Cavity Enhanced Absorption Spectroscopy Research Articles

Dual laser based optical feedback cavity enhanced absorption spectroscopy by polarization division multiplexing

This article presents a dual laser-based optical feedback cavity-enhanced absorption spectroscopy technique using polarization division multiplexing. The technique involves two laser beams with orthogonal polarization that enter a V-shaped cavity from two injection directions. This allows for independent control of feedback phase and eliminates the need for an optical component to combine the beams. The two lasers are detected separately at the two ends of the cavity. Additionally, a differential process is proposed to mitigate residual interference between the two lasers. By employing this technique, simultaneous detection of CH4, CO2 and H2O is achieved, resulting in a detection sensitivity of approximately 2 × 10−11 cm−1. Despite using a moderate cavity finesse in our spectrometer, the minimal detectable concentration for the gases is comparable to that of superior gas analyzers using cavity ringdown spectroscopy (CRDS).

Highly sensitive and selective laser-based BTEX sensor for occupational and environmental monitoring

A mid-infrared laser-based sensor is designed and demonstrated for trace detection of benzene, toluene, ethylbenzene, and xylene isomers at ambient conditions. The sensor is based on a distributed feedback inter-band cascade laser emitting near 3.29 µm and an off-axis cavity-enhanced absorption spectroscopy configuration with an optical gain of 2800. Wavelength tuning and a deep neural network (DNN) model were employed to enable simultaneous and selective BTEX measurements. The sensor performance was demonstrated by measuring BTEX mole fractions in various mixtures. At an integration time of 10 s, minimum detection limits of 11.4, 9.7, 9.1, 10, 15.6, and 12.9 ppb were achieved for benzene, toluene, ethylbenzene, m-xylene, o-xylene, and p-xylene, respectively. The sensor can be used to detect tiny BTEX leaks in petrochemical facilities and to monitor air quality in residential and industrial areas for workplace pollution.

Revisiting the Ultraviolet Absorption Cross Section of Gaseous Nitrous Acid (HONO): New Insights for Atmospheric HONO Budget.

Nitrous acid (HONO) is an important source of hydroxyl radicals (OH) in the atmosphere. Precise determination of the absolute ultraviolet (UV) absorption cross section of gaseous HONO lays the basis for the accurate measurement of its concentration by optical methods and the estimation of HONO loss rate through photolysis. In this study, we performed a series of laboratory and field intercomparison experiments for HONO measurement between striping coil-liquid waveguide capillary cell (SC-LWCC) photometry and incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Specified HONO concentrations prepared by an ultrapure standard HONO source were utilized for laboratory intercomparisons. Results show a consistent ∼22% negative bias in measurements of the IBBCEAS compared with a SC-LWCC photometer. It is confirmed that the discrepancies occurring between these techniques are associated with the overestimation of the absolute UV absorption cross sections through careful analysis of possible uncertainties. We quantified the absorption cross section of gaseous HONO (360-390 nm) utilizing a custom-built IBBCEAS instrument, and the results were found to be 22-34% lower than the previously published absorption cross sections widely used in HONO concentration retrieval and atmospheric chemical transport models (CTMs). This suggests that the HONO concentrations retrieved by optical methods based on absolute absorption cross sections may have been underestimated by over 20%. Plus, the daytime loss rate and unidentified sources of HONO may also have evidently been overestimated in pre-existing studies. In summary, our findings underscore the significance of revisiting the absolute absorption cross section of HONO and the re-evaluation of the previously reported HONO budgets.

Experimental observation of the ν1+3ν3 combination bands of 16O14N18O and 18O14N18O in the near infrared spectral region

The first observation of the ν1+3ν3 combination band of the nitrogen dioxide isotopologue 16O14N18O is presented. The band was measured using Fourier-Transform Incoherent Broad-Band Cavity Enhanced Absorption Spectroscopy (FT-IBBCEAS) in the region between 5870 cm−1 and 5940 cm−1. To confirm the assignment, the band was simulated using a standard asymmetric top Watson Hamiltonian using extrapolated rotational and centrifugal distortion constants. Furthermore, the first experimental observation of the ν1+3ν3 band of the 18O14N18O isotopologue is also reported. The positions of ro-vibrational lines of the ν1+3ν3 band of the naturally most abundant isotopologue 16O14N16O were used for wavenumber calibration of line positions.

Cavity assisted high-resolution THz spectrometer

The analysis of gases by THz radiation offers a high degree of discrimination due to the narrow linewidths that are observed at low pressure. The sensitivity of existing high-resolution instruments is limited by the availability and performance of critical system components. This study uses two key components with physical structures at the wavelength scale to realise a high finesse THz cavity. The cavity is characterised and incorporated into a spectrometer. Sensitivity limits of the instrument are experimentally demonstrated for trace and pure gases. Both CEAS (Cavity Enhanced Absorption Spectroscopy) and CRDS (Cavity Ring-Down Spectroscopy) configurations are shown to give sub-ppm detection levels. The cavity has also been used to measure the atmospheric losses.

A mini broadband cavity enhanced absorption spectrometer for nitrogen dioxide measurement on the unmanned aerial vehicle platform

We developed a small size and light weight analyzer based on the broadband cavity enhanced absorption spectroscopy for measuring nitrogen dioxide (NO2) with high spatial-temporal resolution and high accuracy. The instrument utilizes a LED centered at 450 nm, a short optical cavity, and a spectrometer to determine the extinction coefficients span 435–465 nm, allowing us to retrieve the mixing ratio of NO2 by absorption cross-section. The measurement precision (1σ) for NO2 is 98 ppt in 2 s under laboratory conditions. The uncertainty is estimated at 6% mainly attributed to cross-section and the mirror reflectivity. Good consistency was achieved by comparing with commercial chemiluminescence detector and cavity attenuation phase shift spectrometer (CAPS) (both R2 = 0.99). We further mounted the instrument on an unmanned aerial vehicle (UAV), and maintained the UAV flight at the height of 20 m, the comparative measurement with a CAPS set in a neighbor building with the same sampling height showed a good correlation (R2 = 0.97), which confirmed the instrumental feasibility and stability on the UAV platform. At last, we present a successful NO2 vertical measurement test, the good performance indicates this portable technique has great potential for vertical measurement. In particular, the mini-CEAS technique can further extend to measure the vertical profiles of other trace gas species (such as nitrous acid) with strong optical structural absorptions, which would largely promote the understanding of atmospheric chemistry on a vertical scale.

Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS) Coupled with an Interferometer for On-Band and Off-Band Detection of Glyoxal.

Glyoxal (CHOCHO) is a trace gas in the atmosphere, often used as an indicator of biogenic emissions. It is frequently compared to formaldehyde concentrations, which serve as indicators of anthropogenic emissions, to gain insights into the characteristics of the environmental source. This study employed broadband cavity-enhanced absorption spectroscopy to detect gaseous CHOCHO, methylglyoxal, and NO2. Two different detection methods are compared. Spectrograph and CCD Detection: This approach involves coupling the system to a spectrograph with a charge-coupled device (CCD) detector. It achieved a 1 min 1-σ detection limit of 2.5 × 108 molecules/cm3, or 10 parts per trillion (ppt). Methylglyoxal and NO2 achieved 1 min 1-σ detection limits of 34 ppt and 22 ppt, respectively. Interferometer and PMT Detection: In this method, an interferometer is used in conjunction with a photomultiplier tube (PMT) detector. It resulted in a 2 min 1-σ detection limit of 1.5 × 1010 molecules/cm3, or 600 ppt. The NO2 2 min 1-σ detection limit was determined to be 900 ppt. Concentrations of methylglyoxal were difficult to determine using this method, as they appeared to be below the detection limit of the instrument. This study discusses the advantages and limitations of each of these detection methods.

Spectroscopic detection of radiocarbon dioxide based on optical feedback linear cavity enhanced absorption spectroscopy

AbstractSpectroscopic detection of radiocarbon dioxide (14CO2) offers several advantages, including real‐time detection, on‐site measurement capability, and ease of operation. Here, we propose a novel 14CO2 detection technique that utilizes optical feedback linear cavity enhanced absorption spectroscopy. The feedback phase is actively compensated by adjusting the light path length. The combination of cavity‐based technique and optical feedback enables the recording of stable and enhanced 14CO2 spectra. Through Allan deviation analysis, a minimal detectable 14CO2 concentration of 3.5 parts‐per‐trillion is achieved. This technique has the potential to contribute to the monitoring of the radiocarbon emissions in the air of nuclear power plants.

Ultrafast internal conversion and photochromism in gas-phase salicylideneaniline.

Salicylideneaniline (SA) is an archetypal system for excited-state intramolecular proton transfer (ESIPT) in non-planar systems. Multiple channels for relaxation involving both the keto and enol forms have been proposed after excitation to S1 with near-UV light. Here, we present transient absorption measurements of hot gas-phase SA, jet-cooled SA, and SA in Ar clusters using cavity-enhanced transient absorption spectroscopy (CE-TAS). Assignment of the spectra is aided by simulated TAS spectra, computed by applying time-dependent complete active space configuration interaction (TD-CASCI) to structures drawn from nonadiabatic molecular dynamics simulations. We find prompt ESIPT in all conditions followed by the rapid generation of the trans keto metastable photochrome state and fluorescent keto state in parallel. Increasing the internal energy increases the photochrome yield and decreases the fluorescent yield and fluorescent state lifetime observed in TAS. In Ar clusters, internal conversion of SA is severely hindered, but the photochrome yield is unchanged. Taken together, these results are consistent with the photochrome being produced via the vibrationally excited keto population after ESIPT.

Low-Temperature Cavity-Enhanced Spectroscopy with a Diode Laser: Vibration–Rotation Absorption of CO (3ν) at 80 K and CH3C≡C–H (2ν1) at 165 K

A rotational resolution cavity-enhanced absorption spectroscopy (CEAS) technique is presented for infrared (IR) absorption studies at temperatures between 77 and 300 K. The cavity consists of an aluminum tube with two highly reflecting near-IR mirrors at each end. The cavity is attached to the cold head of a liquid nitrogen cryostat inside a vacuum chamber. In this way, all the cavity components are the temperature of the cold head. The spectra are obtained with a tunable diode laser and lock-in detection. The laser is modulated with an electro-optic modulator and coupled to the optical cavity. To illustrate the use of the technique, the vibrational–rotational overtone transitions (υ = 0→3) of carbon monoxide at 295 and 80 K and the acetylenic C–H (υ = 0→2) bond of CH3C≡C–H at 293 and 165 K are obtained. Temperatures are obtained with a Boltzmann distribution calculation that involves rotational intensities and energies from the spectra. Spectroscopic constants agree with previous determinations using other methods. An average of signals over the entire range of the absorption produces a rotational intensity distribution with some deviations. The calculated temperature based on the Boltzmann distribution is in very good agreement with the temperature measured with a silicon temperature sensor attached to the cell. Comparison with other experimental approaches to CEAS and the importance of the technique for applications in astrochemistry are discussed.

Laboratory Performance Evaluation of a Low-Cost Electrochemical Formaldehyde Sensor.

Formaldehyde is a known human carcinogen and an important indoor and outdoor air pollutant. However, current strategies for formaldehyde measurement, such as chromatographic and optical techniques, are expensive and labor intensive. Low-cost gas sensors have been emerging to provide effective measurement of air pollutants. In this study, we evaluated eight low-cost electrochemical formaldehyde sensors (SFA30, Sensirion®, Staefa, Switzerland) in the laboratory with a broadband cavity-enhanced absorption spectroscopy as the reference instrument. As a group, the sensors exhibited good linearity of response (R2 > 0.95), low limit of detection (11.3 ± 2.07 ppb), good accuracy (3.96 ± 0.33 ppb and 6.2 ± 0.3% N), acceptable repeatability (3.46% averaged coefficient of variation), reasonably fast response (131-439 s) and moderate inter-sensor variability (0.551 intraclass correlation coefficient) over the formaldehyde concentration range of 0-76 ppb. We also systematically investigated the effects of temperature and relative humidity on sensor response, and the results showed that formaldehyde concentration was the most important contributor to sensor response, followed by temperature, and relative humidity. The results suggest the feasibility of using this low-cost electrochemical sensor to measure formaldehyde concentrations at relevant concentration ranges in indoor and outdoor environments.

Comparison of optical feedback cavity enhanced absorption spectroscopy and gas chromatography for the measurement of the main components and impurities in biogas, landfill gas, biomethane and carbon dioxide streams

In this study, we evaluated the performances of a custom-built optical feedback cavity enhanced absorption spectroscopy (OFCEAS) instrument for the determination of the composition of energy gases, focusing on methane and carbon dioxide as main components, and carbon monoxide as impurities, in comparison with the well-established, validated, and traceable gas chromatographic method. A total of 115 real sample gases collected in biogas plants or landfills were analyzed using with both techniques over a period of 12 months. The comparison of the techniques showed that the virtual model which allows the measurement, needs to be optimized using real samples of varied compositions. The OFCEAS measurement technique was found to be capable of measuring both the main components and a trace component in different matrices; to within a 2% measurement uncertainty (higher than the gas chromatograph/thermal conductivity detector (GC/TCD) method). The OFCEAS method exhibits a very fast response, does not require daily calibration, and can be implemented online. The agreements between the OFCEAS technique and the GC/TCD method show that the drift of the OFCEAS instruments remains acceptable in the long term as long as no change is made to the virtual model. Matrix effects were observed, and those need to be taken into consideration when analyzing different types of samples.

Development of a compact 406 nm diode laser-based cavity-enhanced spectrometer for high-sensitive detection of NO2 levels in exhaust gas

Nitrogen dioxide (NO2) is an important air pollutant due to its environmental impact and adverse effects on human health. It is released into the atmosphere primarily through anthropogenic activities. Here, we report on the development of a simple, compact, and cost-effective robust optical detection method exploiting cavity-enhanced absorption spectroscopy for high-sensitive and selective measurement of NO2 levels in real-time using a visible diode laser operating at 406 nm. A typical detection limit of ∼330 ppb for NO2 was achieved with an optimum acquisition time of ∼3.9 s, at optimal cavity pressure of 100 Torr. The sensor system demonstrates an effective optical path-length of 180 m in a high-finesse 50 cm long optical cavity in an interference-free spectral region and aerosol-free conditions. The spectrometer was optimized, calibrated, and demonstrated for the detection of NO2 levels in vehicular exhaust gases.

Ozone Detection via Deep-Ultraviolet Cavity-Enhanced Absorption Spectroscopy with a Laser Driven Light Source.

We present a novel sensing approach for ambient ozone detection based on deep-ultraviolet (DUV) cavity-enhanced absorption spectroscopy (CEAS) using a laser driven light source (LDLS). The LDLS has broadband spectral output which, with filtering, provides illumination between ~230-280 nm. The lamp light is coupled to an optical cavity formed from a pair of high-reflectivity (R~0.99) mirrors to yield an effective path length of ~58 m. The CEAS signal is detected with a UV spectrometer at the cavity output and spectra are fitted to yield the ozone concentration. We find a good sensor accuracy of <~2% error and sensor precision of ~0.3 ppb (for measurement times of ~5 s). The small-volume (<~0.1 L) optical cavity is amenable to a fast response with a sensor (10-90%) response time of ~0.5 s. Demonstrative sampling of outdoor air is also shown with favorable agreement against a reference analyzer. The DUV-CEAS sensor compares favorably against other ozone detection instruments and may be particularly useful for ground-level sampling including that from mobile platforms. The sensor development work presented here can also inform of the possibilities of DUV-CEAS with LDLSs for the detection of other ambient species including volatile organic compounds.

New methods for the calibration of optical resonators: integrated calibration by means of optical modulation (ICOM) and narrow-band cavity ring-down (NB-CRD)

Abstract. Optical resonators are used in spectroscopic measurements of atmospheric trace gases to establish long optical path lengths L with enhanced absorption in compact instruments. In cavity-enhanced broad-band methods, the exact knowledge of both the magnitude of L and its spectral dependency on the wavelength λ is fundamental for the correct retrieval of trace gas concentrations. L(λ) is connected to the spectral mirror reflectivity R(λ), which is often referred to instead. L(λ) is also influenced by other quantities like broad-band absorbers or alignment of the optical resonator. The established calibration techniques to determine L(λ), e.g. introducing gases with known optical properties or measuring the ring-down time, all have limitations: limited spectral resolution, insufficient absolute accuracy and precision, inconvenience for field deployment, or high cost of implementation. Here, we present two new methods that aim to overcome these limitations: (1) the narrow-band cavity ring-down (NB-CRD) method uses cavity ring-down spectroscopy and a tunable filter to retrieve spectrally resolved path lengths L(λ); (2) integrated calibration by means of optical modulation (ICOM) allows the determination of the optical path length at the spectrometer resolution with high accuracy in a relatively simple setup. In a prototype setup we demonstrate the high accuracy and precision of the new approaches. The methods facilitate and improve the determination of L(λ), thereby simplifying the use of cavity-enhanced absorption spectroscopy.

Optical Methods of Methane Detection

Methane is the most frequently analyzed gas with different concentrations ranging from single ppm or ppb to 100%. There are a wide range of applications for gas sensors including urban uses, industrial uses, rural measurements, and environment monitoring. The most important applications include the measurement of anthropogenic greenhouse gases in the atmosphere and methane leak detection. In this review, we discuss common optical methods used for detecting methane such as non-dispersive infrared (NIR) technology, direct tunable diode spectroscopy (TDLS), cavity ring-down spectroscopy (CRDS), cavity-enhanced absorption spectroscopy (CEAS), lidar techniques, and laser photoacoustic spectroscopy. We also present our own designs of laser methane analyzers for various applications (DIAL, TDLS, NIR).

Absorption cross-sections for the 5th and 6th vibrational overtones in a series of short chained alcohols using incoherent broadband cavity enhanced-absorption spectroscopy (IBBCEAS)

Absorption cross-sections for the 5th (6 ← 0) and 6th (7 ← 0) OH overtones for gas-phase methanol, ethanol, and isopropanol were measured using a slow flow cell and Incoherent Broadband Cavity-Enhanced Absorption Spectroscopy (IBBCEAS). Measurements were performed in two wavelength regions, 447–457 nm, and 508–518 nm, using two different instruments. The experimental results are consistent with previous computational predictions of the excitation energies for these transitions. Treating the OH stretch as a local mode allowed for calculation of the fundamental vibrational frequency (ωe), anharmonicity constant (ωexe), and the vertical dissociation energy (VDE) for each alcohol studied. The fundamental vibrational frequency is 3848 ± 18 cm−1, 3807 ± 55 cm−1, and 3813 ± 63 cm−1 for methanol, ethanol, and isopropanol, respectively. The anharmonicity constant was measured to be 84.8 ± 2.1 cm−1, 80.2 ± 5.9 cm−1, and 84.4 ± 6.8 cm−1 for methanol, ethanol, and isopropanol, respectively. The OH vertical dissociation energy was measured to be 499.4 ± 18.4 kJ/mol, 518.0 ± 56.7 kJ/mol, and 492.7 ± 59.9 kJ/mol. The spectroscopically measured values are compared to thermodynamically measured OH bond dissociation energies. The observed differences in previous measurements of the bond dissociation energies compared to the values reported herein can be explained due to the difference between vertical dissociation energies and bond dissociation energies. If the OH overtone stretching mode is excited in methanol to either the 5th or 6th overtone, the bimolecular reaction between methanol and O2 becomes thermodynamically feasible and could contribute to formation of methoxy and HO2 radical under the proper combination of pressure and temperature.

Novel Broadband Cavity-Enhanced Absorption Spectrometer for Simultaneous Measurements of NO2 and Particulate Matter.

A novel instrument based on broadband cavity-enhanced absorption spectroscopy has been developed using a supercontinuum broadband light source, which showcases its ability in simultaneous measurements of the concentration of NO2 and the extinction of particulate matter. Side-by-side intercomparison was carried out with the reference NOx analyzer for NO2 and OPC-N2 particle counter for particulate matter, which shows a good linear correlation with r2 > 0.90. The measurement limits (1σ) of the developed instrument were experimentally determined to be 230 pptv in 40 s for NO2 and 1.24 Mm-1 for the extinction of particulate matter in 15 s. This work provides a promising method in simultaneously monitoring atmospheric gaseous compounds and particulate matter, which would further advance our understanding on gas-particle heterogeneous interactions in the context of climate change and air quality.

Intercomparison of NO3 under Humid Conditions with Open-Path and Extractive IBBCEAS in an Atmospheric Reaction Chamber

We report an open-path incoherent broadband cavity-enhanced absorption spectroscopy (OP-IBBCEAS) technique for in situ simultaneous optical monitoring of NO2, NO3, and H2O in a reaction chamber. The measurement precision values (1σ) are 2.9 ppbv and 2.9 pptv for NO2 and NO3 in 2 s, respectively, and the measurement uncertainties are 6% for NO2 and 14% for NO3. Intercomparison of measured concentrations of NO2 and NO3 by open-path and extractive IBBCEAS was carried out in the SAES-ARC reaction chamber during the reaction of NO2 with O3. The measurement accuracy of OP-IBBCEAS is verified by an NO2 intercomparison and the NO3 transmission efficiency of the extractive IBBCEAS is determined by comparison against the in situ NO3 measurement. The relationship between H2O absorption cross section and its mixing ratio at 295 K and 1 atm was analysed. Due to the spectral resolution of IBBCEAS system, the strong and narrow absorption lines of H2O are unresolved and exhibit non-Beer–Lambert Law behaviour. Therefore, a correction method is used to obtain the effective absorption cross section for fitting the H2O structure. An inappropriate H2O absorption cross section can cause an overestimation of NO3 concentration of about 28% in a humid atmosphere (H2O = 1.8%). This spectroscopic correction provides an approach to obtain accurate NO3 concentrations for open-path optical configurations, for example in chamber experiments or field campaigns. The measurement precision values are improved by a factor of 3 to 4 after applying Kalam filtering, achieving sub-ppbv (0.8 ppbv) and sub-pptv (0.9 pptv) performance in 2 s for NO2 and NO3, respectively.

CO Volume Fraction Measurement Based on Wavelength Modulated Cavity-Enhanced Absorption Spectroscopy

CO Volume Fraction Measurement Based on Wavelength Modulated Cavity-Enhanced Absorption Spectroscopy