Cavity Ring-down 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).

Accurate reference spectra of HD in an H2--He bath for planetary applications

The hydrogen deuteride (HD) molecule is an important deuterium tracer in astrophysical studies. The atmospheres of gas giants are dominated by molecular hydrogen, and the simultaneous observation of H$_2$ and HD lines provides reliable information on the D/H ratios on these planets. The reference spectroscopic parameters play a crucial role in such studies. Under the thermodynamic conditions encountered in these atmospheres, spectroscopic studies of HD require not only the knowledge of line intensities and positions but also accurate reference data on pressure-induced line shapes and shifts. Our aim is to provide accurate collision-induced line-shape parameters for HD lines that cover any thermodynamic conditions relevant to the atmospheres of giant planets, namely any relevant temperature, pressure, and perturbing gas composition (the H$_2$--He mixture). We performed quantum-scattering calculations on our new, highly accurate ab initio potential energy surface (PES) and we used scattering S matrices obtained in this way to determine the collision-induced line-shape parameters. We used cavity ring-down spectroscopy to validate our theoretical methodology. We report accurate collision-induced line-shape parameters for the pure rotational R(0), R(1), and R(2) lines, the most relevant HD lines for investigations of the atmospheres of the giant planets. Besides the basic Voigt-profile collisional parameters (i.e., the broadening and shift parameters), we also report their speed dependences and the complex Dicke parameter, which can influence the effective width and height of the HD lines up to almost a factor of 2 for giant planet conditions. The sub-percent-level accuracy reached in this work is a considerable improvement over previously available data. All the reported parameters (and their temperature dependences) are consistent with the HITRAN database format, hence allowing for the use of the HITRAN Application Programming Interface (HAPI) for generating the beyond-Voigt spectra of HD.

High-resolution investigation of the spin-rotation doublets of 14NO2 at 6.2 µm mid-infrared region using cavity ring-down spectroscopy

Nitrogen dioxide (14NO2) exhibits a unique doublet structure due to the presence of its unpaired electron, which results in a nonzero electronic angular momentum in the ground electronic state of the molecule. In this study, an investigation into high-resolution rovibrational spectral features associated with the spin-rotation doublets of 14NO2 was conducted using an external-cavity quantum cascade laser (EC-QCL)-coupled cavity ring-down spectrometer operating at 6.2 μm. Four spin-split doublets belonging to the RR branch of the (001)-(000) fundamental band were probed in the mid-IR spectral region. The air broadening and self-broadening coefficients were reported explicitly for each doublet component for the first time, to the best of our knowledge. The line-intensities were also quantified, and they were compared to the HITRAN database, revealing good agreement (<4% discrepancy).

Evaluation of Aeris mid-infrared absorption (MIRA), Picarro CRDS (cavity ring-down spectroscopy) G2307, and dinitrophenylhydrazine (DNPH)-based sampling for long-term formaldehyde monitoring efforts

Abstract. Current formaldehyde (HCHO) measurement networks rely on the TO-11A offline chemical derivatization technique, which can be resource intensive and limited in temporal resolution. In this work, we evaluate the field performance of three new commercial instruments for continuous in situ formaldehyde monitoring: the Picarro cavity ring-down spectroscopy G2307 gas concentration analyzer and Aeris Technologies' mid-infrared absorption Pico and Ultra gas analyzers. All instruments require regular drift correction, which is accomplished through instrument zeroing using dinitrophenylhydrazine (DNPH)-coated cartridges, Drierite, or molecular sieves, while heated Hopcalite failed to remove all incoming HCHO. We show that a modified precision estimate accounting for regular instrument zeroing results in values of 0.09, 0.20, and 0.22 ppb at a 20 min integration time for the G2307, Ultra, and Pico, respectively. After applying standard addition and dynamic dilution calibrations, all instruments agreed within 13 % and were well correlated with each other (all r ≥ 0.90). TO-11A HCHO observations resulted in a normalized mean bias of −58 % compared to co-located Picarro G2307 measurements (r=0.62, slope = 0.38, int = 0.07 ppb HCHO). Using a 6-month deployment period in the Atlanta metropolitan area, we determined that the Picarro G2307 and Aeris units have sufficient accuracy and precision to capture the Atlanta spatial HCHO gradient. We find that midday HCHO concentrations have decreased by 22.3 % since 1999 in the city's urban core, and DNPH measurements at a nearby Photochemical Assessment Monitoring Station (PAMS) site show a greater decrease of 53 %.

Advancement of Langmuir probe-based laser photo-detachment technique for negative ion density measurement in a high-power helicon plasma source.

In the pursuit of precise diagnostics for measuring negative ion density in a helicon plasma source (HPS), a new approach utilizing a radio frequency (RF) broadband transformer-based Langmuir probe is developed specifically for laser photo-detachment (LPD) analysis. This inductively coupled LPD technique is useful for high power RF systems in which capacitive RF noise is in the same scale as the pulsed photo-detachment signal. The signal acquired by this transformer-based probe is compared against the conventional Langmuir probe-based LPD technique, revealing a remarkable enhancement in signal fidelity through an improved signal-to-noise ratio (SNR) achieved by the RF broadband transformer methodology. In addition, the localized hydrogen negative ion density measurements obtained through this probe are harmoniously aligned with the line-averaged negative ion density derived from the cavity ringdown spectroscopy (CRDS) technique. These concurrence measurements highlight the RF broadband transformer-based approach's accuracy in capturing localized negative ion density during helicon mode operation in an HPS setup. Furthermore, the correlation of negative ion density values with RF input exhibits a consistent trend in tandem with background plasma density. Notably, both CRDS and LPD measurements ascertain negative ion densities ranging from ∼5 to 6×1016m-3 under an RF power of 500-700W and a pressure of 8 × 10-3mbar, all under the influence of a 55G axial magnetic field. These specific parameters represent the optimal operational configuration for effective negative ion production with the present experimental HPS setup. Due to its better SNR, the RF broadband transformer-based Langmuir probe emerges as a useful tool for LPD diagnostics, particularly in the presence of pervasive RF noise.

Investigation of non-target gas interferences on a multi-gas cavity ring-down spectrometer

Emissions from agriculture are a worldwide problem as it is the major anthropogenic source of ammonia, methane, and nitrous oxide. Several efforts have been made to mitigate emissions. To achieve this, reliable measuring techniques are necessary to quantify the impact of the emissions. Different techniques relying on different principles are available. Generally, these techniques demonstrate good agreement on their measurements but there is a lack of studies that thoroughly investigate cross-interferences. In this work, three different models of Cavity Ring-Down Spectrometers measuring ammonia, nitrous oxide, and methane were tested in parallel for potential biases due to interference from ammonia, water vapor, and twelve volatile organic compounds commonly present in agricultural environments. Our results showed a small negative bias with increasing humidity on nitrous oxide and minor interferences of ammonia on nitrous oxide and methane. None of the tested volatile organic compounds interfered with ammonia, methane, or nitrous oxide measurements. Overall, concentration measurements of ammonia, nitrous oxide, and methane with cavity ring-down spectrometry have proven reliable under typical agricultural conditions. Minor interferences were only observed under exceptional conditions.

A novel approach to estimate methanogenic pathways in biogas reactors via stable carbon isotope analysis

Two microbial pathways are responsible for most of the methane produced during anaerobic digestion: acetoclastic methanogenesis (AM) and hydrogenotrophic methanogenesis (HM) coupled with syntrophic acetate oxidation (SAO). Identifying the dominant methanogenic pathway active in a system provides the information necessary to manage and optimize productivity, stability, process control, and gas quality in biogas reactors. In this study, a modified method is proposed to estimate methanogenic pathways in different biogas systems via short-term parallel incubations with methyl-labeled acetate (2-13C-acetate). Cavity ring-down spectroscopy was applied to measure the δ13C–CH4 and δ13C–CO2 isotopic signatures of produced biogas. Preliminary experiments demonstrated that longer incubation times led to significant variations in δ13C–CH4 and δ13C–CO2 and consequently interfered with the calculated fraction of CH4 produced from HM (fHM). This variability is likely caused by the dilution of 13CH4 and 13CO2 as 2-13C-acetate is consumed, along with potential changes in organic matter quality and quantity, microbial community composition, and environmental factors such as pH, volatile fatty acid content, and ammonia levels, during longer incubations. We applied this new approach to sludge from six full-scale reactors (three mesophilic and three thermophilic) and validated its potential with consistent estimates of fHM with minimal variation. Mesophilic reactors exhibited AM dominance, while HM was the dominant pathway in thermophilic reactors, aligning with reports in the literature.

Mid-infrared trace detection with parts-per-quadrillion quantitation accuracy: Expanding frontiers of radiocarbon sensing

Detection sensitivity is a critical characteristic to consider during selection of spectroscopic techniques. However, high sensitivity alone is insufficient for spectroscopic measurements in spectrally congested regions. Two-color cavity ringdown spectroscopy (2C-CRDS), based on intra-cavity pump-probe detection, simultaneously achieves high detection sensitivity and selectivity. This combination enables mid-infrared detection of radiocarbon dioxide ([Formula: see text]CO[Formula: see text]) molecules in room-temperature CO[Formula: see text] samples, with 1.4 parts-per-quadrillion (ppq, 10[Formula: see text]) sensitivity (average measurement precision) and 4.6-ppq quantitation accuracy (average calibrated measurement error for 21 samples from four separate trials) demonstrated on samples with [Formula: see text]C/C up to [Formula: see text]1.5[Formula: see text] natural abundance ([Formula: see text]1,800 ppq). These highly reproducible measurements, which are the most sensitive and quantitatively accurate in the mid-infrared, are accomplished despite the presence of orders-of-magnitude stronger, one-photon signals from other CO[Formula: see text] isotopologues. This is a major achievement in laser spectroscopy. A room-temperature-operated, compact, and low-cost 2C-CRDS sensor for [Formula: see text]CO[Formula: see text] benefits a wide range of scientific fields that utilize [Formula: see text]C for dating and isotope tracing, most notably atmospheric [Formula: see text]CO[Formula: see text] monitoring to track CO[Formula: see text] emissions from fossil fuels. The 2C-CRDS technique significantly enhances the general utility of high-resolution mid-infrared detection for analytical measurements and fundamental chemical dynamics studies.

Investigating the influence of solvent type and pH on protein adsorption onto silica surface by evanescent-wave cavity ring-down spectroscopy.

Several studies have explored the adsorption of various proteins onto solid-liquid interfaces, revealing the crucial role of buffer solutions in biological processes. However, a comprehensive evaluation of the buffer's influence on protein absorption onto fused silica is still lacking. This study employs evanescent-wave cavity ring-down spectroscopy (EW-CRDS) to assess the influence of buffer solutions and pH on the adsorption kinetics of three globular proteins: hemoglobin (Hb), myoglobin (Mb), and cytochrome c (Cyt-C) onto fused silica. The EW-CRDS tool, with a ring-down time of and a minimum detectable absorbance of , enabled precise optical measurements at solid-liquid interfaces. The three heme proteins' adsorption behavior was investigated at pH 7 in three different solvents: deionized (DI) water, tris(hydroxymethyl)-aminomethane hydrochloride (Tris-HCl), and phosphate buffered saline (PBS). For each protein, the surface coverage, the adsorption and desorption constants, and the surface equilibrium constant were optically measured by our EW-CRDS tool. Depending on the nature of each solvent, the proteins showed a completely different adsorption trend on the silica surface. The adsorption of Mb on the silica surface was depressed in the presence of both Tris-HCl and PBS buffers compared with unbuffered (DI water) solutions. In contrast, Cyt-C adsorption appears to be relatively unaffected by the choice of buffer, as it involves strong electrostatic interactions with the surface. Notably, Hb exhibits an opposite trend, with enhanced protein adsorption in the presence of Tris-HCl and PBS buffer. The pH investigations demonstrated that the electrostatic interactions between the proteins and the surface had a major influence on protein adsorption on the silica surface, with adsorption being greatest when the pH values were around the protein's isoelectric point. This study demonstrated the ability of the highly sensitive EW-CRDS tool to study the adsorption events of the evanescent-field-confined protein species in real-time at low surface coverages with fast resolution, making it a valuable tool for studying biomolecule kinetics at solid-liquid interfaces.

Rovibrational Energies of 13C16O2 Determined with Kilohertz Accuracy.

Accurate spectroscopic data of carbon dioxide are widely used in many important applications, such as carbon monitoring missions. Here, we present comb-locked cavity ring-down saturation spectroscopy of the second most abundant isotopologue of CO2, 13C16O2. We determined the positions of 88 lines in three vibrational bands in the 1.6 μm region, 30011e/30012e/30013e-00001e, with an accuracy of a few kHz. Based on the analysis of combination differences, we obtained for the first time the ground-state rotational energies with kHz accuracy. We also provide a set of hybrid line positions for 150 13C16O2 transitions. The rotational energies (J < 50) in the 30013e vibrational state can be fitted by a set of rotational and centrifugal constants with deviations within a few kHz, indicating that the 30013e state is free of perturbations. These precise isotopic line positions will be utilized to improve the Hamiltonian model and quantitative remote sensing of carbon dioxide. Moreover, they will help to track changes in the carbon source and sink through isotopic analysis.

A protocol for distilling animal body water from biological samples and measuring oxygen and hydrogen stable isotopes via cavity ring-down spectroscopy

ABSTRACT The application of stable isotope analysis (SIA) to the fields of ecology and animal biology has rapidly expanded over the past three decades, particularly with regards to water analysis. SIA now provides the opportunity to monitor migration patterns, examine food webs, and assess habitat changes in current and past study systems. While carbon and nitrogen SIA of biological samples have become common, analyses of oxygen or hydrogen are used more sparingly despite their promising utility for tracing water sources and animal metabolism. Common ecological applications of oxygen or hydrogen SIA require injecting enriched isotope tracers. As such, methods for processing and analyzing biological samples are tailored for enriched tracer techniques, which require lower precision than other techniques given the large signal-to-noise ratio of the data. However, instrumentation advancements are creating new opportunities to expand the applications of high-throughput oxygen and hydrogen SIA. To support these applications, we update methods to distill and measure water derived from biological samples with consistent precision equal to, or better than, ± 0.1 ‰ for δ 17O, ± 0.3 ‰ for δ 18O, ± 1 ‰ for δ 2H, ± 2 ‰ for d-excess, and ± 15 per meg for Δ 17O.

Six years of continuous carbon isotope composition measurements of methane in Heidelberg (Germany) – a study of source contributions and comparison to emission inventories

Abstract. Mitigation of greenhouse gases requires a precise knowledge of their sources at both global and regional scales. With improving measurement techniques, in situ δ(13C,CH4) records are analysed in a growing number of studies to characterise methane emissions and to evaluate inventories at regional and local scales. However, most of these studies cover short time periods of a few months, and the results show a large regional variability. In this study, a 6-year time record of in situ δ(13C,CH4), measured with a cavity ring-down spectroscopy (CRDS) analyser in Heidelberg, Germany, is analysed to obtain information about seasonal variations and trends of CH4 emissions. The Keeling plot method is applied to atmospheric measurements on different timescales, and the resulting source contributions are used to evaluate the CH4 emissions reported by two emission inventories: the Emissions Database for Global Atmospheric Research (EDGAR v6.0) and the inventory of the State Institute for the Environment Baden-Württemberg (LUBW). The mean isotopic carbon source signature for the Heidelberg catchment area derived from atmospheric measurements is (-52.3±0.4) ‰ and shows an annual cycle with 5.8 ‰ more depleted values in summer than in winter. This annual cycle can only be partly explained by seasonal variations in the 13C-enriched emissions from heating and reveals strong seasonal variations in biogenic CH4 emissions in the Heidelberg catchment area, which are not included in EDGAR v6.0. The comparison with emission inventories also shows that EDGAR v6.0 overestimates the CH4 emissions from less depleted sources. In situ CH4 isotope analysers at continental and urban monitoring stations can make an important contribution to the verification and improvement of emission inventories.

A portable instrument for measurement of atmospheric Ox and NO2 based on cavity ring-down spectroscopy

Atmospheric Ox (nitrogen dioxide (NO2) + ozone (O3)) can better reflect the local and regional change characteristics of oxidants compared to O3 alone, so obtaining Ox accurately and rapidly is the basis for evaluating the O3 production rate. Furthermore, Ox has proved to be a more representative indicator and can serve as a reflection of pollution prevention efficacy. A portable instrument for measuring atmospheric Ox and NO2 based on cavity ring-down spectroscopy (Ox/NO2-CRDS) was developed in this work. The NO2 concentration is accurately measured according to its absorption characteristic at 407.86 nm. Ambient O3 is converted into NO2 by chemical titration of high concentrations of nitrogen oxide (NO), and the O3 conversion efficiencies obtained are nearly 99%. The detection limit of the Ox/NO2-CRDS system for Ox is 0.024 ppbv (0.1 s), and the overall uncertainty of the instrument is ± 6%. Moreover, the Kalman filtering technique was applied to improve the measurement accuracy of Ox/NO2-CRDS. The system was applied in a comprehensive field observation campaign at Hefei Science Island from 26 to 30 September 2022, and the time concentration series and change characteristics of Ox and NO2 were obtained for five days. The measured Ox concentrations were compared with those of two commercial instruments, and the consistency was good (R2 = 0.98), indicating that this system can be deployed to accurately and rapidly obtain the concentrations of atmospheric Ox and NO2. It will be a useful tool for assessing the atmospheric oxidation capacity and controlling O3 pollution.摘要大气Ox (二氧化氮(NO2)+臭氧(O3))相比于O3能够更好的反应区域氧化剂的变化特征, Ox也是反应大气污染防治效果的一个关键指标. 本研究基于腔衰荡光谱技术研发了一套大气Ox和NO2同步测量系统 (Ox/NO2-CRDS). NO2浓度是利用其在407.86 nm处的特征吸收获取, 环境大气的O3通过高浓度的NO被转化为NO2进行间接测量, O3转化效率高于99%, Ox/NO2-CRDS的系统探测限为0.024 ppbv (0.1 s), 系统总不确定度为± 6%. 该Ox/NO2-CRDS系统成功应用于2022年9月26日–30日的合肥市科学岛综合外场观测中, 获取了连续5天的NO2和Ox的时间浓度序列和变化特征, 并将Ox的测量结果与商业化的设备进行了对比验证, 二者具有较好的一致性 (R2 = 0.98), 表明Ox/NO2-CRDS能够被应用于大气Ox和NO2的高灵敏探测. 未来该系统也将会变成评估大气氧化性以及控制臭氧污染的重要工具.

Comparative Analysis of Water Isotopic Compositions: Evaluating Isotope Analyzer for Soil and Extraction Method for Stem Water

Stable isotopes of water (δ2H and δ18O) are reliable tracers for the investigation of plant–soil–water interactions in forest ecosystems. However, variations in isotopic compositions may arise due to differences in analytical instruments and water extraction methods. In this study, we conducted three different experiments to identify isotopic differences caused by analytical and methodological variations. First, we analyzed soil water by using the two most commonly applied methods: isotope ratio mass spectrometry (IRMS) and cavity ring-down spectroscopy (CRDS). Second, we compared the isotopes in xylem water extracted from the stems of nine tree species using cryogenic vacuum distillation (CVD) with different heating times. Third, we compared the compositions in xylem water extracted with three different methods: mechanical squeezing using a pressure chamber (PC), an induction module (IM), and CVD. The differences in isotopic composition between IRMS and CRDS were significant but minimal. Soil properties were not significant factors contributing to differences between the two instruments. For the xylem water extraction with CVD, each of the nine tree species required heating for more than three hours. Significant differences were observed in δ2H among the three extraction methods for xylem water. Xylem water extracted by CVD showed more depleted values compared to those obtained by PC and IM. Our results highlight the importance of considering analytical and methodological variations in stable isotope analysis.

The collision-induced absorption of H2 near 1.20 µm: Subatmospheric measurements and validation tests of calculations

The weak binary collision-induced absorption (CIA) of molecular hydrogen is measured at room temperature in the first overtone region near 1.20 µm. Binary absorption coefficients are derived by cavity ring down spectroscopy (CRDS) at 28 selected spectral points sampling the (2–0) band between 7974 and 8650 cm−1. While all previous studies used high density samples, the sensitivity of the CRDS method allowed deriving accurate CIA by using pressure ramps of pure H2 limited to a maximum pressure of 1 atm. After subtraction of the Rayleigh contribution, a purely quadratic pressure dependence is obtained for the absorption coefficient at each measurement point and the CIA binary coefficients are derived with a 1.5 % accuracy. The comparison to theoretical values widely used for astronomical applications shows deviations values between 5 and 25 %.

Affordable event and monthly rain samplers: Improving isotopic datasets to understand meteorological processes.

Water-stable isotopes in rainfall are powerful tracers of atmospheric processes at different spatial and temporal scales. However, commercially available rain samplers for isotopic analysis are prohibitively expensive, especially for high spatial resolution networks and studies conducted in developing countries. A low-cost, simple, and robust sampler was designed for event and monthly rainfall samplings. Rainfall collectors were built based on existing designs provided in the literature and using easily accessible materials. Event samplers were filled with different volumes of reference water and left for 72 h in laboratory conditions to determine the minimum amount of rainfall to be collected to minimize isotopic fractionation, from both postsampling evaporation and equilibration. Samples were analyzed using dual-inlet isotope ratio mass spectrometry and cavity ring-down spectroscopy. For samples larger than 4% of the bottle's capacity, the evaporative enrichment due to Rayleigh distillation is negligible compared to the overall analytical uncertainty. Using a tube connecting the funnel to the water sample has proved to reduce postsampling evaporation by at least five times. To limit water self-diffusion, we recommend collecting the largest rainfall amount possible. Under these conditions, these collectors are suitable for rainfall sampling for isotopic analysis. This low-cost methodology will enable isotopic sampling of precipitation at high spatial resolutions and democratize the use of isotopes for hydrological studies in developing countries. All instructions for building and using these samplers are made openly accessible to the scientific community so they can be repeated and adapted to the needs of each project.

Collision-broadening of vibration-inversion-rotation ammonia spectral lines in Q(J)-branch at 6.2 µm by cavity ring-down spectroscopy

In this experimental investigation, collision broadening effects on the Q(J)-branch vibration-inversion-rotation spectral lines of ammonia (NH3) within the fundamental ν4 asymmetric bending vibrational band in the 6.2 µm mid-IR region are reported. A continuous-wave external-cavity quantum cascade laser coupled with a high-sensitive cavity ring-down spectrometer was employed to selectively probe 10 transitions in high-resolution, including few inversion doublets of gaseous NH3. Pressure-broadening coefficients, γNH3-Xi (Xi = He, Ar, N2, O2, zero-air) in cm−1 atm−1, characterizing the collision interaction between NH3 and various external perturbing gases, including helium, argon, nitrogen, oxygen, and zero-air, were determined at room temperature (296 K). Mean collision times and optical collision diameters of each collision partner were explored to gain deeper insight into the perturber-induced collision dynamics. This investigation elucidates the intricate intermolecular interactions and collision phenomena induced by various foreign perturbers with NH3, with potential implications for future spectroscopic and atmospheric research of this polyatomic molecule.

Detection of negative ions in streamer discharge in air by transient cavity ringdown spectroscopy

Atmospheric-pressure discharges generated in air are expected to be electronegative, but experiments that examine negative ion densities are limited to date. In this work, we measured the temporal variation of the negative ion density in a streamer discharge generated in air. We adopted cavity ringdown spectroscopy, where negative ions were detected via weak optical absorption caused by laser photodetachment. The temporal variation of the absolute negative ion density was deduced by the transient analysis of the ringdown curve. Negative ions were detected after the disappearance of the discharge voltage and current. The negative ion density started the increase at 0.4 µs after the initiation of the discharge. The increase means the enhancement of the electron attachment frequency in the late phase of the secondary streamer with electron cooling. The survival of electrons until 0.4 µs is understood by the steep decrease in the cross section of dissociative recombination with the electron energy. The maximum negative ion density was observed at 1 µs, and it was around the noise level at 1.5 µs. The rapid decay is consistent with the destruction of negative ions by mutual neutralization with positive ions.

Two common pitfalls in the analysis of water‐stable isotopologues with cryogenic vacuum extraction and cavity ring‐down spectroscopy

AbstractWater stable isotopologue analysis is widely used to disentangle ecohydrological processes. Yet, there are increasing reports of measurement uncertainties for established and emerging methods, such as cryogenic vacuum extraction (CVE) or cavity ring‐down spectroscopy (CRDS). With this study, we investigate two pitfalls, that potentially contribute to uncertainties in water‐stable isotopologue research. To investigate fractionation sources in CVE, we extracted pure water of known isotopic composition with cotton, glass wool or without cover and compared the isotopologue results with non‐extracted reference samples. To characterise the dependency of δ2H and δ18O on the water mixing ratio in CRDS, which is of high importance for in‐situ applications with large natural variations in mixing ratios, we chose samples with a large range of isotopic compositions and determined δ2H and δ18O for different water mixing ratios with two CRDS analysers (Picarro, Inc.). Cotton wool had a strong fractionation effect on δ2H values, which increased with more 2H‐enriched samples. δ2H and δ18O values showed a strong dependency on the water mixing ratio analysed with CRDS with differences of up to 34.5‰ (δ2H) and 3.9‰ (δ18O) for the same sample at different mixing ratios. CVE and CRDS, now routinely applied in water stable isotopologue research, come with pitfalls, namely fractionation effects of cover materials and water mixing ratio dependencies of δ2H and δ18O, which can lead to erroneous isotopologue results and thus, invalid conclusions about (ecohydrological) processes. These practical issues identified here should be reported and addressed adequately in water‐stable isotopologue research.

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.