscopy.

Methane is an important energy resource and significant long-lived greenhouse gas. Carbon and hydrogen isotope ratios have been used to better constrain the sources of methane but interpretations based on these two parameters alone can often be inconclusive. The precise measurement of a doubly substituted methane isotopologue, (13)CH3D, is expected to add a critical new dimension to source signatures by providing the apparent temperature at which methane was formed or thermally equilibrated. We have developed a new method to precisely determine the relative abundance of (13)CH3D by using tunable infrared laser direct absorption spectroscopy (TILDAS). The TILDAS instrument houses two continuous wave quantum cascade lasers; one tuned at 8.6 µm to measure (13)CH3D, (12)CH3D, and (12)CH4, and the other at 7.5 µm to measure (13)CH4. With the use of an astigmatic Herriott cell with an effective path length of 76 m, a precision of 0.2‰ (2σ) was achieved for the measurement of (13)CH3D abundance in ca. 10 mL STP (i.e., 0.42 mmol) pure methane samples. Smaller quantity samples (ca. 0.5 mL STP) can be measured at lower precision. The accuracy of the Δ(13)CH3D measurement is 0.7‰ (2σ), evaluated by thermally equilibrating methane with a range of δD values. The precision of ±0.2‰ corresponds to uncertainties of ±7 °C at 25 °C and ±20 °C at 200 °C for estimates of apparent equilibrium temperatures. The TILDAS instrument offers a simple and precise method to determine (13)CH3D in natural methane samples to distinguish geological and biological sources of methane in the atmosphere, hydrosphere, and lithosphere.

Development of a spectroscopic technique for continuous online monitoring of oxygen and site-specific nitrogen isotopic composition of atmospheric nitrous oxide.

Nitrous oxide is an important greenhouse gas and ozone-depleting-substance. Its sources are diffuse and poorly characterized, complicating efforts to understand anthropogenic impacts and develop mitigation policies. Online, spectroscopic analysis of N2O isotopic composition can provide continuous measurements at high time resolution, giving new insight into N2O sources, sinks, and chemistry. We present a new preconcentration unit, "Stheno II", coupled to a tunable infrared laser direct absorption spectroscopy (TILDAS) instrument, to measure ambient-level variations in (18)O and site-specific (15)N N2O isotopic composition at remote sites with a temporal resolution of <1 h. Trapping of N2O is quantitative up to a sample size of ∼4 L, with an optimal sample size of 1200-1800 mL at a sampling frequency of 28 min. Line shape variations with the partial pressure of the major matrix gases N2/O2 and CO2 are measured, and show that characterization of both pressure broadening and Dicke narrowing is necessary for an optimal spectral fit. Partial pressure variations of CO2 and bath gas result in a linear isotopic measurement offset of 2.6-6.0 ‰ mbar(-1). Comparison of IR MS and TILDAS measurements shows that the TILDAS technique is accurate and precise, and less susceptible to interferences than IR MS measurements. Two weeks of measurements of N2O isotopic composition from Cambridge, MA, in May 2013 are presented. The measurements show significant short-term variability in N2O isotopic composition larger than the measurement precision, in response to meteorological parameters such as atmospheric pressure and temperature.

Aircraft emissions of methane and nitrous oxide during the alternative aviation fuel experiment.

Given the predicted growth of aviation and the recent developments of alternative aviation fuels, quantifying methane (CH(4)) and nitrous oxide (N(2)O) emission ratios for various aircraft engines and fuels can help constrain projected impacts of aviation on the Earth's radiative balance. Fuel-based emission indices for CH(4) and N(2)O were quantified from CFM56-2C1 engines aboard the NASA DC-8 aircraft during the first Alternative Aviation Fuel Experiment (AAFEX-I) in 2009. The measurements of JP-8 fuel combustion products indicate that at low thrust engine states (idle and taxi, or 4% and 7% maximum rated thrusts, respectively) the engines emit both CH(4) and N(2)O at a mean ± 1σ rate of 170 ± 160 mg CH(4) (kg Fuel)(-1) and 110 ± 50 mg N(2)O (kg Fuel)(-1), respectively. At higher thrust levels corresponding to greater fuel flow and higher engine temperatures, CH(4) concentrations in engine exhaust were lower than ambient concentrations. Average emission indices for JP-8 fuel combusted at engine thrusts between 30% and 100% of maximum rating were -54 ± 33 mg CH(4) (kg Fuel)(-1) and 32 ± 18 mg N(2)O (kg Fuel)(-1), where the negative sign indicates consumption of atmospheric CH(4) in the engine. Emission factors for the synthetic Fischer-Tropsch fuels were statistically indistinguishable from those for JP-8.

Clinical study of multiple breath biomarkers of asthma and COPD (NO, CO(2), CO and N(2)O) by infrared laser spectroscopy.

Breath analysis is a powerful non-invasive technique for the diagnosis and monitoring of respiratory diseases, including asthma and chronic obstructive pulmonary disease (COPD). Exhaled nitric oxide (NO) and carbon monoxide (CO) are markers of airway inflammation and can indicate the extent of respiratory diseases. We have developed a compact fast response quantum cascade laser system for analysis of multiple gases by tunable infrared absorption spectroscopy. The ARI breath analysis instrument has been deployed in a study of exhaled breath from patients with asthma or COPD. A total of 173 subjects participated, including both adult and pediatric patients. Patients in asthma or COPD exacerbations were evaluated twice-during the exacerbation and at a follow-up visit-to compare variations in breath biomarkers during these events. The change in exhaled NO levels between exacerbation and 'well' visits is consistent with spirometry data collected. Respiratory models are important for understanding the exchange dynamics of nitric oxide and other species in the lungs and airways. At each patient's visit, tests were conducted at four expiratory flow rates. We have applied a trumpet model with axial diffusion to the multi-flow exhaled nitric oxide data, obtaining NO alveolar concentrations and airway fluxes. We found higher airway fluxes for those with more severe asthma and during exacerbation events. The alveolar concentrations from the model were higher in adults with asthma and COPD, but this trend was less clear among the pediatric subjects.

Dual quantum cascade laser trace gas instrument with astigmatic Herriott cell at high pass number.

We have developed and demonstrated a high-sensitivity trace gas instrument employing two mid-infrared quantum cascade lasers and an astigmatic Herriott sample cell with up to a 240 m path length. Several aspects of astigmatic Herriott cell optics have been addressed to enable operation at a high pass number (up to 554), including aberrations and pattern selection to minimize interference fringes. The new instrument design, based on the 200 m cell, can measure various atmospheric trace gases, depending on the installed lasers, with multiple trace gases measured simultaneously. Demonstrated concentration noise levels (1 s average) are 40 parts per trillion [(ppt) 10(-12)] for formaldehyde, 10 ppt for carbonyl sulfide, 110 ppt for hydrogen peroxide (H2O2), and 180 ppt for nitrous acid (HONO). High-precision measurements of nitrous oxide and methane have been recorded at the same time as high-sensitivity measurements of HONO and H2O2.

Monomer, clusters, liquid: an integrated spectroscopic study of methanol condensation.

We have combined static pressure, spectroscopic temperature, Fourier transform infrared spectroscopy (FTIR), and small angle X-ray scattering (SAXS) measurements to develop a detailed picture of methanol condensing from a dilute vapor-carrier gas mixture under the highly supersaturated conditions present in a supersonic nozzle. In our experiments, methanol condensation can be divided into three stages as the gas mixture expands in the nozzle. In the first stage, as the temperature decreases rapidly, small methanol n-mers (clusters) form, increase in concentration, and evolve in size. In the second stage, the temperature decreases more slowly, and the n-mer concentrations continue to rise. Thermodynamic and FTIR experiments cannot, however, definitively establish if the average cluster size is constant or if it continues to increase. Finally, when the vapor becomes supersaturated enough, liquid droplets form via nucleation and growth, consuming more monomer and reducing the concentration of clusters. At the point where liquid first appears, cluster formation has already consumed up to 30% of the monomer. This is significantly more than is predicted by a model that describes the vapor phase as an equilibrium mixture of methanol monomer, dimer, and tetramer. An energy balance suggests that a significant fraction of the cluster population is larger than the tetramer, while preliminary SAXS measurements suggest that these clusters contain, on average, 6 monomers.

Long-term continuous sampling of ¹²CO2, ¹³CO2 and ¹²C¹8O¹6O in ambient air with a quantum cascade laser spectrometer.

A recently developed laser spectroscopic instrument allows real-time continuous measurements of the stable isotopologues of carbon dioxide at ambient concentrations. This compact instrument offers sufficient precision (0.2 per thousand in 1 s, 0.02 per thousand in 60 s) and stability (drift in 1 h of<0.2 per thousand), to allow isotopic studies on a variety of timescales and to study a variety of processes. During the development of the instrument, a prototype was set up to sample ambient air nearly continuously for more than 10 months, in a heterogeneous urban area northwest of Boston, MA. During this long sampling experiment, we continued to improve and modify the instrument and sampling system. In this paper, we present data collected during that long sampling experiment in order to demonstrate some of the possibilities provided by such real-time continuous monitoring. We have observed distinct isotopic signatures in CO(2) variations from timescales of seconds to seasons. We also present a method of performing continuous Keeling regressions on a cascade of timescales and show some results in application of that method to the continuous sampling data set.

Multicomponent Breath Analysis With Infrared Absorption Using Room-Temperature Quantum Cascade Lasers.

Breath analysis is a powerful noninvasive technique for the diagnosis and monitoring of respiratory diseases, including asthma and chronic obstructive pulmonary disease (COPD). Nitric oxide (NO) and carbon monoxide (CO) are markers of airway inflammation and can indicate the extent of respiratory diseases. We have developed a compact fast response laser system for analysis of multiple gases by infrared absorption. The instrument uses room temperature quantum cascade lasers to simultaneously measure NO, CO, carbon dioxide (CO(2)) and nitrous oxide (N(2)O) in exhaled breath. Four breath flow rates are employed to explore their exchange dynamics in the lungs and airways. We obtain 1-s detection precisions of 0.5-0.8 parts-per-billion (ppb) for NO, CO, and N(2)O with an instrument response time of less than 1 s. The breath analysis system has been demonstrated in a preliminary study of volunteers. It is currently deployed in a trial clinical study.

Tunable diode laser absorption spectroscopy study of CH(3)CH(2)ODD(2)O binary condensation in a supersonic Laval nozzle.

We have developed a dual-beam tunable diode laser absorption spectroscopy system to follow the cocondensation of water and ethanol in a supersonic Laval nozzle. We determine the D(2)O monomer concentration in the vapor phase by fitting a Voigt profile to the measured line shape but had to develop a calibration scheme to evaluate the C(2)H(5)OD monomer concentration. To measure the temperature of the gas, we seed the flow with CH(4) and measure two absorption lines with different lower state energies. These data give a far more detailed picture of binary condensation than axially resolved pressure measurements. In particular, we observe that the C(2)H(5)OD monomer starts to be depleted from the gas phase well before D(2)O begins to condense.

Characterization of a near-room-temperature, continuous-wave quantum cascade laser for long-term, unattended monitoring of nitric oxide in the atmosphere.

We report on power, spectral linewidth, and mode purity for a cw 5.3 microm quantum cascade laser operated on a thermo-electric cooler. A totally noncryogenic nitric oxide monitor was constructed by integrating this laser with an astigmatic multipass cell and a thermo-electrically cooled infrared detector. The resulting instrument is capable of continuous unattended monitoring of ambient, atmospheric nitric oxide for several weeks with no operator intervention. The detection method was rapid sweep, direct absorption spectroscopy. A detection sensitivity of 0.03 parts in 10(9) is achieved with 30 s averaging time with a path length of 210 m, corresponding to an absorbance path length product of 1.5 x 10(-10) cm(-1).

What are the instrumentation requirements for measuring the isotopic composition of net ecosystem exchange of CO2 using eddy covariance methods?

Better quantification of isotope ratios of atmosphere-ecosystem exchange of CO2 could substantially improve our ability to probe underlying physiological and ecological mechanisms controlling ecosystem carbon exchange, but the ability to make long-term continuous measurements of isotope ratios of exchange fluxes has been limited by measurement difficulties. In particular, direct eddy covariance methods have not yet been used for measuring the isotopic composition of ecosystem fluxes. In this article, we explore the feasibility of such measurements by (a) proposing a general criterion for judging whether a sensor's performance is sufficient for making such measurements (the criterion is met when the contribution of sensor error to the flux measurement error is comparable to or less than the contribution of meteorological noise inherently associated with turbulence flux measurements); (b) using data-based numerical simulations to quantify the level of sensor precision and stability required to meet this criterion for making direct eddy covariance measurements of the 13C/12C ratio of CO2 fluxes above a specific ecosystem (a mid-latitude temperate forest in central Massachusetts, USA); (c) testing whether the performance of a new sensor-a prototype pulsed quantum cascade laser (QCL) based isotope-ratio absorption spectrometer (and plausible improvements thereon)-is sufficient for meeting the criterion in this ecosystem. We found that the error contribution from a prototype sensor (approximately 0.2 per thousand, 1 SD of 10 s integrations) to total isoflux measurement error was comparable to (1.5 to 2x) the irreducible 'meteorological' noise inherently associated with turbulent flux measurements above this ecosystem (daytime measurement error SD of approximately 60% of flux versus meteorological noise of 30-40% for instantaneous half-hour fluxes). Our analysis also shows that plausible instrument improvements (increase of sensor precision to approximately 0.1 per thousand, 1 SD of 10 s integrations, and increased sensor stability during the half-hour needed to integrate eddy covariance measurements) should decrease the contribution of sensor error to the point where it is less than the contribution from meteorological noise. This suggests that new sensors using QCL-based isotope ratio absorption spectroscopy should make continuous long-term observations of the isotopic composition of CO2 fluxes via eddy covariance methods feasible.

Measurement of nitrogen dioxide in cigarette smoke using quantum cascade tunable infrared laser differential absorption spectroscopy (TILDAS).

Although nitrogen dioxide (NO(2)) has been previously reported to be present in cigarette smoke, the concentration estimates were derived from kinetic calculations or from measurements of aged smoke, where NO(2) was formed some time after the puff was taken. The objective of this work was to use tunable infrared laser differential absorption spectroscopy (TILDAS) equipped with a quantum cascade (QC) laser to determine if NO(2) could be detected and quantified in a fresh puff of cigarette smoke. A temporal resolution of approximately 0.16s allowed measurements to be taken directly as the NO(2) was formed during the puff. Sidestream cigarette smoke was sampled to determine if NO(2) could be detected using TILDAS. Experiments were conducted using 2R4F Kentucky Reference cigarettes with and without a Cambridge filter pad. NO(2) was detected only in the lighting puff of whole mainstream smoke (without a Cambridge filter pad), with no NO(2) detected in the subsequent puffs. The measurement precision was approximately 1.0 ppbVHz(-1/2), which allows a detection limit of approximately 0.2 ng in a 35 ml puff volume. More NO(2) was generated in the lighting puff using a match or blue flame lighter (29+/-21 ng) than when using an electric lighter (9+/-3 ng). In the presence of a Cambridge filter pad, NO(2) was observed in the gas phase mainstream smoke for every puff (total of 200+/-30 ng/cigarette) and is most likely due to smoke chemistry taking place on the Cambridge filter pad during the smoke collection process. Nitrogen dioxide was observed continuously in the sidestream smoke starting with the lighting puff.