Types Of Mass Spectrometers Research Articles

Detection of IDH mutation in glioma by desorption electrospray ionization (DESI) tandem mass spectrometry

Desorption electrospray ionization (DESI) tandem mass spectrometry (MS) is used to assess mutation status of isocitrate dehydrogenase (IDH) in human gliomas. Due to the diffuse nature of gliomas, total gross resection is not normally achieved during surgery, leading to tumor recurrence. The mutation status of IDH has clinical significance due to better prognosis in IDH-mutant patients. The mutant IDH converts alpha-ketoglutaric acid (α-KG) into 2-hydroxyglutarate (2HG), which accumulates abnormally in cells. Immunohistochemical staining (IHC) and genetic testing, the gold standards, are incompatible with intraoperative applications but DESI tandem mass spectrometry (MS/MS) can be used to assess the mutation status of IDH enzyme from tissue intraoperatively. Here, on off-line evaluation is made of the performance of two different types of mass spectrometers in characterization of IDH mutation status. The intensity of 2HG is measured against glutamate (Glu), an intrinsic reference molecule, in both tandem MS measurements. In both cases using DESI clear separation between IDH-mutant (mut) and IDH-wildtype (wt) samples (p < 0.0001) is observed, despite the short analysis time. Due to the higher detection sensitivity, multiple reaction monitoring experiments using a triple quadrupole show slightly better performance compared to product ion MS/MS performed on a simple linear ion trap. Both DESI-MS platforms are capable of providing information on IDH mutation status, which might in future be used at the time of surgery to support decision-making on resection regions, especially at tumor margins.

Implementation and experience of using methods for analyzing the isotopic composition of Sm and Nd, Rb and Sr in rock samples at the Geoanalitik Center for Collective Use

Research subject. AGV-2 and BHVO-2 geochemical reference materials for studying the Sm, Nd and Rb, Sr isotope systems along with various rocks and mineral samples. Materials and Methods. An analysis of the isotopic composition of Sm, Nd and Rb, Sr was carried out using Neptune Plus and Triton Plus mass spectrometers. Aim. To implement analytical techniques for the isotopic composition of Sm and Nd, Rb, and Sr in various rock and mineral samples using two types of multicollector mass spectrometers – inductively coupled plasma NeptunePlus and thermal ionization TritonPlus (Thermo-Fisher), as well as a description of the procedure of processing experimental data and the experience in using techniques at the “Geoanalitik” shared research facilities of the IGG UB RAS for the period 2015-2023. Results. The analytical techniques implemented included (1) column chromatography using various ion-exchange resins, optimised for the ratio of labour costs/quality of analytical results; (2) the measurement of isotope ratios using two types of mass spectrometers; (3) the correction of mass bias of isotope ratios and the determination of Sm and Nd, Rb, and Sr concentrations by the isotope dilution method using 149Sm+150Nd and 85Rb+84Sr spikes. Testing of the techniques was carried out using the AGV-2 and BHVO-2 geochemical reference materials; their metrological characteristics were presented. When using TritonPlus, the reproducibility (BHVO-2, n=60) of measurements of 143Nd/144Nd, 147Sm/144Nd isotope ratios and Sm and Nd concentrations are ±0.000020, ±0.0004, ±1.3 and ±0.4, respectively; indicators of correctness of determining the ratios 143Nd/144Nd and 147Sm/144Nd – 0.001 and 0.25% and concentrations of Sm and Nd – 2%; the reproducibility (BHVO-2, n=63) of measurements of 87Sr/86Sr, 87Rb/86Sr isotope ratios and concentrations (Rb and Sr) are ±0.0025%, ±1.5%, ±2%, respectively. The uncertainty of a single measurement of the 143Nd/144Nd and 87Sr/86Sr isotope ratio, represented by the standard error of the average single measurement in the sample, does not exceed 0.0025%. Conclusions: the results obtained for the geochemical reference materials are in satisfactory agreement with those provided in the GeoReM database, as well as with the certified values provided by the United States Geological Survey (USGS). The described analytical techniques are used at the “Geoanalitik” shared research facilities of the IGG UB RAS to analyse various rock and mineral samples. The work presents a number of experimental results obtained, which are subsequently used in geochronological applications.

A Thorough Examination of the Recent Advances in Mass Spectrometry

Abstract: Mass spectrometry has become an essential tool in pharmaceutical analysis, revolutionizing drug development, quality assurance, and our understanding of complex biological systems. This review provides a comprehensive overview of recent advances in mass spectrometry for pharmaceutical analysis. We discuss the fundamentals of mass spectrometry, including ionization and mass analysis principles, as well as the various types of mass spectrometers used in pharmaceutical analysis. We explore high-resolution mass spectrometry (HRMS), tandem mass spectrometry (MS/MS), ambient ionization mass spectrometry, and mass spectrometry imaging (MSI), highlighting their applications in drug characterization, quantification, imaging, and biomarker discovery. Furthermore, we examine the challenges faced by mass spectrometry, such as matrix effects and data interpretation, and discuss emerging trends and future perspectives. By understanding the recent advancements and addressing the challenges, mass spectrometry can continue to drive advancements in pharmaceutical analysis and quality assurance

Assessment and validation of the p-QuEChERS sample preparation methodology for the analysis of >200 veterinary drugs in various animal-based food matrices

The need remains for veterinary multi-residue methods that reliably quantify and identify veterinary drugs in the various animal-based food matrices. Such a method should not only show good method performance parameters (e.g. recoveries of analytes) but must also be fast and cheap. The proposed method focused on the following points: acceptable analyte trueness (recovery) and precision for a large number (200) of diverse veterinary drugs in the relevant animal-based food matrices (egg, muscle, fatty fish, liver, kidney, and honey). The sample preparation method termed p-QuEChERS uses a salt mixture consisting of potassium phosphates to induce phase separation. The avoidance of conventional QuEChERS salts (e.g. magnesium sulphate) significantly improves recoveries of several critical analytes. Analyte recoveries were further improved by adding a centrifugation and a defatting step before initiating the salt-induced phase separation. This combined clean-up removes a large fraction of the potentially interfering matrix compounds. As a result, matrix effects in the electrospray interface were minimized. These factors were the basis for the obtained good validation data. Two types of high-resolution mass spectrometers coupled to liquid chromatography were compared for analysis. In comparison with conventional QuEChERS, the proposed p-QuEChERS concept improved the recovery of polar analytes such as penicillins, tetracyclines and quinolones. The simplicity of the procedure and the low consumable expenses make the method ideal for the routine control of veterinary drugs in all evaluated animal-based food matrices.

Generalization of an Open Dynamically Harmonized Cell for Ultrahigh FT ICR Resolution.

FT ICR mass spectrometry is the leader in resolving power among all mass spectrometry methods. Introduction of the dynamically harmonized measuring cell─a closed-cylindrical cell with specifically shaped electrodes─helps to reach the resolving power of more than 107 with a magnetic field of about 7 T. From the theory of FT ICR mass spectrometry it follows that the resolving power of this type of instrument depends linearly on the magnetic field under various conditions. However, the results obtained on this type of mass spectrometer with the maximum magnetic field achievable today did not show a proportional increase in resolving power. In one of our previous papers, we assumed that the reason for this was insufficient vacuum inside the cell, since vacuum quality should be at least proportional to the magnetic field, since the mean free run time decreases proportionally to the magnetic field growth. We have presented an open modification of the dynamically harmonized cell that can help improve the cell pumping conditions. However, the electric potential distribution inside this new cell is slightly different from the ideal (harmonic) one, obtained inside the closed version of the cell, and the resolving power may have been limited by this difference.

Where have all the ions gone, long time passing? Tandem quadrupole mass spectrometers with atmospheric pressure ionization sensitivity gains since the mid-1970s. A perspective.

Thegains in sensitivity since 1975 for quadrupole mass spectrometers equipped with atmospheric pressure ionization (API), and in particular triple quadrupole mass spectrometers (QqQs) since 1981, have been driven by the needs of the environmental, biomedical, agricultural, and other scientific research, industrial, regulatory, legal, and sporting communities to continually achieve lower limits of quantitation and identification. QqQs have realized a one-million-fold improvement in sensitivity attempting to address these needs over the past two score years. It is the purpose of this article to describe how that came about, not through an exhaustive review of the literature, but rather by describing what general approaches were used across the industry to improve sensitivity and provide some examples to illustrate its evolution. The majority of the gains came from the ion source and its interface to the vacuum system. "Sampling efficiency" is a measurement of the losses in this area so will be a focus of thisreview. The discovery of the phenomenon of collisional focusing was key to improving sampling efficiency because it enabled designs that increased the ion-containing gas loads from the ion source, using staged differential pumping backed by increasingly larger pumps, and prevented the scattering losses of ions in the resulting gas expansion inside vacuum. Likewise, systems with smaller pumps and lower ion-containing gas loads could be designed with size and cost reduction in mind while maintaining reasonable sampling efficiencies. As a consequence, advancements in the designs of both larger and smaller turbomolecular vacuum pumps were accelerated by pump manufacturers to accommodate the explosive growth in the use of API-QqQ and API-ion trap mass spectrometers that occurred in the 1990s and continued into the new millennium. Sampling efficiency was further improved by increasing the ion yield from electrospray by increasing the rate of droplet desolvation. An estimate of the practical limit to further sensitivity improvements beyond what has been achieved to date is provided to shed light on what to expect in the future. Lastly, the implications and unforeseen consequences of the sensitivity gains are considered with a particular focus on how they have enabled a dramatic increase in daily sample throughput on triple quadrupole and other types of mass spectrometers.

Evaluation of a New DC-Ion Funnel Drift Tube for Use in Proton Transfer Reaction Mass Spectrometry.

We have developed and characterized a novel drift tube called the direct current-ion funnel (DC-ion funnel) drift tube, consisting of 20 traditional ring electrodes and 5 new DC-focusing electrodes (DC-FEs) for use in proton transfer reaction mass spectrometry (PTR-MS). Ion trajectory simulations demonstrate the ion focusing effect of the DC-FE and DC-ion funnel drift tube. Further comparative experiments show that the PTR-MS with the novel DC-ion funnel drift tube has a higher sensitivity (3.8-7.3 times for the volatile organic compounds considered in this work) than the PTR-MS with a traditional drift tube. Different from conventional radiofrequency (rf) focusing methods, the DC-ion funnel drift tube can realize ion focusing with only a DC electric field and no additional rf power supply, which makes it especially suitable for instruments requiring miniaturization and low power consumption to improve detection sensitivity. In addition, the DC-ion funnel drift tube can easily be coupled to other types of mass spectrometers to increase their detection sensitivity.

Infrared pulsed fiber laser-produced silver-109-nanoparticles for laser desorption/ionization mass spectrometry of amino acids.

Application of monoisotopic cationic 109Ag nanoparticles (109AgNPs) obtained by pulsed fiber laser (PFL) 2D galvo-scanner (GS) laser generated nanomaterial (LGN) for both high resolution laser desorption/ionization mass spectrometry and mass spectrometry imaging of amino acids is presented. Four amino acids, alanine, isoleucine, lysine, and phenylalanine were used as test compounds for quantification with matrix-assisted laser desorption/ionization mas (MALDI)-type mass spectrometer. Comparison of commonly made manual measurements with semiautomatic mass spectrometry imaging (MSI) was performed providing very interesting findings. Amino acids were directly tested in 1000 000-fold concentration change conditions ranging from 1mg/ml to 1ng/ml, which equates to 500 ng to 500 fg of amino acid per measurement spot. Methods were also tested on samples of human blood plasma for quantification of endogenous amino acids.

Toxinology in the proteomics era: a review on arachnid venom proteomics.

The word venomics was coined to acknowledge the studies that use omics to investigate venom proteins and peptides. Venomics has evolved considerably over the last 20 years. The first works on scorpion or spider venomics were published in the early 2000’s. Such studies relied on peptide mass fingerprinting (PMF) to characterize venom complexity. After the introduction of new mass spectrometers with higher resolution, sensitivity and mass accuracy, and the next-generation nucleotide sequencing, the complexity of data reported in research on scorpion and spider venomics increased exponentially, which allowed more comprehensive studies. In the present review article, we covered key publications on scorpion venomics and spider venomics, presenting historical grounds and implemented technologies over the last years. The literature presented in this review was selected after searching the PubMed database using the terms “(scorpion venom) AND (proteome)” for scorpion venomics, and “(spider venom) AND (proteome)” for publications on spider venomics. We presented the key aspects related to proteomics in the covered papers including, but not restricted to, the employed proteomic strategy (i.e., PMF, two-dimensional gel electrophoresis, shotgun/bottom-up and/or top-down/peptidome), and the type of mass spectrometer used. Some conclusions can be drawn from the present study. For example, the scorpion genus Tityus is the most studied concerning venomics, followed by Centruroides; whereas for spiders the studied genera were found more equally distributed. Another interesting conclusion is the lack of high throughput studies on post-translational modifications (PTMs) of scorpion and spider proteins. In our opinion, PTMs should be more studied as they can modulate the activity of scorpion and spider toxins.

Permian Ages of “Younger Granites” from Mounio Province (Gouré area, Southeastern Niger)

African formations intruded by the “Younger Granites” ring complex. In the study area, the “Younger Granites” are represented by volcanic to acid plutonic rocks with hyperalkaline trends (pyroclastic rocks, rhyolites, microgranites, granites, syenites), forming in the North, a circular structure called Gouré ring complex. Preliminary geochronological datings of the Mounio granites have yielded Carboniferous ages. However, recent investigations carried out in this province have identified structures similar to Pan-African deformation structures, such as folds and several generations of schistosity/foliation. Analysis of the relationship between deformation and magmatism has removed any ambiguity regarding the relative age of the deformation. This study focuses on the radiometric dating of the “Younger Granites” of Gouré area, in order to update the geochronological data. Thus, three samples (pyroclastitic rock, rhyolite, microgranite) were dated by the K-Ar method on total rock using a mass spectrometertype MI 1201 IG. Radiometric dating results assign a Lower Permian age (293-287 Ma) to the “Younger Granites” Ring Complex of the Mounio Province in Niger, classically considered to be Carboniferous in age.

Untargeted Analysis of Lemna minor Metabolites: Workflow and Prioritization Strategy Comparing Highly Confident Features between Different Mass Spectrometers.

Metabolomics approaches provide a vast array of analytical datasets, which require a comprehensive analytical, statistical, and biochemical workflow to reveal changes in metabolic profiles. The biological interpretation of mass spectrometric metabolomics results is still obstructed by the reliable identification of the metabolites as well as annotation and/or classification. In this work, the whole Lemna minor (common duckweed) was extracted using various solvents and analyzed utilizing polarity-extended liquid chromatography (reversed-phase liquid chromatography (RPLC)-hydrophilic interaction liquid chromatography (HILIC)) connected to two time-of-flight (TOF) mass spectrometer types, individually. This study (introduces and) discusses three relevant topics for the untargeted workflow: (1) A comparison study of metabolome samples was performed with an untargeted data handling workflow in two different labs with two different mass spectrometers using the same plant material type. (2) A statistical procedure was observed prioritizing significant detected features (dependent and independent of the mass spectrometer using the predictive methodology Orthogonal Partial Least Squares-Discriminant Analysis (OPLS-DA). (3) Relevant features were transferred to a prioritization tool (the FOR-IDENT platform (FI)) and were compared with the implemented compound database PLANT-IDENT (PI). This compound database is filled with relevant compounds of the Lemnaceae, Poaceae, Brassicaceae, and Nymphaceae families according to analytical criteria such as retention time (polarity and LogD (pH 7)) and accurate mass (empirical formula). Thus, an untargeted analysis was performed using the new tool as a prioritization and identification source for a hidden-target screening strategy. Consequently, forty-two compounds (amino acids, vitamins, flavonoids) could be recognized and subsequently validated in Lemna metabolic profile using reference standards. The class of flavonoids includes free aglycons and their glycosides. Further, according to our knowledge, the validated flavonoids robinetin and norwogonin were for the first time identified in the Lemna minor extracts.

Planetary Mass Spectrometry for Agnostic Life Detection in the Solar System

For the past fifty years of space exploration, mass spectrometry has provided unique chemical and physical insights on the characteristics of other planetary bodies in the Solar System. A variety of mass spectrometer types, including magnetic sector, quadrupole, time-of-flight, and ion trap, have and will continue to deepen our understanding of the formation and evolution of exploration targets like the surfaces and atmospheres of planets and their moons. An important impetus for the continuing exploration of Mars, Europa, Enceladus, Titan, and Venus involves assessing the habitability of solar system bodies and, ultimately, the search for life—a monumental effort that can be advanced by mass spectrometry. Modern flight-capable mass spectrometers, in combination with various sample processing, separation, and ionization techniques enable sensitive detection of chemical biosignatures. While our canonical knowledge of biosignatures is rooted in Terran-based examples, agnostic approaches in astrobiology can cast a wider net, to search for signs of life that may not be based on Terran-like biochemistry. Here, we delve into the search for extraterrestrial chemical and morphological biosignatures and examine several possible approaches to agnostic life detection using mass spectrometry. We discuss how future missions can help ensure that our search strategies are inclusive of unfamiliar life forms.

Review of techniques, challenges, and new developments for calcium isotope ratio measurements

Calcium isotope meaurements apply to problems spanning the ‘cosmos to benthos.’ Fractionation, source mixing, radioactive decay, and nucleosynthetic processes cause variations in Ca isotope ratios, which can be measured using different types of mass spectrometers. Early measurements employed thermal ionization mass spectrometry (TIMS), which continues to be the most common and precise reference technique. An increasing number of studies use multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Both TIMS and MC-ICPMS can yield high-quality data for δ44/40Ca and δ44/42Ca, respectively, but wide ranges in precision exist. Sample size requirements are lower for TIMS, but MC-ICPMS offers faster throughput. Both techniques require purifying Ca by ion-exchange chromatography when analyzing samples with complex matrices. In-situ techniques, like laser ablation MC-ICPMS (LA-MC-ICPMS) and secondary ion mass spectrometry (SIMS), do not require purification. In-situ techniques provide high spatial resolution, but LA-MC-ICPMS and (nano)-SIMS suffer from relatively poor precision compared to TIMS and MC-ICPMS, and the methods lack well-characterized standards, which are essential for comparing datasets.The past few years have seen advances in Ca purification techniques, including automated methods that accelerate sample throughput. The next generation of Ca purification techniques should focus on complete purification and quantitative separation of low-Ca samples. Application of collision-cell technology for suppressing Ar-related molecular isobaric interferences will improve quantification of 40Ca using certain MC-ICPMS models. Similarly, development of new amplifier technology will foster high-precision Faraday cup measurements of low abundance Ca isotopes. Adopting common reference materials, including newly developed standards with complex matrices, would signficantly aid inter-laboratory comparisons, method development, and data compilation efforts. In general, at least two widely-used standards should be measured along with unknown samples to confirm data quality, as well as improve utilization of published Ca isotope datasets by a broader community.

Ionization and fragmentation of methane, ethane, propane, and benzene induced by keV atomic cations

Collisions of keV atomic cations (He+, Ne+, Ar+, Kr+, Xe+, F+, Cl+, Br+, I+, Se+, Te+, Sb+, and Fe+) with neutral hydrocarbon molecules (methane, ethane, propane, and benzene) were measured using a modified sector type mass spectrometer. The atomic cations were produced in an electron ionization ion source, accelerated and mass selected by a magnetic sector. The beam of cations was subsequently guided into a collision chamber filled with the neutral hydrocarbon molecules. Secondary ions stemming from the ion/molecule interactions were analyzed by a quadrupole mass analyzer placed perpendicularly to the ion beam. Results presented in this paper show strong dependence of product ion formation and relative fragmentation yield (expressed as a Σ[F+i]/(Σ[F+i] + [M+]) ratio) on recombination energy of projectile ions. The influence of center-of-mass collision energy, as well as kinetic energy of the projectile, on secondary ion formation are also explored and discussed.

COMPARANDO O DESEMPENHO DE DOIS ANALISADORES DE MASSAS (FT-ICR MS &amp; LTQ MS): UMA AULA EXPERIMENTAL SOBRE ANÁLISE DE COMPOSTOS ORGÂNICOS

COMPARING THE PERFORMANCE OF TWO MASS ANALYZERS (FT-ICR MS &amp; LTQ MS): AN EXPERIMENTAL CLASS ON ANALYSIS OF ORGANIC COMPOUNDS. Mass spectrometry (MS) is a high-performance analytical technique that allows a measurement of the mass/charge (m/z) ratio of compounds present in a sample. MS is able to separate two m/z ions with determined values (mass resolution), being an important characteristic, especially in the analysis of biochemical components and complex mixtures. Mass analyzers define the resolving power and accuracy of different types of mass spectrometers. Herein, the performance of two mass analyzers (Fourier Transform Ion Cyclotronic Resonance (FT-ICR) and quadrupole ion trap (LTQ)) was tested on low (Mw = 165-679 Da) and high (Mw = 783-8.58 kDa) molecular weight molecules (Phenacetin, Procaine, Benzocaine, Caffeine anhydrous, Lidocaine, two metal porphyrin standards, the first cobalt and the second vanadium, and two protein standards, Ubiquitin and Beauvericin), and finally, for an oil sample. LTQ-MS and FT-ICR-MS had similar performance and high reproducibility. However, the mass accuracy and resolution power of the FT-ICR (error lower than 5 ppm and RP higher than 400,000) was higher, being therefore, it was more suitable for the analysis of proteins and oil, for instance. On the other hand, the CID analysis via LTQ demonstrated its applicability in fragmentation experiments, being able to determinate the chemical connectivity of organic compounds in non-complex mixtures.

Investigation of the molecular structure and VUV-induced ion dissociation dynamics of 2-azetidinone (C3 H5 NO).

RationaleThe class of active components of the group of β‐lactam antibiotics is very important for several fields and applications, although their stability and radiation reactivity properties are not yet well understood. We have studied the interaction of an important building block species, the 2‐azetidinone (C3H5NO) molecule, with monochromatic VUV (synchrotron radiation) photons in the 9.5–21.5 eV range, using time‐of‐flight mass spectrometry (TOF‐MS), electron‐ion coincidence (PEPICO), and high‐level theory methods.MethodsA 2‐azetidinine sample was introduced into the UH‐vacuum chamber, without purification, through an inlet system for the gas‐phase experiments with monochromatic light in the VUV range from the TGM beamline at the Brazilian Synchrotron Facility. A Wiley–McLaren type mass spectrometer in the PEPICO mode was employed to detect and characterize the photoionization and photodissociation products of the 2‐azetidinone. The analysis and discussion of the results were supported by high‐level density functional theory (DFT) and ab initio methods.ResultsThe adiabatic ionization energy was determined experimentally in this work as 9.745 ± 0.020 eV, and this was supported by the high level of theory result with good agreement. The heat of formation for the 2‐azetininone cation has been derived for the first time as 844.2 ± 1.9 kJ/mol. The dominant ion dissociation channel in the VUV energy range up to 21.5 eV is associated with the cation species at m/z 28.ConclusionsThe structural properties, VUV‐induced photoionization, and photodissociation dynamics of the 2‐azetidinone molecule in the gas phase have been successfully investigated in the energy range of 9.5–21.5 eV. PEPICO mass spectra have been determined for the first time for this molecule at several selected photon energies from which the partial ion yields were determined for all cation species produced from this molecule.

Particle size analysis of pristine food-grade titanium dioxide and E 171 in confectionery products: Interlaboratory testing of a single-particle inductively coupled plasma mass spectrometry screening method and confirmation with transmission electron microscopy

Titanium dioxide is a white colourant authorised as food additive E 171 in the EU, where it is used in a range of alimentary products. As these materials may contain a fraction of particulates with sizes below 100 nm and current EU regulation requires specific labelling of food ingredient to indicate the presence of engineered nanomaterials there is now a need for standardised and validated methods to appropriately size and quantify (nano)particles in food matrices.A single-particle inductively coupled plasma mass spectrometry (spICP-MS) screening method for the determination of the size distribution and concentration of titanium dioxide particles in sugar-coated confectionery and pristine food-grade titanium dioxide was developed. Special emphasis was placed on the sample preparation procedure, crucial to reproducibly disperse the particles before analysis. The transferability of this method was tested in an interlaboratory comparison study among seven experienced European food control and food research laboratories equipped with various ICP-MS instruments and using different software packages. The assessed measurands included the particle mean diameter, the most frequent diameter, the percentage of particles (in number) with a diameter below 100 nm, the particles' number concentration and a number of cumulative particle size distribution parameters (D0, D10, D50, D99.5, D99.8 and D100). The evaluated method's performance characteristics were, the within-laboratory precision, expressed as the relative repeatability standard deviation (RSDr), and the between-laboratory precision, expressed as the relative reproducibility standard deviation (RSDR). Transmission electron microscopy (TEM) was used as a confirmatory technique and served as the basis for bias estimation.The optimisation of the sample preparation step showed that when this protocol was applied to the relatively simple sample food matrices used in this study, bath sonication turned out to be sufficient to reach the highest, achievable degree of dispersed constituent particles. For the pristine material, probe sonication was required. Repeatability and reproducibility were below 10% and 25% respectively for most measurands except for the lower (D0) and the upper (D100) bound of the particle size distribution and the particle number concentration. The broader distribution of the lower and the upper bounds could be attributed to instrument-specific settings/setups (e.g. the timing parameters, the transport efficiency, type of mass-spectrometer) and software-specific data treatment algorithms. Differences in the upper bound were identified as being due to the non-harmonised application of the upper counting limit. Reporting D99.5 or D99.8 instead of the effectively largest particle diameter (D100) excluded isolated large particles and considerably improved the reproducibility. The particle number-concentration was found to be influenced by small differences in the sample preparation procedure. The comparison of these results with those obtained using electron microscopy showed that the mean and median particle diameter was, in all cases, higher when using spICP-MS. The main reason for this was the higher size detection limit for spICP-MS plus the fact that some of the analysed particles remained agglomerated/aggregated after sonication.Single particle ICP-MS is a powerful screening technique, which in many cases provides sufficient evidence to confirm the need to label a food product as containing (engineered) titanium dioxide nanomaterial according to the current EU regulatory requirements. The overall positive outcome of the method performance evaluation and the current lack of alternative standardised procedures, would indicate this method as being a promising candidate for a full validation study.

Characterization of nonvolatile polar compounds from Brazilian oils by electrospray ionization with FT-ICR MS and Orbitrap-MS

Among the different types of available high-resolution mass spectrometers, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and Orbitrap-MS are important tools for the study of nonvolatile crude oil fraction composition. No in deep comparison between each analyzer was still performed, mostly with a wide broad of real crude oil samples. Therefore, in this study a representative set of 30 Brazilian crude oils with a wide range of American Petroleum Institute (API) gravity (13.1–53.7) were considered. The ICR and Orbitrap analyzers allowed the elemental composition to be obtained by accurate mass measurements, and the most abundant species were mainly N, N2, O3, O1, O2, NO2, NS, NOS, and OS classes. In general, FT-ICR MS favored the detection of higher molecular weight analytes in relation to Orbitrap-MS. The notable distribution of the heteroatom classes showed that crude oils with intermediate API gravity presented a higher relative abundance of nitrogenous compounds (Nx), while lighter oils presented a higher abundance of oxygenated compounds (O1). The heavier ones had a higher abundance of O2 class, which was not verified by Orbitrap-MS, where a prevalence of O2 class was detected in major crude oils. An increase in average molar weight values was observed when we changed technique (Orbitrap-MS → FT-ICR MS) and ionization mode (negative → positive), since FT-ICR MS detected substances with higher m/z. In this way, this work examines the application of two different high-resolution mass analyzers, and shows the versatility and analytical response of each one within petroleomics.

Analytical Method for Lithium Isotopes Determination by Thermal Ionization Mass Spectrometry: A Useful Tool for Hydrogeochemical Applications

The low temperature realm such as the geothermal systems, characterized by a large variety of near-Earth surface processes, has been the object of several isotopic studies, some of them including lithium isotopes. However, much work can still be done to systematically use lithium as tracer of geochemical processes in deep and shallow Earth reservoirs. A pilot study has been performed for the determination of lithium-isotope ratio by thermal ionization mass spectrometry (TIMS), a technique poorly employed with respect to other methods such as inductively coupled plasma mass spectrometry, being more time consuming. Lithium has been extracted by chromatographic techniques on columns through an ion exchange process from both natural and reference samples. The isotope composition (6Li/7Li) expressed in terms of δ7Li has been determined in dynamic and static mode for comparative purposes, by using two different types of thermal ionization mass spectrometers. The results presented in this work agree with the data reported in the literature, opening a new perspective to future research on continental geothermal systems and groundwater domains, spread over the entire Italian peninsula. This research is based on the use of chemical and isotopic data, whereas it does not include lithium isotopes. These latter may provide a huge contribution in studying both volcanic products and fluids from active volcanic areas, including the superposed geothermal systems, and may represent a new tool for research and surveillance.

Comparison of sensitivity for methods of positive and negative ion mass spectrometry, exemplified by nitrotoluenes

For a model series of nitro aromatic compounds comprising mono-, di- and trinitrotoluenes, and dinitrobenzene, using the same commercial experimental set up consisting of gas chromato-graphy/mass spectrometry (GC/MS) instrument equipped with a quadrupole analyzer, the two types of mass spectra were recorded, of positive ions (in the conventional, standard mode of electron ionization at 70 eV) and of negative ions (NI, generated at low, pre-ionization electron energies by resonant electron capture, REC). The comparative analysis of characteristic fragmentation processes was carried out for molecular ions of both signs. The sensitivity of REC NI MS method was established to enhance upon increasing the number of electron-withdrawing nitro groups, reaching or even outperforming that of the classical method of electron ionization (EI). Thus, the detection limit for trinitrotoluene in a solution was estimated as 5 ppm, which is by an order of magnitude lower as compared to the conventional EI mode of analysis. Comparison of the ion composition of NI mass spectra and of the relative intensities of ion peaks with the corresponding data obtained previously for the studied group of compounds by means of different types of mass spectrometers, has revealed a satisfactory inter-instrumental reproducibility of the NI mass spectra. The results reported herein indicate that the NI generation/registration mode, which can technically be readily available even without modifications of design of commercial GC/MS instrument in their basic configuration, is suitable to be introduced in laboratory practice as the additional tool for increasing the selectivity and reliability in detection/identification of trace amounts of compounds possessing a high electron af nity and for solving extraordinary structural and analytical problems.