Search

δ17O and Δ’17O are emerging tracers increasingly used in isotope hydrology, climatology, and biochemistry. Differentiating small relative abundance changes in the rare 17O isotope from the strong covariance with 18O imposes ultra-high precision requirements for this isotope analysis. Measurements of δ17O by Cavity Ringdown Spectroscopy (CRDS) are attractive due to the ease of sample preparation, automated throughput, and avoidance of chemical conversions needed for isotope-ratio mass spectrometry. However, the CRDS approach requires trade-offs in measurement precision and uncertainty. In this protocol document, we present the following: • New analytical procedures and a software tool for conducting δ17O and Δ’17O measurements by CRDS. • Outline a robust uncertainty framework for Δ’17O determinations. • Description of a CRDS performance framework for optimizing throughput, instrumental stability, and Δ’17O measurement precision and accuracy.

Background: Lung cancer is one of the most common malignant tumors worldwide. Currently, effective screening methods for early lung cancer are still scarce. Breath analysis provides a promising method for the pre-screening or early screening of lung cancer. Isoprene is a potential and important breath biomarker of lung cancer. Material and Methods: To investigate the clinical value of isoprene for diagnosing lung cancer patients, a cavity ringdown spectroscopy (CRDS) based near-real time, sensitive analysis method of breath isoprene is developed in our lab. In this paper, 92 breath samples from lung cancer patients, 17 breath samples from patients with benign lesions, and 107 breath samples from healthy people were collected. Results: Research indicates that breath isoprene concentration is significantly higher in healthy individuals ([Formula: see text][Formula: see text]ppbv) than in patients with lung cancer ([Formula: see text][Formula: see text]ppbv) and benign lung lesions ([Formula: see text][Formula: see text]ppbv). The result of Receiver Operating Characteristic (ROC) curve suggests that the concentration of isoprene is meaningful for the diagnosis of lung cancer ([Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text]). Conclusion: This study demonstrates that the CRDS breath isoprene analysis system can effectively analyze a large sample of human breath isoprene, and preliminarily confirms the use of breath isoprene as a biomarker for lung diseases.

Mid-infrared laser absorption spectroscopy utilizing a high-finesse optical cavity enables high precision trace analysis of gas molecules. In particular, optical detection of radiocarbon (14C) based on cavity ringdown spectroscopy using a quantum cascade laser (QCL) is gaining attention as an alternative to accelerator mass spectrometry. This paper reports a compact-packaged narrow-linewidth QCL system utilizing resonant optical feedback from an external V-shaped cavity. Based on frequency noise analysis, the derived laser linewidth is 44 kHz for 100 μs integration time with the capability to perform seamless frequency scanning around 10 GHz. We installed this laser system within a table-top cavity ringdown spectrometer for 14CO2. A single-shot detection limit of 1.2 × 10−9 cm−1 Hz−1/2 leading to a detectable abundance evaluated from a noise analysis of 0.2 in fraction modern 14C for a 10-s averaging time was achieved. This capability of rapid analysis for 14CO2 is suitable for various applications requiring trace 14C analysis. [ABSTRACT FROM AUTHOR]

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 µ s 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 µ s 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 µ s, and it was around the noise level at 1.5 µ s. The rapid decay is consistent with the destruction of negative ions by mutual neutralization with positive ions. [ABSTRACT FROM AUTHOR]

Forward scattering is an essential tool for investigating the colloidal suspension of polystyrene microspheres (PSMs). Evanescent wave coupled cavity ringdown spectroscopy (EW-CRDS) shows the anomalous extinction behavior in the limit of PSM particles that is much larger than the wavelength. EW-CRDS is a highly sensitive technique that improves weak absorption signals by enhancing the absorption path length, allowing for probing a range of processes at the solid/liquid interface by assessing the extinction properties. Additionally, it possesses the ability to sense a minimum absorbance of 1.2 × 10 -6 . EW-CRDS provides sufficient accuracy to detect correlation effects for PSMs in water at the interfacial region and their influence on forward scattering or extinction. In this work, we discuss the impact of volume fraction on the extinction of scatterers composed of microparticles in aqueous media. The findings of this study will contribute to a deeper understanding of the scattering dynamics in colloidal suspensions, with potential applications in various fields, including biology and metrology.

To effectively monitor highly heterogeneous urban CO2 emissions using atmospheric observations, there is a need to deploy cost-effective CO2 sensors at multiple locations within the city with sufficient accuracy to capture the concentration gradients in urban environments. These dense measurements could be used as input of an atmospheric inversion system for the quantification of emissions at the sub-city scale or to separate specific sectors. Such quantification would offer valuable insights into the efficacy of local initiatives and could also identify unknown emission hotspots that require attention. Here we present the development and evaluation of a mid-cost CO2 instrument designed for continuous monitoring of atmospheric CO2 concentrations with a target accuracy of 1 ppm for hourly mean measurements. We assess the sensor sensitivity in relation to environmental factors such as humidity, pressure, temperature and CO2 signal, which leads to the development of an effective calibration algorithm. Since July 2020, eight mid-cost instruments have been installed within the city of Paris and its vicinity to provide continuous CO2 measurements, complementing the seven high-precision cavity ring-down spectroscopy (CRDS) stations that have been in operation since 2016. A data processing system, called CO2calqual, has been implemented to automatically handle data quality control, calibration and storage, which enables the management of extensive real-time CO2 measurements from the monitoring network. Colocation assessments with the high-precision instrument show that the accuracies of the eight mid-cost instruments are within the range of 1.0 to 2.4 ppm for hourly afternoon (12:00–17:00 UTC) measurements. The long-term stability issues require manual data checks and instrument maintenance. The analyses show that CO2 measurements can provide evidence for underestimations of CO2 emissions in the Paris region and a lack of several emission point sources in the emission inventory. Our study demonstrates promising prospects for integrating mid-cost measurements along with high-precision data into the subsequent atmospheric inverse modeling to improve the accuracy of quantifying the fine-scale CO2 emissions in the Paris metropolitan area. [ABSTRACT FROM AUTHOR]

We developed a cavity ringdown spectrometer by utilizing a step-scanning and dithering method for matching laser wavelengths to optical resonances of an optical cavity. Our approach is capable of working with two and more lasers for quasi-simultaneous measurements of multiple gas species. The developed system was tested with two lasers operating around 1654 nm and 1658 nm for spectral detections of 12CH4 and its isotope 13CH4 in air, respectively. The ringdown time of the empty cavity was about 340 µs. The achieved high detection sensitivity of a noise-equivalent absorption coefficient was 2.8 × 10−11 cm−1 Hz−1/2 or 1 × 10−11 cm−1 by averaging for 30 s. The uncertainty of the high precision determination of δ13CH4 in air is about 1.3‰. Such a system will be useful for future applications such as environmental monitoring.

We present an ultra-sensitive continuous wave cavity ringdown spectroscopy (cw-CRDS) spectrometer to record high resolution spectra of reactive radicals and ions in a pulsed supersonic plasma. The spectrometer employs a home-made external cavity diode laser as the tunable light source, with its wavelength modulated by radio-frequency white noise. The ringdown cavity with a finesse of ∼105 is arranged with an off-axis alignment. The combination of the off-axis cavity and the white-noise perturbed laser yields quasi-continuum laser-cavity coupling without the need of mode matching. The cavity is further incorporated with an extra multi-pass cavity for optical re-injection of light reflected off the master cavity, which significantly increases the throughput power of the high-finesse cavity. A fast switchable semiconductor optical amplifier is used to modulate the cw laser beam to square wave pulses and to initialize timing controlled ringdown events, which are synchronized to the plasma pulses with an accuracy of ∼3 µs. The performance and potential of the cw-CRDS spectrometer are illustrated and discussed, based on the high resolution near-infrared spectroscopic detection of trace 13C13C radicals generated in a pulsed supersonic C2H2/Ar plasma with a pulse duration of ∼50 µs., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

The argon excimer ( Ar 2 * ) species is considered to play an important role in the chemistry of cold atmospheric plasma jets, notably in the formation of reactive oxygen and nitrogen species. In the present work, we demonstrate that cavity ringdown spectroscopy can be used to detect and quantitatively measure Ar 2 * in the effluent of a cold atmospheric plasma jet, the so-called kINPen-Sci. The spectroscopic features of the 5p π 3 Π g ← a3 Σ u + Δ ν = 0 and 7p σ 3 Σ g + ← a3 Σ u + (ν ′ - ν ″) systems were clearly identified allowing unambiguous assignment to the Ar 2 * species. A predominant absorption feature at 512 nm was used to determine the integrated density along the axis perpendicular to the gas flow. Assuming a homogeneous density distribution in the kINPen-Sci effluent, Ar 2 * densities from 1.8 × 1011 molecule · cm−3 at 0 mm to 1.3 × 1010 molecule · cm−3 at 4.2 mm below the nozzle tip were determined. [ABSTRACT FROM AUTHOR]

Optical feedback cavity ringdown spectroscopy is presented with a linear Fabry–Pérot cavity and a cost-effective DFB laser. To circumvent the low coupling efficiency caused by the broad laser linewidth, an optical feedback technique is used, and an enhanced coupling efficiency of 31%, mainly limited by impedance mismatch and mode mismatch, is obtained. The trigger of the ringdown event is realized by the shutoff of the laser driving current, and a novel method with the aid of one electronic switch is applied to avoid the ringdown events excited by the unexpected cavity modes during the process of laser current recovery. As a result, the ringdown signal with a signal-to-noise ratio of 2500 is achieved. Through continuous monitoring, the fractional uncertainty of the empty cavity ringdown times is assessed to be 0.04%. An Allan variance analysis indicates a detection sensitivity of 4.3 × 10−10 cm−1 is resulted at an integration time of 120 s, even with a moderate finesse cavity. To further improve the long-term stability, we regularly rectify the empty cavity ringdown time, and an improvement factor of 2.5 is demonstrated.

The present study addresses advanced monitoring techniques for particles and airborne molecular contaminants (AMCs) in cleanroom environments, which are crucial for ensuring the integrity of semiconductor manufacturing processes. We focus on quantifying particle levels and a representative AMC, hydrogen chloride (HCl), having known detrimental effects on equipment longevity, product yield, and human health. We have developed a compact laser sensor based on open-path cavity ring-down spectroscopy (CRDS) using a 1742 nm near-infrared diode laser source. The sensor enables the high-sensitivity detection of HCl through absorption by the 2-0 vibrational band with an Allan deviation of 0.15 parts per billion (ppb) over 15 min. For quantifying particle number concentrations, we examine various detection methods based on statistical analyses of Mie scattering-induced ring-down time fluctuations. We find that the ring-down distributions' 3rd and 4th standard moments allow particle detection at densities as low as ~105 m−3 (diameter > 1 μm). These findings provide a basis for the future development of compact cleanroom monitoring instrumentation for wafer-level monitoring for both AMC and particles, including mobile platforms. [ABSTRACT FROM AUTHOR]

Ammonia (NH3) is a pyramidal symmetric top molecule with inversion motion and it exists in two distinct nuclear spin isomeric forms, ortho-NH3 (K = 3n) and para-NH3 (K ≠ 3n). Here, a pair of electric dipole-allowed [RQ(4,3) and PP(2,2)] and weak forbidden [OP(3,3) and SQ(8,1)] transitions of gas-phase NH3 were probed in the ν4 fundamental vibrational band occurring at 6.2 µm mid-IR interference-free spectral region using an external-cavity quantum cascade laser coupled cavity ring-down spectrometer. We have experimentally achieved the ortho-to-para ratio (OPR) of (1.03 ± 0.24) and (1.08 ± 0.14) at room temperature (296 K) for the allowed and forbidden transitions of NH3, respectively. Furthermore, our experimental findings confirm that the nuclear spin-symmetry is conserved under the nonreactive perturber-induced collisional processes. This study paves the way to directly probe the nuclear spin-isomers of gas-phase NH3 and thus may lead to an in-depth understanding of nuclear spin-isomerism associated with various physical and chemical processes. This work shows the high-resolution probing of ortho- and para-nuclear spin-isomers of NH3 in the gas phase at room temperature using quantum cascade laser coupled cavity ring-down spectroscopy at 6.2 µm mid-IR spectral region. [ABSTRACT FROM AUTHOR]

In situ measurements of water vapour isotopic composition in polar regions has provided needed constrains of post-deposition processes involved in the archiving of the climatic signal in ice core records. During polar winter, the temperatures, and thus the specific humidity, are so low that current commercial techniques are not able to measure the vapour isotopic composition with enough precision. Here, we make use of new developments in infrared spectroscopy and combine an optical-feedback frequency-stabilised laser source (OFFS technique) using a V-shaped cavity optical feedback (VCOF) cavity and a high-finesse cavity ring-down spectroscopy (CRDS) cavity to increase the signal-to-noise ratio while measuring absorption transitions of water isotopes. We present a laboratory infrared spectrometer leveraging all these techniques dedicated to measure water vapour isotopic composition at low humidity levels. At 400 ppmv , the instrument demonstrates a precision of 0.01 ‰ and 0.1 ‰ in δ18O and d-excess, respectively, for an integration time of 2 min. This set-up yields an isotopic composition precision below 1 ‰ at water mixing ratios down to 4 ppmv , which suggests an extrapolated precision in δ18O of 1.5 ‰ at 1 ppmv. Indeed, thanks to the stabilisation of the laser by the VCOF, the instrument exhibits extremely low drift and very high signal-to-noise ratio. The instrument is not hindered by a strong isotope–humidity response which at low humidity can create extensive biases on commercial instruments. [ABSTRACT FROM AUTHOR]

Accurate measurement of water vapor isotopes (δ18O and δ2H) is fundamental for advancing our understanding of the hydrological cycle and improving hydrological model accuracy. This study introduces an innovative calibration methodology using a controlled evaporation mixer (CEM) for determining stable isotopic ratios in atmospheric water vapor via cavity ring-down spectroscopy. The CEM technique reliably produces a stable water vapor stream, crucial for enhancing the precision and accuracy of isotopic measurements. Its rapid adaptation to changes in water vapor concentration and compatibility with different water standards enhance calibration reliability. Demonstrated reproducibility in generating water vapor across a broad concentration range from 900 to over 25,000 ppmv, coupled with a substantial reduction in memory effects, makes this approach highly effective in both laboratory and field settings. This calibration advancement greatly enhances research capabilities for continuous atmospheric water vapor analysis, providing deeper insights into hydrological processes and atmospheric dynamics. [ABSTRACT FROM AUTHOR]

A wide-range, calibration-free tunable diode laser spectrometer is established by combining wavelength modulation and direct absorption spectroscopy (WM-DAS) with continuous wave cavity ringdown spectroscopy (CW-CRDS). This spectrometer combines the benefits of absolute concentration measurements, wide range, and high speed, using WM-DAS with enhanced noise reduction in CW-CRDS. The accurate baseline ringdown time, τ0, is calculated by the absorption peak (measured by WM-DAS) and the ringdown time containing gas absorption information (measured by CW-CRDS at the center wavelength of the spectral line). The gas concentration is obtained without measuring τ0 in real time, thus, greatly improving the measuring speed. A WM-DAS/CW-CRDS spectrometer at 1.57 μm for CO detection was assembled for experimental validation of the multiplexing scheme over a concentration ranging from 4 ppm to 1.09% (0.1 MPa, 298 K). The measured concentration of CO at 6374.406 cm−1 shows that the dynamic range of this tunable diode laser absorption spectrometer is extendable up to five orders of magnitude and the corresponding precision is improved. The measurement speed of this spectrometer can extend up to 10 ms, and the detection limit can reach 35 ppb within 25 s.

We report a proof-of-principle demonstration of intracavity pump–probe, cavity ringdown (CRD) detection in a three-mirror, traveling-wave cavity. With cavity-enhanced pump power and probe absorption path length, the technique is a generally applicable, high-sensitivity, high-selectivity detection method. In our experiments, the pump radiation is switched off during every other probe ringdown, which allows uncorrelated measurements of analyte and background cavity decay rates. The net, two-color signal from the difference between the pump-on and pump-off decay rates is immune to empty-CRD drifts and spectral overlaps from non-target molecular transitions. The immunity to the ringdown drifts allows longer signal-averaging and, thus, higher detection sensitivity. The ability to compensate for the background absorption enhances the detection selectivity in spectrally congested regions. Our technique is well-suited for trace-detection in the mid-IR region, where pump–probe schemes based on strong rovibrational transitions can be applied. In this work, two-color CRD detection is implemented on a ladder-type, three-level system based on the N2O, ν3 = 1 ← 0, P(19) (pump) and ν3 = 2 ← 1, R(18) (probe), rovibrational transitions. By frequency-locking two-quantum cascade lasers to the p-polarization (pump, Finesse = 5280) and s-polarization (probe, Finesse = 67 700) cavity modes, we achieve high intracavity pump power (36 W) and high probe ringdown rates (>2 kHz). The observed two-color spectra are simulated by a density-matrix, three-level system model that is solved under the constraints of the cavity resonance conditions. In addition to its background compensation capability, experimental flexibility in the selection of pump–probe schemes and signal insensitivity to intracavity laser power are further features that enhance the utility of our technique for mid-IR trace-detection. [ABSTRACT FROM AUTHOR]

The N-H⋯OC hydrogen bond (H-bond) plays a key role in stabilizing the geometry and energy of biomolecules such as protein folding and DNA double strand. To investigate N-H⋯OC H-bonds in a microscopic view, we apply IR cavity ringdown spectroscopy (IR-CRDS) and density functional theory (DFT) calculation to pyrrole-diethyl ketone (Py-Dek) clusters in the gas phase. Dek exhibits a pentane carbon chain, which provides various conformations such as anti , gauche , and their mixtures. An introduction of the carbon-chain flexibility to Py-Dek clusters is expected to cause a diversity of the N-H⋯OC H-bond formation. In the observed IR spectra, there are seven prominent bands of the NH stretches due to Py-Dek clusters. These bands are classified into three groups: one for Py 1 -Dek 1 , two for Py 1 -Dek 2 , and four for Py 2 -Dek 1 . Stable structures and their harmonic frequencies obtained by DFT calculations provide the proper NH band assignments and appropriate cluster structures. Py 1 -Dek 1 exhibits a single isomer, which is formed by an ordinary N-H⋯OC H-bond between Py and anti-conformation of Dek (Dek(a)) with a linear carbon-chain. Py 1 -Dek 2 shows two isomeric structures, in which both isomers are commonly constructed by the N-H⋯OC H-bond for the first Dek and by the stacking interaction between π electrons of Py and the second Dek. Both isomers exhibit the Dek(a) for the stacking interaction, but are distinguished between Dek(a) and gauche -conformation Dek (Dek(g)) for the N-H⋯OC H-bond. Py 2 -Dek 1 shows a triangular cyclic structure, which is formed by the N-H⋯OC H-bond, the N-H⋯π H-bond, and the stacking interaction between Py and Dek. The observed four bands are assigned to two N-H⋯OC and two N-H⋯π H-bonds for two isomeric structures due to Dek(a) and Dek(g). Not only smaller clusters but also higher hetero-tetramers are characterized based on the architecture of smaller clusters. In particular, Py 2 -Dek(a) 2 (I) was the first to be found with a highly symmetric ( C i ) cyclic structure. Calculated potential energy surfaces of Py-Dek clusters shed light on the impact of Dek flexibility on N-H⋯OC H-bond diversity. Selective formation of isomeric structures for Py-Dek clusters is discussed in terms of a mechanism of a two- and three-body collision process in a supersonic expansion.

A small dimension Laval nozzle connected to a compact high enthalpy source equipped with cavity ringdown spectroscopy (CRDS) is used to produce vibrationally hot and rotationally cold high-resolution infrared spectra of polyatomic molecules in the 1.67 µm region. The Laval nozzle was machined in isostatic graphite, which is capable of withstanding high stagnation temperatures. It is characterized by a throat diameter of 2 mm and an exit diameter of 24 mm. It was designed to operate with argon heated up to 2000 K and to produce a quasi-unidirectional flow to reduce the Doppler effect responsible for line broadening. The hypersonic flow was characterized using computational fluid dynamics simulations, Pitot measurements, and CRDS. A Mach number evolving from 10 at the nozzle exit up to 18.3 before the occurrence of a first oblique shock wave was measured. Two different gases, carbon monoxide (CO) and methane (CH4), were used as test molecules. Vibrational (Tvib) and rotational (Trot) temperatures were extracted from the recorded infrared spectrum, leading to Tvib = 1346 ± 52 K and Trot = 12 ± 1 K for CO. A rotational temperature of 30 ± 3 K was measured for CH4, while two vibrational temperatures were necessary to reproduce the observed intensities. The population distribution between vibrational polyads was correctly described with T vib I = 894 ± 47 K , while the population distribution within a given polyad (namely, the dyad or the pentad) was modeled correctly by T vib II = 54 ± 4 K , testifying to a more rapid vibrational relaxation between the vibrational energy levels constituting a polyad. [ABSTRACT FROM AUTHOR]

Background: Lung cancer is one of the most common malignant tumors worldwide. Currently, effective screening methods for early lung cancer are still scarce. Breath analysis provides a promising method for the pre-screening or early screening of lung cancer. Isoprene is a potential and important breath biomarker of lung cancer. Material and Methods: To investigate the clinical value of isoprene for diagnosing lung cancer patients, a cavity ringdown spectroscopy (CRDS) based near-real time, sensitive analysis method of breath isoprene is developed in our lab. In this paper, 92 breath samples from lung cancer patients, 17 breath samples from patients with benign lesions, and 107 breath samples from healthy people were collected. Results: Research indicates that breath isoprene concentration is significantly higher in healthy individuals (2 2 1. 3 ± 1 2 2. 2 ppbv) than in patients with lung cancer (1 1 2. 0 ± 3 6. 6 ppbv) and benign lung lesions (1 2 7. 9 ± 4 1. 2 ppbv). The result of Receiver Operating Characteristic (ROC) curve suggests that the concentration of isoprene is meaningful for the diagnosis of lung cancer (AUC = 0. 8 2 2 , sensitivity = 6 3. 6 % , specificity = 9 0. 2 % , P < 0. 0 1). Conclusion: This study demonstrates that the CRDS breath isoprene analysis system can effectively analyze a large sample of human breath isoprene, and preliminarily confirms the use of breath isoprene as a biomarker for lung diseases. [ABSTRACT FROM AUTHOR]

δ 17 O and Δ' 17 O are emerging tracers increasingly used in isotope hydrology, climatology, and biochemistry. Differentiating small relative abundance changes in the rare 17 O isotope from the strong covariance with 18 O by Cavity Ringdown Spectroscopy (CRDS) are attractive due to the ease of sample preparation, automated throughput, and avoidance of chemical conversions needed for isotope-ratio mass spectrometry. However, the CRDS approach requires trade-offs in measurement precision and uncertainty. In this protocol document, we present the following:•New analytical procedures and a software tool for conducting δ 17 O by Cavity Ringdown Spectroscopy (CRDS) are attractive due to the ease of sample preparation, automated throughput, and avoidance of chemical conversions needed for isotope-ratio mass spectrometry. However, the CRDS approach requires trade-offs in measurement precision and uncertainty. In this protocol document, we present the following:•New analytical procedures and a software tool for conducting δ 17 O and Δ' 17 O measurements by CRDS.•Outline a robust uncertainty framework for Δ' 17 O determinations.•Description of a CRDS performance framework for optimizing throughput, instrumental stability, and Δ' 17 O measurement precision and accuracy., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 International Atomic Energy Agency. Published by Elsevier B.V.)

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 δ17O, ± 0.3 ‰ for δ18O, ± 1 ‰ for δ2H, ± 2 ‰ for d-excess, and ± 15 per meg for Δ17O. [ABSTRACT FROM AUTHOR]

Rationale: 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 lowcost, simple, and robust sampler was designed for event and monthly rainfall samplings. Methods: 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. Results: 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. Conclusions: 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. [ABSTRACT FROM AUTHOR]

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 %. [ABSTRACT FROM AUTHOR]

The reaction of HO 2 with NO is one of the most important steps in radical cycling throughout the stratosphere and troposphere. Previous literature experimental work revealed a small yield of nitric acid (HONO 2 ) directly from HO 2 + NO. Atmospheric models previously treated HO 2 + NO as radical recycling, but inclusion of this terminating step had large effects on atmospheric oxidative capacity and the concentrations of HONO 2 and ozone (O 3 ), among others. Here, the yield of HONO 2 , φ HONO 2 , from the reaction of HO 2 + NO was investigated in a flow tube reactor using mid-IR pulsed-cavity ringdown spectroscopy. HO 2 , produced by pulsed laser photolysis of Cl 2 in the presence of methanol, reacted with NO in a buffer gas mixture of N 2 and CO between 300 and 700 Torr at 278 and 300 K. HONO 2 and its weakly bound isomer HOONO were directly detected by their v 1 absorption bands in the mid-IR region. CO was used to suppress HONO 2 produced from OH + NO 2 and exploit a chemical amplification scheme, converting OH back to HO 2 . Under the experimental conditions described here, no evidence for the formation of either HONO 2 or HOONO was observed from HO 2 + NO. Using a comprehensive chemical model, constrained by observed secondary reaction products, all HONO 2 detected in the system could be accounted for by OH + NO 2 . At 700 ± 14 Torr and 300 ± 3 K, φ HONO 2 = 0.00 ± 0.11% (2σ) with an upper limit of 0.11%. If all of the observed HONO 2 was attributed to the HO 2 + NO reaction, φ HONO 2 = 0.13 ± 0.07% with an upper limit of 0.20%. At 278 ± 2 K and 718 ± 14 Torr, we determine an upper limit, φ HONO 2 ≤ 0.37%. Our measurements are significantly lower than those previously reported, lying outside of the uncertainty of the current experimental and recommended literature values.

Rationale: The presence of substantial amounts of dissolved salts creates serious difficulties in isotope analyses of water samples using conventional isotope ratio mass spectrometry. Although nowadays laser‐based instruments are increasingly used for this purpose, a comprehensive assessment of isotope effects associated with direct analyses of aqueous saline solutions using this technology is lacking. Methods: Here we report the results of laboratory experiments aimed at quantifying isotope effects associated with direct, δ2H, δ18O and δ17O analyses of single‐salt solutions and double‐salt mixtures prepared with a water of known isotopic composition. Three single‐salt solutions (NaCl, CaCl2 and MgSO4) and two double‐salt mixtures (NaCl + CaCl2 and NaCl + MgSO4) were prepared and investigated for a wide range of molalities. The triple‐isotope composition of the prepared solutions was analysed with the aid of a Picarro L2140‐i Cavity Ring‐Down Spectroscopy analyser. Results: The NaCl and CaCl2 solutions revealed small negative salt effects, independent of molality and comparable with measurement uncertainty. The MgCl2 solution showed the highest salt effects, reaching saturated solution ca. +2.7‰ (2H), −3.5‰ (18O) and −1.7‰ (17O). Salt effects for the double‐salt mixtures generally mirrored the effects observed for the single‐salt solutions. The observed salt effects are discussed in the context of processes occurring during the injection of the salt solutions into the vaporizer unit of the CRDS analyser. Conclusions: The presented study has demonstrated feasibility of direct, triple‐isotope analyses of aqueous salt solutions using a Picarro L2140‐i CRDS analyser for a broad range of salinities up to saturated conditions. Large uncertainties of 17O‐excess determinations for solutions forming hydrated salts preclude the use of this parameter for interpretation purposes. [ABSTRACT FROM AUTHOR]

To effectively monitor the highly heterogeneous urban CO2 emissions using atmospheric observations, there is a need to deploy cost-effective CO2 sensors at multiple locations within the city with sufficient accuracy to capture the concentration gradients in urban environments. Its measurements could be used as input of an atmospheric inversion system for the quantification of emissions at the sub-city scale or separate specific sectors. Such quantification would offer valuable insights into the efficacy of local initiatives and could also identify unknown emission hotspots that require attention. Here we present the development and evaluation of a mid-cost CO2 instrument designed for continuous monitoring of atmospheric CO2 concentrations with a target accuracy of 1 ppm on hourly mean measurement. We assess the sensor sensitivity in relation to environmental factors such as humidity, pressure, temperature and CO2 signal, which leads to the development of an effective calibration algorithm. Since July 2020, eight mid-cost instruments have been installed within the city of Paris and its vicinity to provide continuous CO2 measurements, complementing the seven high-precision Cavity Ring-Down Spectroscopy (CRDS) stations that have been in operation since 2016. A data processing system, called CO2 calqual, has been implemented to automatically handle data quality control, calibration and storage, which enables the management of extensive real-time CO2 measurements from the monitoring network. Colocation assessments with the high-precision instrument show that the accuracies of the eight mid-cost instruments are within the range of 1.0 to 2.4 ppm for hourly afternoon (12–17 UTC) measurements. The long-term stability issues require manual data checks and instrument maintenance. The analyses show that CO2 measurements can provide evidence for underestimations of CO2 emissions in the Paris region and a lack of several emission point sources in the emission inventory. Our study demonstrates promising prospects in integrating mid-cost measurements along with high precision data into the subsequent atmospheric inverse modeling to improve the accuracy of quantifying the fine-scale CO2 emissions in the Paris metropolitan area. [ABSTRACT FROM AUTHOR]

We have applied cavity ring-down spectroscopy (CRDS) to the study of the 166Er isotope in an atomic beam. These measurements were realized with an external cavity diode laser tuned to the 400.9 nm atomic transition of erbium and a customized high-finesse ring-down optical cavity under vacuum. Erbium atomic beams of different number densities were generated in a tantalum foil micro-crucible within the cavity. Absorbance values of the 166Er isotope between 3 × 10−6 and 7 × 10−5 were measured with a best-case precision on the order of 10−6, which is remarkable when considering the extreme temperatures at which the measurements were conducted, and the short detection path which is characteristic of collimated atomic beams. Number densities of erbium atoms were inferred to be between 2 × 106 and 6 × 107 cm−3. This work demonstrates for the first time the ability of studying dilute atomic beams of refractory materials with high accuracy utilizing CRDS. In these initial studies, we used erbium as a model system, but we expect to extend the proposed approach to the measurement of isotopes of uranium and plutonium for nuclear non-proliferation applications. [ABSTRACT FROM AUTHOR]

The article presents a dual‐optimized adaptive algorithm based on continuous wavelet transform and derivative precise peak capture is developed for fiber cavity ring‐down spectroscopy. Adaptive spectral signal processing is achieved so that peak selection blindness can be effectively solved. To verify the performance of the dual‐optimized adaptive algorithm, a highly sensitive refractive index sensor using a bandgap fiber‐based linear fiber cavity is demonstrated. The developed dual‐optimized adaptive algorithm is compared with the conventional maximum extraction algorithm, and the results show that the dual‐optimized adaptive algorithm has a better performance in suppressing noise and processing superimposed peaks. A stable enhancement factor of 5 is obtained, indicating that the newly developed dual‐optimized adaptive algorithm can generate a high‐quality cavity ring‐down spectrum for applications including refractive index sensors, biosensors, strain gauges, and pressure sensors. [ABSTRACT FROM AUTHOR]