Mass Spectrometry Instrumentation Research Articles

A study of the transient gas flow affected ion transmission in atmospheric pressure interfaces based on large eddy simulation for electrospray ionization mass spectrometry

Modern atmosphere pressure interface (API) enables high-efficiency coupling between mass analyzers in high vacuum and atmosphere ionization sources such as electrospray ionization (ESI) source. The transient gas flow entering API possesses strong compressibility and turbulent characteristics, which exerts a huge impact on ion transmission. However, the instantaneous nature and vortical morphology of the turbulence in API and its affection in ion transmission were hardly covered in the reported research. Here we conduct a transient turbulent flow-affected ion transmission evaluation for two typical APIs, the ion funnel and the S-lens, based on scale-resolving large eddy simulation and electro-hydrodynamical ion tracing simulation. In our simulation, the transient properties of the gas flow in the two APIs are illustrated and analyzed in-depth. After experimentally validated on a homemade ESI-TOF-MS platform, the results suggest that the ion funnel can achieve a higher droplet desolvation rate by introducing a unique droplet recirculation mechanism. Meanwhile, the less-dispersed gas flow in S-lens is beneficial in actuating ions axially. In conclusion, the application of the scale-resolving turbulence model helps us to understand the complicated fluid-ion interaction mechanism in APIs and is promising in the development of mass spectrometry instruments of higher performance.

Post-translational modifications of proteins in cardiovascular diseases examined by proteomic approaches.

Over 400 different types of post-translational modifications (PTMs) have been reported and over 200 various types of PTMs have been discovered using mass spectrometry (MS)-based proteomics. MS-based proteomics has proven to be a powerful method capable of global PTM mapping with the identification of modified proteins/peptides, the localization of PTM sites and PTM quantitation. PTMs play regulatory roles in protein functions, activities and interactions in various heart related diseases, such as ischemia/reperfusion injury, cardiomyopathy and heart failure. The recognition of PTMs that are specific to cardiovascular pathology and the clarification of the mechanisms underlying these PTMs at molecular levels are crucial for discovery of novel biomarkers and application in a clinical setting. With sensitive MS instrumentation and novel biostatistical methods for precise processing of the data, low-abundance PTMs can be successfully detected and the beneficial or unfavorable effects of specific PTMs on cardiac function can be determined. Moreover, computational proteomic strategies that can predict PTM sites based on MS data have gained an increasing interest and can contribute to characterization of PTM profiles in cardiovascular disorders. More recently, machine learning- and deep learning-based methods have been employed to predict the locations of PTMs and explore PTM crosstalk. In this review article, the types of PTMs are briefly overviewed, approaches for PTM identification/quantitation in MS-based proteomics are discussed and recently published proteomic studies on PTMs associated with cardiovascular diseases are included.

Role of Hydroperoxyl Radicals in Heterogeneous Oxidation of Oxygenated Organic Aerosols.

Heterogeneous oxidative aging of organic aerosols (OA) occurs ubiquitously in the atmosphere, initiated by oxidants, such as the hydroxyl radicals (•OH). Hydroperoxyl radicals (HO2•) are also an important oxidant in the troposphere, and its gas-phase chemistry has been well studied. However, the role of HO2• in heterogeneous OA oxidation remains elusive. Here, we carry out •OH-initiated heterogeneous oxidation of several OA model systems under different HO2• conditions in a flow tube reactor and characterize the molecular oxidation products using a suite of mass spectrometry instrumentation. By using hydrogen-deuterium exchange (HDX) with thermal desorption iodide-adduct chemical ionization mass spectrometry, we provide direct observation of organic hydroperoxide (ROOH) formation from heterogeneous HO2• and peroxy radicals (RO2•) reactions for the first time. The ROOH may contribute substantially to the oxidation products, varied with the parent OA chemical structure. Furthermore, by regulating RO2• reaction pathways, HO2• also greatly influence the overall composition of the oxidized OA. Last, we suggest that the RO2• + HO2• reactions readily occur at the OA particle interface rather than in the particle bulk. These findings provide new mechanistic insights into the heterogeneous OA oxidation chemistry and help fill the critical knowledge gap in understanding atmospheric OA oxidative aging.

Biomonitoring: Developing a Beehive Air Volatiles Profile as an Indicator of Environmental Contamination Using a Sustainable In-Field Technique

The wellbeing of the honey bee colonies and the health of humans are connected in numerous ways. Therefore, ensuring the wellbeing of bees is a crucial component of fostering sustainability and ecological harmony. The colony collapse disorder (CCD) phenomenon was first reported in 2006 when the majority of bee colonies in Europe died out, due to an increase in infections, contamination of hives with agrochemical pesticides, and persistent organic pollutants (POPs). Only 6 years after the emergence of CCD, more than 6.5 million premature deaths were reported, as a consequence of persistent human exposure to air pollution. The insect species such as the honey bee Apis mellifera L. and the air matrix inside the beehive can be used as tools in biomonitoring, instead of traditional monitoring methods. This may have advantages in terms of cost-effective bioindicators of the environmental health status, showing the ability to record spatial and temporal pollutant variations. In this study, we present the sustainable in-field usage of the portable membrane inlet mass spectrometry (MIMS) instrument for an instant and effective determination of the level of environmental pollution by analytical identification of hive atmosphere volatile organic compound (VOC) contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), monocyclic aromatic hydrocarbons (BTEX) compounds, and pesticides. The samples were taken from hives located in urbanized and rural regions, highlighting variations in contamination. The MIMS results were benchmarked against a conventional laboratory sampling technique, such as GC-MS.

Characterization of Regolith And Trace Economic Resources (CRATER): An Orbitrap-based laser desorption mass spectrometry instrument for in situ exploration of the Moon.

Characterization of Regolith And Trace Economic Resources (CRATER), an Orbitrap™-based laser desorption mass spectrometry instrument designed to conduct high-precision, spatially resolved analyses of planetary materials, is capable of answering outstanding science questions about the Moon's formation and the subsequent processes that have modified its (sub)surface. Here, we describe the baseline design of the CRATER flight model, which requires <20 000 cm3 volume, <10kg mass, and <60 W peak power. The analytical capabilities and performance metrics of a prototype that meets the full functionality of the flight model are demonstrated. The instrument comprises a high-power, solid-state, pulsed ultraviolet (213 nm) laser source to ablate the surface of the lunar sample, a custom ion optical interface to accelerate and collimate the ions produced at the ablation site, and an Orbitrap mass analyzer capable of discriminating competing isobars via ultrahigh mass resolution and high mass accuracy. The CRATER instrument can measure elemental and isotopic abundances and characterize the organic content of lunar surface samples, as well as identify economically valuable resources for future exploration. An engineering test unit of the flight model is currently in development to serve as a pathfinder for near-term mission opportunities.

Application of Weighted Gene Co-Expression Network Analysis to Metabolomic Data from an ApoA-I Knockout Mouse Model.

As the ability to collect profiling data in metabolomics increases substantially with the advances in Liquid Chromatography-Mass Spectrometry (LC-MS) instruments, it is urgent to develop new and powerful data analysis approaches to match the big data collected and to extract as much meaningful information as possible from tens of thousands of molecular features. Here, we applied weighted gene co-expression network analysis (WGCNA), an algorithm popularly used in microarray or RNA sequencing, to plasma metabolomic data and demonstrated several advantages of WGCNA over conventional statistical approaches such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA). By using WGCNA, a large number of molecular features were clustered into a few modules to reduce the dimension of a dataset, the impact of phenotypic traits such as diet type and genotype on the plasma metabolome was evaluated quantitatively, and hub metabolites were found based on the network graph. Our work revealed that WGCNA is a very powerful tool to decipher, interpret, and visualize metabolomic datasets.

Contaminant Spot Check and Removal Assay (ContamSPOT) for Mass Spectrometry Analysis.

Mass spectrometry (MS) analysis is often challenged by contaminations from detergents, salts, and polymers that compromise data quality and can damage the chromatography and MS instruments. However, researchers often discover contamination issues only after they acquire the data. There is no existing contaminant assay that is sensitive enough to detect trace amounts of contaminants from a few microliters of samples prior to MS analysis. To address this crucial need in the field, we developed a sensitive, rapid, and cost-effective contaminant spot check and removal assay (ContamSPOT) to detect and quantify trace amounts of contaminants, such as detergents, salts, and other chemicals commonly used in the MS sample preparation workflow. Only 1 μL of the sample was used prior to MS injection to quantify contaminants by ContamSPOT colorimetric or fluorometric assay on a thin layer chromatography (TLC) plate. We also optimized contaminant removal methods to salvage samples with minimal loss when ContamSPOT showed a positive result. ContamSPOT was then successfully applied to evaluate commonly used bottom-up proteomic methods regarding the effectiveness of removing detergent, peptide recovery, reproducibility, and proteome coverage. We expect ContamSPOT to be widely adopted by MS laboratories as a last-step quality checkpoint prior to MS injection. We provided a practical decision tree and a step-by-step protocol with a troubleshooting guide to facilitate the use of ContamSPOT by other researchers. ContamSPOT can also provide a unique readout of sample cleanliness for developing new MS-based sample preparation methods in the future.

Perspective on SPME-MS: Green and high-performance methods for rapid screening

The direct coupling of solid-phase microextraction (SPME) with mass spectrometry (MS) offers rapid analysis with high sensitivity and low matrix effects by benefiting from the integration of sampling, high enrichment, and clean-up functions of SPME. Eliminating chromatographic separation reduces the amount of gas/solvent needed for analysis, while direct desorption in SPME-MS consumes none or few microliters of organic solvents per sample, further enhancing the greenness of the SPME technology. Over the past two decades, the rapid evolution of SPME-MS has given rise to numerous novel technologies that employ diverse ionization techniques and interfaces, several of which have already been commercialized. Drawing from an extensive review published earlier this year and our research experience, we provide perspectives on three aspects of these technologies: interface design and automation, integration with state-of-art MS instrumentation, and anticipated future developments.

PGFinder, an Open-Source Software for Peptidoglycomics: The Structural Analysis of Bacterial Peptidoglycan by LC-MS.

Peptidoglycan is a major and essential component of the bacterial cell envelope that confers cell shape and provides protection against internal osmotic pressure. This complex macromolecule is made of glycan strands cross-linked by short peptides, and its structure is continually modified throughout growth via a process referred to as "remodeling." Peptidoglycan remodeling allows cells to grow, adapt to their environment, and release fragments that can act as signaling molecules during host-pathogen interactions. Preparing peptidoglycan samples for structural analysis first requires purification of the peptidoglycan sacculus, followed by its enzymatic digestion into disaccharide peptides (muropeptides). These muropeptides can then be characterized by liquid chromatography coupled mass spectrometry (LC-MS) and used to infer the structure of intact peptidoglycan sacculi. Due to the presence of unusual crosslinks, noncanonical amino acids, and amino sugars, the analysis of peptidoglycan LC-MS datasets cannot be handled by traditional proteomics software. In this chapter, we describe a protocol to perform the analysis of peptidoglycan LC-MS datasets using the open-source software PGFinder. We provide a step-by-step strategy to deconvolute data from various mass spectrometry instruments, generate muropeptide databases, perform a PGFinder search, and process the data output.

Mass spectrometry-intensive top-down proteomics: an update on technology advancements and biomedical applications.

Proteoforms are all forms of protein molecules from the same gene because of variations at the DNA, RNA, and protein levels, e.g., alternative splicing and post-translational modifications (PTMs). Delineation of proteins in a proteoform-specific manner is crucial for understanding their biological functions. Mass spectrometry (MS)-intensive top-down proteomics (TDP) is promising for comprehensively characterizing intact proteoforms in complex biological systems. It has achieved substantial progress in technological development, including sample preparation, proteoform separations, MS instrumentation, and bioinformatics tools. In a single TDP study, thousands of proteoforms can be identified and quantified from a cell lysate. It has also been applied to various biomedical research to better our understanding of protein function in regulating cellular processes and to discover novel proteoform biomarkers of diseases for early diagnosis and therapeutic development. This review covers the most recent technological development and biomedical applications of MS-intensive TDP.

Prototyping an ionization source for non-engineers.

Novel mass spectrometry (MS) based analytical platforms have enabled scientists to detect and quantify molecules within biological and environmental samples more accurately. Novel MS instrumentation starts as a prototype and, after years of development, can become a commercial product to be used by the larger MS community. Without the initial prototype, many MS-based instruments today would not be produced. Additionally, biotechnology companies are the main drivers for research, development, and production of novel instruments, but the tools for prototyping instrumentation have never been more accessible. Here, we present a tutorial on prototyping instrumentation through the case study of developing the Next Generation IR-MALDESI source to show that an engineering degree is not required to design and construct a prototype instrument with modern hardware and software. We discuss the prototyping process, the necessary skills required for efficient prototyping, and information about common hardware and software used within initial prototypes.

Optimizing an airborne mass-balance methodology for accurate emission rate quantification of industrial facilities: A case study of industrial facilities in South Korea

Accurate estimation of emissions from industrial point sources is crucial in understanding the effectiveness of reduction efforts and establishing reliable emission inventories. In this study, we employ an airborne Chemical Ionization Mass Spectrometry (CIMS) instrument to quantify sulfur dioxide (SO2) emissions from prominent industrial facilities in South Korea, including power plants, a steel mill, and a petrochemical facility. Our analysis utilizes the box mass balance technique to derive SO2 emissions and associated uncertainty. We evaluate the interpolation methods between 2D kriging and 3D radial basis function. The results demonstrate that the total uncertainty of the box mass balance technique ranges from 5 % to 28 %, with an average of 20 %. Mixing ratio ground extrapolation from the lowest altitude of the airborne sampling to the ground emerges as the dominant source of uncertainty, followed by the determination of the boundary layer height. Adequate sampling at multiple altitudes is found to be essential in reducing the overall uncertainty by capturing the full extent of the plume. Furthermore, we assess the uncertainty of the single-height transect mass balance method commonly employed in previous studies. Our findings reveal an average precision of 47 % for this method, with the potential for overestimating emissions by up to 206 %. Samplings at fewer altitudes or with larger altitude gaps increase the risk of under-sampling and elevate method uncertainties. Therefore, this study provides a quantitative basis to evaluate previously airborne observational emission constraints.

Reproducibility in nontarget screening (NTS) of environmental emerging contaminants: Assessing different HLB SPE cartridges and instruments

Non-targeted screening (NTS) methods are integral in environmental research for detecting emerging contaminants. However, their efficacy can be influenced by variations in hydrophilic-lipophilic balance (HLB) solid phase extraction (SPE) cartridges and high-resolution mass spectrometry (HRMS) instruments across different laboratories. In this study, we scrutinized the influence of five HLB SPE cartridges (Nano, Weiqi, CNW, Waters, and J&K) and four LC-HRMS platforms (Agilent, Waters, Thermo, and AB SCIEX) on the identification of emerging environmental contaminants. Our results demonstrate that 87.6 % of the target compounds and over 59.6 % of the non-target features were consistently detected across all tested HLB cartridges, with an overall 71.2 % universally identified across the four LC-HRMS systems. Discrepancies in detection rates were primarily attributable to variations in retention time stability, mass stability of precursors and fragments, system cleanliness affecting fold change and p-values, and fragment response. These findings confirm the necessity of refining parameter criteria for NTS. Moreover, our study confirms the efficacy of the PyHRMS tool in analyzing and processing data from multiple instrumental platforms, reinforcing its utility for multi-platform NTS. Overall, our findings underscore the reliability and robustness of NTS methods in identifying potential water contaminants, while also highlighting factors that may influence these outcomes.

Recent Contributions of Mass Spectrometry-Based "Omics" in the Studies of Breast Cancer.

Breast cancer (BC) is one of the most heterogeneous groups of cancer. As every biotype of BC is unique and presents a particular "omic" signature, they are increasingly characterized nowadays with novel mass spectrometry (MS) strategies. BC therapeutic approaches are primarily based on the two features of human epidermal growth factor receptor 2 (HER2) and estrogen receptor (ER) positivity. Various strategic MS implementations are reported in studies of BC also involving data independent acquisitions (DIAs) of MS which report novel differential proteomic, lipidomic, proteogenomic, phosphoproteomic, and metabolomic characterizations associated with the disease and its therapeutics. Recently many "omic" studies have aimed to identify distinct subsidiary biotypes for diagnosis, prognosis, and targets of treatment. Along with these, drug-induced-resistance phenotypes are characterized by "omic" changes. These identifying aspects of the disease may influence treatment outcomes in the near future. Drug quantifications and characterizations are also done regularly and have implications in therapeutic monitoring and in drug efficacy assessments. We report these studies, mentioning their implications toward the understanding of BC. We briefly provide the MS instrumentation principles that are adopted in such studies as an overview with a brief outlook on DIA-MS strategies. In all of these, we have chosen a model cancer for its revelations through MS-based "omics".

Detection rates of pesticide residues in Saudi Arabian produce as influenced by season

Pesticide residues and persistent organic pollutants (POPs) are known hazardous chemicals that exhibits bioaccumulation in organisms and the ecosystem in general. There is limited evidence on the levels of these contaminants among common Saudi crops grown as well as the effects of season on their levels. Hence, the present investigated the levels of pesticide residues in major fruit and vegetable crops collected during the winter and summer seasons in Saudi Arabia (SA). A total of 392 samples taken from 28 locally produced vegetables and fruits were purchased from local markets in Riyadh, SA during peak summer (N = 263) (June-August 2022) and peak winter (N = 129) (December-February 2022). Food samples were extracted and cleaned up using the modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) technique. Liquid chromatography with tandem mass spectrometry (LC-MS/MS) and gas chromatography–tandem mass spectrometry (GC–MS/MS) instruments were used to determine pesticide residues. Crops that had the highest percentage exceeding the maximum residue limit (MRL) include pepper (7.9 %) as well as apricot, fig and pomegranates (3.1 %). Cypermethrin was the most prevalent pesticide residue in both winter and summer samples with detection rates of 13.2 % and 14.1 % respectively (p = 0.33). Thiamethoxam detection rates was significantly higher in winter (7.8 %) than summer (3.0 %) (p = 0.04). There is a high detection rate of pesticide residues in SA independent of season, with cypermethrin being the most common. Thiamethoxam is more commonly detected in winter than summer crops. The study should be extended to include other potential sources of pesticide residues such as fishes grown in aqua farms and other poultry products.

Automated Identification of Modified Nucleosides during HRAM-LC-MS/MS using a Metabolomics ID Workflow with Neutral Loss Detection.

The role of post-transcriptional modification in biological processes has been an ongoing field of study for several decades. Improvements in liquid chromatography platforms and mass spectrometry instrumentation have resulted in the enhanced identification, characterization, and quantification of modified nucleosides in biological systems. One consequence of the rapid technological improvements in the analytical acquisition of modified nucleosides has been a dearth of robust data processing workflows for analyzing more than a handful of samples at a time. To improve the utility of LC-MS/MS for batch analyses of modified nucleosides, a workflow for automated nucleoside identification has been developed. We adapted the Thermo Fisher Scientific metabolomics identification software package, Compound Discoverer, to accurately identify modified nucleosides from batch LC-MS/MS acquisitions. Three points of identification are used: accurate mass from a monoisotopic mass list, spectral matching from a spectral library, and neutral loss identification. This workflow was applied to a batch (n = 24) of urinary nucleosides, resulting in the accurate identification and relative quantification of 16 known nucleosides in less than 1 h.

The Use of Mass Spectrometry in Therapeutic Protein Biologics License Applications: A Retrospective Review Revisited.

Biologic license applications (BLAs) for 93 therapeutic proteins approved between 2016 and 2020 were analyzed for use of mass spectrometry (MS) as a follow up to a previous study that assessed MS use in BLAs from 2000 to 2015. Thirty percent of these BLAs were biosimilars, while only one biosimilar BLA was approved prior to 2016. This analysis evaluated the use of a variety of MS techniques and instrumentation. Results were further interpreted based on the relationship of MS use over time, between drug types, and between new drugs and biosimilars. MS data were included in 93 BLAs examined. The top eight quality attributes most assessed by MS in rank order were amino acid sequence, molecular mass, oxidation, disulfide bonds, deamidation, glycosylation, N-terminal sequence variants, and C-terminal sequence variants. These attributes were the same top attributes seen previously from BLAs approved between 2000 and 2015, and the use of MS to analyze them generally continued to increase across the new time frame. The average number of attributes analyzed by MS per BLA also continued to increase over the extended time frame of 21 years. High-resolution, accurate mass instrumentation such as the Orbitrap and time-of-flight (TOF) usage increased over time for all assessed attributes, while matrix-assisted laser desorption/ionization (MALDI)-TOF/(TOF) usage decreased. From highest to lowest rank, the top 11 attributes were antibody drug conjugate (ADC) characterization (i.e., drug load distribution/drug to antibody ratio (DAR), ADC and linkage site, and synthetic linker), isomerization, folding/higher-order structure (HOS), truncation, host cell proteins (HCPs), sequence variants (amino acid substitutions), succinimidation, glycation, PEGylation, charge variants, and oxidation.

Development and validation of a liquid chromatography-tandem mass spectrometry assay to quantify plasma 24(S)-hydroxycholesterol and 27-hydroxycholesterol: A new approach integrating the concept of ion ratio

Accurate quantification of 24(S)-hydroxycholesterol and 27-hydroxycholesterol holds substantial biological significance due to their involvement in pivotal cellular processes, encompassing cholesterol homeostasis, inflammatory responses, neuronal signaling, and their potential as disease biomarkers. The plasma determination of these oxysterols is challenging considering their low concentrations and similarities in terms of empirical formulae, molecular structure, and physicochemical properties across all human endogenous plasma oxysterols. To overcome these sensitivity and specificity issues, we developed and validated a quantification method using liquid chromatography coupled to a tandem mass spectrometry instrument. Validation studies were designed inspired by Clinical and Laboratory Standards Institute (CLSI) C62-A Guidelines. The linearity ranged between 20 and 300 nM for both oxysterols with limits of quantification at 20 nM and 30 nM for 24(S)-OHC and 27-OHC, respectively. Inter-day precision coefficient variations (CV) were lower than 10% for both oxysterols. An optimal separation of 25-OHC was obtained from 24(S)-OHC and 27-OHC with a resolution (Rs) > 1.25. The determination and validation of ion ratios for 24(S)-OHC and 27-OHC enabled another quality check in identifying interferents that could impact the quantification. Our developed and validated LC-MS/MS method allows consistent and reliable quantification of human plasmatic 24(S)-OHC and 27-OHC that is warranted in fundamental and clinical research projects.

Depth profile analyses by femtosecond laser ablation (multicollector) inductively coupled plasma mass spectrometry for resolving chemical and isotopic gradients in minerals

Abstract. Femtosecond laser ablation (fs-LA) coupled to a multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) instrument has been proven to be a powerful means to analyze isotope ratios of “non-traditional” stable isotope systems with high spatial resolution, precision, and accuracy. The technique has been successfully applied, e.g., to investigate diffusion-generated isotopic zoning of the elements Li, Mg, and Fe in magmatic crystals. Here, we present a novel sampling technique employing a fs-LA system that is equipped with a computer numerical control (CNC) laser stage, using the open-source software LinuxCNC. Combining this laser set up with ICP-MS or MC-ICP-MS allows us to perform depth profile analyses of major and trace elements, respectively, as well as metal stable isotope variations of Fe and Mg in olivine crystals and in experimental diffusion couples. Samples are ablated in circular patterns with profile diameters of 100–200 µm using a laser spot size of 25–30 µm. Depending on the scan speed and the repetition rate of the laser, each ablated sample layer is between 300 nm and 3.0 µm thick. The integrated signal of one ablated layer represents one data point of the depth profile. We have tested this technique by analyzing 5–50 µm deep depth profiles (consisting of 15–25 individual layers) of homogeneous and chemically zoned olivine crystal cuboids. The minor and trace element analyses of the zoned cuboids, conducted by fs-LA-ICP-MS, were compared with “horizontal” profiles analyzed in polished sections of the cuboids with electron probe microanalysis (EPMA). Furthermore, we analyzed Fe–Mg isotopic depth profiles of the same cuboids with fs-LA-MC-ICP-MS, of which the chemically zoned ones also showed isotopic zoning at identical scales. Isotopic depth profiles were also conducted on an unzoned olivine cuboid that was coated with a 26Mg- and 56Fe-enriched olivine thin film (of ∼ 800 nm) in order to investigate top-to-bottom contamination during depth profiling. Our results indicate that (i) concentration data acquired by fs-LA depth profiling match well with EPMA data, (ii) precise and accurate Fe and Mg isotopic data can be obtained (i.e., precision and accuracy are ≤ 0.12 ‰ and ≤ 0.15 ‰ for both δ26Mg and δ56Fe, respectively), and (iii) potential top-to-bottom contamination during depth profiling of isotope ratios can be avoided. The technique presented herein is particularly suitable for the investigation of minerals or glasses with chemical and/or isotopic gradients (e.g., diffusion zoning) vertical to planar surfaces. It can also be applied in materials sciences in order to analyze thin films, coatings, or surface contaminations on solids.

Mass spectrometry analysis of drugs using an integrated thermal desorption corona discharge ionization device

In this study, we introduce the design, characterization, and application of an integrated thermal desorption corona discharge ionization (TD-CDI) device, which was developed for direct mass spectrometry (MS) analysis of drugs in solid or liquid samples. The structure and operational parameters of the TD module were optimized through simulation and experimental investigations. For the CDI module, a hollow needle was used as the discharge electrode and sample inlet, allowing self-aspiration and efficient ionization of the desorbed samples. The TD-CDI device was tested and characterized using different mass spectrometers, exhibiting satisfactory stability and quantitative performance. Owing to its compact structure, it can be coupled to a miniature MS instrument to implement rapid identification of various drugs in urine solutions.