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An Aerodyne tunable infrared laser direct absorption spectrometer with a multipass cell with a 413 m pathlength for the detection of ethylene oxide (EtO) is presented (TILDAS-FD-EtO). This monitor achieves precisions of ppt or ppb s−1 and ppt in 100 s (1σ). We demonstrate precisions averaging down to 4 ppt h−1 (1σ precision) when operated with frequent humidity-matched zeroes. A months-long record of 2022 ambient concentrations at a site in the eastern United States is presented. Average ambient EtO concentration is on the order of 18 ppt (22 ppt standard deviation, SD). Enhancement events of EtO lasting a few hours are observed, with peaks as high as 600 ppt. Back-trajectory simulations suggest an EtO source nearly 35 km away. This source along with another are confirmed as emitters through mobile near-source measurements, with downwind concentrations in the 0.5 to 700 ppb range depending on source identity and distance downwind.

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 CO 2 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 (17 O abundance in the sample. A temperature calibration based on 406 analyses of CO 2 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.

Using laser absorption spectrometry for the measurement of stable isotopes of atmospheric CO2 instead of the traditional isotope ratio mass spectrometry method decreases sample preparation time significantly, and uncertainties in the measurement accuracy due to CO2 extraction and isobaric interferences are avoided. In this study we present the measurement performance of a new dual-laser instrument developed for the simultaneous measurement of the δ13C , δ18O and δ17O of atmospheric CO2 in discrete air samples, referred to as the Stable Isotopes of CO2 Absorption Spectrometer (SICAS). We compare two different calibration methods: the ratio method, based on the measured isotope ratio and a CO2 mole fraction dependency correction, and the isotopologue method, based on measured isotopologue abundances. Calibration with the ratio method and isotopologue method is based on three different assigned whole-air references calibrated on the VPDB (Vienna Pee Dee Belemnite) and the WMO 2007 (World Meteorological Organization) scale for their stable isotope compositions and their CO2 mole fractions, respectively. An additional quality control tank is included in both methods to follow long-term instrument performance. Measurements of the quality control tank show that the measurement precision and accuracy of both calibration methods is of similar quality for δ13C and δ18O measurements. During one specific measurement period the precision and accuracy of the quality control tank reach WMO compatibility requirements, being 0.01 ‰ for δ13C and 0.05 ‰ for δ18O . Uncertainty contributions of the scale uncertainties of the reference gases add another 0.03 ‰ and 0.05 ‰ to the combined uncertainty of the sample measurements. Hence, reaching WMO compatibility for sample measurements on the SICAS requires reduction of the scale uncertainty of the reference gases used for calibration. An intercomparison of flask samples over a wide range of CO2 mole fractions has been conducted with the Max Planck Institute for Biogeochemistry, resulting in a mean residual of 0.01 ‰ and −0.01 ‰ and a standard deviation of 0.05 ‰ and 0.07 ‰ for the δ13C measurements calibrated using the ratio method and the isotopologue method, respectively. The δ18O could not be compared due to depletion of the δ18O signal in our sample flasks because of storage times being too long. Finally, we evaluate the potential of our Δ17O measurements as a tracer for gross primary production by vegetation through photosynthesis. Here, a measurement precision of ‰ would be a prerequisite for capturing seasonal variations in the Δ17O signal. Lowest standard errors for the δ17O and Δ17O of the ratio method and the isotopologue method are 0.02 ‰ and 0.02 ‰ and 0.01 ‰ and 0.02 ‰, respectively. The accuracy results show consequently results that are too enriched for both the δ17O and Δ17O measurements for both methods. This is probably due to the fact that two of our reference gases were not measured directly but were determined indirectly. The ratio method shows residuals ranging from 0.06 ‰ to 0.08 ‰ and from 0.06 ‰ to 0.1 ‰ for the δ17O and Δ17O results, respectively. The isotopologue method shows residuals ranging from 0.04 ‰ to 0.1 ‰ and from 0.05 ‰ to 0.13 ‰ for the δ17O and Δ17O results, respectively. Direct determination of the δ17O of all reference gases would improve the accuracy of the δ17O and thereby of the Δ17O measurements.

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 r...

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.

Methane emissions from offshore oil and gas facilities in the Gulf of Mexico were quantified from a ship. Continuous laser-based measurement of the carbon-13 and deuterium isotopes of methane shows isotopic variation site-to-site.

Using laser absorption spectrometry for the measurement of stable isotopes of atmospheric CO2 instead of the traditional Isotope Ratio Mass Spectrometry (IRMS) method decreases sample preparation time significantly, and uncertainties in the measurement accuracy due to CO2 extraction and isobaric interferences are avoided. In this study we present the measurement performance of a new dual-laser instrument developed for the simultaneous measurement of the δ13C, δ18O and δ17O of atmospheric CO2 in discrete air samples, referred to as the Stable Isotopes of CO2 Absorption Spectrometer (SICAS). We compare two different calibration methods: the ratio method (RM) based on measured isotope ratio and a CO2 mole fraction dependency correction (CMFD), and the isotopologue method (IM) based on measured isotopologue abundances. Calibration with the RM and IM is based on three different assigned whole air references calibrated on the VPBD scale. An additional quality control tank (QC) is included in both methods to follow long-term instrument performance. Measurements of the QC tank show that best performance is achieved with the RM for both the δ13C and δ18O measurements with mean residuals of 0.007 ‰ and 0.016 ‰ and mean standard errors of 0.009 ‰ and 0.008 ‰ respectively, during periods of optimal measurement conditions. The δ17O standard error in the same measurement period is 0.013 ‰. In addition, intercomparing a total of 14 different flask samples covering a CO2 mole fraction range of 344–439 ppm with the Max Planck Institute for Biogeochemistry shows a mean residual of 0.002 ‰ and a standard deviation of 0.063 ‰ for δ13C, using the RM. The δ18O could not be compared due to depletion of the δ18O signal in our sample flasks because of too long storage times. Finally, we evaluated the potential of our Δ17O measurements as a tracer for Gross Primary Production (GPP) by vegetation through photosynthesis. Here, a measurement precision of

We present precise measurements of doubly deuterated methane (

Stomatal conductance influences both photosynthesis and transpiration, thereby coupling the carbon and water cycles and affecting surface-atmosphere energy exchange. The environmental response of stomatal conductance has been measured mainly at the leaf scale, and theoretical canopy models are relied on to upscale stomatal conductance for application in terrestrial ecosystem models and climate prediction. Here we estimate stomatal conductance and associated transpiration in a temperate deciduous forest directly at the canopy scale via two independent approaches: (i) from heat and water vapor exchange, and (ii) from carbonyl sulfide (OCS) uptake. We use the eddy covariance method to measure the net ecosystem-atmosphere exchange of OCS, and we use a flux-gradient approach to separate canopy OCS uptake from soil OCS uptake. We find that the seasonal and diurnal patterns of canopy stomatal conductance obtained by the two approaches agree (to within ±6 % diurnally), validating both methods. Canopy stomatal conductance increases linearly with above-canopy light intensity (in contrast to the leaf scale, where stomatal conductance shows declining marginal increases), and otherwise depends only on the diffuse light fraction, the canopy-average leaf-to-air water vapor gradient, and the total leaf area. Based on stomatal conductance, we partition evapotranspiration (ET) and find that evaporation increases from 0 % to 40 % of ET as the growing season progresses, driven primarily by rising soil temperature and secondarily by rainfall. Counter-intuitively, evaporation peaks at the time of year when the soil is dry and the air is moist. Our method of ET partitioning relies minimally on modeling and avoids concerns about mismatched scales or measurement types because both ET and transpiration are derived from eddy covariance data. Neither of two ecosystem models tested predicts the observed dynamics of evaporation or transpiration, indicating that ET partitioning such as that provided here is needed to further model development and improve our understanding of carbon and water cycling.

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 ‰ in 1 s, 0.02 ‰ in 60 s) and stability (drift in 1 h of

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.

We report concentrations of atmospheric NO x , nitric acid (HNO 3 ), peroxyacetyl nitrate (PAN), and NO y ; eddy covariance fluxes of NO x and NO y ; inferred fluxes of HNO 3 at the mixed deciduous Harvard Forest field site, June–November 2000. A novel Tunable Diode Laser Absorption Spectrometer (TDLAS) produced sensitive, hourly HNO 3 concentration data, which were used to evaluate systematic error in the Dry Deposition Inferential Method (DDIM), often employed to estimate weekly HNO 3 flux at deposition monitoring network sites. Due to the weak diurnal variation in HNO 3 concentration at Harvard Forest, no systematic bias was found in the application of this method to compute daily and weekly average fluxes. The sum of individually measured reactive nitrogen species concentrations and fluxes were approximately equal to total NO y concentrations and fluxes for clean Northwesterly flows, but fell short of the total NO y values for the more polluted Southwesterly transport regime. The concentration and deposition velocity of the unmeasured reactive nitrogen compounds were consistent with prior estimates and recent measurements of alkyl- and hydroxyalkyl nitrates, suggesting that these compounds play an important role in reactive nitrogen deposition processes where anthropogenic NO x emissions and natural hydrocarbons are present.

A compact, fast response, infrared spectrometer using four pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream (MS) and sidestream (SS) cigarette smoke. QC lasers have many advantages over the traditional lead-salt tunable diode lasers, including near room temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The new instrument uses two 36 m, 0.3 l multiple pass absorption gas cells to obtain a time response of 0.1 s for the MS smoke system and 0.4 s for the SS smoke system. The concentrations of ammonia, ethylene, nitric oxide, and carbon dioxide for three different reference cigarettes were measured simultaneously in MS and SS smoke. A data rate of 20 Hz provides sufficient resolution to determine the concentration profiles during each 2 s puff in the MS smoke. Concentration profiles before, during and after the puffs also have been observed for these smoke constituents in SS smoke. Also, simultaneous measurements of CO 2 from a non-dispersive infrared (NDIR) analyzer are obtained for both MS and SS smoke. In addition, during this work, nitrous oxide was detected in both the MS and SS smoke for all reference cigarettes studied.

Recent technological advances have allowed the development of robust, relatively compact, low power, rapid response (approximately 1 s) instruments with sufficient sensitivity and specificity to quantify many trace gases and aerosol particle components in the ambient atmosphere. Suites of such instruments can be deployed on mobile platforms to study atmospheric processes, map concentration distributions of atmospheric pollutants, and determine the composition and intensities of emission sources. A mobile laboratory containing innovative tunable infrared laser differential absorption spectroscopy (TILDAS) instruments to measure selected trace gas concentrations at sub parts-per-billion levels and an aerosol mass spectrometer (AMS) to measure size resolved distributions of the nonrefractory chemical components of fine airborne particles as well as selected commercial fast response instruments and position/velocity sensors is described. Examples of the range of measurement strategies that can be undertaken using this mobile laboratory are discussed, and samples of measurement data are presented.

A compact, fast-response, infrared spectrometer using pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream and sidestream cigarette smoke. QC lasers have many advantages over the traditional lead salt tunable diode lasers, including near-room-temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The instrument uses a 36-m, 0.3-L multiple pass absorption gas cell to obtain a time response of 0.1 s for the mainstream system and 0.4 s for the sidestream system. A precision of 10-4 absorbance units in 1 s is achieved using pulse normalization to reduce pulse-to-pulse intensity variations. Laser line widths (hwhm) of 0.006 cm-1 at 967 and 0.010 cm-1 at 1900 cm-1 are obtained in pulsed operation. With this instrument, we have measured the concentrations of ammonia and ethylene using a QC laser at 967 cm-1 and nitric oxide using a laser at 1900 cm-1 in both mainstream and sidestream smoke from two types of cigarettes. ...

Measurement of the isotopic compositions of carbon dioxide and methane is a powerful tool for quantifying their atmospheric sources and sinks, which is especially important considering the dramatic increase in these greenhouse gases during the industrial era. Laser absorption spectroscopy is a technique which has demonstrated the high sensitivity needed for isotopic measurement. A significant problem in the spectroscopic measurement of isotopic abundances is the large difference in concentrations of the major and minor isotopic constituents. The measurement of two isotopic species using lines of similar strength but very unequal concentrations leads to low precision, with either the minor constituent having too small an absorption depth, or the major constituent having too great an absorption depth. If lines with unequal strength are chosen to compensate for the absorption depth imbalance, then precision tends to suffer due to the greater temperature sensitivity of the weaker line strength. We describe the development of a compact instrument for isotopic analysis CO2 and CH4 using tunable infrared laser absorption spectroscopy which combines novel optical design and signal processing methods to address this problem. The design compensates for the large difference in concentration between major and minor isotopes by measuring them with pathlengths which differ by a factor of 72 within the same multipass cell. We have demonstrated the basic optical design and signal processing by determining delta13C (CO2) isotopic ratios with precision as small as 0.2/1000 using a lead salt diode laser based spectroscopic instrument.

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.

Methane emissions were measured at nine U.S. landfill sites using chamber and/or tracer flux techniques. These flux measurement methodologies were compared at two sites, and excellent agreement (

Atmospheric tracer release techniques have been used to quantify low-level fugitive methane emissions from components and facilities in all sectors of the natural gas system in the United States. The emission data are collected as part of a program to extrapolate the emissions from the entire U.S. natural gas industry and thus reduce uncertainties in the environmental impact of increased natural gas use. In these experiments, the total methane emission from a site is measured by releasing a tracer gas (SF6) at the natural gas facility to simulate the source. Both methane and tracer levels are measured with real-time instruments deployed in a mobile laboratory downwind of the site. A large range of emission levels for the different sectors of the entire system was determined. Within any one group of a particular facility type there is also much variability in the emission rates. The exact nature and number of gas system components in a facility are important factors in determining its emission level.

We have investigated methane emissions from urban sources in the former East Germany using innovative measurement techniques including a mobile real-time methane instrument and tracer release experiments. Anthropogenic and biogenic sources were studied with the emphasis on methane emissions from gas system sources, including urban distribution facilities and a production plant. Methane fluxes from pressure regulating stations ranged from 0.006 to 24. l/min. Emissions from diffuse sources in urban areas were also measured with concentration maps and whole city flux experiments. The area fluxes of the two towns studied were 0.37 and 1.9 μg/m2/s. The emissions from individual gas system stations and total town emissions of this study are comparable to results of similar sites examined in the United States.

We report results from high precision spectroscopic instruments for atmospheric trace gases using with mid-IR quantum cascade lasers. Numerous gases can be measured with 1s absorption noise ∼1×10−6, allowing e.g. 1s OCS precision of 10−12.

A fast-response, high precision, tunable diode laser spectrometer has been developed for field measurements of methane and nitrous oxide fluxes using the eddy correlation method. The instrument uses a novel multiple-pass absorption cell with astigmatic mirrors to provide a long absorption path length (36 m) in a small volume (0.3 l). The combination permits rapid response with sufficient sensitivity for eddy correlation flux measurements over a wide range of meteorological conditions. Signal processing uses a least-squares fitting algorithm to determine absolute trace gas concentrations directly from the absorption spectra using spectral line parameters at data rates up to 20 Hz. The precision for methane and nitrous oxide is 0.1% of ambient levels with a 1 s averaging time. Extensions of the method to measurements of surface-reactive gases such as nitric acid and ammonia are possible using rapid sampling techniques to minimize surface interactions.

[1] We have developed a mid-infrared continuous-wave quantum cascade laser direct-absorption spectrometer (QCLS) capable of high frequency (≥1 Hz) measurements of 12CH4 and 13CH4 isotopologues of methane (CH4) with in situ 1-s RMS precision of 1.5 ‰ and Allan-minimum precision of 0.2 ‰. We deployed this QCLS in a well-studied New Hampshire fen to compare measurements of CH4 isoflux by eddy covariance (EC) to Keeling regressions of data from automated flux chamber sampling. Mean CH4 fluxes of 6.5 ± 0.7 mg CH4 m−2 hr−1 over two days of EC sampling in July, 2009 were indistinguishable from mean autochamber CH4 fluxes (6.6 ± 0.8 mgCH4 m−2 hr−1) over the same period. Mean composition of emitted CH4 calculated using EC isoflux methods was −71 ± 8 ‰ (95% C.I.) while Keeling regressions of 332 chamber closing events over 8 days yielded a corresponding value of −64.5 ± 0.8 ‰. Ebullitive fluxes, representing ∼10% of total CH4 fluxes at this site, were on average 1.2 ‰ enriched in 13C compared to diffusive fluxes. CH4 isoflux time series have the potential to improve process-based understanding of methanogenesis, fully characterize source isotopic distributions, and serve as additional constraints for both regional and global CH4 modeling analysis.

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.

The construction of an atmospheric methane measurement instrument based on a Zeeman-split IR He-Ne laser is reported. The laser has a tranverse magnetic field over about 2/3 of its gain length and can oscillate at an (unsplit) frequency (2947.91/cm) centered on a methane absorption line, or on either of two frequencies split by + or - 0.055/cm from the center, with low CH4 absorption. The laser is tuned to dwell sequentially at each frequency, giving two differential absorption measurements in each 46-ms tuning cycle. Atmospheric measurements are made using two multiple pass absorption cells, one with fast (0.75-s) and one with slow (5-s) flow response times. Fluctuations in ambient CH4 of about 20-ppb (rms, 1-s averaging) are detected, with interference fringe effects the dominant noise source. The instrument has operated in a field experiment (NASA GTE/ABLE-3A) in Alaska.

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 of0.2 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.

Newly developed quantum cascade laser spectroscopic instrumentation allows high precision measurements of atmospheric trace gases, including measurements of small fractional (−3) changes in stable gases (e.g. N2O), and isotopic ratios (e.g. 13CO2/12CO2, 13CH4/12CH4).

The advent of continuous wave quantum cascade lasers operating at near room temperature has greatly expanded the capability of spectroscopic detection of atmospheric trace gases using infrared absorption at wavelengths from 4 to 12 μm. The high optical power, narrow line width, and high degree of single mode purity result in minimal fractional absorptions of 5x10-6 Hz-1/2 detectable in direct absorption with path lengths up to 210 meters. The Allan plot minima correspond to a fractional absorbance of 1x10-6 or a minimum absorption per unit path length 5x10-11 cm-1 in 50s. This allows trace gas mixing ratio detection limits in the low part-per-trillion (1 ppt = 10-12) range for many trace gases of atmospheric interest. We present ambient measurements of NO2 with detection precision of 10 ppt Hz-1/2. The detection precision for the methane isotopologue 13CH4 is 25 ppt Hz-1/2 which allows direct measurements of ambient ratios of 13CH4/12CH4 with a precision of 0.5‰ in 100 s without pre-concentration. Projections are given for detection limits for other gases including COS, HONO and HCHO as CWRT lasers become available at appropriate wavelengths.

Real time methods to monitor the stable isotopic ratios of carbon dioxide and methane are needed to quantify the sources and sinks of these important greenhouse gases. High resolution molecular spectroscopy provides an attractive solution. However, this is an extreme instrumental challenge since the ratios need to be measured with an accuracy of approximately one part in ten thousand or 0.1%. We use tunable infrared laser differential absorption spectroscopy with quantum cascade (QC) lasers to address this challenge. QC lasers are attractive optical sources since they do not need cryogenic fluids, they have stable single mode spectral output and offer optical simplicity. We have used a pulsed-QCL instrument to perform long term (>10 months) monitoring of ambient air from the roof top of our laboratory with time resolution of one second. The resulting data set shows both short term and long term isotopic variations. We observe clear seasonal changes in both 13C/12C and 18O/16O. We have recently extended this technique to the even more challenging case of 13CH4 using continuous wave QCLs. Preliminary results of these measurements will be presented as well.

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.

We report CO2 isotopic ratios (13C, 18O) measured in air using a pulsed quantum cascade laser at 2310 cm-1. Performance is improved by analyzing the deviations between the sample spectra and simultaneously acquired reference spectra.

[1] Atmospheric mixing ratios of formaldehyde and formic acid have been measured from the NOAA WP-3 aircraft during the New England Air Quality Study (NEAQS) of July and August 2004 using a newly developed quantum cascade laser (QCL) spectrometer operating at a wavelength of 5.6 mm. The laser operates in pulsed mode with thermoelectric cooling. The detection is based on direct absorption in a compact 76-m multiple pass absorption cell. The laser is swept over a 0.5 cm 1 spectral region containing multiple lines of both HCHO and HCOOH. Absolute concentrations are retrieved by simultaneous spectral fitting routines with a detection limit (2s) for HCHO of 0.3 parts in 10 9 (ppbv) with an averaging time of 60 s under stable flight conditions. HCHO mixing ratios in the range from 0.3 to 5 ppb were encountered during flight conditions. Some of the highest mixing ratios of HCHO were observed over heavily vegetated areas of Florida during the test flights where the ratios of HCHO to methacrolein and methyl vinyl ketone, measured by proton transfer mass spectroscopy, are consistent with formaldehyde production by isoprene oxidation. The highest mixing ratios of HCOOH, up to 10 ppbv, were observed in an aged forest fire plume encountered over northern Canada, in which ratios of HCOOH/CO are greater than previous observations, while the ratios of HCHO/CO are less than previous reports from forest fire plumes. Observations of HCHO/CO and HCOOH/CO in urban plumes are indicative of a mixture of sources from direct emissions and secondary oxidation of anthropogenic and biogenic hydrocarbons. The ability to measure both HCHO and HCOOH simultaneously is of value in assessing the oxidation mechanisms of atmospheric hydrocarbons and secondary organic aerosol formation and oxidation.

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.

We have developed a compact, robust, atmospheric trace gas detector based on mid-infrared absorption spectroscopy using pulsed quantum cascade (QC) lasers. The spectrometer is suitable for airborne measurements of ammonia, nitric acid, formaldehyde, formic acid, methane, nitrous oxide, carbon monoxide, nitrogen dioxide and other gases that have line-resolved absorption spectra in the mid-infrared spectral region. The QC laser light source operates near room temperature with thermal electric cooling instead of liquid nitrogen which has been previously required for semiconductor lasers in the mid-infrared spectral region. The QC lasers have sufficient output power so that thermal electric cooled detectors may be used in many applications with lower precision requirements. The instrument developed in this program has been used in several field campaigns from both the Aerodyne Mobile Laboratory and from the NOAA WP3 aircraft. The Phase II program has resulted in more than 10 archival publications describing the technology and its applications. Over 12 instruments based on this design have been sold to research groups in Europe and the United States making the program both a commercial as well as a technological success. Anticipated Benefits The development of a sensitive, cryogen-free, mid-infrared absorption method for atmospheric trace gas detection will have wide benefits for atmospheric and environmental research and broader potential commercial applications in areas such as medical diagnostic and industrial process monitoring of gaseous compounds. Examples include air pollution monitoring, breath analysis, combustion exhaust diagnostics, and plasma diagnostics for semi-conductor fabrication. The substitution of near-room temperature QC lasers for cryogenic lead salt TDLs and the resulting simplifications in instrument design and operation will greatly expand the range of applications.

A large and increasing fraction of the planet’s population lives in megacities, especially in the developing world. These large metropolitan areas generally have very high levels of both gaseous and particulate air pollutants that have severe impacts on human health, ecosystem viability, and climate on local, regional, and even continental scales. Emissions fluxes and ambient pollutant concentration distributions are generally poorly characterized for large urban areas even in developed nations. Much less is known about pollutant sources and concentration patterns in the faster growing megacities of the developing world. New methods of locating and measuring pollutant emission sources and tracking subsequent atmospheric chemical transformations and distributions are required. Measurement modes utilizing an innovative van based mobile laboratory equipped with a suite of fast response instruments to characterize the complex and “nastier” chemistry of the urban boundary layer are described. Instrumentation and measurement strategies are illustrated with examples from the Mexico City and Boston metropolitan areas. It is shown that fleet average exhaust emission ratios of formaldehyde (HCHO), acetaldehyde (CH3CHO) and benzene (C6H6) are substantial in Mexico City, with gasoline powered vehicles emitting higher levels normalized by fuel consumption. NH3 exhaust emissions from newer light duty vehicles in Mexico City exceed levels from similar traffic in Boston. A mobile conditional sampling air sample collection mode designed to collect samples from intercepted emission plumes for later analysis is also described.

The atmospheric abundances of carbon dioxide and methane have increased dramatically during the industrial era. Measurements of the isotopic composition of these gases can provide a powerful tool for quantifying their sources and sinks. This report describes the development of a portable instrument for isotopic analysis CO{sub 2} and CH{sub 4} using tunable infrared laser absorption spectroscopy. This instrument combines novel optical design and signal processing methods with a widely tunable mid-infrared laser source based on difference frequency generation (DFG) which will can access spectral regions for all the isotopes of CO{sub 2} and CH{sub 4} with a single instrument. The instrument design compensates for the large difference in concentration between major and minor isotopes by measuring them with path lengths which differ by a factor of 100 within the same multipass cell. During Phase I we demonstrated the basic optical design and signal processing by determining {sup 13}CO{sub 2} isotopic ratios with precisions as small as 0.2{per_thousand} using a conventional lead salt diode laser. During Phase II, the DFG laser source was coupled with the optical instrument and was demonstrated to detect {sup 13}CH{sub 4}/{sup 12}CH{sub 4} ratios with a precision of 0.5{per_thousand} and an averaging time of 20more » s using concentrated methane in air with a mixing ratio of 2700 ppm. Methods for concentrating ambient air for isotopic analysis using this technique have been evaluated. Extensions of this instrument to other species such as {sup 13}CO{sub 2}, C{sup 18}OO, and CH{sub 3}D are possible by substituting lasers at other wavelengths in the DFG source module. The immediate commercial application of this instrument will be to compete with existing mass spectrometric isotope instruments which are expensive, large and relatively slow. The novel infrared source developed in this project can be applied to the measurement of many other gas species and will have wide application in atmospheric monitoring, industrial process control, and medical research and diagnostic development.« less

The International Space Station Carbon Dioxide Removal Assembly (CDRA) uses regenerable adsorption technology to remove carbon dioxide (COP) from cabin air. Product water vapor measurements from a CDRA test bed at the NASA Marshall Space Flight Center were made using a tunable infrared diode laser differential absorption spectrometer (TILDAS) provided by NASA Glenn Research Center. The TILDAS instrument exceeded all the test specifications, including sensitivity, dynamic range, time response, and unattended operation. During the COP desorption phase, water vapor concentrations as low as 5 ppmv were observed near the peak of CO2 evolution, rising to levels of approx. 40 ppmv at the end of a cycle. Periods of high water concentration (>100 ppmv) were detected and shown to be caused by an experimental artifact. Measured values of total water vapor evolved during a single desorption cycle were as low as 1 mg.

[1] Eddy covariance flux measurements of NO, NO2, and O3 were obtained above the mixed deciduous canopy at Harvard Forest in central Massachusetts from April to November 2000. Net deposition of NOx was observed throughout the measurement period, with average velocity of ∼0.2 cm s−1. At night, NO2 is deposited at a rate that depends nonlinearly on NO2 concentration and cannot be explained by N2O5 hydrolysis, suggesting HONO formation by heterogeneous disproportionation of NO2. During the day, photochemically driven NOx fluxes conform to the predicted behavior based on gradients of light and eddy diffusivity through the canopy, with residual net flux attributable to both stomatal and nonstomatal processes. The results were consistent with a compensation point for NO2 near 1.5 nmol mol−1. These results were confirmed by independent evidence from NO, NO2, and O3 profiles acquired at the site over several years. If the rate of NOx deposition observed at this site in April through November continues during the winter, it would have a larger potential impact on tropospheric chemistry because mixing depths are shallow and chemical NOx oxidation is slow during winter; the impact at night is important for the same reasons. The results contradict widely used parameterizations of NO2 deposition that both overestimate stomatal uptake and do not allow for surface uptake when stomates are closed.

We report the application of quantum cascade (QC) lasers to measurement of atmospheric trace gases in both closed path and open path configurations. The QC laser, a recently available commercial device, is Peltier cooled and pulsed, with emission near 965 cm-1. We use direct absorption with a rapid sweep integration and spectral fits to derive absolute concentrations from tabulated line parameters without calibration. In the closed path configuration, with absorption in a long pathlength multipass cell (210 m, 50 Torr), we examined laser line widths and sensitivity limits. We measured ammonia with a precision of 0.05 nmole/mole (0.05 ppbv) RMS at 1 Hz, limited by detector noise. The laser linewith was 0.007 cm-1 HWHM, based on measurements of ethylene absorption line shapes with a current pulse width of ~14 ns. In the open path configuration, we measured ammonia in the exhaust of automobiles driving through a probe beam. Atmospheric pressure line broadening and turbulence limit the sensitivity, giving a column density noise level at 20 Hz of 1.4 ppm-m. We observed ammonia column densities up to 40 ppm-m in the exhaust plumes. In future systems we will include a CO2 channel, allowing normalization to fuel use rate.

A dual tunable diode laser absorption spectrometer (TDLAS) for continuous field measurement of nitric acid and nitrogen dioxide eddy covariance fluxes is described and preliminary field results are presented. The dual TDLAS simultaneously measures nitric acid (HNO3) and nitrogen dioxide (NO2) by direct absorption spectroscopy over a long path enclosed in an astigmatic Herriott multipass cell. The technique provides sufficient precision and time response (200 ppt RMS in 1 second) needed to record ambient variations and deposition rates by the eddy-covariance method. Real-time fitting of the integrated spectra over multiple absorption features makes the system appropriate for continuous field measurements while retaining the highly selective quality of direct absorption measurements and minimizing potential interferences. This method also produces an absolute, spectroscopic determination of concentration within the multipass cell, eliminating the need for calibrated gas mixtures in the field.© (1999) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

A dual infrared tunable diode laser system (IR-TDL) has been developed for the simultaneous detection of multiple gaseous components in cigarette smoke. The high spectral resolution (0.001 cm -1 ) and rapid time response (20 Hz) of the TDL system are ideal for separating the absorptions from the multitude of gas phase components found in this matrix. The combustion products are sampled into a 0.3 liter, 18 meter multiple pass absorption cell with a flow response time of 0.15 seconds, which provides ample time resolution to observe variations within each 2-second puff. Two independent beam paths allow simultaneous detection in two wavelength regions; the first for ethylene and ammonia and the second for formaldehyde. Rapid scan-sweep integration with direct absorption permits absolute gas concentrations to be determined on-line. A non-linear least squares procedure is used for “fingerprint” fitting of up to four gases with each diode. Results demonstrating the instrument sensitivity and time response, along with potential caveats, for several gaseous components will be presented.

This paper discusses recent advances in our techniques for monitoring atmospheric trace gases using lead salt liquid nitrogen cooled diode lasers. Our approach employs an optical system with all reflective optics. Our closed path systems rely on a proprietary astigmatic multipass cell to achieve long optical path lengths in a low volume sampling cell. We have also developed open path systems which we have used for remote sensing of automobile and aircraft engine exhaust. Our data acquisition method uses rapid frequency sweeping followed by nonlinear least squares analysis of the retrieved spectrum. Recent advances include an emphasis on multi-laser multi-species detection systems, such as simultaneously monitoring the nitric oxide, carbon monoxide and carbon dioxide concentrations in automobile exhaust. Other advances are focused on achieving improved detection sensitivity. In support of this goal, we have demonstrated astigmatic multipass cells with very long optical paths, we have improved the nonlinear least squares spectral fitting routines allowing them to fit complex multi-peak spectra and we have introduced photolytic modulation as a method to discriminate spectra of photolytically active species from background absorption and optical interference fringes. These techniques are being applied to the monitoring of a wide variety of atmospheric molecules including CH4, CO, CO2, N2O, NO, NO2, HONO, HNO3, O3 and HOCl.

Recent requirements for better characterization of the trace species in the exhausts of advanced aircraft engines have resulted in the development, under NASA sponsorship, of a tunable infrared diode laser system capable of making both in situ and extractive sampling measurements. In this paper, we describe the first application of this instrument to nonintrusive, cross-flow measurements in the exhaust of an aircraft engine operating in an altitude test cell. Simultaneous absorption measurements of NO, NO2 and H2O using the combined beams from two lasers were made at a variety of engine and flight conditions. The utility of measuring concentrations of major species such as H2O to convert line of sight observations of trace species into mass fluxes is discussed, as are uncertainties in the measurement resulting from fluctuations in the absorption spectra and from conversion from integrated column density to concentration profiles.© (1995) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

The atmospheric effects of stratospheric aircraft component of the NASA High Speed Research Program will require measurements of trace gas concentrations in the exhausts of high speed civil transport engines. In parallel with the development of these engines by NASA and its industrial partners, a portable infrared tunable diode laser apparatus has been assembled and tested which is capable of both in situ and extractive sampling of combustion gas flows. Infrared diode laser absorption is sensitive, quantitative, and applicable to a wide range of molecular species. In the present apparatus, sensitive detection is achieved by rapid frequency scanning and real-time nonlinear least squares fitting and background subtraction. Sensitivity is further increased for extractive sampling by an advanced design multiple pass cell which gives longer path lengths in smaller volumes. Observations of a laboratory flat flame burner are reported. These observations and spectroscopic models are used to predict detection sensitivities in exhausts and other combustion systems.

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 (TILDAS). 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 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.