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At least 649 records · Page 36

Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration

In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

NASA Discipline Exobiology↗

Developing Mass Spectrometry for Water Quantitation and Volatiles Analysis from In-Situ Regolith

With a revived focus to create a sustainable hu-man presence on the moon, and in preparation for future Mars exploration, it is imperative that all resources are utilized to their fullest potential [1]. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable in-dependent operation of missions while reducing the dependence on the complex supply chain created between the Earth, the moon and Mars. One of the most critical resources that has been identified for ISRU on the lunar surface is water [2]. Water is a versatile resource that can be used in various space operations, such as ra-diation shielding and conversion to oxygen (O2) for propellant [3,4]. One of the most water rich resources is thought to be within the regolith lo-cated in the permanently shadowed regions (PSR) of the Moon; several upcoming missions, such as PRIME-1 and VIPER, are already sched-uled to confirm this hypothesis [5,6]. However, there are currently no missions planned to quanti-fy the abudance of water at these regions. The quantity of water contained in the ice will inform and help the development of future ISRU plants and operation. Water and other volatile gases can be detect-ed upon controlled heating of icy lunar regolith for an accurate quantification of water. This method is similar to thermogravimetric analysis, which was used to analyze Apollo lunar regolith sam-ples. However, losses via sublimation/evaporation or contamination may have occurred with the samples due to the transit and exposure to the terrestrial environment. Furthermore, water would not be expected for these samples since they were not collected from a PSR. Thus, for more accurate results, icy lunar regolith should be ana-lyzed in situ to provide the most representative composition of both water and other volatile gas-es. The Light Water Analysis and Volatile Extract (LightWAVE) project aims to address this knowledge gap. A system has been developed to collect, heat and analyze evolved gases from lu-nar regolith on the lunar surface. The gases will be analyzed by a modified commercial off the shelf (COTS) residual gas analyzer (RGA) quad-rupole mass spectrometer. Evolved gases from heated regolith samples can be identified by the observed mass-to-charge (m/z) ratios, and the peak intensities correlate to the abundances of the observed gases for quantitation. Therefore, our group is developing a calibration methodology utilizing a COTS RGA to quantitate water from in-situ regolith samples on the lunar surface. The partial pressure of water and ideal gas law will be used to quantify the total water evolved from a regolith sample. Here we present our methodol-ogy for the design and calibration for water quan-titation using a COTS RGA.

Nilab Azim↗

Large-Volume Injection and Assessment of Reference Standards for n -Alkane δD and δ 13 C Analysis via Gas Chromatography Isotope Ratio Mass Spectrometry

Compound-specific stable isotope analysis of hydrogen (δD) and carbon (δ 13 C) in organic compounds is a valuable tool in biogeochemical research. A key limitation of this method is the relatively large amount of sample required to achieve desirable precision. We developed a large-volume (20 μL) injection method that allows for high throughput analysis of less concentrated samples and tested it for δ 13 C and δD measurements of n-alkanes. We also conducted a comparison of reference standards and assessed several methods to normalize and correct n-alkane δD and δ13C measurements. The mean precision of the δD method based on 233 environmental n-alkane samples (two to three replications per sample) is 4.0‰ (1σ, estimated from the weighted mean of the pooled unbiased standard deviations) and 0.46‰ (1σ) for δ 13 C from 37 environmental samples (two to three replications per sample). The evaluation of reference standards shows that the use of n-alkane standards with large offsets in δD values in adjacent n-alkane chains can lead to biases in measurement correction. The large-volume injection method shows good reproducibility of δ 13 C and δD measurements of n-alkanes and reduces the required sample concentration by about 80%. We propose that for δD measurements, a reference standard set should be used in which each reference standard has a limited range of δD values and no adjacent n-alkane chains, to minimize memory effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of ion-pairing reagents on the separation of intact glycoproteins using hydrophilic-interaction liquid chromatography - high-resolution mass spectrometry

Hydrophilic-interaction liquid chromatography (HILIC) of intact proteins offers high-resolution separations of glycoforms of glycoproteins differing in the number of (neutral) glycans. However, to obtain efficient separations it is essential that the positively charged sites of the proteins are shielded by acidic (negative) ion-pair reagents (IPRs), so as to enhance the contribution of the hydroxyl groups of the (neutral) sugars in the glycoprotein. Here, we studied the influence of various IPRs that differ in physico-chemical properties, such as hydrophobicity and acidity, on the capillary-scale HILIC separation of intact (glyco)proteins. We evaluated the use of fluoroacetic acid (MFA), difluoroacetic acid (DFA), trifluoroacetic acid (TFA), and heptafluorobutyric acid (HFBA) as diluents for sample preparation, as solvents for sample loading on a reversed-phase trap prior to the HILIC separation, and as mobile-phase components for HILIC and HILIC-MS. To reduce the contribution of ion-exchange interaction with the (silica-based) stationary phase, we used an acrylamide-based monolithic column. We studied the influence of the different IPRs on each step of the separation of a mixture of proteins of different size and hydrophilicity and on the separation of the five glycoforms of ribonuclease B. The content of IPR in the sample was shown not to affect the separation and the MS detection. However, a low content of TFA and DFA in the mobile phase is favourable, as it reduces adduct formation and leads to higher signal intensity. The optimized HILIC conditions successfully resolved nine major glycoforms groups of a ~40 kDa glycoprotein horseradish peroxidase (HRP), as an example of a complex glycoprotein.

59 BASIC BIOLOGICAL SCIENCES↗