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Soil microbes vigorously produce and consume gases that reflect active soil biogeochemical processes. Soil gas measurements are therefore a powerful tool to monitor microbial activity. Yet, the majority of soil gases lack non-disruptive subsurface measurement methods at spatiotemporal scales relevant to microbial processes and soil structure. To address this need, we developed a soil gas sampling system that uses novel diffusive soil probes and sample transfer approaches for high-resolution sampling from discrete subsurface regions. Probe sampling requires transferring soil gas samples to above-ground gas analyzers where concentrations and isotopologues are measured. Obtaining representative soil gas samples has historically required balancing disruption to soil gas composition with measurement frequency and analyzer volume demand. These considerations have limited attempts to quantify trace gas spatial concentration gradients and heterogeneity at scales relevant to the soil microbiome. Here, we describe our new flexible diffusive probe sampling system integrated with a modified, reduced volume trace gas analyzer and demonstrate its application for subsurface monitoring of biogeochemical cycling of nitrous oxide (N2O) and its site-specific isotopologues, methane, carbon dioxide, and nitric oxide in controlled soil columns. The sampling system observed reproducible responses of soil gas concentrations to manipulations of soil nutrients and redox state, providing a new window into the microbial response to these key environmental forcings. Using site-specific N2O isotopologues as indicators of microbial processes, we constrain the dynamics of in situ microbial activity. Unlocking trace gas messengers of microbial activity will complement -omics approaches, challenge subsurface models, and improve understanding of soil heterogeneity to disentangle interactive processes in the subsurface biome.

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.

Microbial metabolic functions and biogeochemical pathways of the complex rhizosphere-soil-microbe interactions change with aboveground vegetation and the ecosystem response to environmental changes. Soil trace gases and current genomic approaches have been valuable to characterize in-situ microbial activity. However, there is a lack of understanding of the complexity of the belowground processes, the time frame of microbial community responses to environmental changes and the degree to which microbial activity can be inferred current -omics approaches. In the nitrogen cycling at a field scale, microbial diversity or gene abundance sometimes does not explain N2O emissions or even gene expression, there some bacteria that cannot be cultivated, and in general –omics involve destructive soil sampling that is prone to changes of the in-situ soil conditions. Additionally, field soil sampling may not capture the heterogeneity of the soil or specific area of study.Volatile Organic Compounds (VOCs) produced in the rhizosphere play an important role in microbial nutrient cycling. VOCs are produced by plants and microorganisms as a response to biotic or biotic stressors or the type of carbon sources available.Here, we present how subsurface soil gas measurements in an enclosed ecosystem during the Water, Atmosphere, and Life Dynamics experiment (B2-WALD) at the Tropical Rainforest biome of Biosphere 2 (Arizona, USA) during an induced controlled drought. We present initial results of a unique non-destructive approach that simultaneously couples a) new hydrophobic-porous subsurface soil probes, b) high-resolution Tunable Infrared Laser Direct Absorption Spectrometers (TILDAS) to analyze in situ trace gas isotopomers, and c) a proton transfer reaction mass spectrometer (VOCUS, high resolution volatile organic compound gas analyzer) for VOC quantification. We measured soil gas isotopic composition of N2O and VOCs-- comparing rhizosphere and control areas before and during the drought. We will focus our discussion on VOCs and its potential as makers of microbial interactions and signaling as a response to an environmental stressor like drought.In this project, we demonstrate the feasibility of online coupling of soil probes with high-resolution instrumentation to measure products from nitrogen cycling and nonmethane VOC production in soils as a response to soil-plant microbe interactions. In addition, this approach could be a potential tool to constraint inferences derived from different –omics approaches.

Soil gases are efficient messengers of the subsurface biogeochemical processes that underlie important nutrient cycles. Recent advances in subsurface gas sampling techniques can be combined with high precision trace gas instrumentation to yield novel insights into these processes and their mechanisms.We present measurements of a wide range of trace gases before, during, and after a simulated rainfall upon northeastern US temperature forest soil in meso-scale columns. Subsurface concentrations and above-ground fluxes of N2O and its isotopes, CH4 and its isotopes, CO2, NO, NO2, NH3, and a wide range of volatile organic compounds (e.g. monoterpenes, sesquiterpenes, isoprene, acetonitrile, aromatics) were quantified in real time with 30 minute temporal resolution. Small molecules were measured using Aerodyne TILDAS instruments, while VOCs were measured using a Vocus mass spectrometer.Addition of water to the dried soil column produced a classic Birch effect pulse of both C and N species, including for VOCs. We explore correlations between responses of trace gases above- and below-ground, and relate the small molecule pulses to the larger VOC responses. In addition, we demonstrate the value of isotopic signatures for these studies, with the observation of fast, large isotopic shifts in the 15N2O isotopomers. We compare these isotopic signatures to simple kinetic models to provide insight into the mechanisms underlying the nitrogen Birch effect.

The direct measurement of soil gases provides insight into the biogeochemical processes responsible for micro- and macro-nutrient cycling, respiration, signaling, and environmental responses. The concentrations and isotopic signatures of soil gases are effective messengers of the microbial pathways active in the soil. We have developed and deployed a high frequency sensor consisting of new diffusive soil probes coupled with a Tunable Infrared Laser Direct Absorption Spectrometer (TILDAS) to monitor a range of soil gas species to investigate biogeochemical soil processes.An array of soil probes was deployed at the Tropical Rainforest at Biosphere 2 in Arizona as part of the Water Atmosphere and Life Dynamics (WALD) experiment in 2019-2020. Probes were located in a root zone and nearby control area, and at several depths via a soil pit. These probes were coupled with a TILDAS to monitor isotopologues of nitrous oxide (N2O) including 14N15NO, 15N14NO, N218O, and methane (13CH4 and 12CH4), as well as CO2. During the WALD experiment, the probe-TILDAS system followed the impact on the soil biome of a 2 month induced drought in the rainforest and the subsequent return of rain. The high temporal resolution of the system allowed us to monitor each probe every 2 hours and thus observe changes in the composition of soil gases that reflect biogeochemical processes and pathways. CO2 and thus respiration decreased significantly during the drought and was slow to recover. Differences in N2O mixing ratios and isotopic signatures (both site preference and bulk 15N) in the root zone versus a controlled soil region were observed during both drought and rewetting periods. Changes in nitrogen and carbon cycles and the microbial pathways during the induced drought and rewetting as reflected in these observations will be discussed.

Modern microbial and ecosystem sciences require diverse interdisciplinary teams that are often challenged in “speaking” to one another due to different languages and data product types. Here we introduce the IsoGenie Database (IsoGenieDB; https://isogenie-db.asc.ohio-state.edu/), a de novo developed data management and exploration platform, as a solution to this challenge of accurately representing and integrating heterogenous environmental and microbial data across ecosystem scales. The IsoGenieDB is a public and private data infrastructure designed to store and query data generated by the IsoGenie Project, a ~10 year DOE-funded project focused on discovering ecosystem climate feedbacks in a thawing permafrost landscape. The IsoGenieDB provides (i) a platform for IsoGenie Project members to explore the project’s interdisciplinary datasets across scales through the inherent relationships among data entities, (ii) a framework to consolidate and harmonize the datasets needed by the team’s modelers, and (iii) a public venue that leverages the same spatially explicit, disciplinarily integrated data structure to share published datasets. The IsoGenieDB is also being expanded to cover the NASA-funded Archaea to Atmosphere (A2A) project, which scales the findings of IsoGenie to a broader suite of Arctic peatlands, via the umbrella A2A Database (A2A-DB). The IsoGenieDB’s expandability and flexible architecture allow it to serve as an example ecosystems database.

We present precise measurements of doubly deuterated methane (

We review our recent results in development of high-precision laser spectroscopic instrumentation using mid-infrared quantum cascade lasers, interband cascade lasers and antimonide diode lasers. These instruments are primarily for high-precision and high-sensitivity measurements of atmospheric trace gases, as required for atmospheric research. The instruments are based on direct absorption spectroscopy with rapid sweeps, integration and precision fitting, under the control of high-capability software. By operating in the mid-infrared with long absorption path lengths at reduced pressure, we achieve excellent sensitivity. Some instruments have demonstrated a fractional precision of 10−4 for atmospheric trace gases at ambient concentration, allowing real-time isotopologue measurements of CO2, CO, CH4, N2O and H2O. Trace gas detection in ambient air at the low part-per-trillion levels is feasible. We also describe signal processing methods to identify and reduce measurement noise. Analysis of spectral information is largely based on loading spectra into arrays and then applying block operations such as filters, Fourier analysis, multivariate fitting and principal component analysis. We present mathematical expressions for averaged spectra in arrays and note different ways frequency aliasing can occur. We present an extended example of analysis of instrument noise and find an electronic signal mixing with an interference fringe.

Data from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Reference Method for monitoring the ambient concentrations of NO2. Measurements of NO2 from standard chemiluminescence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measurement is shown to account for up to 50% of ambient NO2 concentration during afternoon hours. As expected, this interference correlates well with non-NOx reactive nitrogen species (NOz) as well as with ambient O3 concentrations, indicating a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the percentage contribution of HNO3 to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concentrations as high as several ppb inside the city, on par with the highest values previously observed in other urban locations. Averaged over the MCMA-2003 field campaign, the chemiluminescence monitor interference resulted in an average measured NO2 concentration up to 22% greater than that from co-located spectroscopic measurements. Thus, this interference has the potential to initiate regulatory action in areas that are close to non-attainment and may mislead atmospheric photochemical models used to assess control strategies for photochemical oxidants.

The equilibrium inorganic aerosol model ISORROPIA was embedded in a Markov Chain Monte Carlo algorithm to develop a powerful tool to analyze aerosol data and predict gas phase concentrations where these are unavailable. The method directly incorporates measurement uncertainty, prior knowledge, and provides a formal framework to combine measurements of different quality. The method was applied to particle- and gas-phase precursor observations taken at La Merced during the Mexico City Metropolitan Area (MCMA) 2003 Field Campaign and served to discriminate between diverging gas-phase observations of ammonia and predict gas-phase concentrations of hydrochloric acid. The model reproduced observations of particle-phase ammonium, nitrate, and sulfate well. The most likely concentrations of ammonia were found to vary between 4 and 26 ppbv, while the range for nitric acid was 0.1 to 55 ppbv. During periods where the aerosol chloride observations were consistently above the detection limit, the model was able to reproduce the aerosol chloride observations well and predicted the most likely gas-phase hydrochloric acid concentration varied between 0.4 and 5 ppbv. Despite the high ammonia concentrations observed and predicted by the model, when the aerosols were assumed to be in the efflorescence branch they are predicted to be acidic (pH~3).

A quantum cascade laser operating near room temperature with thermoelectric (TE) cooling has been used in both continuous-wave (cw) mode (-9 °C) and pulsed mode (+45 °C) to detect atmospheric nitric oxide using spectral lines at 1900.07 cm-1 (5.3 μm). The totally non-cryogenic spectrometer integrates the laser with a 69-m astigmatic multi-pass cell and a TE-cooled infrared detector to enable operation for extended time periods without operator attention. The pattern of reflections on the astigmatic cell mirrors has been designed to minimize optical interference fringes, which are substantially greater with cw mode than with pulsed operation. The detection method uses direct absorption with rapid- scan sweep integration to achieve sub-second time response. Detection precision for NO in air of 0.5 parts in 109 Hz-1/2 (1σ) is obtained in pulsed mode with an Allan variance minimum corresponding to 0.1 parts in 109 after 30-s averaging time. The precision in cw mode improves to 0.1 parts in 109 Hz-1/2 and 0.03 parts in 109 after 30-s averaging, corresponding to an absorbance per unit path length of 2×10-10 cm-1. The advantages and disadvantages of cw compared to pulsed operation are discussed.

We describe a prototype instrument using a Peltier cooled quantum cascade laser for precise measurement of stable carbon (13C/12C) isotopologue ratios in atmospheric CO2. Using novel optics and signal processing techniques in a compact instrument, we are able to detect the difference between sample and reference with a precision of 0.1‰ (2σ standard error of mean of 11 samples) in 10min of analysis time. The standard deviation of 0.18‰ for individual 30 s measurements shows that this prototype instrument already approaches the best reported literature values using continuous wave lead alloy tunable diode lasers. The application of pulsed near room-temperature quantum cascade lasers to this demanding problem opens the possibility of field worthy rapid response isotopic instrumentation and attests to the maturity of these lasers as spectroscopic sources.

The Aerodyne Mobile Laboratory "chased" in-use curbside passenger buses operated by various operators in New York City. With the cooperation of New York State's Metropolitan Transit Authority, the relationships between the emissions of the several gas-phase species and particulate loadings were investigated across several bus technologies, bus types, and fuels (diesel, ultralow sulfur diesel, and compressed natural gas, CNG). The CNG buses followed did not employ an oxidation catalyst. The buses characterized were not prescreened in any fashion and were measured while deployed on their normal in-service routes. This paper focuses on the fuel-based mass emissions of SO2, H2CO, and CH4, measured using tunable infrared laser differential absorption spectroscopy. Sulfur dioxide emissions from buses known to be burning ultralow sulfur diesel (

We used a tunable diode laser absorption spectrometer to follow the condensation of D(2)O in a supersonic Laval nozzle. We measured both the concentration of the condensible vapor and the spectroscopic temperature as a function of position and compared the results to those inferred from static pressure measurements. Upstream and in the early stages of condensation, the quantitative agreement between the different experimental techniques is good. Far downstream, the spectroscopic results predict a lower gas phase concentration, a higher condensate mass fraction, and a higher temperature than the pressure measurements. The difference between the two measurement techniques is consistent with a slight compression of the boundary layers along the nozzle walls during condensation.

In August 2001, the Aerodyne Mobile Laboratory simultaneously measured NO, NO2, and CO2 within 350 m of a taxiway and 550 m of a runway at John F. Kennedy Airport. The meteorological conditions were such that taxi and takeoff plumes from individual aircraft were clearly resolved against background levels. NO and NO2 concentrations were measured with 1 s time resolution using a dual tunable infrared laser differential absorption spectroscopy instrument, utilizing an astigmatic multipass Herriott cell. The CO2 measurements were also obtained at 1 s time resolution using a commercial non-dispersive infrared absorption instrument. Plumes were measured from over 30 individual planes, ranging from turbo props to jumbo jets. NOx emission indices were determined by examining the correlation between NOx (NO + NO2) and CO2 during the plume measurements. Several aircraft tail numbers were unambiguously identified, allowing those specific airframe/engine combinations to be determined. The resulting NOx emission indices from positively identified in-service operating airplanes are compared with the published International Civil Aviation Organization engine certification test database collected on new engines in certification test cells.

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.

Infrared absorption lines of hydrazine are broad and typically not baseline resolved, with line strengths approximately 100 times weaker than the more widely studied compound ammonia. Hardware and software improvements have been made to a two-color infrared tunable diode laser (IR-TDL) spectrometer in order to improve the limit of detection (LOD) of hydrazine (N2H4) in the cigarette smoke matrix. The detection limit in the smoke matrix was improved from 25 parts-per-million-by-volume (ppmv) to 4.2 ppmv using a 100 m pathlength cell with acquisition of background spectra immediately prior to each sample and 100 ms temporal resolution. This study did not detect hydrazine in cigarette smoke in the 964.4-964.9 cm(-1) spectral region, after mathematically subtracting the spectral contributions of ethylene, ammonia, carbon dioxide, methanol, acrolein, and acetaldehyde. These compounds are found in cigarette smoke and absorb in this spectral region. The LOD is limited by remaining spectral structure from unidentified smoke species. The pseudo random noise (root mean square) in the improved instrument was 2 x 10(-4) absorbance units (base e) which is equivalent to a 0.09 ppmv hydrazine gas sample in the multipass cell. This would correspond to a detection limit of 0.44 ppmv of hydrazine, given the dilution of the smoke by a factor of 5 by the sampling system. This is a factor of 10 less than the 4.2 ppmv detection limit for hydrazine in the smoke matrix, and indicates that the detection limit is primarily a result of the complexity of the matrix rather than the random noise of the TDL instrument.

Non-cryogenic, laser-absorption spectroscopy in the mid-infrared has wide applications for practical detection of trace gases in the atmosphere. We report measurements of nitric oxide in air with a detection limit less than 1 nmole/mole (

Infrared line positions, linestrengths, and pressure-broadening coefficients are required to determine absolute trace gas concentrations from high-resolution absorption spectra. We have measured these values for the infrared absorption lines in the ν 12 band (antisymmetric wag) of hydrazine between 965.4 and 965.7 cm −1 using a high-resolution tunable diode laser system with 0.0006 cm −1 spectral resolution and an 18-m path length multiple pass absorption cell. A continuous flow of hydrazine diluted to 100–500 parts per million in nitrogen at pressures between 0.1 and 50 Torr was used to prevent decomposition in the sampling cell. The total integrated linestrength from 965.477 to 965.663 cm −1 is (2.20±0.14)×10 −20 cm 2 molecule −1 cm −1 . The strongest line in this region at 965.5557 cm −1 has a strength of 2.8×10 −21 cm 2 molecule −1 cm −1 . The only isolated line in this region, at 965.4905 cm −1 , has a broadening coefficient by nitrogen of 0.11±0.01 cm −1 atm −1 at 295 K. These results are compared to the qualitative high resolution spectra determined by other researchers using FTIR spectroscopy, and have been used to construct a HITRAN-format line list that can be used both to spectroscopically distinguish hydrazine from other components and to determine its concentration in a complex gas phase mixture.

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 (eN 2 O), and carbon dioxide (eCO 2 ) 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 eN 2 O nor eCO 2 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.

An infrared spectroscopic technique has been developed to measure ammonia, ethylene, and formaldehyde in single puffs of whole cigarette smoke with millisecond resolution. Since formaldehyde levels in smoke decrease with increasing ammonia levels, this effect was studied by simultaneous measurement of the two compounds during a puff. Ethylene was measured since it is inert and hydrophobic. The spectral lines chosen for quantitation were determined to be linear with concentration and free from interferences from other smoke constituents. The limit of detection for ammonia at 965.353 cm −1 was 2 ng (80 ppbv) and for ethylene at 965.459 cm −1 was 324 ng (8 ppmv) in a puff of 35 ml volume and 2 s duration. Others have reported that hydrazine is present in smoke at 70 ppbv per puff using trapping and derivatization methods. Attempts here to detect hydrazine in smoke without trapping and derivatization were unsuccessful at the current limit of detection of 25 ppm in the 958 cm −1 spectral region. This limit is due to interferences from unidentified smoke components. The reactivity of hydrazine in smoke was determined by adding 520 ppm hydrazine to the smoke matrix, where 83% was consumed in the first second of a three-second sample.

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 (

Published estimates of removal of atmospheric methyl bromide (CH3Br) by agricultural soils are 2.7 Gg yr−1 (Gg = 109 g) [Shorter et al., 1995] and 65.8 Gg yr−1 [Serca et al., 1998]. The Serca et al. estimate, if correct, would suggest that the current value for total removal of atmospheric CH3Br by all sinks of 206 Gg yr−1 (based on Shorter et al., 1995) would be 30% too low. We have calculated a new rate of global agricultural soil uptake of atmospheric CH3Br from a larger sampling of cultivated soils collected from 40 sites located in the United States, Costa Rica, and Germany. First order reaction rates were measured during static laboratory incubations. These data were combined with uptake measurements we reported earlier based on field and laboratory experiments [Shorter et al. 1995]. Tropical (10.2°–10.4°N) and northern (45°–61°N) soils averaged lower reaction rate constants than temperate soils probably due to differing physical and chemical characteristics as well as microbial populations. Our revised global estimate for the uptake of ambient CH3Br by cultivated soils is 7.47±0.63 Gg yr−1, almost three times the value that we reported in 1995.

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.

Methane (CH4) emissions were measured from the Nashua, New Hampshire municipal landfill using static enclosure and atmospheric tracer methods. The spatial variability of emissions was also examined using geostatistical methods. One hundred and thirty nine enclosure measurements were performed on a regular grid pattern over the emitting surface of the landfill resulting in an estimate of whole landfill emissions of 15,800 L CH4 min−1. Omnidirectional variograms displayed spatial correlation among CH4 fluxes below a separation distance of 7 m. Eleven tracer tests, using sulfur hexafluoride (SF6) as a tracer gas, resulted in a mean emissions estimate of 17,750 L CH4 min−1. The favorable agreement between the emission estimates was further refined using the observed relationship between atmospheric pressure and CH4 flux. This resulted in a pressure-corrected tracer flux estimate of whole landfill emissions of 16,740 L CH4 min−1.

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.

Field measurements of methane emissions from landfills are essential if one is to accurately constrain uncertainties in current estimates of global methane emissions from landfills and document emissions reductions realized by currently available control technology. Two experimental techniques for the measurement of methane flux from landfills, flux chamber measurements and tracer flux techniques, have been evaluated at a 24 hectare landfill site in New England. Agreement between the two techniques was quite good, with the flux chamber technique giving a landfill wide methane flux of 16.4 m 3 CH 4 min -1 while a series of seven tracer flux tests resulted in a mean flux of 17.8 m 3 CH 4 min -1 . Model estimates suggest that the installation of gas recovery measures at the five largest landfill sites in the state of New Hampshire and the ten largest sites in Massachusetts would reduce landfill emissions in each state by approximately 75%, resulting in a total emissions reduction of 65 x 10 9 g CH 4 /yr.

Methyl bromide (CH(3)Br) is considered to be a major source of stratospheric Br, which contributes to the destruction of ozone. It is therefore necessary to understand the natural sinks of this compound and to accurately measure ambient mixing ratios. Methodology is described for the measurement of atmospheric CH(3)Br by cryotrapping-gas chromatography and its application to soil kinetics. A 2-propanol/dry ice cryotrap was used to preconcentrate CH(3)Br in standard and air samples, with subsequent detection using a gas chromatograph equipped with an O(2)-doped electron capture detector (GC-ECD). The GC-ECD cryotrapping method had a detection limit of 0.23 pmol of CH(3)Br. This is equivalent to the amount of CH(3)Br in a 500 mL sample of ambient air at the estimated northern hemisphere atmospheric mixing ratio of 11 parts per trillion by volume (pptv). A dynamic dilution system was developed to produce mixing ratios of CH(3)Br ranging between 4 and 1000 pptv. Calibrated mixing ratios of CH(3)Br produced with the dilution system were used to determine soil uptake kinetics employing a dynamic soil incubation method.

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 NO(v,J)‐fragment population distributions and recoil energies were measured for the vibrational predissociation of NO⋅HF following excitation of the H–F stretch. Most of the available energy appears in NO vibration and/or HF rotation. There is little recoil momentum. All NO(v,J) fragments are formed with near δ‐function recoil kinetic energies, correlated with HF fragments in a single rotational level. Two dissociation channels proceed with similar probability to produce NO(v=0) and NO(v=1). Only two rotational levels of HF are populated. One of the HF rotational states is correlated exclusively with NO(v=0) fragments, the other is paired with NO(v=1) fragments. Constraints on fragment angular momenta as well as energetics appear important for the dissociation dynamics. The presence of significant amounts of vibrationally excited NO fragments, in the absence of observable spectroscopic perturbations, implies that intramolecular vibrational redistribution proceeds as the dimer dissociates. The data sup...

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.

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.

We have developed a compact instrument for sensitive, rapid and continuous measurement of trace gases in air, with results presented here for methane (CH4), nitric oxide (NO), nitrous oxide (N2O) and ammonia (NH3). This instrument takes advantage of recent technology in quantum cascade (QC) lasers and infrared detectors, which allows high sensitivity without cryogenic liquids, e.g., 0.2 ppb (0.2×10-9) of NH3 in air in 1 s. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument operates continuously, requiring little operator attention, and web-based remote access is provided for instrument control, calibration and data retrieval. The instrument design includes a thermoelectrically (TE) cooled pulsed distributed feedback (DFB) QC laser, a low volume (0.5 l) multipass cell offering 76 m absorption path length and a TE cooled detector. Integrated software for laser control and data analysis using direct absorption provides quantitative trace gas measurements without calibration gases. The instrument may be applied to field measurements of gases of environmental concern.

We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.

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.

[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.

Infrared rotational line-broadening coefficients in air are one of the parameters required to determine absolute trace gas concentrations from high-resolution absorption spectra. Air-broadening coefficients have been measured for two infrared absorption lines of the ν 2 band of HO 35 Cl; the 8 1,7 ←7 1,6 and 14 1,14 ←13 1,13 lines at 1247.3169 and 1252.8437 cm −1 , respectively. We obtain values of 0.112 cm −1 atm −1 [half-width half-maximum (HWHM)] for the J″ = 7 line and 0.0955 cm −1 atm −1 (HWHM) for the J″ = 13 line. These measurements were made over the pressure range 2–200 Torr (760 Torr atm −1 ) using a high-resolution tunable diode laser system with an optical pathlength of 100 m. The results of these measurements are essential for the implementation of such an instrument to measure HOCl in the lower atmosphere.

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.

New diesel engine technologies and alternative fuel engines are being introduced into fleets of mass transit buses to try to meet stricter emission regulations of nitrogen oxides and particulates. Real-time instruments including an Aerodyne Research tunable infrared laser differential absorption spectrometer (TILDAS) were deployed in a mobile laboratory to assess the impact of the implementation of the new technologies on nitrogen oxide emissions in real world driving conditions. Using a "chase" vehicle sampling strategy, the mobile laboratory followed target vehicles, repeatedly sampling their exhaust. Nitrogen oxides from approximately 170 in-use New York City mass transit buses were sampled during the field campaigns. Emissions from conventional diesel buses, diesel buses with continuously regenerating technology (CRT), diesel hybrid electric buses, and compressed natural gas (CNG) buses were compared. The chase vehicle sampling method yields real world emissions that can be included in more realistic emission inventories. The NOx emissions from the diesel and CNG buses were comparable. The hybrid electric buses had approximately one-half the NOx emissions. In CRT diesels, NO2 accounts for about one-third of the NOx emitted in the exhaust, while for non-CRT buses the NO2 fraction is less than 10%. (A)

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.

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.

We present an overview of the dual QC laser spectrometer developed at Aerodyne Research and various examples of its application for atmospheric trace gas detection. The instrument incorporates two pulsed QC lasers, a compact 76-m (or 56-m) multipass absorption cell, a dual HgCdTe detector, and a sophisticated signal generation, data acquisition and processing system. Recent findings and hardware innovations are highlighted. Our results show that the precision and minimal detectable absorbance obtainable with pulsed QC lasers are comparable to those achieved with cryogenically cooled CW Pb-salt lasers in spite of the broader laser linewidths inherent to pulsed operation. This is demonstrated through in situ measurements of several trace gases, including methane, nitrous oxide, carbon monoxide, formaldehyde, formic acid, nitrous acid and ethylene. Recent measurements of HCHO and HCOOH on board a NOAA aircraft are presented. The precision, stability and intrinsic accuracy of the instrument were assessed through inter-comparisons measuring CH4 and CO. These measurements were made either comparing two QC lasers sweeping over different transitions or comparing the dual QCL spectrometer and a standard instrument (NDIR CO). The absorbance precision achieved is typically 2x10-5 Hz-1/2. For long-lived species, such as CH4 and N2O, this implies 1-Hz fractional precisions of 0.1% or better, which fulfill the requirement for meaningful measurements from aircraft platforms. Spectroscopically derived mixing ratios are accurate within 5% or better. The spectrometer is equipped to perform automatic, periodic calibrations with zero and span gases whenever higher accuracy is required.

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.