Chad Roller

Mid-infrared quantum cascade laser based off-axis integrated cavity output spectroscopy for biogenic nitric oxide detection

Tunable-laser absorption spectroscopy in the mid-IR spectral region is a sensitive analytical technique for trace-gas quantification. The detection of nitric oxide (NO) in exhaled breath is of particular interest in the diagnosis of lower-airway inflammation associated with a number of lung diseases and illnesses. A gas analyzer based on a continuous-wave mid-IR quantum cascade laser operating at approximately 5.2 microm and on off-axis integrated cavity output spectroscopy (ICOS) has been developed to measure NO concentrations in human breath. A compact sample cell, 5.3 cm in length and with a volume of < 80 cm3, that is suitable for on-line and off-line measurements during a single breath cycle, has been designed and tested. A noise-equivalent (signal-to-noise ratio of 1) sensitivity of 10 parts in 10(9) by volume (ppbv) of NO was achieved. The combination of ICOS with wavelength modulation resulted in a 2-ppbv noise-equivalent sensitivity. The total data acquisition and averaging time was 15 s in both cases. The feasibility of detecting NO in expired human breath as a potential noninvasive medical diagnostic tool is discussed.

Pulsed quantum-cascade laser-based sensor for trace-gas detection of carbonyl sulfide

Simultaneous exhaled carbonyl sulfide (OCS) and carbon dioxide concentration measurements in human breath are demonstrated with a compact pulsed quantum-cascade laser-based gas sensor. We achieved a noise-equivalent sensitivity (1sigma) of 1.2 parts per billion by measuring a well-isolated OCS P(11) absorption line in the v3 band at 2057.6 cm(-1) using an astigmatic Herriott cell of 36-m optical path length and 0.4-s acquisition time.

Monitoring of ethylene by a pulsed quantum cascade laser

We report on the development and performance of a gas sensor based on a quantum cascade laser operating at a wavelength of approximately 10 microns to measure ethylene (C2H4) concentrations by use of a rotational component of the fundamental nu 7 band. The laser is thermoelectrically cooled and operates in a pulsed mode. The influence of pulse-to-pulse fluctuations is minimized by use of a reference beam and a single detector with time discriminating electronics. Gas absorption is recorded in a 100-m optical path-length astigmatic Herriott cell. With a 10-kHz pulse repetition rate and an 80-s total acquisition time, a noise equivalent sensitivity of 30 parts per billion has been demonstrated. The sensor has been applied to monitor C2H4 in vehicle exhaust as well as in air collected in a high-traffic urban tunnel.

Role of convection in redistributing formaldehyde to the upper troposphere over North America and the North Atlantic during the summer 2004 INTEX campaign

Measurements of formaldehyde (CH2O) from a tunable diode laser absorption spectrometer (TDLAS) were acquired onboard the NASA DC-8 aircraft during the summer 2004 INTEX-NA campaign to test our understanding of convection and CH2O production mechanisms in the upper troposphere (UT, 6–12 km) over continental North America and the North Atlantic Ocean. The present study utilizes these TDLAS measurements and results from a box model to (1) establish sets of conditions by which to distinguish “background” UT CH2O levels from those perturbed by convection and other causes; (2) quantify the CH2O precursor budgets for both air mass types; (3) quantify the fraction of time that the UT CH2O measurements over North America and North Atlantic are perturbed during the summer of 2004; (4) provide estimates for the fraction of time that such perturbed CH2O levels are caused by direct convection of boundary layer CH2O and/or convection of CH2O precursors; (5) assess the ability of box models to reproduce the CH2O measurements; and (6) examine CH2O and HO2 relationships in the presence of enhanced NO. Multiple tracers were used to arrive at a set of UT CH2O background and perturbed air mass periods, and 46% of the TDLAS measurements fell within the latter category. In general, production of CH2O from CH4 was found to be the dominant source term, even in perturbed air masses. This was followed by production from methyl hydroperoxide, methanol, PAN-type compounds, and ketones, in descending order of their contribution. At least 70% to 73% of the elevated UT observations were caused by enhanced production from CH2O precursors rather than direct transport of CH2O from the boundary layer. In the presence of elevated NO, there was a definite trend in the CH2O measurement–model discrepancy, and this was highly correlated with HO2 measurement–model discrepancies in the UT.

Measurement of acetaldehyde in exhaled breath using a laser absorption spectrometer

A high-resolution liquid-nitrogen-free mid-infrared tunable diode laser absorption spectroscopy (TDLAS) system was used to perform real-time measurement of acetaldehyde concentrations in human exhaled breath following ingestion of an alcoholic beverage. Acetaldehyde absorption features were measured near 5.79 mum (1727 cm(-1)) using a IV-VI semiconductor laser, a 100 m long path optical gas cell, and second- harmonic detection coupled with wavelength modulation. Acetaldehyde levels were measured with a minimum detection limit of 80 ppb for 5 s integration time. The variations in exhaled acetaldehyde levels over time were analyzed prior to and following ingestion of two different amounts of white wine. A method to calibrate acetaldehyde measurements internally using water vapor absorption lines was investigated to eliminate the need for system calibration with gas standards. The potential of a TDLAS system to be used as a noninvasive clinical tool for measurements of large volatile compounds with possible applications in cancer detection is demonstrated.

Breath-Analysis Using Mid-Infrared Tunable Laser Spectroscopy

Breath analysis is becoming an attractive technique for the noninvasive monitoring of various molecular constituents in exhaled breath. Nitric oxide (NO) is a widely studied biomarker in breath and is known to indicate the lower airway inflammation associated with asthma. A mid-IR laser-based spectroscopic sensor and associated electronics were designed to measure exhaled NO simultaneously with CO2. To evaluate the sensor performance, a large observational clinical field study consisting of more than 2200 volunteers was performed over a period of two years. The generated distributions of the measured exhaled NO and CO2 levels were found to be log-normal and Gaussian, respectively. In addition, preliminary results of measuring exhaled nitrous oxide (N2O) are given as well as suggestions for future applications in infectious disease.

Measurement of exhaled nitric oxide in beef cattle using tunable diode laser absorption spectroscopy

Measurement of nitric oxide (NO) in the expired breath of crossbred calves received at a research facility was performed using tunable diode laser absorption spectroscopy. Exhaled NO (eNO) concentrations were measured using NO absorption lines at 1912.07 cm(-1) and employing background subtraction. The lower detection limit and measurement precision were determined to be approximately 330 parts in 10(12) per unit volume. A custom breath collection system was designed to collect lower airway breath of spontaneously breathing calves while in a restraint chute. Breath was collected and analyzed from calves upon arrival and periodically during a 42 day receiving period. There was a statistically significant relationship between eNO, severity of bovine respiratory disease (BRD) in terms of number of times treated, and average daily weight gain over the first 15 days postarrival. In addition, breathing patterns and exhaled CO2 showed a statistically significant relationship with BRD morbidity.

Carbon isotopomers measurement using mid-IR tunable laser sources

Recent developments of two mid-infrared tunable laser spectrometers dedicated to carbon isotope ratio determination are presented. First, a field deployable quantum cascade laser-based sensor is described, along with line selection strategy for 13/12CO2 ratio measurements. Secondly, an instrument architecture based on difference frequency generation is presented. The analyses of fundamental limitations, specifically temperature and pressure stability, and water vapor collision broadening, are detailed.

IV-VI semiconductor lasers for gas phase biomarker detection

A promising absorption spectroscopy application for mid-IR lasers is exhaled breath analysis where sensitive, selective, and speedy measurement of small gas phase biomarker molecules can be used to diagnose disease and monitor therapies. Many molecules such as nitric oxide, ethane, formaldehyde, acetaldehyde, acetone, carbonyl sulfide, and carbon disulfide have been connected to diseases or conditions such as asthma, oxidative stress, breast cancer, lung cancer, diabetes, organ transplant rejection, and schizophrenia. Measuring these and other, yet to be discovered, biomarker molecules in exhaled breath with mid-IR lasers offers great potential for improving health care since such tests are non-invasive, real-time, and do not require expensive consumables or chemical reagents. Motivated by these potential benefits, mid-IR laser spectrometers equipped with presently available cryogenically-cooled IV-VI lasers mounted in compact Stirling coolers have been developed for clinical research applications. This paper will begin with a description of the development of mid-IR laser instruments and their use in the largest known exhaled breath clinical study ever performed. It will then shift to a description of recent work on the development of new IV-VI semiconductor quantum well materials and laser fabrication methods that offer the promise of low power consumption (i.e. efficient) continuous wave emission at room temperature. Taken together, the demonstration of compelling clinical applications with large market opportunities and the clear identification of a viable pathway to develop low cost mid-IR laser instrumentation can create a renewed focus for future research and development efforts within the mid-IR materials and devices area.

Chemical sensors based on quantum cascade lasers

Quantum cascade lasers operating in the 3.5 to 24 micron spectral range can be used for trace gas detection in ambient air based on absorption spectroscopy. Recent advances in spectroscopic detection techniques have been employed to achieve minimum detectable absorption coefficients of 10/sup -9/ cm/sup -1/ in several real world applications.