We have constructed a cavity ring-down spectrometer employing a near-IR external cavity diode laser capable of measuring 13C/12C isotopic ratios in CO2 in human breath. The system, which has a demonstrated minimum detectable absorption loss of 3.2 x 10(-11) cm(-1) Hz(-1/2), determines the isotopic ratio of 13C16O16O/12C16O16O by measuring the intensities of rotationally resolved absorption features of each species. As in isotope ratio mass spectrometry (IRMS), the isotopic ratio of a sample is compared to that of a standard CO2 sample calibrated to the Pee Dee Belemnite scale and reported as the sample's delta13C value. Measurements of eight replicate CO2 samples standardized by IRMS and consisting of 5% CO2 in N2 at atmospheric pressure demonstrated a precision of 0.22/1000 for the technique. Delta13C values were also obtained for breath samples from individuals testing positive and negative for the presence of Helicobacter pylori, the leading cause of peptic ulcers in humans. This study demonstrates the ability of the instrument to obtain delta13C values in breath samples with sufficient precision to serve as a useful medical diagnostic.

[1] The recent Department of Energy Atmospheric Radiation Measurement (ARM) Aerosol Intensive Operations Period (AIOP, May 2003) yielded one of the best measurement sets obtained to date to assess our ability to measure the vertical profile of ambient aerosol extinction s ep (l) in the lower troposphere. During one month, a heavily instrumented aircraft with well-characterized aerosol sampling ability carrying well-proven and new aerosol instrumentation devoted most of the 60 available flight hours to flying vertical profiles over the heavily instrumented ARM Southern Great Plains (SGP) Climate Research Facility (CRF). This allowed us to compare vertical extinction profiles obtained from six different instruments: airborne Sun photometer (AATS-14), airborne nephelometer/absorption photometer, airborne cavity ring-down system, groundbased Raman lidar, and two ground-based elastic backscatter lidars. We find the in situ measured s ep (l) to be lower than the AATS-14 derived values. Bias differences are 0.002-0.004 Km À1 equivalent to 13-17% in the visible, or 45% in the near-infrared. On the other hand, we find that with respect to AATS-14, the lidar s ep (l) are higher: Bias differences are 0.004 Km À1 (13%) and 0.007 Km À1 (24%) for the two elastic backscatter lidars (MPLNET and MPLARM, l = 523 nm) and 0.029 Km À1 (54%) for the Raman lidar (l = 355 nm). An unnoticed loss of sensitivity of the Raman lidar had occurred leading up to AIOP, and we expect better agreement from the recently restored system. Looking at the collective results from six field campaigns conducted since 1996, airborne in situ measurements of s ep (l) tend to be biased slightly low (17% at visible wavelengths) when compared to airborne Sun photometer s ep (l). On the other hand, s ep (l) values derived from lidars tend to have no or positive biases. From the bias differences we conclude that the typical systematic error associated with measuring the tropospheric vertical profile of the ambient aerosol extinction with current state-of-the-art instrumentation is 15-20% at visible wavelengths and potentially larger in the UV and near-infrared.

[1] In May 2003, the Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Program sponsored the Aerosol Intensive Operating Period (AIOP) which was conducted over the ARM Climate Research Facility (ACRF) in central Oklahoma. One new instrument that flew in the AIOP, called Cadenza, employed a cavity ring-down technique to measure extinction coefficient and a reciprocal nephelometer technique to simultaneously measure scattering coefficient. This instrument is described in this paper, and measurements are compared to those of conventional instrumentation. Agreement between Cadenza extinction coefficient and that derived from combining nephelometer scattering and PSAP absorption (Neph + PSAP) was excellent, about 2%. Agreement between Cadenza scattering coefficient and TSI nephelometer scattering was also excellent, about 2%, well within the uncertainty of the nephelometer and Cadenza scattering measurements. Comparisons between these instruments, made for the special case of plumes, showed that Cadenza measured extinction and scattering several percent higher on average than the Neph + PSAP and nephelometer alone. This difference is likely due to differences in the instrument response time: The response time for Cadenza is 1 s while that for the nephelometer is a minimum of 8 s. Plumes, identified as originating from Siberian biomass burning, are characterized. Composite size distributions from wing-mounted probes showed that two of the plumes had significant large particle modes that resulted in high values of the effective radius. The effect of the large particle mode was not seen in the Å ngström coefficient calculated from the in-cabin scattering measurements because of the characteristics of the aircraft inlet.

An autonomous instrument based on off-axis integrated cavity output spectroscopy has been developed and successfully deployed for measurements of carbon monoxide in the troposphere and tropopause onboard a NASA DC-8 aircraft. The instrument (Carbon Monoxide Gas Analyzer) consists of a measurement cell comprised of two high-reflectivity mirrors, a continuous-wave quantum-cascade laser, gas sampling system, control and data-acquisition electronics, and data-analysis software. CO measurements were determined from high-resolution CO absorption line shapes obtained by tuning the laser wavelength over the R(7) transition of the fundamental vibration band near 2172.8 cm(-1). The instrument reports CO mixing ratio (mole fraction) at a 1-Hz rate based on measured absorption, gas temperature, and pressure using Beer's Law. During several flights in May-June 2004 and January 2005 that reached altitudes of 41,000 ft (12.5 km), the instrument recorded CO values with a precision of 0.2 ppbv (1-s averaging time) and an accuracy limited by the reference CO gas cylinder (uncertainty < 1.0%). Despite moderate turbulence and measurements of particulate-laden airflows, the instrument operated consistently and did not require any maintenance, mirror cleaning, or optical realignment during the flights.

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