Cavity Ring-down Spectroscopy System Research Articles

The discrete Fourier transform algorithm for determining decay constants—Implementation using a field programmable gate array.

Cavity ringdown spectroscopy (CRDS) uses the exponential decay constant of light exiting a high-finesse resonance cavity to determine analyte concentration, typically via absorption. We present a high-throughput data acquisition system that determines the decay constant in near real time using the discrete Fourier transform algorithm on a field programmable gate array (FPGA). A commercially available, high-speed, high-resolution, analog-to-digital converter evaluation board system is used as the platform for the system, after minor hardware and software modifications. The system outputs decay constants at maximum rate of 4.4 kHz using an 8192-point fast Fourier transform by processing the intensity decay signal between ringdown events. We present the details of the system, including the modifications required to adapt the evaluation board to accurately process the exponential waveform. We also demonstrate the performance of the system, both stand-alone and incorporated into our existing CRDS system. Details of FPGA, microcontroller, and circuitry modifications are provided in the Appendix and computer code is available upon request from the authors.

Eddy covariance flux measurements of gaseous elemental mercury using cavity ring-down spectroscopy.

A newly developed pulsed cavity ring-down spectroscopy (CRDS) system for measuring atmospheric gaseous elemental mercury (GEM) concentrations at high temporal resolution (25 Hz) was used to successfully conduct the first eddy covariance (EC) flux measurements of GEM. GEM is the main gaseous atmospheric form, and quantification of bidirectional exchange between the Earth's surface and the atmosphere is important because gas exchange is important on a global scale. For example, surface GEM emissions from natural sources, legacy emissions, and re-emission of previously deposited anthropogenic pollution may exceed direct primary anthropogenic emissions. Using the EC technique for flux measurements requires subsecond measurements, which so far has not been feasible because of the slow time response of available instrumentation. The CRDS system measured GEM fluxes, which were compared to fluxes measured with the modified Bowen ratio (MBR) and a dynamic flux chamber (DFC). Measurements took place near Reno, NV, in September and October 2012 encompassing natural, low-mercury (Hg) background soils and Hg-enriched soils. During nine days of measurements with deployment of Hg-enriched soil in boxes within 60 m upwind of the EC tower, the covariance of GEM concentration and vertical wind speed was measured, showing that EC fluxes over an Hg-enriched area were detectable. During three separate days of flux measurements over background soils (without Hg-enriched soils), no covariance was detected, indicating fluxes below the detection limit. When fluxes were measurable, they strongly correlated with wind direction; the highest fluxes occurred when winds originated from the Hg-enriched area. Comparisons among the three methods showed good agreement in direction (e.g., emission or deposition) and magnitude, especially when measured fluxes originated within the Hg-enriched soil area. EC fluxes averaged 849 ng m(-2) h(-1), compared to DFC fluxes of 1105 ng m(-2) h(-1) and MBR fluxes of 1309 ng m(-2) h(-1). This study demonstrated that a CRDS system can be used to measure GEM fluxes over Hg-enriched areas, with a conservative detection limit estimate of 32 ng m(-2) h(-1).

Quantifying methane emission from fugitive sources by combining tracer release and downwind measurements – A sensitivity analysis based on multiple field surveys

Using a dual species methane/acetylene instrument based on cavity ring down spectroscopy (CRDS), the dynamic plume tracer dispersion method for quantifying the emission rate of methane was successfully tested in four measurement campaigns: (1) controlled methane and trace gas release with different trace gas configurations, (2) landfill with unknown emission source locations, (3) landfill with closely located emission sources, and (4) comparing with an Fourier transform infrared spectroscopy (FTIR) instrument using multiple trace gasses for source separation. The new real-time, high precision instrument can measure methane plumes more than 1.2km away from small sources (about 5kgh−1) in urban areas with a measurement frequency allowing plume crossing at normal driving speed. The method can be used for quantification of total methane emissions from diffuse area sources down to 1kg per hour and can be used to quantify individual sources with the right choice of wind direction and road distance. The placement of the trace gas is important for obtaining correct quantification and uncertainty of up to 36% can be incurred when the trace gas is not co-located with the methane source. Measurements made at greater distances are less sensitive to errors in trace gas placement and model calculations showed an uncertainty of less than 5% in both urban and open-country for placing the trace gas 100m from the source, when measurements were done more than 3km away. Using the ratio of the integrated plume concentrations of tracer gas and methane gives the most reliable results for measurements at various distances to the source, compared to the ratio of the highest concentration in the plume, the direct concentration ratio and using a Gaussian plume model. Under suitable weather and road conditions, the CRDS system can quantify the emission from different sources located close to each other using only one kind of trace gas due to the high time resolution, while the FTIR system can measure multiple trace gasses but with a lower time resolution.

Fabrication of low-loss hollow waveguide with multiple dielectric layers for infrared cavity ring-down spectroscopy

Low-loss hollow waveguides with a multiple dielectric layer are designed and fabricated for use in cavity ring-down spectroscopy (CRDS). Calculations of the waveguide design revealed that hollow waveguides for infrared CRDS system need to have transmission loss of 0.1 dB/m or less. We fabricated rectangular hollow waveguides with multiple dielectric layers to obtain low-loss properties. The waveguides are composed of four glass strips each with a dielectric multilayer deposited on the surface in advance. Experimental results show that the waveguides with double dielectric layers have lower losses at a target wavelength in the infrared than those with a single dielectric layer. The measured transmission loss of a 10-cm long waveguide deposited with a multilayer of Si/Al 2 O 3 /Ag for the transverse magnetic wave and Al 2 O 3 /Ag for the transverse electric wave was 0.24 dB at a target wavelength of 5.2 μm. The loss of the waveguide will be reduced when only the lowest-order mode is excited in the waveguide.

Cavity ring-down spectroscopy sensor development for high-time-resolution measurements of gaseous elemental mercury in ambient air

Abstract. We describe further development of a previous laboratory prototype pulsed cavity ring-down spectroscopy (CRDS) sensor into a field-deployable system for high-time-resolution, continuous, and automated measurement of gaseous elemental mercury (GEM) concentrations in ambient air. We employed an external, isotopically enriched Hg cell for automated locking and stabilization of the laser wavelength on the GEM peak absorption during measurements. Further, we describe implementation of differential absorption measurements via a piezoelectric tuning element for pulse-by-pulse tuning of the laser wavelength onto and off of the GEM absorption line. This allowed us to continuously correct (at 25 Hz) for system baseline extinction losses unrelated to GEM absorption. Extensive measurement and calibration data obtained with the system were based on spike addition in both GEM-free air and ambient air. Challenges and interferences that occurred during measurements (particularly in ambient air) are discussed including temperature and ozone (O3) concentration fluctuations, and steps taken to reduce these. CRDS data were highly linear (r2 ≥ 0.98) with data from a commercial Tekran 2537 Hg analyzer across a wide range of GEM concentrations (0 to 127 ng m−3) in Hg-free and ambient air. Measurements during periods of stable background GEM concentrations provided a conservative instrument sensitivity estimate of 0.35 ng m−3 for the CRDS system when time averaged for 5 min. This sensitivity, along with concentration patterns observed in ambient air (with the CRDS system and verified with the Tekran analyzer), showed that the sensor was capable of characterizing GEM fluctuations in ambient air. The value of fast-response GEM measurements was shown by a series of GEM spike additions – highlighting that high-temporal-resolution measurement allowed for detailed characterization of fast concentration fluctuations not possible with traditional analyzers.

Optical-Fiber-Type Broadband Cavity Ring-Down Spectroscopy Using Wavelength-Tunable Ultrashort Pulsed Light

We proposed an optical-fiber-type broadband cavity ring-down spectroscopy system using wavelength-tunable ultrashort pulsed light. The absorbance of glucose in various concentrations in water was derived from the ring-down plots of intensities of the interference waveforms generated using a Mach–Zehnder interferometer with different optical delay path lengths, which were shifted by an automatic optical switching module. The absorption spectrum of glucose was obtained in the wavelength region from 1620 to 1690 nm by varying the wavelength using wavelength-tunable ultrashort pulsed light, which was generated from a femtosecond pulsed laser and polarization-maintaining fiber. The measurement error of concentration was improved using multiple linear regression analysis of absorption spectra. The results demonstrate that the optical-fiber-type cavity ring-down spectroscopy system has the potential to measure broadband absorption spectra with high sensitivity.

A DFG-based cavity ring-down spectrometer for trace gas sensing in the mid-infrared

Continuing studies into an all-diode laser-based 3.3 μm difference frequency generation cavity ring-down spectroscopy system are presented. Light from a 1,560 nm diode laser, amplified by an erbium-doped fibre amplifier, was mixed with 1,064 nm diode laser radiation in a bulk periodically poled lithium niobate crystal to generate 16 μW of mid-IR light at 3,346 nm with a conversion efficiency of $$0.05\,\%\,{\text{W}}^{-1}\,{\text{cm}}^{-1}$$ . This radiation was coupled into a 77 cm long linear cavity with average mirror reflectivities of 0.9996, and a measured baseline ring-down time of $$6.07\pm 0.03\,\upmu{\rm s}$$ . The potential of such a spectrometer was illustrated by investigating the $$P(3)$$ transition in the fundamental $$\nu_{3}(F_{2})$$ band of $${\text{CH}}_4$$ both in a 7.5 ppmv calibrated mixture of $${\text{CH}}_4$$ in air and in breath samples from methane and non-methane producers under conditions where the minimum detectable absorption coefficient ( $$\alpha_{\rm min}$$ ) was $$2.8 \times 10^{-8}\,{\rm cm}^{-1}$$ over 6 s using a ring-down time acquisition rate of 20 Hz. Allan variance measurements indicated an optimum $$\alpha_{\rm min}$$ of $$2.9\times 10^{-9}\,{\rm cm}^{-1}$$ over 44 s.

Off-axis re-entrant cavity ring-down spectroscopy with a mid-infrared continuous-wave optical parametric oscillator

We demonstrate an off-axis cavity ring-down spectroscopy system, which uses a mid-infrared continuous-wave optical parametric oscillator as a light source. Off-axis injection with re-entrant configuration of the ring-down cavity is used to achieve high spectral resolution while maintaining high measurement speed. This makes the setup suitable for sensitive molecular spectroscopy in the mid-infrared region, particularly for studies that require high temporal resolution. Formaldehyde (H2CO) absorption spectrum at 3.4 µm is measured using the off-axis re-entrant cavity ring-down spectrometer.

Reducing and correcting for contamination of ecosystem water stable isotopes measured by isotope ratio infrared spectroscopy

Concern exists about the suitability of laser spectroscopic instruments for the measurement of the (18)O/(16)O and (2)H/(1)H values of liquid samples other than pure water. It is possible to derive erroneous isotope values due to optical interference by certain organic compounds, including some commonly present in ecosystem-derived samples such as leaf or soil waters. Here we investigated the reliability of wavelength-scanned cavity ring-down spectroscopy (CRDS) (18)O/(16)O and (2)H/(1)H measurements from a range of ecosystem-derived waters, through comparison with isotope ratio mass spectrometry (IRMS). We tested the residual of the spectral fit S(r) calculated by the CRDS instrument as a means to quantify the difference between the CRDS and IRMS δ-values. There was very good overall agreement between the CRDS and IRMS values for both isotopes, but differences of up to 2.3‰ (δ(18)O values) and 23‰ (δ(2)H values) were observed in leaf water extracts from Citrus limon and Alnus cordata. The S(r) statistic successfully detected contaminated samples. Treatment of Citrus leaf water with activated charcoal reduced, but did not eliminate, δ(2)H(CRDS) - δ(2)H(IRMS) linearly for the tested range of 0-20% charcoal. The effect of distillation temperature on the degree of contamination was large, particularly for δ(2)H values but variable, resulting in positive, negative or no correlation with distillation temperature. S(r) and δ(CRDS) - δ(IRMS) were highly correlated, in particular for δ(2)H values, across the range of samples that we tested, indicating the potential to use this relationship to correct the δ-values of contaminated plant water extracts. We also examined the sensitivity of the CRDS system to changes in the temperature of its operating environment. We found that temperature changes ≥4 °C for δ(18)O values and ≥10 °C for δ(2)H values resulted in errors larger than the CRDS precision for the respective isotopes and advise the use of such instruments only in sufficiently temperature-stabilised environments.

Adaptation of continuous‐flow cavity ring‐down spectroscopy for batch analysis of δ13C of CO2 and comparison with isotope ratio mass spectrometry

Measurements of δ(13)C in CO(2) have traditionally relied on samples stored in sealed vessels and subsequently analyzed using magnetic sector isotope ratio mass spectrometry (IRMS), an accurate but expensive and high-maintenance analytical method. Recent developments in optical spectroscopy have yielded instruments that can measure δ(13)CO(2) in continuous streams of air with precision and accuracy approaching those of IRMS, but at a fraction of the cost. However, continuous sampling is unsuited for certain applications, creating a need for conversion of these instruments for batch operation. Here, we present a flask (syringe) adaptor that allows the collection and storage of small aliquots (20-30 mL air) for injection into the cavity ring-down spectroscopy (CRDS) instrument. We demonstrate that the adaptor's precision is similar to that of traditional IRMS (standard deviation of 0.3‰ for 385 ppm CO(2) standard gas). In addition, the concentration precision (±0.3% of sample concentration) was higher for CRDS than for IRMS (±7% of sample concentration). Using the adaptor in conjunction with CRDS, we sampled soil chambers and found that soil-respired δ(13)C varied between two different locations in a piñon-juniper woodland. In a second experiment, we found no significant discrimination between the respiration of a small beetle (~5 mm) and its diet. Our work shows that the CRDS system is flexible enough to be used for the analysis of batch samples as well as for continuous sampling. This flexibility broadens the range of applications for which CRDS has the potential to replace magnetic sector IRMS.

连续波腔衰荡光谱系统的电路设计与应用

连续波腔衰荡光谱系统的电路设计与应用

Toward real-time measurement of atmospheric mercury concentrations using cavity ring-down spectroscopy

Abstract. Cavity ring-down spectroscopy (CRDS) is a direct absorption technique that utilizes path lengths up to multiple kilometers in a compact absorption cell and has a significantly higher sensitivity than conventional absorption spectroscopy. This tool opens new prospects for study of gaseous elemental mercury (Hg0) because of its high temporal resolution and reduced sample volume requirements (<0.5 l of sample air). We developed a new sensor based on CRDS for measurement of (Hg0) mass concentration. Sensor characteristics include sub-ng m−3 detection limit and high temporal resolution using a frequency-doubled, tuneable dye laser emitting pulses at ~253.65 nm with a pulse repetition frequency of 50 Hz. The dye laser incorporates a unique piezo element attached to its tuning grating allowing it to tune the laser on and off the Hg0 absorption line on a pulse-to-pulse basis to facilitate differential absorption measurements. Hg0 absorption measurements with this CRDS laboratory prototype are highly linearly related to Hg0 concentrations determined by a Tekran 2537B analyzer over an Hg0 concentration range from 0.2 ng m−3 to 573 ng m−3, implying excellent linearity of both instruments. The current CRDS instrument has a sensitivity of 0.10 ng Hg0 m−3 at 10-s time resolution. Ambient-air tests showed that background Hg0 levels can be detected at low temporal resolution (i.e., 1 s), but also highlight a need for high-frequency (i.e., pulse-to-pulse) differential on/off-line tuning of the laser wavelength to account for instabilities of the CRDS system and variable background absorption interferences. Future applications may include ambient Hg0 flux measurements with eddy covariance techniques, which require measurements of Hg0 concentrations with sub-ng m−3 sensitivity and sub-second time resolution.

Applications of cavity ring-down spectroscopy to high precision isotope ratio measurement of 13C/12C in carbon dioxide

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‰, for 4% CO2 concentrations, and also achieved 0.15–0.25‰ 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 × 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 μm 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.

Development of Alternative Plasma Sources for Cavity Ring-Down Measurements of Mercury

We have been exploring innovative technologies for elemental and hyperfine structure measurements using cavity ring-down spectroscopy (CRDS) combined with various plasma sources. A laboratory CRDS system utilizing a tunable dye laser is employed in this work to demonstrate the feasibility of the technology. An in-house fabricated sampling system is used to generate aerosols from solution samples and introduce the aerosols into the plasma source. The ring-down signals are monitored using a photomultiplier tube and recorded using a digital oscilloscope interfaced to a computer. Several microwave plasma discharge devices are tested for mercury CRDS measurement. Various discharge tubes have been designed and tested to reduce background interference and increase the sample path length while still controlling turbulence generated from the plasma gas flow. Significant background reduction has been achieved with the implementation of the newly designed tube-shaped plasma devices, which has resulted in a detection limit of 0.4 ng/mL for mercury with the plasma source CRDS. The calibration curves obtained in this work readily show that linearity over 2 orders of magnitude can be obtained with plasma-CRDS for mercury detection. In this work, the hyperfine structure of mercury at the experimental plasma temperatures is clearly identified. We expect that plasma source cavity ring-down spectroscopy will provide enhanced capabilities for elemental and isotopic measurements.

Triplet excited states probed by cavity ringdown spectroscopy

Despite their photochemical importance, molecular triplet states have received relatively little attention in spectroscopic studies. This is primarily due to the challenge of detecting the spin-forbidden T n ←S 0 transitions. To meet the challenge, we have implemented cavity ringdown (CRD) spectroscopy, a high-sensitivity absorption technique, in our studies of photochemically relevant triplet species. In this article we outline the sensitivity requirements for observing singlet–triplet transitions and show how CRD detection achieves the needed sensitivity. We also specify the construction and operating details we used to set up the CRD spectroscopy system in our laboratory. Finally, we review investigations from our laboratory and others that have exploited the sensitivity of CRD detection to obtain triplet data that was not previously available. These studies include measurement of vibronically resolved T n ←S 0 spectra of some cyclic enones and conjugated hydrocarbons.

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.

Exploration of microwave plasma source cavity ring-down spectroscopy for elemental measurements.

We are exploring sensitive techniques for elemental measurements using cavity ring-down spectroscopy (CRDS) combined with a compact microwave plasma source as an atomic absorption cell. The research work marries the high sensitivity of CRDS with a low-power microwave plasma source to develop a new instrument that yields high sensitivity and capability for elemental measurements. CRDS can provide orders of magnitude improvement in sensitivity over conventional absorption techniques. Additional benefit is gained from a compact microwave plasma source that possesses the advantages of low power and low-plasma gas flow rate, which are of benefit for atomic absorption measurements. A laboratory CRDS system consisting of a tunable dye laser is used in this work for developing a scientific base and demonstrating the feasibility of the technique. A laboratory-designed and -built sampling system for solution sample introduction is used for testing. The ring-down signals are monitored using a photomultiplier tube and recorded using a digital oscilloscope interfaced to a computer. Lead is chosen as a typical element for the system optimization and characterization. The effects of baseline noise from the plasma source are reported. A detection limit of 0.8 ppb (10(-)(10)) is obtained with such a device.

Cavity ringdown spectroscopy with a continuous-wave laser: calculation of coupling efficiency and a new spectrometer design

For the efficient operation of a cavity ringdown spectroscopy (CRDS) system utilized with a continuous-wave (cw) laser, we numerically analyze the coupling efficiency of a cw laser to a ringdown cavity in terms of changes in the scanning rate, the laser linewidth, and the mirror reflectivity. We also demonstrate a new simple design for a CRDS system that can produce a CRDS signal with only a piezoelectric transducer (PZT), without the acousto-optic modulator that is usually adopted to switch off the cw laser beam that enters the cavity. Furthermore, we investigate the feasibility of the cw CRDS technique with a fast-scanning PZT by recording a CRDS spectrum of acetylene overtones. The detection sensitivity that corresponds to the noise-equivalent absorption is found to be approximately 3 x 10(-9)/cm.