High-Precision Triple Oxygen Isotope Analysis of Carbon Dioxide by Tunable Infrared Laser Absorption Spectroscopy.

Precision measurements of the stable isotope ratios of oxygen (18O/16O and 17O/16O) in CO2 are critical to atmospheric monitoring and terrestrial climate research. High-precision 17O measurements by isotope ratio mass spectrometry (IRMS) are challenging because they require complicated sample preparation procedures, long measurement times, and relatively large samples sizes. Recently, tunable infrared laser direct absorption spectroscopy (TILDAS) has shown significant potential as an alternative technique for triple oxygen isotope analysis of CO2, although the ultimate level of reproducibility is unknown, partly because it is unclear how to relate TILDAS measurements to an internationally accepted isotope abundance scale (e.g., VSMOW2-SLAP2). Here, we present a method for high-precision triple oxygen isotope analysis of CO2 by TILDAS, requiring ∼8-9 µmol of CO2 (or 0.9 mg carbonate) in 50 min, plus ∼1.5 h for sample preparation and dilution of CO2 in N2 to a nominal 400 µmol mol-1. Overall reproducibility of Δ'17O (CO2) was 0.004‰ (4 per meg) for IAEA603 (SE, n = 6) and 10 per meg for NBS18 (SE, n = 4). Values corrected to the VSMOW2-SLAP2 scale are in good agreement with established techniques of high-precision IRMS, with the exception of Δ'17O measured by platinum-catalyzed exchange of CO2 with O2. Compared to high-precision IRMS, TILDAS offers the advantage of ∼10 times less sample, and greater throughput, without loss of reproducibility. The flexibility of the technique should allow for many important applications to global biogeochemical monitoring and investigation of 17O anomalies in a range of geological materials.

A rapid high-precision analytical method for triple oxygen isotope analysis of CO2 gas using tunable infrared laser direct absorption spectroscopy.

RATIONALE: The simultaneous analysis of the three stable isotopes of oxygen-triple oxygen isotope analysis-has become an important analytical technique in natural sciences. Determination of the abundance of the rare 17 O isotope in CO2 gas using magnetic sector isotope ratio mass spectrometry is complicated by the isobaric interference of 17 O by 13 C (13 C16 O16 O and 12 C16 O17 O, both have mass 45 amu). A number of analytical techniques have been used to measure the 17 O/16 O ratio of CO2 gas. They either are time consuming and technically challenging or have limited precision. A rapid and precise alternative to the available analytical methods is desirable. METHODS: We present the results of triple oxygen isotope analyses using an Aerodyne tunable infrared laser direct absorption spectroscopy (TILDAS) CO2 analyzer configured for 16 O, 17 O, and 18 O combined with a custom gas inlet system. We evaluate the sensitivity of our results to a number of parameters. CO2 samples with a wide range of δ18 O values (from -9.28‰ to 39.56‰) were measured and compared to results using the well-established fluorination-gas source mass spectrometry method. RESULTS: The TILDAS system has a precision (standard error, 2σ) of better than ±0.03‰ for δ18 O and ±10 per meg for Δ'17 O values, equivalent to the precision of previous analytical methods. Samples as small as 3 µmol CO2 (equivalent to 300 µg CaCO3 ) can be analyzed with a total analysis time of ~30 min. CONCLUSIONS: We have successfully developed an analytical technique for the simultaneous determination of the δ17 O and δ18 O values of CO2 gas. The precision is equal to or better than that of existing techniques, with no additional chemical treatments required. Analysis time is rapid, and the system is easily automated so that large numbers of samples can be analyzed with minimal effort.

Precise Measurements of 12CH2D2 by Tunable Infrared Laser Direct Absorption Spectroscopy.

We present precise measurements of doubly deuterated methane (12CH2D2) in natural methane samples using tunable infrared laser direct absorption spectroscopy (TILDAS). Using a 413 m optical path length astigmatic Herriott cell and two quantum cascade lasers (QCLs) scanning the spectral regions of 1090.46 ± 0.1 and 1200.23 ± 0.1 cm-1, the instrument simultaneously measures the five main isotopologues of methane. The ratios 13CH3D/12CH4 and 12CH2D2/12CH4 are measured at 0.01‰ and 0.5‰ (1σ) instrumental precision, respectively. The instrumental accuracy was assessed by measuring a series of methane gases with a range of δ13C and δD values but with the abundances of all isotopologues driven to thermal equilibrium at 250 °C. The estimated accuracy of Δ12CH2D2 is 1‰ (1σ) on the basis of the results of the heated methane samples. This new TILDAS instrument provides a simple and rapid technique to explore the sources of methane in the environment.

A global database of water vapor isotopes measured with high temporal resolution infrared laser spectroscopy.

The isotopic composition of water vapour provides integrated perspectives on the hydrological histories of air masses and has been widely used for tracing physical processes in hydrological and climatic studies. Over the last two decades, the infrared laser spectroscopy technique has been used to measure the isotopic composition of water vapour near the Earth's surface. Here, we have assembled a global database of high temporal resolution stable water vapour isotope ratios (δ18O and δD) observed using this measurement technique. As of March 2018, the database includes data collected at 35 sites in 15 Köppen climate zones from the years 2004 to 2017. The key variables in each dataset are hourly values of δ18O and δD in atmospheric water vapour. To support interpretation of the isotopologue data, synchronized time series of standard meteorological variables from in situ observations and ERA5 reanalyses are also provided. This database is intended to serve as a centralized platform allowing researchers to share their vapour isotope datasets, thus facilitating investigations that transcend disciplinary and geographic boundaries.

Optimum signal-to-noise ratio in off-axis integrated cavity output spectroscopy.

The signal-to-noise ratio (SNR) in off-axis integrated cavity output spectroscopy (OA-ICOS) is investigated and compared to direct absorption spectroscopy using multipass absorption cells [tunable diode laser absorption spectroscopy (TDLAS)]. Applying measured noise characteristics of a near-IR tunable diode laser and detector, it is shown that the optimum SNR is not generally reached at the highest effective absorption path length. Simulations are used to determine the parameters for maximized SNR of OA-ICOS.

Multipass cell design for Stark-modulation spectroscopy.

A multipass cell for absorption measurements with an additionally applied homogeneous electric field for Stark effect measurements is described. The configuration is based on two ring mirrors, where the laser beam propagates between two nested cylindrical-wall electrodes. The total optical path length achieved is 40 m. The beam pointing stability of this setup is investigated and compared to a confocal-type Herriott cell of the same base length, employing numerical simulations. The exit beam pointing stability is found to be very good. The response measurements show fast exchange times, which agree well with theoretical values.

A new concept for sensitive in situ stable isotope ratio infrared spectroscopy based on sample modulation.

Diode-laser absorption spectroscopy finds increasing applications in the emerging field of stable isotope research. To meet the requirements of the water isotopes measurement challenge in environmental research, ways have to be found to cope with the present limitations of spectroscopic systems. In this article, we discuss an approach based on the Stark effect in molecular spectra to reduce the influence of time-dependent, unwanted background structures generally superimposed on the desired signal from the spectral feature under investigation. A road map to high-sensitivity isotopic ratio measurements of water isotopes is presented. On the basis of an Allan Variance analysis of measured data, the detection limits have been calculated as a function of the integration time. To achieve the required optical density of about 6 x 10(-7) for H(2)(17)O measurements, the duty cycle has to be optimized and the implementation of a sample modulation within an optical multipass cell is a promising approach to increase the stability of spectroscopic instrumentation required for ecosystem research and airborne atmospheric platforms.