Simple Monte Carlo methods to estimate the spectra evaluation error in differential-optical-absorption spectroscopy

Differential-optical-absorption spectroscopy (DOAS) permits the sensitive measurement of concentrations of trace gases in the atmosphere. DOAS is a technique of well-defined accuracy; however, the calculation of a statistically sound measurement precision is still an unsolved problem. Usually one evaluates DOAS spectra by performing least-squares fits of reference absorption spectra to the measured atmospheric absorption spectra. Inasmuch as the absorbance from atmospheric trace gases is usually very weak, with optical densities in the range from 10(-5) to 10(-3), interference caused by the occurrence of nonreproducible spectral artifacts often determines the detection limit and the measurement precision. These spectral artifacts bias the least-squares fitting result in two respects. First, spectral artifacts to some extent are falsely interpreted as real absorption, and second, spectral artifacts add nonstatistical noise to spectral residuals, which results in a significant misestimation of the least-squares fitting error. We introduce two new approaches to investigate the evaluation errors of DOAS spectra accurately. The first method, residual inspection by cyclic displacement, estimates the effect of false interpretation of the artifact structures. The second method applies a statistical bootstrap algorithm to estimate properly the error of fitting, even in cases when the condition of random and independent scatter of the residual signal is not fulfilled. Evaluation of simulated atmospheric measurement spectra shows that a combination of the results of both methods yields a good estimate of the spectra evaluation error to within an uncertainty of ~10%.     

Shot-noise-limited dual-beam detector for atmospheric trace-gas monitoring with near-infrared diode lasers

A dual-beam detector is used to measure atmospheric trace species by differential absorption spectroscopy with commercial near-infrared InGaAs laser diodes. It is implemented on the Spectromètre à Diodes Laser Accordables, a balloonborne tunable diode laser spectrometer devoted to the in situ monitoring of CH(4) and H(2)O. The dual-beam detector is made of simple analogical subtractor circuits combined with InGaAs photodiodes. The detection strategy consists in taking the balanced analogical difference between the reference and the sample signals detected at the input and the output of an open optical multipass cell to apply the full dynamic range of the measurements (16 digits) to the weak molecular absorption information. The obtained sensitivity approaches the shot-noise limit. With a 56-m optical cell, the detection limit obtained when the spectra is recorded within 8 ms is ~10(-4) (expressed in absorbance units). The design and performances of both a simple substractor and an upgraded feedback substractor circuit are discussed with regard to atmospheric in situ CH(4) absorption spectra measured in the 1.653-mum region. Mixing ratios are obtained from the absorption spectra by application of a nonlinear least-squares fit to the full molecular line shape in conjunction with in situP and T measurements.     

Long-path measurement of atmospheric NO2 with an obstruction flashlight and a charge-coupled-device spectrometer

A novel method of differential optical absorption spectroscopy (DOAS) is proposed and demonstrated to monitor the concentration of atmospheric pollutant gas. In contrast to conventional DOAS measurements with continuous light sources, the present method relies on white flashlights such as aviation obstruction lights that are generally installed on tall constructions. A simple detection system is devised by means of a telescope and a compact CCD spectrometer. A path length of 5.5 km allows us to measure atmospheric NO2 concentration with a detection limit of approximately 1 part per billion. We also discuss the possibility of deriving the aerosol optical thickness through the horizontal atmosphere from this pulsed DOAS measurement.     

Acousto-optic differential optical absorption spectroscopy for atmospheric measurement of nitrogen dioxide in Hong Kong

Measurement of the atmospheric concentration of nitrogen dioxide (NO(2)) pollutant was demonstrated by differential optical absorption spectroscopy (DOAS) using a visible acousto-optic tunable filter. In a traditional spectral scanning DOAS system for atmospheric concentration monitoring, a highly stable light source is required. When the light intensity fluctuates during scanning, the concentration retrieval will be inaccurate. In order to reduce the error due to intensity fluctuations, a modified DOAS system has been developed by introducing a broadband light intensity monitoring channel. Using the measured intensity of the broadband channel as the intensity of the light source, the spectrum can be de-biased and the residual intensity variation will primarily result from atmospheric extinction. In addition, by employing the lock-in detection technique, the background light interference is also removed in the modified DOAS system. The atmospheric NO(2) concentration measurement was performed at the campus of City University of Hong Kong, and the results were compared with the concentration reported from a nearby monitoring station in Sham Shui Po, operated by the Hong Kong Environmental Protection Department.     

Numerical analysis and estimation of the statistical error of differential optical absorption spectroscopy measurements with least-squares methods

Differential optical absorption spectroscopy (DOAS) has become a widely used method to measure trace gases in the atmosphere. Their concentration is retrieved by a numerical analysis of the atmospheric absorption spectra, which often are a combination of overlapping absorption structures of several trace gases. A new analysis procedure was developed, modeling atmospheric spectra with the absorption structures of the individual trace gases, to determine their concentrations. The procedure also corrects differences in the wavelength-pixel mapping of these spectra. A new method to estimate the error of the concentrations considers the uncertainty of this correction and the influence of random residual structures in the absorption spectra.     

Differential optical absorption spectroscopy system used for atmospheric mercury monitoring

A high-resolution differential optical absorption spectroscopy (DOAS) system for long-path atmospheric pollution monitoring is described. The system, consisting of a broadband lamp and a dispersive, fast-scanning optical receiver, separated by a few kilometers, was used in measurements of different pollutants, highlighted by the monitoring of the local concentration of atomic mercury. Mercury levels in the ppt (1:10(12)) range were assessed by comparisons with laboratory measurements.     

Applicability of light-emitting diodes as light sources for active differential optical absorption spectroscopy measurements

We present what is to our knowledge the first use of light-emitting diodes (LEDs) as light sources for long-path differential optical absorption spectroscopy (LP-DOAS) measurements of trace gases in the open atmosphere. Modern LEDs represent a potentially advantageous alternative to thermal light sources, in particular to xenon arc lamps, which are the most common active DOAS light sources. The radiative properties of a variety of LEDs were characterized, and parameters such as spectral shape, spectral range, spectral stability, and ways in which they can be influenced by environmental factors were analyzed. The spectra of several LEDs were found to contain Fabry-Perot etalon-induced spectral structures that interfered with the DOAS evaluation, in particular when a constant temperature was not maintained. It was shown that LEDs can be used successfully as light sources in active DOAS experiments that measure NO2 and NO3 near 450 and 630 nm, respectively. Average detection limits of 0.3 parts in 10(9) and 16 parts in 10(12) respectively, were obtained by use of a 6 km light path in the open atmosphere.     

Concurrent multiaxis differential optical absorption spectroscopy system for the measurement of tropospheric nitrogen dioxide

The development of a new concurrent multiaxis (CMAX) sky viewing spectrometer to monitor rapidly changing urban concentrations of nitrogen dioxide is detailed. The CMAX differential optical absorption spectroscopy (DOAS) technique involves simultaneous spectral imaging of the zenith and off-axis measurements of spatially resolved scattered sunlight. Trace-gas amounts are retrieved from the measured spectra using the established DOAS technique. The potential of the CMAX DOAS technique to derive information on rapidly changing concentrations and the spatial distribution of NO2 in an urban environment is demonstrated. Three example data sets are presented from measurements during 2004 of tropospheric NO2 over Leicester, UK (52.62 degrees N, 1.12 degrees W). The data demonstrate the current capabilities and future potential of the CMAX DOAS method in terms of the ability to measure real-time spatially disaggregated urban NO2.     

Ground-based imaging differential optical absorption spectroscopy of atmospheric gases

We describe a compact remote-sensing instrument that permits spatially resolved mapping of atmospheric trace gases by passive differential optical absorption spectroscopy (DOAS) and present our first applications of imaging of the nitrogen dioxide contents of the exhaust plumes of two industrial emitters. DOAS permits the identification and quantification of various gases, e.g., NO2, SO2, and CH2O, from their specific narrowband (differential) absorption structures with high selectivity and sensitivity. With scattered sunlight as the light source, DOAS is used with an imaging spectrometer that is simultaneously acquiring spectral information on the incident light in one spatial dimension (column). The second spatial dimension is scanned by a moving mirror.     

Intracavity absorption spectroscopy with a tunable multimode traveling-wave ring Ti:sapphire laser

A tunable multimode unidirectional traveling-wave Ti:sapphire laser was developed to measure in situ the atmospheric absorption spectra using intracavity absorption spectroscopy. The effective absorption path length was 2100 km. O2 and H2O vapor lines in atmosphere with absorption coefficients of 10(-6)-10(-8) cm(-1) were measured with uncertainties <5%, and the absorption coefficients were in agreement with those estimated from the HITRAN database. By tuning the wavelength, a weak absorption line with an absorption coefficient of 10(-9) cm(-1) was measured with a sensitivity of 2×10(-10) cm(-1). The sensitivity was limited by the residual parasitic variation that appeared in the spectrum.     

Measurements of cavity ringdown spectroscopy of acetone in the ultraviolet and near-infrared spectral regions: potential for development of a breath analyzer

We report a study on the cavity ringdown spectroscopy of acetone in both the ultraviolet (UV) and the near-infrared (NIR) spectral regions to explore the potential for development of a breath analyzer for disease diagnostics. The ringdown spectrum of acetone in the UV (282.4-285.0 nm) region is recorded and the spectrum is in good agreement with those obtained by other spectral techniques reported in the literature. The absorption cross-section of the C-H stretching overtone of acetone in the NIR (1632.7-1672.2 nm) is reported for the first time and the maximum absorption cross-section located at 1666.7 nm is 1.2 x 10(-21) cm(2). A novel, compact, atmospheric cavity with a cavity length of 10 cm has been constructed and implemented to investigate the technical feasibility of the potential instrument size, optical configuration, and detection sensitivity. The detection limit of such a mini cavity employing ringdown mirrors of reflectivity of 99.85% at 266 nm, where acetone has the strongest absorption, is approximately 1.5 ppmv based on the standard 3 criteria. No real breath gas samples are used in the present study. Discussions on the detection sensitivity and background spectral interferences for the instrument development are presented. This study demonstrates the potential of developing a portable, sensitive breath analyzer for medical applications using the cavity ringdown spectral technique.     

Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 2. Closure study

Spectral particle extinction coefficients of atmospheric aerosols were measured with, to the best of our knowledge, a newly designed differential optical absorption spectroscopy (DOAS) instrument. A closure study was carried out on the basis of optical and microphysical aerosol properties obtained from nephelometer, particle soot/absorption photometer, hygroscopic tandem differential mobility analyzer, twin differential mobility particle sizer, aerodynamic particle sizer, and Berner impactors. The data were collected at the urban site of Leipzig during a period of 10 days in March 2000. The performance test also includes a comparison of the optical properties measured with DOAS to particle optical properties calculated with a Mie-scattering code. The computations take into account dry and ambient particle conditions. Under dry particle conditions the linear regression and the correlation coefficient for particle extinction are 0.95 and 0.90, respectively. At ambient conditions these parameters are 0.89 and 0.97, respectively. An inversion algorithm was used to retrieve microphysical particle properties from the extinction coefficients measured with DOAS. We found excellent agreement within the retrieval uncertainties.     

Improving long-path differential optical absorption spectroscopy with a quartz-fiber mode mixer

Long-path differential optical absorption spectroscopy (DOAS) has become an increasingly important method for determination of the concentration of tropospheric trace gases (e.g., O(3), NO(2), BrO, ClO). The use of photodiode array (PDA) detectors enhances long-path DOAS systems considerably owing to PDA's higher sensitivity resulting from the multiplex advantage. The detection limits of these systems are expected to be 1 order of magnitude lower than systems of similar optical setup with scanning detectors. When the scanning detector is simply replaced by a PDA, unwanted spectral structures of as much as 8 x 10(-3) appear. The size of these randomly changing structures exceeds the photon noise level by 2-3 orders of magnitude thus severely limiting the sensitivity. We show that an angular dependence of the response of the PDA causes this structure in combination with unavoidable changes in the illumination. A quartz-fiber mode mixer, which makes the illumination of the spectrograph-detector system nearly independent of the angular intensity distribution of the measured light, was developed and tested. This new device reduces the unwanted structures in laboratory and field experiments by a factor of 10. The detection limits of long-path DOAS instruments with PDA detectors are improved by the same amount and are thus lower than those of currently used systems with scanning detectors. At the same time a much shorter measurement time (by ~1 order of magnitude) becomes possible.     

Particle extinction measured at ambient conditions with differential optical absorption spectroscopy. 1. system setup and characterization

We describe an instrument for measuring the particle extinction coefficient at ambient conditions in the spectral range from 270 to 1000 nm. It is based on a differential optical absorption spectroscopy (DOAS) system, which was originally used for measuring trace-gas concentrations of atmospheric absorbers in the ultraviolet-visible wavelength range. One obtains the particle extinction spectrum by measuring the total atmospheric extinction and subtracting trace-gas absorption and Rayleigh scattering. The instrument consists of two nested Newton-type telescopes, which are simultaneously used for emitting and detecting light, and two arrays of retroreflectors at the ends of the two light paths. The design of this new instrument solves crucial problems usually encountered in the design of such instruments. The telescope is actively repositioned during the measurement cycle. Particle extinction is simultaneously measured at several wavelengths by the use of two grating spectrometers. Optical turbulence causes lateral movement of the spot of light in the receiver telescope. Monitoring of the return signals with a diode permits correction for this effect. Phase-sensitive detection efficiently suppresses background signals from the atmosphere as well as from the instrument itself. The performance of the instrument was tested during a measurement period of 3 months from January to March 2000. The instrument ran without significant interruption during that period. A mean accuracy of 0.032 km(-1) was found for the extinction coefficient for an 11-day period in March.     

Detection of benzene and other gases with an open-path, static Fourier-transform UV spectrometer

Releases of benzene and other gases have been detected and quantified using a novel optical, open-path instrument based on a deuterium light source and a static Fourier-transform spectrometer. The spectrometer uses Wollaston prisms to form an interferogram in the spatial domain that is recorded by use of a detector array. The instrument is designed to operate in the ultraviolet region of the spectrum between 200 and 270 nm, which coincides with strong absorption features in the spectra of many gases of environmental and health interest. Using the instrument with a 5-s measurement period provides a path-integrated concentration sensitivity to benzene of 2 parts in 10(6) times meter, which corresponds to a 20-parts in 10(9) detection limit over a typical path length of 100 m.     

Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics

We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments.     

Off-axis cavity ringdown spectroscopy: application to atmospheric nitrate radical detection

Atmospheric nitrate radicals (NO3) are detected using off-axis cavity ringdown spectroscopy (CRDS) for the first time to our knowledge with a room-temperature continuous-wave (cw) diode laser operating near 662 nm. A prototype instrument was constructed that achieved a 1sigma absorption sensitivity of 5 x 10(-10) cm(-1) Hz(-1/2), corresponding to a 1.4 part per trillion by volume 2sigma detection limit in 4.6 s at 80 degrees C. This sensitivity is a significant improvement over a recent implementation of off-axis cavity-enhanced absorption spectroscopy and comparable to that of the most advanced cw CRDS and pulsed CRDS applications for atmospheric detection of NO3. A comparison of measurements of ambient air in Fairbanks, Alaska, recorded with the off-axis CRDS instrument and a previously characterized conventional cw CRDS instrument showed good agreement (R2 = 0.97).     

Quantitative concentration measurements of atomic sodium in an atmospheric hydrocarbon flame with asynchronous optical sampling

We report the development of a pump-probe instrument that uses a high-repetition-rate (82-MHz) picosecond laser. To maximize laser power and to minimize jitter between the pump- and the probe-pulse trains, we choose the asynchronous optical sampling (ASOPS) configuration. Verification of the method is obtained through concentration measurements of atomic sodium in an atmospheric methane-air flame. For the first time to our knowledge, ASOPS measurements are made on a quantitative basis. This is accomplished by calibration of the sodium concentration with atomic absorption spectroscopy. ASOPS measurements are taken at a rate of 155.7 kHz with only 128 averages, resulting in a corresponding detection limit of 5 × 10(9) cm(-3). The quenching-rate coefficient is obtained in a single measurement with a variation of ASOPS, which we call dual-beam ASOPS. The value of this coefficient is in excellent agreement with literature values for the present flame conditions. Based on our quantitative results for detection of atomic sodium, a detection limit of 2 × 10(17) cm(-3) is predicted for the Q(1) (9) line of A (2)Σ(+) (v = 0)-X(2)II (v = 0) hydroxyl at 2000 K. Although this value is too large for practical flame studies, a number of improvements that should lower the ASOPS detection limit are suggested.     

Wind speed measurements of Doppler-shifted absorption lines using two-beam interferometry

Wind speed can be measured remotely, with varying degrees of success, using interferometry of Doppler-shifted optical spectra. Under favorable conditions, active systems using laser pulse backscatter are capable of high resolution; passive systems, which measure Doppler shifts of atmospheric emission lines in the mesosphere, have also been shown. Two-beam interferometry of Doppler-shifted absorption lines has not been previously investigated; we describe such an effort here. Even in a well-defined environment, measuring absorption line Doppler shifts requires overcoming several technical hurdles in order to obtain sensitivity to wind speeds on the order of 10 m/s. These hurdles include precise knowledge of the shape of the absorption line, tight, stable filtering, and understanding precisely how an interferometer phase should respond to a change in the absorption profile. We discuss the instrument design, a Michelson interferometer and Fabry-Perot filter, and include an analysis of how to choose the optimal optical path difference of the two beams for a given spectrum and filter. We discuss two beam interferometric measurements of emission line and absorption line Doppler shifts, and include an illustration of the effects of filtering on LIDAR Doppler interferometry. Finally, we discuss the construction and implementation of a Michelson interferometer used to measure Doppler shifts of oxygen absorption lines and present results obtained with 5 m/s wind speed measurement precision. Although the theoretical shot noise limited Doppler wind speed measurement of the system described can be less than 1 m/s, the instrument's resolution limit is dominated by residual filter instability. Application of absorption line interferometry to determine atmospheric wind speeds remains problematic.     

Acousto-optic measurements of tropospheric nitrogen dioxide column density by solar spectroscopy

Measurements of column densities of atmospheric gases can be achieved by a solar spectroscopic method that uses differential optical absorption spectroscopy. Because of the scintillation of sunlight intensity in the atmosphere, the variation in intensity will introduce a low-frequency modification of the measured solar spectrum. A spectral capturing-type CCD spectrometer takes milliseconds to capture a solar spectrum, and the effect of sunlight scintillation is negligible. In contrast, without scintillation correction, a scanning-type spectrometer spending minutes to obtain a complete solar spectrum will introduce some amount of errors. We demonstrate an intensity-compensation technique in a scanning-type spectrometer, based on a solid-state acousto-optic tunable filter, for solar spectroscopic measurements.