Traditional Isotope Ratio Mass Spectrometry Research Articles

Fingerprinting Organofluorine Molecules via Position-Specific Isotope Analysis.

Organofluorine substances are found in a wide range of materials and solvents commonly used in industry and homes, as well as pharmaceuticals and pesticides. In the environment, organofluorine molecules are now recognized as an important class of anthropogenic pollutants. Fingerprinting organofluorine compounds via their carbon isotope ratios (13C/12C) is crucial for correlating molecules with their source. Here we apply a 19F nuclear magnetic resonance spectroscopy (NMR) technique to obtain the first position-specific carbon isotope ratios for a diverse set of organofluorine molecules. In contrast to traditional isotope ratio mass spectrometry, the 19F NMR method provides 13C/12C isotope ratios at each carbon position where a C-F bond is present, and does not require fragmentation or combustion to CO2, overcoming challenges posed by the robust C-F covalent bonds. The method was validated with 2,2,2-trifluoroethanol, and applied to analyze heptafluorobutanoic acid, 5-fluorouracil and fipronil. Results reveal distinct intramolecular carbon isotope distributions, enabling differentiation of chemically identical molecules. Notably, the NMR method accurately analyzes carbon isotopes within target molecules despite impurities. Potential applications include the detection of counterfeit products and drugs, and ultimately pollution tracking in the environment.

Position-specific carbon stable isotope analysis of glyphosate: isotope fingerprinting of molecules within a mixture.

Glyphosate [N-(phosphonomethyl) glycine] is a widely used herbicide and a molecule of interest in the environmental sciences, due to its global use in agriculture and its potential impact on ecosystems. This study presents the first position-specific carbon isotope (13C/12C) analyses of glyphosates from multiple sources. In contrast to traditional isotope ratio mass spectrometry (IRMS), position-specific analysis provides 13C/12C ratios at individual carbon atom positions within a molecule, rather than an average carbon isotope ratio across a mixture or a specific compound. In this work, glyphosate in commercial herbicides was analyzed with only minimal purification, using a nuclear magnetic resonance (NMR) spectroscopy method that detects 1H nuclei with bonds to either 13C or 12C, and isolates the signals of interest from other signals in the mixture. Results demonstrate that glyphosate from different sources can have significantly different intramolecular 13C/12C distributions, which were found to be spread over a wide range, with δ13C Vienna Peedee Belemnite (VPDB) values of -28.7 to -57.9‰. In each glyphosate, the carbon with a bond to the phosphorus atom was found to be depleted in 13C compared to the carbon at the C2 position, by 4 to 10‰. Aminomethylphosphonic acid (AMPA) was analyzed for method validation; AMPA contains only a single carbon position, so the 13C/12C results provided by the NMR method could be directly compared with traditional isotope ratio mass spectrometry. The glyphosate mixtures were also analyzed by IRMS to obtain their average 13C/12C ratios, for comparison with our position-specific results. This comparison revealed that the IRMS results significantly disguise the intramolecular isotope distribution. Finally, we introduce a 31P NMR method that can provide a position-specific 13C/12C ratio for carbon positions with a C-P chemical bond, and the results obtained by 1H and 31P for C3 carbon agree with one another within their analytical uncertainty. These analytical tools for position-specific carbon isotope analysis permit the isotopic fingerprinting of target molecules within a mixture, with potential applications in a range of fields, including the environmental sciences and chemical forensics.

Fungi in ant-plant interactions: a key to enhancing plant nutrient-acquisition strategies.

This article is a Commentary on Gegenbauer et al. (2023), 238: 2210–2223.

Simultaneous measurement of <i>δ</i><sup>13</sup>C, <i>δ</i><sup>18</sup>O and <i>δ</i><sup>17</sup>O of atmospheric CO<sub>2</sub> – performance assessment of a dual-laser absorption spectrometer

Abstract. Using laser absorption spectrometry for the measurement of stable isotopes of atmospheric CO2 instead of the traditional isotope ratio mass spectrometry method decreases sample preparation time significantly, and uncertainties in the measurement accuracy due to CO2 extraction and isobaric interferences are avoided. In this study we present the measurement performance of a new dual-laser instrument developed for the simultaneous measurement of the δ13C, δ18O and δ17O of atmospheric CO2 in discrete air samples, referred to as the Stable Isotopes of CO2 Absorption Spectrometer (SICAS). We compare two different calibration methods: the ratio method, based on the measured isotope ratio and a CO2 mole fraction dependency correction, and the isotopologue method, based on measured isotopologue abundances. Calibration with the ratio method and isotopologue method is based on three different assigned whole-air references calibrated on the VPDB (Vienna Pee Dee Belemnite) and the WMO 2007 (World Meteorological Organization) scale for their stable isotope compositions and their CO2 mole fractions, respectively. An additional quality control tank is included in both methods to follow long-term instrument performance. Measurements of the quality control tank show that the measurement precision and accuracy of both calibration methods is of similar quality for δ13C and δ18O measurements. During one specific measurement period the precision and accuracy of the quality control tank reach WMO compatibility requirements, being 0.01 ‰ for δ13C and 0.05 ‰ for δ18O. Uncertainty contributions of the scale uncertainties of the reference gases add another 0.03 ‰ and 0.05 ‰ to the combined uncertainty of the sample measurements. Hence, reaching WMO compatibility for sample measurements on the SICAS requires reduction of the scale uncertainty of the reference gases used for calibration. An intercomparison of flask samples over a wide range of CO2 mole fractions has been conducted with the Max Planck Institute for Biogeochemistry, resulting in a mean residual of 0.01 ‰ and −0.01 ‰ and a standard deviation of 0.05 ‰ and 0.07 ‰ for the δ13C measurements calibrated using the ratio method and the isotopologue method, respectively. The δ18O could not be compared due to depletion of the δ18O signal in our sample flasks because of storage times being too long. Finally, we evaluate the potential of our Δ17O measurements as a tracer for gross primary production by vegetation through photosynthesis. Here, a measurement precision of <0.01 ‰ would be a prerequisite for capturing seasonal variations in the Δ17O signal. Lowest standard errors for the δ17O and Δ17O of the ratio method and the isotopologue method are 0.02 ‰ and 0.02 ‰ and 0.01 ‰ and 0.02 ‰, respectively. The accuracy results show consequently results that are too enriched for both the δ17O and Δ17O measurements for both methods. This is probably due to the fact that two of our reference gases were not measured directly but were determined indirectly. The ratio method shows residuals ranging from 0.06 ‰ to 0.08 ‰ and from 0.06 ‰ to 0.1 ‰ for the δ17O and Δ17O results, respectively. The isotopologue method shows residuals ranging from 0.04 ‰ to 0.1 ‰ and from 0.05 ‰ to 0.13 ‰ for the δ17O and Δ17O results, respectively. Direct determination of the δ17O of all reference gases would improve the accuracy of the δ17O and thereby of the Δ17O measurements.

An automated, laser-based measurement system for nitrous oxide isotope and isotopomer ratios at nanomolar levels.

Nitrous oxide (N2 O) is an atmospheric trace gas regulating Earth's climate, and is a key intermediate of many nitrogen cycling processes in aquatic ecosystems. Laser-based technology for N2 O concentration and isotopic/isotopomeric analyses has potential advantages, which include high analytical specificity, low sample size requirement and reduced cost. An autosampler with a purge-and-trap module is coupled to a cavity ring-down spectrometer to achieve automated and high-throughput measurements of N2 O concentrations, N2 O isotope ratios (δ15 Nbulk and δ18 O values) and position-specific isotopomer ratios (δ15 Nα and δ15 Nβ values). The system provides accuracy and precision similar to those for measurements made by traditional isotope ratio mass spectrometry (IRMS) techniques. The sample sizes required were 0.01-1.1 nmol-N2 O. Measurements of four N2 O isotopic/isotopomeric references were cross-calibrated with those obtained by IRMS. With a sample size of 0.50 nmol-N2 O, the measurement precision (1σ) for δ15 Nα , δ15 Nβ , δ15 Nbulk and δ18 O values was 0.61, 0.33, 0.41 and 0.43‰, respectively. Correction schemes were developed for sample size-dependent isotopic/isotopomeric deviations. The instrumental system demonstrated consistent measurements of dissolved N2 O concentrations, isotope/isotopomer ratios and production rates in seawater. The coupling of an autosampler with a purge-and-trap module to a cavity ring-down spectrometer not only significantly reduces sample size requirements, but also offers comprehensive investigation of N2 O production pathways by the measurement of natural abundance and tracer level isotopes and isotopomers. Furthermore, the system can perform isotopic analyses of dissolved and solid nitrogen-containing samples using N2 O as the analytical proxy.

Optimization of instrument setup and post‐run corrections for oxygen and hydrogen stable isotope measurements of water by isotope ratio infrared spectroscopy (IRIS)

Light stable isotope analyses of hydrogen (2H/1H) and oxygen (18O/16O) of water are used in many terrestrial and marine aquatic studies. The advantage of using stable isotope ratios is that water molecules serve as ubiquitous and already present natural tracers. Within recent years, these analyses have been revolutionized by the development of new isotope ratio laser spectroscopy (IRIS) systems that are cheaper, more robust, and mobile compared with traditional isotope ratio mass spectrometry (IRMS). Although easier to operate, laser systems also need thorough calibration with international reference materials, and raw data need correction for analytical effects (i.e., memory and drift). This study presents modifications to the hardware for liquid water injection, an optimized sequence layout and a simple post‐run correction procedure. These protocols will maximize precision, accuracy, and sample throughput via an efficient memory correction. The number of injections per unknown sample can be reduced to 4 or less. This procedure meets the demands of faster throughput with reduced costs per analysis. Procedures presented here are based on real analyses. They were also verified by an international proficiency test and traditional IRMS techniques.

Water isotopic ratios from a continuously melted ice core sample

Abstract. A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW–SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.

Accuracy and precision of a laser-spectroscopy approach to the analysis of δ2H and δ18O in human urine

The isotope ratio analysis of body water often involves large sample numbers and lengthy sample processing. Here we demonstrate the ability of isotope ratio infrared spectroscopy (IRIS) to rapidly and accurately analyse the isotope ratios of water in urine. We analysed water extracted from human urine using traditional isotope ratio mass spectrometry (IRMS) and compared those values with IRIS-analysed extracted water and un-extracted urine. Regression analyses for δ2H and δ18O values between (1) extracted water analysed via IRMS and IRIS and (2) urine and extracted water analysed via IRIS were significant (R 2=0.99). These results indicate that cryogenic distillation of urine was not required for an accurate estimate of the isotopic composition of urine when using IRIS.

Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters

The use of isotope ratio infrared spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has many advantages over traditional isotope ratio mass spectrometry (IRMS), it may also be prone to errors that do not impact upon IRMS analyses. Of particular concern is the potential for contaminants in the water sample to interfere with the spectroscopy, thus leading to erroneous stable isotope data. Water extracted from plant and soil samples may often contain organic contaminants. The extent to which contaminants may interfere with IRIS and thus impact upon data quality is presently unknown. We tested the performance of IRIS relative to IRMS for water extracted from 11 plant species and one organic soil horizon. IRIS deviated considerably from IRMS for over half of the samples tested, with deviations as large as 46 per thousand (delta(2)H) and 15.4 per thousand (delta(18)O) being measured. This effect was reduced somewhat by using activated charcoal to remove organics from the water; however, deviations as large as 35 per thousand (delta(2)H) and 11.8 per thousand (delta(18)O) were still measured for these cleaned samples. Interestingly, the use of activated charcoal to clean water samples had less effect than previously thought for IRMS analyses. Our data show that extreme caution is required when using IRIS to analyse water samples that may contain organic contaminants. We suggest that the development of new cleaning techniques for removing organic contaminants together with instrument-based software to flag potentially problematic samples are necessary to ensure accurate plant and soil water analyses using IRIS.

Measuring stable isotopes of hydrogen and oxygen in ice by means of laser spectrometry: the Bølling transition in the Dye-3 (south Greenland) ice core

AbstractWe report on the first application of a new technique in ice-core research, based on direct absorption infrared laser spectrometry (LS), for measuring 2H, 17Oand 18O isotope ratios. the data are used to calculate the deuterium excess d (defined as δ2H– 8δ18O) for a section of the Dye-3 (south Greenland) deep ice core around the Bølling transition (14 500 BP). the precision of LS is slightly better than that of most traditional methods for deuterium, but not for the oxygen isotopes. the ability to measure δ17O is new and is used here to improve the precision of the δ18O determination. Still, the final precision for δ18O remains inferior to traditional isotope ratio mass spectrometry (IRMS). Therefore, deuterium excess was calculated from a combination of the LS and IRMS isotope determinations.