pyisotopomer: A Python package for obtaining nitrous oxide isotopocules from isotope ratio mass spectrometry

Obtaining nitrous oxide isotopocule measurements with isotope ratio mass spectrometry (IRMS) requires measuring the m/z ratios of the nitrous oxide (N2O) molecule as well as those of the NO+ fragment ion. This measurement depends on correcting for a phenomenon referred to as “scrambling” in the ion source, whereby the NO+ fragment ion contains the outer N atom from the N2O molecule. While descriptions of the scrambling correction exist in the literature, there has yet to be published a unified software package and method for performing this correction. We developed a user-friendly Python package (pyisotopomer), with a MATLAB alternative, to determine two coefficients that describe scrambling in the ion source of a given IRMS, and then to use this calibration to obtain N2O isotopocule measurements. We assess the sensitivity of pyisotopomer to its input parameters and discuss the relevant assumptions. We show that the scrambling behavior of an IRMS can vary with time, necessitating regular calibrations. We show that to obtain a relative uncertainty in site preference of <1‰, the relative uncertainty in each scrambling coefficient should be <0.2%. Finally, we present an intercalibration between two IRMS laboratories, using pyisotopomer to calculate scrambling and obtain N2O isotopocule data. Given these considerations, we discuss how to use this software package to obtain high-quality N2O isotopocule data from IRMS systems, including the use of appropriate reference materials and frequency of calibration.

Determination of Floral Origin Markers of Latvian Honey by Using IRMS, UHPLC-HRMS, and 1H-NMR

The economic significance of honey production is crucial; therefore, modern and efficient methods of authentication are needed. During the last decade, various data processing methods and a combination of several instrumental methods have been increasingly used in food analysis. In this study, the chemical composition of monofloral buckwheat (Fagopyrum esculentum), clover (Trifolium repens), heather (Calluna vulgaris), linden (Tilia cordata), rapeseed (Brassica napus), willow (Salix cinerea), and polyfloral honey samples of Latvian origin were investigated using several instrumental analysis methods. The data from light stable isotope ratio mass spectrometry (IRMS), ultra-high performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC-HRMS), and nuclear magnetic resonance (NMR) analysis methods were used in combination with multivariate analysis to characterize honey samples originating from Latvia. Results were processed using the principal component analysis (PCA) to study the potential possibilities of evaluating the differences between honey of different floral origins. The results indicate the possibility of strong differentiation of heather and buckwheat honeys, and minor differentiation of linden honey from polyfloral honey types. The main indicators include depleted δ15N values for heather honey protein, elevated concentration levels of rutin for buckwheat honey, and qualitative presence of specific biomarkers within NMR for linden honey.

Effect of Age of Agave tequilana Weber Blue Variety on Quality and Authenticity Parameters for the Tequila 100% Agave Silver Class: Evaluation at the Industrial Scale Level

Due to the oversupply and scarcity cycles of the Agave tequilana Weber blue variety, the effect of agave age (harvested in 4, 5, and 6 years) as raw material for the tequila 100% agave silver class was studied for each stage in a full-scale (industrial) process. Harvested plants showed differences in their morphological characteristics that affected the amount of juice; this had an impact in the fermentation stage since must composition was modified in the nitrogen content and juice/exudate ratio. This was noticed due to an increase in the production of higher alcohols attributed to the odd-chain fatty of the exudate, which affects n-propanol production. The characterization of the final product showed the feasibility to use agaves (less than 7 years) to produce the Tequila 100% agave silver class and to comply with the quality criteria. Furthermore, the final product was analyzed with the gas chromatography-isotope ratio mass-spectrometry technique to determine its authenticity. The δ13CVPDB isotopic parameter (−13.40‰ in average) values show the type of plant used as a raw material for ethanol production, while the δ18OVSMOW (20.52‰ in average) isotopic parameter can be helpful in corroborating and ensuring the traceability of the product and the geographical location of the beverage production.

Recent Progresses in Stable Isotope Analysis of Cellulose Extracted from Tree Rings

In this work, the challenges and progression in stable isotope investigation, from the analytical tools and technical sample preparation procedures to the dendroclimatological experiments, were reviewed in terms of their use to assess tree physiological responses to environmental changes. Since the isotope signature of whole wood is not always a reliable tool in studying the climate changes, cellulose is often preferred as the study material in paleoclimatic studies. Nevertheless, the isotope analysis of cellulose is challenging due to the difficulty to remove the other wood components (extractives, lignin, pectin, and hemicelluloses). Additionally, in the case of hydrogen isotope analysis, about 30% of the hydrogen atoms of cellulose are exchanged with the surrounding water, which complicates the isotope analysis. In recent years, more automated isotope analysis methods were developed based on high temperature pyrolysis of cellulose, followed by the chromatographic separation of H2 from CO and by their individual isotope analysis using isotope ratio mass spectrometry. When used to investigate climate factors, the combined isotope analysis δ13C and δ18O appears to be the most promising isotope tool. In contrast, the role of δ2H values is yet to be elucidated, together with the development of new methods for hydrogen isotope analysis.

Beryl Reference Materials for In Situ Oxygen Isotope Determination

The mineral beryl (Be3Al2(SiO3)6) has the most abundant phase with industrial value for extracting a critical metal—beryllium. Due to multi-stage, fluid-induced growth, individual beryl grains may yield complex geochemical records, revealing variations in the oxygen isotopes of the fluids from which they crystallize. Secondary ion mass spectrometry (SIMS) with high sensitivity and high spatial resolution represents a good tool for in situ isotopic analysis. SIMS oxygen analyses require matrix-matched reference materials to calibrate instrumental mass fractionations during measurement. In this work, the oxygen isotope homogeneities of six beryl samples with different compositions (BS1, BS2, BS3, BS4, BS5, and BS6) were documented by SIMS. These samples’ recommended oxygen isotope compositions were characterized by laser fluorination isotope ratio mass spectrometry (IRMS). This study suggests that there is no matrix effect related to composition variation in beryl SIMS oxygen isotope analysis. The recommended δ18O values of the four reference materials, BS1, BS2, BS4, and BS5, were 15.01 ± 0.34‰ (2 standard deviations, 2 SD), 7.53 ± 0.16‰ (2 SD), 2.38 ± 0.14‰ (2 SD), and 10.72 ± 0.44‰ (2 SD), respectively. Therefore, BS1, BS2, BS4, and BS5 are recommended as suitable reference materials for in situ mineral beryl oxygen isotope microanalysis.