Cavity Ring-down Spectrometer Research Articles

V-cavity stabilized quantum cascade laser-based cavity ringdown spectroscopy for rapid detection of radiocarbon below natural abundance

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.

CRDS measurements of air-broadened lines in the 1.6 µm band of 12CO2: Line shape parameters with their temperature dependence

The 12CO2 band at 1.6 µm is used for carbon dioxide monitoring in the Earth atmosphere. The targeted accuracy of these measurements motivates important efforts to improve the quality of the spectroscopic parameters in atmospheric conditions. In the present work, the line shapes of the R(6), R(12), R(16), R(18) and R(20) transitions of the 30013-00001 band of 12CO2 in air are studied with a cavity ring down spectrometer (CRDS). For each transition, high signal-to-noise ratio spectra (between 2000 and 20000) are recorded at different temperatures (250, 274, 285, 295 and 320 K) and total pressures (50, 100, 250, 500 and 750 Torr). To this end, a spectrally narrowed and stable (sub-kHz) laser source is coupled into a temperature regulated high-finesse optical cavity. The frequency scale of each spectrum is accurately determined from measurements of the frequency of the beat note between a part of the laser light and the closest tooth of a frequency comb referenced to a rubidium clock. A multi-spectrum fit procedure with quadratic speed dependent Nelkin-Ghatak profiles, including line-mixing effects, has been used to derive for each transition, the different spectroscopic parameters and their temperature dependence. Results are discussed in comparison with previous experimental data, HITRAN2020 database and values obtained from requantized classical molecular dynamics simulations (rCMDS).

EUREC<sup>4</sup>A observations from the SAFIRE ATR42 aircraft

Abstract. As part of the EUREC4A (Elucidating the role of cloud–circulation coupling in climate) field campaign, which took place in January and February 2020 over the western tropical Atlantic near Barbados, the French SAFIRE ATR42 research aircraft (ATR) conducted 19 flights in the lower troposphere. Each flight followed a common flight pattern that sampled the atmosphere around the cloud base level, at different heights of the subcloud layer, near the sea surface and in the lower free troposphere. The aircraft's payload included a backscatter lidar and a Doppler cloud radar that were both horizontally oriented; a Doppler cloud radar looking upward; microphysical probes; a cavity ring-down spectrometer for water isotopes; a multiwavelength radiometer; a visible camera; and multiple meteorological sensors, including fast rate sensors for turbulence measurements. With this instrumentation, the ATR characterized the macrophysical and microphysical properties of trade-wind clouds together with their thermodynamical, turbulent and radiative environment. This paper presents the airborne operations, the flight segmentation, the instrumentation, the data processing and the EUREC4A datasets produced from the ATR measurements. It shows that the ATR measurements of humidity, wind and cloud base cloud fraction measured with different techniques and samplings are internally consistent; that meteorological measurements are consistent with estimates from dropsondes launched from an overflying aircraft (the High Altitude and LOng Range Research Aircraft, HALO); and that water-isotopic measurements are well correlated with data from the Barbados Cloud Observatory. This consistency demonstrates the robustness of the ATR measurements of humidity, wind, cloud base cloud fraction and water-isotopic composition during EUREC4A. It also confirms that through their repeated flight patterns, the ATR and HALO measurements provided a statistically consistent sampling of trade-wind clouds and of their environment. The ATR datasets are freely available at the locations specified in Table 11.

Fate of Methane Released From a Destroyed Oil Platform in the Gulf of Mexico

In 2004, destruction of a Gulf of Mexico oil platform by Hurricane Ivan initiated a discharge of oil and gas from a water depth of 135 m, where its bundle of well conductors was broken below the seafloor near the toppled wreckage. Discharge continued largely unabated until 2019, when findings partly reported herein prompted installation of a containment device that could trap oil before it entered the water column. In 2018, prior to containment, oil and gas bubbles formed plumes that rose to the surface, which were quantified by acoustic survey, visual inspection, and discrete collections in the water column. Continuous air sampling with a cavity ring-down spectrometer (CRDS) over the release site detected atmospheric methane concentrations as high as 11.7, ∼6 times greater than an ambient baseline of 1.95 ppmv. An inverse plume model, calibrated to tracer-gas release, estimated emission into the atmosphere of 9 g/s. In 2021, the containment system allowed gas to escape into the water at 120 m depth after passing through a separator that diverted oil into storage tanks. The CRDS detected transient peaks of methane as high as 15.9 ppmv ppm while oil was being recovered to a ship from underwater storage tanks. Atmospheric methane concentrations were elevated 1–2 ppmv over baseline when the ship was stationary within the surfacing plumes of gas after oil was removed from the flow. Oil rising to the surface was a greater source of methane to the atmosphere than associated gas bubbles.

D-depleted water isotopic measurement with a miniaturized cavity ring-down spectrometer aiming for exploration of lunar water

A miniaturized cavity ring-down spectrometer (mini-CRDS) with 5 cm cavity length using a near-infrared laser diode was developed, aiming for exploration of lunar water. This mini-CRDS enables us to measure a water vapor sample of limited amount at low pressure (< 100 Pa) by an unique mechanism using Peltier element modules that changes the resonance point to interpolate the gap of the free spectral range (FSR) of the cavity. We measured aqua samples with different D/H ratios and applied Voigt profile fitting to the absorption spectra, then obtained a calibration line of HDO isotope. The signal to noise ratio (SNR) of HDO peak at δD = − 980‰ was 7.17, which was enough higher than the detection limit of 3.

Line mixing in the oxygen B band head.

We present the results of direct measurements of the line mixing parameters for two pairs of overlapping transitions at the band head of the oxygen B band. Measurements were performed with the frequency-stabilized cavity ring-down spectrometer assisted by an optical frequency comb. The recorded spectra were analyzed with line profiles comprising speed dependence, Dicke narrowing, and line mixing. Incorporation of the line mixing into the model eliminated previous discrepancies for pressure shift and their speed dependence coefficients. First-order line mixing was determined directly from the line shape fitting at relatively low pressure (0.04 atm) together with other line shape parameters and compared with that calculated by Sung et al. [J. Quant. Spectrosc. Radiat. Transfer 235, 232-243 (2019)].

17 O-excess and d-excess of atmospheric water vapor measured by cavity ring-down spectrometry: Evidence of a matrix effect and implication for the calibration procedure.

Producing robust high-frequency time series of raw atmospheric water vapor isotope data using laser spectrometry requires accurate calibration. In particular, the chemical composition of the analyzed sample gas can cause isotope bias. This study assesses the matrix effect on calibrated δ17 O, δ18 O, δ2 H, 17 O-excess, and d-excess values of atmospheric water vapor. A Picarro L2140-i cavity ring-down spectrometer with an autosampler and a vaporizer is used to analyze δ17 O, δ18 O, δ2 H, 17 O-excess, and d-excess of two water standards. Isotope data obtained using synthetic air and dry ambient air as carrier gas at water mixing ratios ranging from 2000 to 30 000 ppmv are compared. Based on the results, atmospheric water vapor measurements are calibrated. The expected precision is estimated by Monte Carlo simulation. The dry air source strongly impacts raw isotope values of the two water standards but has no effect on the mixing ratio dependency functions. When synthetic air is used, δ17 O, δ18 O, and 17 O-excess of calibrated atmospheric water vapor are overestimated by 0.6‰, 0.7‰, and 217 per meg, respectively, whereas δ2 H and d-excess are underestimated by 1.5‰ and 7.3‰. Optimum precisions for the calibrated δ17 O, δ18 O, δ2 H, 17 O-excess, and d-excess values and 12 min integration time are 0.02‰, 0.03‰, 0.4‰, 14 per meg, and 0.4‰, respectively. Regarding the obtained results, recommendations for the calibration of atmospheric water vapor isotope measurements are presented. The necessity to use dry ambient air as dry air source when running the standards for calibration is pointed out as a prerequisite for accurate atmospheric water vapor 17 O-excess and d-excess measurements.

Quantifying the Influence of a Burn Event on Ammonia Concentrations Using a Machine-Learning Technique

Although combustion is considered a common source of ammonia (NH3) in the atmosphere, field measurements quantifying such emissions of NH3 are still lacking. In this study, online measurements of NH3 were performed by a cavity ring-down spectrometer, in the cold season at a rural site in Xianghe on the North China Plain. We found that the NH3 concentrations were mostly below 65 ppb during the study period. However, from 18 to 21 November 2017, a close burn event (~100 m) increased the NH3 concentrations to 145.6 ± 139.9 ppb. Using a machine-learning technique, we quantified that this burn event caused a significant increase in NH3 concentrations by 411%, compared with the scenario without the burn event. In addition, the ratio of ∆NH3/∆CO during the burn period was 0.016, which fell in the range of biomass burning. Future investigations are needed to evaluate the impacts of the NH3 combustion sources on air quality, ecosystems, and climate in the context of increasing burn events worldwide.

Acetylene [formula omitted] hot band revisited

The acetylene ν1+ν5 (Πu)←ν4 (Πg) hot band has been reinvestigated at high resolution (≤10−3cm−1). Vibrationally excited but rotationally cold C2H2 (≈ 30 K) is probed in a supersonically expanding planar plasma by a continuous-wave (cw) mid-infrared cavity ring-down spectrometer at nearly Doppler free condition. Low J-value rovibrational transitions corresponding to the Q-branch are recorded for the first time. The improved resolution and newly observed transitions, combined with the existing data from the literature allow for retrieving improved molecular parameters for this hot band.

High-Precision Static Alignment Scheme Based on the Eigenfrequency Separation Characteristics of Same-Order Hermite-Gaussian Mode in Triangular Ring-Down Cavities

Triangular cavities are increasingly used in cavity ring-down spectrometers (CRDS) to compensate for the existence of optical feedback and other disadvantages of straight cavities. However, at the same time, the difficulty of the cavity mounting alignment process is increased. Consequently, the fast and stable establishment of resonance between the optical source and the triangular ring-down cavity has been widely explored for CRDS-based applications. The Hermite-Gaussian theory has unique advantages for the description of the Gaussian resonant beams characteristics in triangular cavities, while the theory is of great importance for the alignment in high finesse triangular ring-down cavities. Along these lines, in this work, the eigenfrequency separation characteristics of the Hermite-Gaussian modes in the triangular cavity, in the meridional and sagittal planes, as well as the excitation and transmission characteristics of the first-order mode in the high finesse cavity were verified. A static alignment method was established for the high-finesse triangular ring-down cavity, and the transmission suppression of the Hermite-Gaussian modes by the high-finesse cavity was overcome in the experiment. Finally, by leveraging the advantageous features of the fundamental and the first-order mode that are complementary to each other, the tilt and axis shift errors of each specified plane with directional high accuracy can be aligned. The static alignment scheme of the triangular cavity based on the Hermite-Gaussian theory that was established here paves the way for the mounting alignment of the CRDS instrument before the ring-down experiment, whereas the system accuracy of CRDS is further improved.

The origin of GHG's emission from self-heating coal waste dump: Atmogeochemical interactions and environmental implications

The aim of this work was to analyse the origin of the exhaust gases containing large amount of carbon dioxide (CO2) and methane (CH4) from self-heating coal waste dump and its potential health and environmental impact. Air samples were collected from the coal waste dump and its vicinity in Nowa Ruda − Słupiec (NR-S), Southwestern Poland, during ground survey campaigns in spring (March 30, 2019) and winter (December 1, 2019). In order to detect the origin of the exhaust plume emission, stable carbon isotopic composition (δ13C) of CH4 and CO2 was measured using a cavity ring-down spectrometer (CRDS). We investigated the gases collected from the hotspots at the surface of the coal-mine dump, from the air above the dump and finally from surroundings of the dump. This allowed to estimate the stage and magnitude of CH4 oxidation inside the coal dump. Many gas seeps from the places, where the dump is actively burning were identified during the ground surveys. CH4 mole fraction in those seeps (hot-spots) reached up to 10,000 ppm. Methane found in the most of the air samples collected from the dump was strongly enriched in 13C, with an average of −27.4 ± 5.8‰, which is heavier than methane coming out from formerly excavated coal seams what indicate coal pyrolysis as the predominant source of methane seeps. The covarying with methane, CO2 mole fraction from active burn dump sites reached up to 73,000 ppm with an average δ13C value of −27.3 ± 8.4‰. Therefore, CO2 resembles isotopically it's predominant precursor, the pyrolytic methane, via incomplete combustion in the shallow oxygenated parts of the hot spots.Substantial amounts of methane escape from the self-ignited spots on the NR-S coal waste dump, however, the mobile surveys did not reveal the enhanced methane mole fraction at the ground level in distance between 1 and 3 km from the dump. Even at distances of 150 m from the hot spots impact was limited, implying convective transport of these localized hot pollutant plumes. The results highlight changes in the fire intensity, prevailing winds, dump architecture, and surface roughness in the surrounding regions are the most important factors of air pollutant emission from complex coal mine dump system.

Photochemical method for removing methane interference for improved gas analysis

Abstract. The development of laser spectroscopy has made it possible to measure minute changes in the concentrations of trace gases and their isotopic analogs. These single or even multiply substituted species occur at ratios from percent to below parts per million and contain important information concerning trace gas sources and transformations. Due to their low abundance, minimizing spectral interference from other gases in a mixture is essential. Options including traps and membranes are available to remove many specific impurities. Methods for removing CH4, however, are extremely limited as methane has low reactivity and adsorbs poorly to most materials. Here we demonstrate a novel method for CH4 removal via chlorine-initiated oxidation. Our motivation in developing the technique was to overcome methane interference in measurements of N2O isotopic analogs when using a cavity ring-down spectrometer. We describe the design and validation of a proof-of-concept device and a kinetic model to predict the dependence of the methane removal efficiency on the methane concentration [CH4], chlorine photolysis rate JCl2, chlorine concentration [Cl2] and residence time tR. The model was validated by comparison to experimental data and then used to predict the possible formation of troublesome side products and by-products including CCl4 and HCl. The removal of methane could be maintained with a peak removal efficiency &gt;98 % for ambient levels of methane at a flow rate of 7.5 mL min−1 with [Cl2] at 50 ppm. These tests show that our method is a viable option for continuous methane scrubbing. Additional measures may be needed to avoid complications due to the introduction of Cl2 and formation of HCl. Note that the method will also oxidize most other common volatile organic compounds. The system was tested in combination with a cavity ring-down methane spectrometer, and the developed method was shown to be successful at removing methane interference.

Synchronous detection of multiple optical characteristics of atmospheric aerosol by coupled photoacoustic cavity

Owing to the influence of sampling loss, cavity difference and detecting source, the multi-optical parameter measurement of atmospheric aerosol cannot be detected simultaneously in the same reference environment. In order to solve this problem, a new method of simultaneously detecting the aerosol optical parameters by coupling cavity ring-down spectrometer with photoacoustic spectroscopy is proposed. Firstly, the coupled photoacoustic cavity is formed by the organic fusion of the photoacoustic cavity and the ring-down cavity. Secondly, the integrated design of the coupling spectroscopy system is carried out. Finally, the extinction coefficient and absorption coefficient of aerosol are measured simultaneously by the system, and then the aerosol scattering coefficient and single albedo are calculated indirectly. The accuracy of the system is verified by comparing with the data from the environmental quality monitoring station, which provides a new idea for the detection of multi-optical characteristics of atmospheric aerosol.

Lamb-dip cavity ring-down spectroscopy of acetylene at 1.4 μm

Doppler-free saturated-absorption Lamb dips are observed for weak vibration-rotation transitions of C2H2 between 7167 and 7217 cm−1, using a frequency-comb assisted cavity ring-down spectrometer based on the use of a pair of phase-locked diode lasers. We measured the absolute center frequency of sixteen lines belonging to the 2 band, targeting ortho and para states of the molecule. Line pairs of the P and Q branches were selected so as to form a ‘V’-scheme, sharing the lower energy level. Such a choice made it possible to determine the rotational energy separations of the excited vibrational state for J-values from 11 to 20. Line-center frequencies are determined with an overall uncertainty between 3 and 13 kHz. This is over three orders of magnitude more accurate than previous experimental studies in the spectral region around the wavelength of 1.4 μm. The retrieved energy separations provide a stringent test of the so-called MARVEL method recently applied to acetylene.

A simulation chamber for absorption spectroscopy in planetary atmospheres

Abstract. A novel simulation chamber, PASSxS (Planetary Atmosphere Simulation System for Spectroscopy), has been developed for absorption measurements performed with a Fourier transform spectrometer (FTS) and, possibly, a cavity ring-down (CRD) spectrometer with a sample temperature ranging from 100 up to 550 K, while the pressure of the gas can be varied from 10 mbar up to 60 bar. These temperature and pressure ranges cover a significant part of the planetary atmospheres in the solar system, and the absorption chamber can thus be used to simulate planetary atmospheres of solar planets and extrasolar planets with similar physical conditions. The optical absorption path for the FTS absorption measurements is 3.2 m due to the implementation of a multi-pass setup inside the chamber. The FTS measurements cover a wide spectral range, from the visible to the mid-infrared, with a sensitivity sufficient for medium-strength absorption bands. The FTS has been used previously to measure high-pressure atmospheres, including collision-induced absorption bands and continuum absorption at ambient temperatures. PASSxS allows the measurement of the temperature dependence of collision-induced bands and continuum absorption, which is important for both the modeling of planetary atmospheres and fundamental processes involving collisions between molecules and atoms.

Quasi-Simultaneous Sensitive Detection of Two Gas Species by Cavity-Ringdown Spectroscopy with Two Lasers.

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 in air is about 1.3‰. Such a system will be useful for future applications such as environmental monitoring.

A GC-SSIM-CRDS system: Coupling a gas chromatograph with a Cavity Ring-Down Spectrometer for onboard Twofold analysis of molecular and isotopic compositions of natural gases during ocean-going research expeditions

Carbon dioxide (CO2) and methane (CH4) are two climate-sensitive components of gases migrating within sediments and emitted into the water column on continental margins. They are involved in several key biogeochemical processes entering into the global carbon cycle. In order to perform onboard measurements of both the molecular and stable carbon isotope ratios (δ13C) of CH4 and CO2 of natural gases during oceanic cruises, we have developed a novel approach coupling gas chromatography (GC) with cavity ring-down spectroscopy (CRDS). The coupled devices are connected to a small sample isotope module (SSIM) to form a system called GC-SSIM-CRDS. Small volumes of natural gas samples (<1 mL) are injected into the GC using a headspace autosampler or a gas-tight syringe to separate the chemical components using a Shincarbon ST packed column and for molecular quantification by thermal conductivity detection (TCD). Subsequently, CO2 from the sample is trapped in a 7 mL loop at 32 °C before being transferred to the CRDS analyzer for sequential determination of the stable carbon isotope ratios of CH4 and CO2 in 24 min. The loop is an open column (without stationary phase). This approach does not require the use of adsorbents or cooling for the trapping step. Optimization of the separation step prior to analysis was focused on the influence of two key separation factors 1) the flow of the carrier gas and 2) the temperature of the oven. Our analytical system and the measurement protocol were validated on samples collected from gas seeps in the Sea of Marmara (Turkey). Our results show that the GC-SSIM-CRDS system provides a reliable determination of the molecular identification of CH4 and CO2 in complex natural gases, followed by the stable carbon isotope ratios of methane and carbon dioxide.

Validation of a new cavity ring-down spectrometer for measuring tropospheric gaseous hydrogen chloride

Abstract. Reliable, sensitive, and widely available hydrogen chloride (HCl) measurements are important for understanding oxidation in many regions of the troposphere. We configured a commercial HCl cavity ring-down spectrometer (CRDS) for sampling HCl in the ambient atmosphere and developed validation techniques to characterize the measurement uncertainties. The CRDS makes fast, sensitive, and robust measurements of HCl in a high-finesse optical cavity coupled to a laser centred at 5739 cm−1. The accuracy was determined to reside between 5 %–10 %, calculated from laboratory and ambient air intercomparisons with annular denuders. The precision and limit of detection (3σ) in the 0.5 Hz measurement were below 6 and 18 pptv, respectively, for a 30 s integration interval in zero air. The response time of this method is primarily characterized by fitting decay curves to a double exponential equation and is impacted by inlet adsorption/desorption, with these surface effects increasing with relative humidity and decreasing with decreasing HCl mixing ratios. The minimum 90 % response time was 10 s and the equilibrated response time for the tested inlet was 2–6 min under the most and least optimal conditions, respectively. An intercomparison with the EPA compendium method for quantification of acidic atmospheric gases showed good agreement, yielding a linear relationship statistically equivalent to unity (slope of 0.97 ± 0.15). The CRDS from this study can detect HCl at atmospherically relevant mixing ratios, often performing comparably or better in sensitivity, selectivity, and response time than previously reported HCl detection methods.

Characterisation of gas reference materials for underpinning atmospheric measurements of stable isotopes of nitrous oxide

Abstract. The precise measurement of the amount fraction of atmospheric nitrous oxide (N2O) is required to understand global emission trends. Analysis of the site-specific stable isotopic composition of N2O provides a means to differentiate emission sources. The availability of accurate reference materials of known N2O amount fractions and isotopic composition is critical for achieving these goals. We present the development of nitrous oxide gas reference materials for underpinning measurements of atmospheric composition and isotope ratio. Uncertainties target the World Metrological Organisation Global Atmosphere Watch (WMO-GAW) compatibility goal of 0.1 nmol mol−1 and extended compatibility goal of 0.3 nmol mol−1, for atmospheric N2O measurements in an amount fraction range of 325–335 nmol mol−1. We also demonstrate the stability of amount fraction and isotope ratio of these reference materials and present a characterisation study of the cavity ring-down spectrometer used for analysis of the reference materials.

High-resolution stable isotope signature of a land-falling atmospheric river in southern Norway

Abstract. Heavy precipitation at the west coast of Norway is often connected to elongated meridional structures of high integrated water vapour transport known as atmospheric rivers (ARs). Here we present high-resolution measurements of stable isotopes in near-surface water vapour and precipitation during a land-falling AR in southwestern Norway on 7 December 2016. In our analysis, we aim to identify the influences of moisture source conditions, weather system characteristics, and post-condensation processes on the isotope signal in near-surface water vapour and precipitation. A total of 71 precipitation samples were collected during the 24 h sampling period, mostly taken at sampling intervals of 10–20 min. The isotope composition of near-surface vapour was continuously monitored in situ with a cavity ring-down spectrometer. Local meteorological conditions were in addition observed from a vertical pointing rain radar, a laser disdrometer, and automatic weather stations. We observe a stretched, “W”-shaped evolution of isotope composition during the event. Combining paired precipitation and vapour isotopes with meteorological observations, we define four different stages of the event. The two most depleted periods in the isotope δ values are associated with frontal transitions, namely a combination of two warm fronts that follow each other within a few hours and an upper-level cold front. The d-excess shows a single maximum and a step-wise decline in precipitation and a gradual decrease in near-surface vapour. Thereby, the isotopic evolution of the near-surface vapour closely follows that of the precipitation with a time delay of about 30 min, except for the first stage of the event. Analysis using an isotopic below-cloud exchange framework shows that the initial period of low and even negative d-excess in precipitation was caused by evaporation below cloud base. The isotope signal from the cloud level became apparent at ground level after a transition period that lasted up to several hours. Moisture source diagnostics for the periods when the cloud signal dominates show that the moisture source conditions are then partly reflected in surface precipitation and water vapour isotopes. In our study, the isotope signal in surface precipitation during the AR event reflects the combined influence of atmospheric dynamics, moisture sources, and atmospheric distillation, as well as cloud microphysics and below-cloud processes. Based on this finding, we recommend careful interpretation of results obtained from Rayleigh distillation models in such events, in particular for the interpretation of surface vapour and precipitation from stratiform clouds.