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Recent measurements of carbon isotopes in carbon dioxide using near-infrared, diode-laser-based cavity ring-down spectroscopy (CRDS) are presented. The CRDS system achieved good precision, often better than 0.2 per thousand, for 4% CO2 concentrations, and also achieved 0.15-0.25 per thousand precision in a 78 min measurement time with cryotrap-based pre-concentration of ambient CO2 concentrations (360 ppmv). These results were obtained with a CRDS system possessing a data rate of 40 ring-downs per second and a loss measurement of 4.0 x 10(-11) cm(-1) Hz(-1/2). Subsequently, the measurement time has been reduced to under 10 min. This standard of performance would enable a variety of high concentration (3-10%) isotopic measurements, such as medical human breath analysis or animal breath experiments. The extension of this ring-down to the 2 microm region would enable isotopic analysis at ambient concentrations, which, combined with the small size, robust design, and potential for frequent measurements at a remote site, make CRDS technology attractive for remote atmospheric measurement applications.

An historical overview of laser-based, spectroscopic methods that employ high-finesse optical resonators is presented. The overview begins with the early work in atomic absorption (1962) and optical cavities (1974) that led to the first mirror reflectivity measurements in 1980. This paper concludes with very recent extensions of cavity-enhanced methods for the study of condensed-phase media and biological systems. Methods described here include cavity ring-down spectroscopy, integrated cavity output spectroscopy, and noise-immune cavity-enhanced optical heterodyne molecular spectroscopy. Given the explosive growth of the field over the past decade, this review does not attempt to present a comprehensive bibliography of all work published in cavity-enhanced spectroscopy, but rather strives to illustrate the rich history, creative diversity, and broad applications potential of these methods. PACS No.: 39.30.+w

Large uncertainties in the effects that aerosols have on climate require improved in situ measurements of extinction coefficient and single-scattering albedo. This paper describes the use of continuous wave cavity ring-down (CW-CRD) technology to address this problem. The innovations in this instrument are the use of CW-CRD to measure aerosol extinction coefficient, the simultaneous measurement of scattering coefficient, and small size suitable for a wide range of aircraft applications. Our prototype instrument measures extinction and scattering coefficient at 690 nm and extinction coefficient at 1550 nm. The instrument itself is small (60 x 48 x 15 cm) and relatively insensitive to vibrations. The prototype instrument has been tested in our lab and used in the field. While improvements in performance are needed, the prototype has been shown to make accurate and sensitive measurements of extinction and scattering coefficients. Combining these two parameters, one can obtain the single-scattering albedo and absorption coefficient, both important aerosol properties. The use of two wavelengths also allows us to obtain a quantitative idea of the size of the aerosol through the Angstrom exponent. Minimum sensitivity of the prototype instrument is 1.5 x 10(exp -6)/m (1.5 M/m). Validation of the measurement of extinction coefficient has been accomplished by comparing the measurement of calibration spheres with Mie calculations. This instrument and its successors have potential to help reduce uncertainty currently associated with aerosol optical properties and their spatial and temporal variation. Possible applications include studies of visibility, climate forcing by aerosol, and the validation of aerosol retrieval schemes from satellite data.

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.

A system is described that employs a diode-pumped Nd:YAG continuous-wave laser source servolocked to a three-mirror optical cavity and an analog detection circuit that extracts the ring-down rate from the exponentially decaying ring-down waveform. This scheme improves on traditional cavity ring-down spectroscopy setups by increasing signal acquisition rates to tens of kilohertz and reducing measurement noise sources. For example, an absorption spectrum of a weak CO2 transition at 1064 nm is obtained in less than 10 s at a spectral resolution of 75 kHz employing a cavity with an empty-cavity ring-down decay lifetime of 2.8 μs and a total roundtrip path length of 42 cm. The analog detection system enables laser frequency scan rates greater than 500 MHz/s. The long-term sensitivity of this system is 8.8×10−12 cm−1 Hz−1/2 and the short-term sensitivity is 1.0×10−12 cm−1 Hz−1/2.

Pulse stacking, or synchronous pumping, is a novel approach that offers important advantages in cavity ring-down spectroscopy. Using an ultrashort pulse, high repetition rate laser source we have shown that it is possible to resonantly stack pulses in a high finesse cavity, significantly enhancing the decay wave forms obtained when the laser source is abruptly terminated. We have achieved signal-to-noise ratio improvements of several orders of magnitude compared to single pulse injection systems, demonstrating a sensitivity of 2×10−9 cm−1 at 5.38 μm.

Polarization-selective optical heterodyne detection is shown to enhance the practical sensitivity of cavity ring-down spectroscopy. Initial experiments demonstrate a signal-to-noise ratio above 31 dB. Minor improvements should yield shot-noise-limited operation.

We have used cavity ringdown spectroscopy CRDS to measure near-infrared overtone transitions of water in . atmospheric flames propane premixed jet and laminar methane-air flat flame burner . The strong signal output with a well-defined laser beam direction and the insensitivity to strong background emission present in hostile environments make CRDS ideal for the study of combustion environments. We have obtained spectra of water vapor from within a flame and extracted a profile of the rotational temperature and concentration of water vapor as a function of distance from the plane burner surface. q 1998 Elsevier Science B.V.

By using an acousto-optic modulator, we have stabilized a free-running continuous wave (CW) laser diode in the presence of strong reflections from a high finesse Fabry–Perot resonator. The laser diode linewidth can be stabilized from several MHz, for high resolution spectroscopy of species at low pressures, to several hundred MHz, for lower resolution spectroscopy of species at atmospheric pressures. We demonstrated CW cavity ring-down spectroscopy of water vapor at both 1 atm and 5 Torr. We achieved ring-down repetition rates of 10–50 kHz, and a noise level of 2×10−8 cm−1.

We have investigated the implications of using a pulsed, nearly Fourier-transform-limited, single-mode light source for cavity ring-down spectroscopy (CRDS) in the mid-infrared spectral range. We show that in the case where the coherence time and duration of the light pulse exceeds the cavity roundtrip time, mode beating generates oscillations in the ring-down waveform. When the period of the oscillations is comparable to the ring-down time, it becomes difficult to obtain meaningful decay constants. This situation can be avoided by careful choice of cavity geometry and mode matching conditions together with suitable electronic filtering.

We describe the application of cavity ring-down spectroscopy (CRDS) to the detection of trace levels of ethylene in ambient air in a cold storage room of a fruit packing facility over a several month period. We compare these results with those obtained using gas chromatography (GC), the current gold standard for trace ethylene measurements in post-harvest applications. The CRDS instrument provided real-time feedback to the facility, to optimize the types of fruit stored together, and the amount of room ventilation needed to maintain sub-10 ppb ethylene levels for kiwi fruit storage. Our CRDS instrument achieved a detection limit of two parts-per-billion volume (ppbv) in 4.4 minutes of measurement time.

High fluences inside cavity ring-down spectroscopy optical resonators lend themselves to fluorescence or nonlinear optical spectroscopy. An instrument at 488 nm was developed to measure extinction, and fluorescence of aerosols. A detection limit of 6×10-9 cm- 1Hz-1/2 (0.6 Mm-1Hz-1/2) was achieved. The fluorescence spectral power collected from a single fluorescent microsphere was 10 to 20 pW/nm. This power is sufficient to obtain the spectrum of a single microsphere with a resolution of 10 nm and signal-to-noise ratio of ~10. The relative concentrations of two types of fluorescent microspheres were determined from a time-integrated fluorescence measurement of a mixture of both.

Cavity ringdown spectra of ammonia at 10 parts in 10(9) by volume (ppbv) and higher concentrations were recorded by use of a 16-mW continuous-wave quantum-casacde distributed-feedback laser at 8.5 mum whose wavelength was continuously temperature tuned over 15 nm. A sensitivity (noise-equivalent absorbance) of 3.4x10(-9) cm(-1) Hz(-1/2) was achieved for ammonia in nitrogen at standard temperature and pressure, which corresponds to a detection limit of 0.25 ppbv.

We describe the use of liquid-phase continuous-wave cavity ring-down spectroscopy for the detection of an HPLC separation. This technique builds on earlier work by Snyder and Zare using pulsed laser sources and improves upon commercially available UV-visible detectors by a factor of up to 50. The system employs a compact doubled-diode single-mode continuous-wave laser operating at 488 nm and a previously described Brewster's-angle flow cell. Ring-down time constants as long as 5.8 micros were observed with liquid samples in a 0.3-mm path length cell. The baseline noise during an HPLC separation was only 2 x 10(-7) absorbance units (AU) peak to peak, as compared to 1 x 10(-5) AU for a state-of-the-art commercial UV-visible detector.

We report a simple and compact all-solid-state laser generating 488 nm light with continuously variable output power in the range from 1 mW to over 120 mW. We frequency double single frequency radiation from an external cavity semiconductor laser in a periodically poled MgO:LiNbO 3 ridge waveguide. The laser maintains a high quality TEM 00 circular beam with M 2 < 1.1 and very low r.m.s. noise of less than 0.06% over the entire range of output power. Less than 0.1% peak-to-peak output power variation was measured during 14 hours of operation. No degradation of the conversion efficiency has been observed for operation at an output power of 70 mW for 3.5 months. The prototype laser has a small footprint of 5x8 cm.

Cavity ring-down spectroscopy (CRDS) can provide high sensitivity, high precision, and absolute calibration in a wide range of environments. We report on a compact cavity ring-down spectrometer that can measure atmospheric toxic industrial compounds such as hydrides and hydrazines. The ring-down spectrometer is fully contained in two 5 ¼" tall, 19" wide rack mount enclosures and utilizes a robust, near-infrared, fiber-coupled tunable diode laser. The instrument has a baseline sensitivity of 8 x 10 -11 cm -1 /Hz ½ . We will present the results of this study, which demonstrates the capability to detect toxic gases such as arsine, silane, and hydrazine (simulated using ammonia) in air at parts per billion (ppb) concentrations in less than 1 minute. We will also present results on CRDS instrument performance, including zero drift, precision, absolute accuracy, and linearity over a wide range of environmental operating conditions.

We report on robustness testing of a highly reliable frequency-doubled, external cavity semiconductor laser (DECSL). The laser module has been demonstrated to survive 6G operating vibration swept from 100 Hz to 500 Hz at 0.25 octaves/min. Impact shock to destruction was performed, and the unit passed operating specifications up to 300G. Good pointing stability and laser start times are shown as a function of repeated environmental temperature cycling between operating extremes.

Photoacoustic spectra of ammonia and water vapor were recorded by use of a continuous-wave quantum-cascade distributed-feedback (QC-DFB) laser at 8.5 ?m with a 16-mW power output. The gases were flowed through a cell that was resonant at 1.6??kHz, and the QC-DFB source was temperature tuned over 35??nm for generation of spectra or was temperature stabilized on an absorption feature peak to permit real-time concentration measurements. A detection limit of 100 parts in 109 by volume ammonia at standard temperature and pressure was obtained for a 1-Hz bandwidth in a measurement time of 10??min.

Recent advances in broadly tunable telecommunications lasers will enable new approaches to laser absorption spectroscopy and greatly expand the ability of existing laser-based systems to perform trace gas detection. Researchers have already begun adopting these lasers in tunable diode laser absorption spectroscopy, photo-acoustic absorption spectroscopy and cavity ring-down spectroscopy.

Recent advances in biotechnology have created a need for compact, efficient and reliable 488-nm cyan lasers, a trend which has hastened the development of technologies to replace air-cooled argon-ion lasers in biomedical instrumentation applications.

Cavity ring-down spectroscopy has the potential to revolutionize environmental and agricultural monitoring, industrial process control and the detection and identification of hazardous materials.

When the frequency of light coupled into a cavity is suddenly shifted, the radiation emanating from the input port of the previously excited cavity can beat with the reflection of the frequency-shifted input on the surface of a photodetector. When the beat frequency is stable, the time decay of the resulting optical heterodyne signal can be used to measure intracavity absorption spectra with near quantum-limited sensitivity.