Pulsed Cavity Ring-down Spectroscopy Research Articles

Intercomparison of measurements of NO<sub>2</sub> concentrations in the atmosphere simulation chamber SAPHIR during the NO3Comp campaign

Abstract. NO2 concentrations were measured by various instruments during the NO3Comp campaign at the atmosphere simulation chamber SAPHIR at Forschungszentrum Jülich, Germany, in June 2007. Analytical methods included photolytic conversion with chemiluminescence (PC-CLD), broadband cavity ring-down spectroscopy (BBCRDS), pulsed cavity ring-down spectroscopy (CRDS), incoherent broadband cavity-enhanced absorption spectroscopy (IBB\\-CEAS), and laser-induced fluorescence (LIF). All broadband absorption spectrometers were optimized for the detection of the main target species of the campaign, NO3, but were also capable of detecting NO2 simultaneously with reduced sensitivity. NO2 mixing ratios in the chamber were within a range characteristic of polluted, urban conditions, with a maximum mixing ratio of approximately 75 ppbv. The overall agreement between measurements of all instruments was excellent. Linear fits of the combined data sets resulted in slopes that differ from unity only within the stated uncertainty of each instrument. Possible interferences from species such as water vapor and ozone were negligible under the experimental conditions.

Determination of Inlet Transmission and Conversion Efficiencies for in Situ Measurements of the Nocturnal Nitrogen Oxides, NO3, N2O5 and NO2, via Pulsed Cavity Ring-Down Spectroscopy

Pulsed cavity ring-down spectroscopy is a highly sensitive method for direct absorption spectroscopy that has been applied to in situ detection of NO3, N2O5 and NO2 in the atmosphere from a variety of platforms, including ships, aircraft, and towers. In this paper, we report the development of schemes to significantly improve the accuracy of these measurements. This includes the following: (1) an overall improvement in the inlet transmission efficiencies (92 +/- 2% for NO3 and 97 +/- 1% for N2O5) achieved primarily through a reduction in the inlet residence time; and (2) the development of a calibration procedure that allows regular determination of these efficiencies in the field by addition of NO3 or N2O5 to the inlet from a portable source followed by conversion of NO3 to NO2. In addition, the dependence of the instrument's sensitivity and accuracy to a variety of conditions encountered in the field, including variations in relative humidity, aerosol loading, and VOC levels, was systematically investigated. The rate of degradation of N2O5 transmission efficiency on the inlet and filter system due to the accumulation of inorganic aerosol was determined, such that the frequency of filter changes required for accurate measurements could be defined. In the absence of aerosol, the presence of varying levels of relative humidity and reactive VOC were found to be unimportant factors in the instrument's performance. The 1 sigma accuracy of the NO3, N2O5, and NO2 measured with this instrument are -9/+12, -8/+11, +/- 6%, respectively, where the -/+ signs indicate that the actual value is low/high relative to the measurement. The largest contribution to the overall uncertainty is now due to the NO3 absorption cross section rather than the inlet transmission efficiency.

The vibrationless Ã←X̃ transition of the jet-cooled deuterated methyl peroxy radical CD3O2 by cavity ringdown spectroscopy

The nearly rotationally resolved spectrum of the A (2)A(')<--X (2)A(") 0(0)(0) transition of perdeutero methyl peroxy near 1.35 microm has been studied via pulsed cavity ringdown spectroscopy. Albeit, this is a weak transition, it is possible to observe the spectrum under jet-cooled conditions (approximately 15 K) by combining a source of narrow-bandwidth radiation (approximately 250 MHz) with a supersonic slit-jet expansion incorporating an electric discharge. The near infrared radiation was obtained by using stimulated Raman scattering and a pulsed, nearly Fourier-transform-limited Ti:sapphire amplifier seeded by a scanable cw Ti:sapphire ring laser. The experimental spectrum has been fitted using a model Hamiltonian that includes the rigid body rotation of an asymmetric top and the spin-rotation interaction. An excellent quality fit was obtained resulting in the determination of 15 molecular parameters characterizing the A and X states. Other results reported for CD(3)O(2) include an estimate of the radical concentration and the vibronic transition dipole from the observed absorption intensities. Details about the spectral linewidths are also discussed.

Optical properties of micrometer size water droplets studied by cavity ringdown spectroscopy

Optical extinction by homogeneous, pure water droplets of 30 to 70 microm diameter produced by a vibrating orifice aerosol generator has been studied by pulsed cavity ringdown (CRD) spectroscopy at lambda=560 nm under ambient conditions. Experimental sensitivity of better than 1% achieved in measurements of CRD times enabled detection of changes in laser light losses per pass due to changes in the number and size of particles within the laser beam volume. By systematically changing the droplet size in the cavity while recording the CRD time, a periodic modulation in the value of the loss per pass was observed. The modulation is caused by the oscillatory nature of the extinction efficiency, which was subsequently inferred and compared with the results of theoretical calculations based on Mie theory.

Pulsed quantum cascade laser-based cavity ring-down spectroscopy for ammonia detection in breath

Breath analysis can be a valuable, noninvasive tool for the clinical diagnosis of a number of pathological conditions. The detection of ammonia in exhaled breath is of particular interest for it has been linked to kidney malfunction and peptic ulcers. Pulsed cavity ringdown spectroscopy in the mid-IR region has developed into a sensitive analytical technique for trace gas analysis. A gas analyzer based on a pulsed mid-IR quantum cascade laser operating near 970 cm(-1) has been developed for the detection of ammonia levels in breath. We report a sensitivity of approximately 50 parts per billion with a 20 s time resolution for ammonia detection in breath with this system. The challenges and possible solutions for the quantification of ammonia in human breath by the described technique are discussed.

Pulsed slit jet cavity ring-down spectroscopy with a midinfrared lead salt diode laser

We report the design, construction, and evaluation of a midinfrared continuous wave cavity ring-down spectrometer based on a lead salt diode laser. A pulsed molecular beam assembly with a homemade slit nozzle was constructed and incorporated into the spectrometer. A computer program was developed to automate and to synchronize the timing of the cavity ring-down experiments with the pulsed molecular beam. To initiate a cavity ring-down event, a frequency detuning scheme is exploited to effectively block the laser from entering the ring-down cavity by rapidly shifting the laser frequency. The standard deviation of the experimental ring-down time, i.e., σ(τ)∕⟨τ⟩, was 0.63%, corresponding to a noise-equivalent absorption of 8.0×10−7 at a fixed laser frequency with an evacuated cavity with ten averaging cycles. A room temperature infrared spectrum of methane and a jet cooled infrared spectrum of propylene oxide at 3.3μm are presented.

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).

Theoretical analysis on the dynamic absorption saturation in pulsed cavity ringdown spectroscopy

We perform a theoretical analysis on the transient dynamics of absorption saturation in pulsed cavity ringdown spectroscopy. Based on a coupled rate equation approach, modelling of the dynamic saturation is carried out to account for time-evolving intracavity photon density and absorbing population. Master equations are derived in terms of normalized system parameters, which enables one to systematically study the non-exponential feature of saturated cavity ringdown signals. Erroneous quantification of sample absorbance by the conventional ringdown time analysis is numerically simulated, and the saturated spectral feature showing a Lamb dip is obtained for a Doppler broadened sample. Finally a novel numerical recipe is proposed to handle saturated ringdown signals and retrieve unsaturated spectra, allowing relevant absorption parameters without degrading the measurement signal-to-noise ratio.

Linewidths and line intensity measurements in the weak 3A2(000) ← 1A1(000) band of ozone by pulsed cavity ringdown spectroscopy

Pulsed cavity ringdown spectroscopy in the near‐infrared spectral range was employed to measure linewidths of the 3A2(000) ← 1A1(000) band of ozone in direct comparison with intracavity laser absorption spectroscopy. It is demonstrated that also for a small ratio, V, which is the ratio of the absorption linewidth and the laser bandwidth, correct linewidths can be determined from a forward modeling of the experimental line profiles, taking explicitly into account the laser bandwidth and the cavity modes. The obtained linewidths have been compared with those measured by intracavity laser absorption spectroscopy and found to agree quantitatively within experimental error. Linewidths as a function of pressure have been analyzed to obtain pressure‐broadening coefficients and the effective linewidth at zero pressure, which is a measure for the excited state lifetimes of the ozone in the excited triplet states. The observed linewidths are a direct observable for the intramolecular dynamics in the low‐lying excited 3A2 triplet state of ozone. In any case, the observed lifetimes for the excited 3A2(000) state in the range between 20 and 130 picoseconds (ps) rule out metastability of this state. Beyond linewidth measurements we have also refined the spectroscopic parameters of this electronically excited state and determined the integrated absorption of the corresponding 3A2(000) ← 1A1(000) transition.

Cavity ring-down measurements in flames using a single-mode tunable laser system

High-resolution pulsed cavity ring-down spectroscopy (CRDS) of OH in a flame has been demonstrated using a novel single-mode tunable laser (STL). This system operates by pulse amplification of the output of a single-mode diode laser in a modeless dye laser. Ring-down curves obtained using the narrow-bandwidth STL, for both strong and weak transitions, are shown to be well fitted by single exponentials. These results are demonstrated to be in direct contrast with those obtained using a standard dye laser, for which the bandwidth is comparable to the transition linewidths and ring-down curves require multi-exponential fits. Accurate lineshape analysis is thus made possible using the STL, allowing the temperature to be derived from the measured Doppler width. The resulting measurement is in good agreement with the value derived from a Boltzmann plot of data obtained using a conventional laser in a similar flame. The advantages of using the STL system for quantitative CRDS measurements are discussed, together with a suggestion for quantitative measurements of the ASE content of narrowband lasers using CRDS.

Continuous wave cavity ring-down spectroscopy applied to in situ detection of dinitrogen pentoxide (N2O5)

We describe an instrument using cavity ring-down spectroscopy (CRDS), an ultrasensitive detection method, to detect NO3 and N2O5 (via thermal dissociation to NO3 at 80 °C). We use continuous-wave (cw) cavity ring-down spectroscopy, allowing a highly reliable diode laser to act as the light source. This instrument uses all solid-state laser and optical components, and it is compact, portable, and power efficient. Advantages and disadvantages of cw CRDS compared to pulsed CRDS are discussed. Inlet losses and possible interferences were extensively investigated. We show field observations of N2O5 mixing ratios in ambient air. Dinitrogen pentoxide was measured because low ambient temperatures shift the equilibrium between NO3, NO2, and N2O5 strongly towards N2O5. Therefore, only N2O5 is assumed to be present in significant quantities in Fairbanks, AK, during winter. From these data, we identify times where the N2O5 mixing ratio must be zero (due to the absence of ozone indicating presence of NO) and use these time periods to measure the system’s operational detection limit. The 2σ detection limit for N2O5 is 2.4 parts per trillion by volume (pptv) in a 25 s average. Prediction of the N2O5 detection limit from estimates of ring-down signal noise indicates a detection limit of 1.6 pptv, in the same averaging period. The observed detection limit is about 50% larger than the predicted detection limit, indicating that other noise sources affect the true detection limit. A similar instrument using pulsed CRDS was described in the last year, and we compare our instrument to this instrument for detection of N2O5.

Cavity ring-down spectroscopy as a detector for liquid chromatography.

We have demonstrated the use of cavity ring-down spectroscopy (CRDS) as a detector for high performance liquid chromatography (HPLC). For this use, we have designed and implemented a Brewster's angle flow cell such that cavity ring-down spectroscopy can be performed on microliter volumes of liquids. The system exhibits a linear dynamic range of 3 orders of magnitude (30 nM to 30 microM quinalizarin at 470 nm) for static measurements and 2 orders of magnitude (0.5 microM to 50 microM) for HPLC measurements. For the static measurements, the baseline noise is 2.8 x 10(-6) AU rms and 1.0 x 10(-5) AU peak-to-peak, and for the HPLC separations, it is 3.2 x 10(-6) AU rms and 1.3 x 10(-5) AU peak-to-peak. The baseline noise is determined after the data are smoothed by an 11-point boxcar average. The peak areas detected from HPLC separations are reproducible to within 2-3%. The HPLC mass detection limit for a molecule with epsilon = 9 x 10(3) M(-1) cm(-1) in a 300-microm path length cell (illuminated volume, 0.5 microL) is reported as 2.5 x 10(-8) g/mL. These results were obtained using a simple pulsed CRDS system and are comparable to, if not better than, a high-quality commercial UV-vis absorption detector for the same path length.

Numerical analysis of beam propagation in pulsed cavity ring-down spectroscopy.

A numerical simulation of pulsed cavity ring-down spectroscopy (CRDS) is developed with the commercially available software package GENERAL LASER ANALYSIS AND DESIGN. The model is verified through a series of numerical experiments. Several issues of concern in CRDS are investigated, including spatial resolution, misalignment, non-Gaussian beam input, and the effect of flames inside a ring-down cavity. Suggestions for the design of pulsed CRDS instruments are provided.

High resolution pulsed infrared cavity ringdown spectroscopy: Application to laser ablated carbon clusters

We report the design and performance of a tunable, pulsed high resolution mid infrared cavity ringdown spectrometer. Stimulated Raman scattering in H2/D2 is used to downconvert the output of a SLM Alexandrite ring laser (720–800 nm) to the mid infrared (3–8 μm). The infrared frequency bandwidth was determined to be 90±5 MHz from measurements of Doppler broadened OCS transitions at 5 μm. The minimum detectable per pass fractional absorption is 1 ppm. We observe a frequency dependent ringdown cavity transmission of ±5 ppm due to spatial variations of the mirror reflectivity. The υ6 band of linear C9 formed by laser ablation of graphite in a He molecular beam was measured, showing a factor of 2 improvement in sensitivity relative to previous IR diode laser experiments. Based on calculated IR intensities, the number density of C9 in the molecular beam is 1.3*1011 molec/cm3 and the minimum detectable density is 1*109 molec/cm3. We expect this spectrometer to be a powerful tool for the study of transient species formed in molecular beams.

Optimization of the mode matching in pulsed cavity ringdown spectroscopy by monitoring non-degenerate transverse mode beating

A simple and reliable method is presented for optimizing the mode matching of a laser beam to the high-finesse cavity used in pulsed cavity ringdown spectroscopy (CRDS). The method is based on minimizing the excitation of higher-order transverse cavity modes through monitoring the non-degenerate transverse mode beating which becomes visible with induced cavity asymmetry caused by slight misalignment. No additional instrument is required other than a pinhole aperture, thus this method can be applied for CRDS experiments in the whole wavelength range. Measurements of the CRDS absorption spectrum of acetylene (C2H2) near 571 nm demonstrate that the mode-matching optimization improves the sensitivity of pulsed CRDS.

Pulsed cavity ring-down spectroscopy of NO and NO 2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO2 in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ2Π ground state to the A2Σ+ state at 226 nm. For NO2, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO2, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NOx emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO2 at the sub-ppm level.

Cavity ring-down spectroscopy of molecularly thin iodine layers

Cavity ring-down spectroscopy (CRDS) has so far mostly been used for measurements in the gas phase. Only in 1999 was a first spectrum of condensed phase published. This spectrum was measured by using a coated plate between the cavity mirrors. Rather than using this method, our measurements were made using the cavity mirrors as a substrate. This way, the scattering losses could be reduced by approximately a factor of 100. In our measurements we investigated molecularly thin layers of iodine. The iodine spectra were taken in the frequency range from 16200 to 17200 cm-1 using pulsed CRDS.

Cavity Ring-Down Polarimetry (CRDP): A New Scheme for Probing Circular Birefringence and Circular Dichroism in the Gas Phase

Cavity ring-down polarimetry (CRDP), a new, ultrasensitive method for probing circular birefringence and circular dichroism, has been developed by extending the well-established technique of pulsed cavity ring-down spectroscopy (CRDS). The concurrent incorporation of polarization elements into the stable resonator, injection optics, and detection train of a conventional CRDS apparatus is found to permit the quantitative measurement of optical rotation and differential absorption induced by the presence of chiral compounds. The sensitivity of this novel scheme is sufficient to allow (low-pressure) gas-phase species to be interrogated under ambient conditions, a fact highlighted by the direct determination of specific rotation at 355 nm for gaseous samples of α-pinene, β-pinene, cis-pinane, limonene, fenchone, and propylene oxide. Although usually precluded by the signal discrimination limits imposed upon traditional polarimeters, such gas-phase studies of nonresonant optical activity in the visible and nea...

Nonlinear effects in pulsed cavity ringdown spectroscopy of lithium vapour

We report cavity ringdown spectra of lithium vapour generated in the heat-pipe oven. Evaluation of ringdown decay curves in early and late time windows gives the change of absorption peak values as well as in the line shape profiles. Pronounced dips in the line center occur depending on molecular densities, injected laser pulse energies and chosen time window.

High resolution absorption spectroscopy of the ν1=2–6 acetylenic overtone bands of propyne: Spectroscopy and dynamics

The rotationally resolved nν1 (n=2–6) overtone transitions of the CH acetylenic stretching of propyne (CH3–C≡C–H) have been recorded by using Fourier transform spectroscopy (n=2), various intracavity laser absorption spectrometers (n=3, 4, and 6) and cavity ring down spectroscopy (CRDS) (n=5). The 2ν1, 3ν1, and 6ν1 bands exhibit a well-resolved and mostly unperturbed J-rotational structure, whose analysis is reported. The 5ν1 band recorded by pulsed CRDS shows an unresolved rotational envelope. In the region of 12 700 cm−1, an anharmonic interaction is confirmed between 4ν1 and 3ν1+ν3+ν5. The band at a higher wave number in this dyad exhibits a partly resolved K-structure, whose analysis is reported. The mixing coefficient of the two interacting states is determined consistently using different procedures. The 1/35 anharmonic resonance evidenced in the 4ν1 manifold induces weaker intensity borrowing from the 2ν1 and 3ν1 levels to the ν1+ν3+ν5 and 2ν1+ν3+ν5 level, respectively, which have been predicted and identified. Several hot bands around the 2ν1, 3ν1, and 3ν1+ν3+ν5 bands arising from the ν9=1 and ν10=1 and 2 bending levels are identified and rotationally analyzed, also leading to determine x1,9 [−20.3(3) cm−1], x1,10 [−1.7975(75) cm−1], and x3,10 [−6.56 cm−1]. The J-clumps of the P and R branches in the 6ν1 band at 18 499 cm−1 show a Lorentzian homogeneous profile mostly J-independent with an average full width at half maximum (FWHM) of 0.17 cm−1, attributed to arising from the intramolecular vibrational energy redistribution towards the bath of vibrational states. A detailed comparative examination of the fine structure in all investigated nν1 (n=2 to 7) overtone bands and the similar behavior of the cold and hot bands arising from ν10=1 definitively suggests that a highly specific low-order anharmonic coupling, still unidentified, dominates the hierarchy of interaction mechanisms connecting the nν1 levels to the background states.