Sector Mass Spectrometry Research Articles

Spectral Reconstruction Improvement in a Cycloidal Coded-Aperture Mass Spectrometer.

Spatial aperture coding is a technique used to improve throughput without sacrificing resolution both in optical spectroscopy and sector mass spectrometry (MS). Previous work demonstrated that aperture coding combined with a position-sensitive array detector in a miniature cycloidal mass spectrometer was successful in providing high-throughput, high-resolution measurements. However, due to poor alignment and field nonuniformities, reconstruction artifacts were present. Recently, significant progress was made in eliminating most of the reconstruction artifacts with improved field uniformity and alignment. However, artifacts as large as 1/3 of the main peak were still observed at low mass (<17 u). Such artifacts will reduce accuracy in identification and quantification of analytes, reducing the impact of the throughput advantage gained by using a coded aperture. The artifacts were hypothesized to be a result of a mass dependent in curvature of ions in the ion source. Ions with higher mass (m/z > 17 u) and a larger curvature did not pass through all slits in the coded aperture. Therefore, when reconstructing with a system response derived from the aperture image from a higher mass m/z = 32 u ion, reconstruction artifacts appeared for m/z < 17 u. In this work, two methods were implemented to significantly reduce the presence of artifacts in reconstructed data. First, we modified the reconstruction algorithm to incorporate a mass-dependent system response function across the mass range (10-110 u). This method reduced the size of the artifacts by 82%. Second, to validate the hypothesis that the mass-dependent system response function was a result of differences in curvature of ions in the ion source, we modified the design of the ion source by shifting the coded aperture slits relative to the center of the ionization volume. This method resulted in ions of all masses passing through all slits in the coded aperture, a constant system response function across the entire mass range. Artifacts were reduced by 94%.

A New Approach for the Synthesis of 2,3,4а,6,7,8а,9,10-Octaaza-4,8-dioxo-3,4,4a,7,8,8а,9,9a,10,10а-decahydroanthracene and High-Energy Performance Characterization of Its Dinitramide Salt

A simple, one-pot regioselective method for the synthesis of a high-nitrogen tricycle, 2,3,4а,6,7,8а,9,10-octaaza-4,8-dioxo-3,4,4a,7,8,8а,9,9a,10,10а-decahydroanthracene, with a yield of 27% was developed on a starting urea basis as a result of studies focused on finding new, more efficient approaches to the synthesis of high-energy derivatives of dinitramic acid (DNA). This tricycle was further treated to furnish 2,3,4а,6,7,8а,9,10-octaaza-4,8-dioxo-3,4,4a,7,8,8а,9a,10а-octohydroanthracene-9,10-ion-bis(dinitramide). The resultant salt of dinitramic acid exhibited inhibitory properties towards the burning rate of pyrotechnic compositions, reducing it by 30%, and possessed good thermal stability due to a high decomposition temperature above 260 °C and a low sensitivity to mechanical stimuli. The structural features of the new tricycle-based dinitramide salt were characterized via 2D NMR spectroscopy and double-focusing sector mass spectrometry (DFS).

New ultra-sensitive radioanalytical technologies for new science

Recent developments in radiometric and mass spectrometry technologies have been associated in the radiometric sector mainly with underground operations of large volume Ge detectors, while the mass-spectrometry sector, represented mainly by accelerator mass spectrometry and inductively coupled plasma mass spectrometry has become the most sensitive technique for ultra-low-level analyses of long-lived radionuclides. These new developments have had great impact on investigations of rare nuclear processes and applications of radionuclides in environmental, life and space sciences. New scientific investigations have been carried out therefore which have not been possible before either because of lack of sensitivity or required large sample size.

Compatibility of Spatially Coded Apertures with a Miniature Mattauch-Herzog Mass Spectrograph.

In order to minimize losses in signal intensity often present in mass spectrometry miniaturization efforts, we recently applied the principles of spatially coded apertures to magnetic sector mass spectrometry, thereby achieving increases in signal intensity of greater than 10× with no loss in mass resolution Chen et al. (J. Am. Soc. Mass Spectrom. 26, 1633-1640, 2015), Russell et al. (J. Am. Soc. Mass Spectrom. 26, 248-256, 2015). In this work, we simulate theoretical compatibility and demonstrate preliminary experimental compatibility of the Mattauch-Herzog mass spectrograph geometry with spatial coding. For the simulation-based theoretical assessment, COMSOL Multiphysics finite element solvers were used to simulate electric and magnetic fields, and a custom particle tracing routine was written in C# that allowed for calculations of more than 15 million particle trajectory time steps per second. Preliminary experimental results demonstrating compatibility of spatial coding with the Mattauch-Herzog geometry were obtained using a commercial miniature mass spectrograph from OI Analytical/Xylem.

Order of Magnitude Signal Gain in Magnetic Sector Mass Spectrometry Via Aperture Coding.

Miniaturizing instruments for spectroscopic applications requires the designer to confront a tradeoff between instrument resolution and instrument throughput [and associated signal-to-background-ratio (SBR)]. This work demonstrates a solution to this tradeoff in sector mass spectrometry by the first application of one-dimensional (1D) spatially coded apertures, similar to those previously demonstrated in optics. This was accomplished by replacing the input slit of a simple 90° magnetic sector mass spectrometer with a specifically designed coded aperture, deriving the corresponding forward mathematical model and spectral reconstruction algorithm, and then utilizing the resulting system to measure and reconstruct the mass spectra of argon, acetone, and ethanol. We expect the application of coded apertures to sector instrument designs will lead to miniature mass spectrometers that maintain the high performance of larger instruments, enabling field detection of trace chemicals and point-of-use mass spectrometry.

Simultaneous and highly sensitive determination of PCBs and PBDEs in environmental water and sediments by gas chromatography coupled to high resolution magnetic sector mass spectrometry

Sensitive and simultaneous determination of PCBs and PBDEs in environmental samples (water and sediments) using high resolution magnetic sector mass spectrometry.

Two-dimensional aperture coding for magnetic sector mass spectrometry.

In mass spectrometer design, there has been a historic belief that there exists a fundamental trade-off between instrument size, throughput, and resolution. When miniaturizing a traditional system, performance loss in either resolution or throughput would be expected. However, in optical spectroscopy, both one-dimensional (1D) and two-dimensional (2D) aperture coding have been used for many years to break a similar trade-off. To provide a viable path to miniaturization for harsh environment field applications, we are investigating similar concepts in sector mass spectrometry. Recently, we demonstrated the viability of 1D aperture coding and here we provide a first investigation of 2D coding. In coded optical spectroscopy, 2D coding is preferred because of increased measurement diversity for improved conditioning and robustness of the result. To investigate its viability in mass spectrometry, analytes of argon, acetone, and ethanol were detected using a custom 90-degree magnetic sector mass spectrometer incorporating 2D coded apertures. We developed a mathematical forward model and reconstruction algorithm to successfully reconstruct the mass spectra from the 2D spatially coded ion positions. This 2D coding enabled a 3.5× throughput increase with minimal decrease in resolution. Several challenges were overcome in the mass spectrometer design to enable this coding, including the need for large uniform ion flux, a wide gap magnetic sector that maintains field uniformity, and a high resolution 2D detection system for ion imaging. Furthermore, micro-fabricated 2D coded apertures incorporating support structures were developed to provide a viable design that allowed ion transmission through the open elements of the code.

Multi-residue analysis of pharmaceuticals in wastewater by liquid chromatography–magnetic sector mass spectrometry: Method quality assessment and application in a Belgian case study

Through systematic research a novel analytical method using solid-phase extraction (SPE) and liquid chromatography magnetic sector mass spectrometry was developed for the measurement of 43 pharmaceuticals in wastewater. A thorough method validation quantified the contribution of both the extraction recovery and matrix effects in the overall method process efficiency, and a detailed uncertainty analysis was performed to elaborate a quality labelling strategy to be used in data interpretation. Compounds for which a precise (relative standard deviation <20%) process efficiency between 60% and 140% was determined, were labelled as ‘quantitative’ whereas the results for other compounds should be interpreted as ‘indicative’.Method application on influent and effluent samples of (i) a conventional active sludge system and (ii) a parallel membrane bioreactor/conventional active sludge wastewater treatment plant in Belgium revealed the occurrence of 22 pharmaceuticals. The anti-inflammatory drug diclofenac and the antidepressant venlafaxine were measured in the effluents at concentrations ranging from 0.5 to 1.8μgL−1 and 0.2 to 0.5μgL−1, respectively, which indicated to be of high potential environmental risk for the receiving river Dender, Belgium.

Mass spectrometric characterization of halogenated flame retardants

Concerns about the adverse health effects of ubiquitous flame retardants spurred our interest in the development of a sensitive and reliable analytical method for these toxic compounds in various sample matrices. This study focuses on the investigation of fragmentation pathways and the structures of target ions of thirteen new halogenated flame retardants. In this study, we use gas chromatography (GC)/high-resolution double-focusing sector mass spectrometry to characterize the fragmentation pathways of these new flame retardants. Along with the isotope patterns, accurate mass data were acquired to verify the molecular formula. The fragmentation pathways are classified based on the types of bond dissociations, e.g. σ-bond cleavage, α-bond cleavage and multiple-bond dissociations with a hydrogen shift. The α-bond dissociation occurs among 1,2-bis-(2,4,6-tribromophenoxy)ethane, allyl 2,4,6-tribromophenyl ether (ATE), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE) and 2-bromoallyl 2,4,6-tribromophenyl ether (BATE). The peak clusters that dominated ATE, BATE and hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) spectra correspond to two fragments as proved by accurate mass data and isotope patterns. These two fragments are formed as the result of two competing fragmentation pathways of radical loss and hydrogen shift. Fragmentation pathways of the other compounds are complex, involving cleavage of multiple bonds and hydrogen shifts. The accurate-mass-based GC/MS method offers great selectivity and sensitivity for quantitative analysis of the persistent organic pollutants. Thus, elucidation of the structures of the fragments is of prime importance for building an accurate-mass-based isotopic method. In addition, this study is useful for GC/MS/MS method development because multiple reaction monitoring (MRM) transitions of precursor ions and product ions may be easily elucidated based on these fragmentation patterns.

Deposition of Ni thin films from Ni(II) β-diketonates derivatives with 1,3-diaminopropane

Two octahedral nickel complexes namely Ni(pda)(hfac)2 and Ni(pda)(thd)2 (pda—1,3-diaminopropane, hfac—1,1,1,5,5,5-hexafluoro-2,4-pentanedionato (−), thd—2,2,6,6-tetramethyl-3,5-heptanedionato (−)) were tested in a Metal-Organic Chemical Vapor Deposition (MOCVD) process. Based on density functional theory (DFT) calculations, the thermodynamic stability of molecules in the gas phase was estimated. The intramolecular bond was found in case of complex Ni(pda)(hfac)2. The different fragmentation mechanisms of complexes in the gas phase were examined by double focusing sector (DFS) mass spectrometry. According to TG/DTA analyses and P/T measurements compounds have good volatility. Deposition conditions resulting in one phase Ni films were established. Films compositions and structures were confirmed by XRD, EXAFS, XPS, and SEM. According to XRD and SEM, the average crystallite sizes and thicknesses of films deposited from Ni(pda)(hfac)2 were 12–34nm and 135–320nm, whereas from Ni(pda)(thd)2 they were 10–24nm and 100–380nm, respectively. The dependences of films thicknesses as a function of substrate temperatures have shown that complex Ni(pda)(hfac)2 is more stable in the gas phase than Ni(pda)(thd)2.

Heterogeneous photocatalysis of moxifloxacin: Identification of degradation products and determination of residual antibacterial activity

TiO2-mediated heterogeneous photocatalysis of the fluoroquinolone antibiotic moxifloxacin in water is investigated with respect to both the formation of degradation products and the evaluation of residual antibacterial activity after photocatalytic treatment. High-resolution magnetic sector mass spectrometry coupled to high performance liquid chromatograph is used to determine the accurate mass of the measured degradation products. Eight main photoproducts are identified at both acidic, neutral and alkaline pH. A molecular structure is proposed by using the accurate mass, the double bond equivalent and by taking into account the structural formula of the parent compound. The photocatalytic degradation does not take place at the quinolone core and defluorination was not observed. A general initial photocatalytic pathway for moxifloxacin is proposed. Time profiles of the different degradation products reveal that the solution pH influences their relative abundance during reaction but the observed degradation products show no pH dependency. Residual antibacterial activity of the photocatalytic reaction solutions against Escherichia coli (G−), Staphylococcus carnosus (G+), Streptococcus mutans (G+) and Klebsiella pneumoniae (G−) is evaluated by means of agar diffusion tests. A reduction in antibacterial activity is noticed for all investigated pH levels with a complete inactivation at neutral pH after 12min of photocatalytic treatment.

From multi-residue screening to target analysis of pharmaceuticals in water: Development of a new approach based on magnetic sector mass spectrometry and application in the Nairobi River basin, Kenya

This paper presents the development and application of a new multi-residue analytical method providing the first data on the environmental occurrence of human pharmaceuticals in Africa, particularly the Nairobi River basin (Kenya).Based on pharmaceutical consumption data available for the Nairobi region, 43 ‘priority’ pharmaceutically active ingredients (PAIs) were selected for this study. On the basis of magnetic sector high-resolution mass spectrometry, a new methodology involving both full-scan screening and selective target analysis has been developed to investigate the presence of the defined priority PAIs. Subsequent analysis of the corresponding standard compounds provided the full confirmation and indicative concentrations (low ng/L–high μg/L) of 10 human PAIs in the Nairobi River. The detected compounds belong to different classes, i.e. antibiotics, analgesic/anti-inflammatory and anti-epileptic drugs, antimalarials and antiretrovirals. Ibuprofen, paracetamol, sulfamethoxazole and zidovudine showed to be the most concentrated PAIs (about 10–30μg/L). The concentration of the antiretrovirals (lamivudine, zidovudine and nevirapine) is clearly higher than those reported in the literature, although environmental data on this class of PAIs are still very limited. To the best of our knowledge, this is the first study that provides evidence of detection of lamivudine in surface water. The presented unique data on the occurrence of selected PAIs in the aquatic environment of Africa clearly show that the high prevalence of specific diseases like HIV/AIDS infection in developing countries might result in a different pattern of PAIs in environmental waters compared to the more developed regions.

Selective accurate-mass-based analysis of 11 oxy-PAHs on atmospheric particulate matter by pressurized liquid extraction followed by high-performance liquid chromatography and magnetic sector mass spectrometry

An innovative analytical method based on high-performance liquid chromatography and atmospheric pressure chemical ionization magnetic sector mass spectrometry was developed and optimized to determine trace concentrations of 11 compounds belonging to the group of the seldom-analyzed oxy-PAHs (phenanthrene-9,10-dione, chrysene-5,6-dione, benzo[a]pyrene-4,5-dione, benzo[a]pyrene-1,6-dione, benzo[a]pyrene-3,6-dione, benzo[a]pyrene-6,12-dione, 4-oxa-benzo[def]chrysene-5-one, pyrene-1-carboxaldehyde, benzo[de]anthracene-7-one, benzo[a]anthracene-7,12-dione, and napthacene-5,12-dione) on airborne particulate matter (PM(10)). The mass spectrometer was operated in multiple ion detection mode, allowing for selective accurate mass detection (mass resolution of 12,000 full width at half maximum) of the oxy-PAHs characteristic ions. Optimization of both the vaporizer (450 °C) and capillary temperature (350 °C) resulted into instrumental detection limits in the range between 7 (benzo[a]pyrene-1,6-dione) and 926 pg (benzo[a]anthracene-7,12-dione). The advanced pressurized liquid extraction (PLE) and the more traditionally used ultrasonic extraction (USE) were compared using ethyl acetate as an extraction solvent. For both techniques, high recoveries from spiked quartz fiber filters (PLE, 82-110%; USE, 67-97%) were obtained. Recoveries obtained from real PM(10) samples were also high (76-107%), and no significant matrix effects (ME) on the ionization process (enhancement or suppression) were found (ME, 89-123%). Method limits of quantification (S/N = 10) were in the range between 2 and 336 pg/m(3). This method was used to analyze real PM samples collected at several urban and rural locations in the Antwerp area. For the first time, concentrations for Belgium are provided. Concentrations of individual oxy-PAHs are in the lower pictograms per cubic meter to 6 ng/m(3) range. High concentration differences between individual compounds are found as exemplified by the 75th percentile of the phenanthrene-9,10-dione and benzo[de]anthracene-7-one concentrations being a factor of 4 to 22 higher compared with the other target oxy-PAHs.

Cryogenic zone compression for the measurement of dioxins in human serum by isotope dilution at the attogram level using modulated gas chromatography coupled to high resolution magnetic sector mass spectrometry

A liquid nitrogen jet-cooled thermal modulator dedicated to comprehensive two-dimensional gas chromatography has been mounted in a GC oven coupled to a high resolution magnetic sector mass spectrometry instrument. The data acquisition parameters of the slow double-focusing magnetic sector MS instrument have been optimized to accommodate the description of the narrow modulated GC peaks. Acquisition rates were increased to 20 Hz, while maintaining high mass resolution. Selected ion monitoring (SIM) descriptors, typically including several ions for both native and labeled analytes, were thus reduced to one or two to ensure enough MS cycle time. For maximization of the sensitivity enhancement due to cryogenic zone compression (CZC), the entire GC peak of interest was trapped and remobilized in one event. Optimization of the method resulted in the ability to detect low attogram (ag) amounts of 2,3,7,8-tetrachlorodibenzo- p-dioxin (2,3,7,8-TCDD) (313 ag gives a S/N of 400:1), a level that had not yet been attained using classical GC–HRMS. An isotope-dilution calibration curve was constructed using 13C 12-2,3,7,8-TCDD as the internal standard over the range of 500 ag/μL to 35,000 ag/μL ( R 2 = 0.9953). Analyses of a standard natural human reference serum-matrix NIST SRM 1589a containing 223 ag of 1,2,3,7,8-pentachlorodibenzo- p-dioxin (1,2,3,7,8-PeCDD) (70% recovery rate assumed) resulted in a peak with a S/N of 188:1 (4 sigma, m/ z = 355.8546). Measurement of 2,2-bis (4-chlorophenyl-1,1,1-trichloroethane) (DDE) and 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153) in human dried-blood spot (DBS) samples is also reported to illustrate the usefulness of such a sensitive technique. Finally, some of the challenges related to sample preparation, blank levels, and to the fact of measuring of such a limited number of molecules (less than 600,000 TCDD molecules) are discussed.

Catalytic partial oxidation of ethanol on alumina-supported rhodium catalysts: An experimental study

The catalytic partial oxidation of ethanol is experimentally studied over an alumina rhodium coated monolithic honeycomb catalyst at short contact times. The product distribution is analyzed as function of carbon-to-oxygen ratio (C/O) for two different space velocities by a variety of simultaneously applied methods such as Fourier transform infrared spectroscopy, sector mass spectrometry, paramagnetic gas analyzer and gas chromatography combined with mass spectrometry. Low C/O resulted in highly selective synthesis gas production, whereas by-products like methane, ethylene, acetaldehyde and diethyl ether became eminent with increasing C/O.

Trends in radiometrics and mass spectrometry technologies: synergy in environmental analyses

The dominant development in the radiometrics techniques for the analysis of short and medium-lived radionuclides in the environment was the utilisation of large volume Ge detectors in underground laboratories with additional anti-cosmic shielding. In the mass spectrometry sector, applications of Accelerator Mass Spectrometry (AMS) and Inductively Coupled Plasma Mass Spectrometry (ICPMS) for the analysis of long-lived radionuclides in the environment are the most important recent achievements. These developments in both sectors did not only considerably decrease the detection limits for several radionuclides (up to several orders of magnitude), but they also enable to decrease sample volumes so that sampling, e.g. of the water column, can be much easier and more effective. Applications of radiometrics and mass spectrometry techniques in isotope oceanography, specifically on the distribution of 3H, 14C, 90Sr, 129I, 137Cs, 239Pu and 240Pu in the water column of the North Pacific and South Indian Oceans are presented and discussed.

Determination of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater using high resolution magnetic sector inductively coupled mass spectrometry (HR-ICP-MS)

A novel method, combining isotope dilution with standard additions, was developed for the analysis of eight elements (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) in seawater. The method requires just 12 mL of sample and employs an off-line pre-concentration step using the commercially available chelating resin Toyopearl AF-Chelate-650M prior to determination by high resolution inductively coupled plasma magnetic sector mass spectrometry (ICP-MS). Acidified samples were spiked with a multi-element standard of six isotopes ( 57Fe, 62Ni, 65Cu, 68Zn, 111Cd and 207Pb) enriched over natural abundance. In addition, standard additions of a mixed Co and Mn standard were performed on sub-sets of the same sample. All samples were irradiated using a low power (119 mW cm −2; 254 nm) UV system, to destroy organic ligands, before pre-concentration and extraction from the seawater matrix. Ammonium acetate was used to raise the pH of the 12 mL sub-samples (off-line) to pH 6.4 ± 0.2 prior to loading onto the chelating resin. The extracted metals were eluted using 1.0 M Q-HNO 3 and determined using ICP-MS. The method was verified through the analysis of certified reference material (NASS-5) and the SAFe inter-comparison samples (S1 and D2), the results of which are in good agreement with the certified and reported consensus values. We also present vertical profiles of the eight metals taken from the Bermuda Atlantic Time Series (BATS) station collected during the GEOTRACES inter-comparison cruise in June 2008.

A new automated method for measuring noble gases and their isotopic ratios in water samples

A method is presented for precisely measuring all five noble gases and their isotopic ratios in water samples using multiple programmed multistage cryogenic traps in conjunction with quadrupole mass spectrometry and magnetic sector mass spectrometry. Multiple automated cryogenic traps, including a two‐stage cryotrap used for removal of water vapor, an activated charcoal cryotrap used for helium separation, and a stainless steel cryotrap used for neon, argon, krypton, and xenon separation, allow reproducible gas purification and separation. The precision of this method for gas standards is ±0.10% for He, ±0.14% for Ne, ±0.10% for Ar, ±0.14% for Kr, and ±0.17% for Xe. The precision of the isotopic ratios of the noble gases in gas standards are ±1.9‰ for 20Ne/22Ne, ±2.0‰ for 84Kr/86Kr, ±2.5‰ for 84Kr/82Kr, ±0.9‰ for 132Xe/129Xe, and ±1.3‰ for 132Xe/136Xe. The precision of this method for water samples, determined by measurement of duplicate pairs, is ±1% for He, ±0.9% for Ne, ±0.3% for Ar, ±0.3% for Kr, and ±0.2% for Xe. An attached magnetic sector mass spectrometer measures 3He/4He with precisions of ±0.1% for air standards and ±0.14% for water samples.

High-Energy Collision Induced Dissociation of Biomolecules: MALDITOF/ RTOF Mass Spectrometry in Comparison to Tandem Sector Mass Spectrometry

MALDI in combination with high-energy collision-induced dissociation (CID) performed by tandem time-of-flight mass spectrometry (TOF/RTOF) is a relatively new technology for the structural analysis of various classes of biomolecules as e.g., peptides, carbohydrates, glycoconjugate drugs and lipids. Fragmentation mechanisms for these classes of compounds as well as corresponding fragment ion nomenclatures based mainly on data from tandem magnetic sector mass spectrometers are summarized in this article. The major instrumental differences between the present commercially available TOF/RTOFs are compiled (e.g., ion gate, gas-collision cell, type of reflectron, etc.). Whereas peptides have been investigated by MALDI-TOF/RTOF and their CID spectra are well understood, other classes of compounds (e.g., carbohydrates or lipids) are far less well investigated. By comparing data from two different MALDI-TOF/RTOF-instruments, it becomes evident that as they are operated at rather different collision energies for CID (1 versus 20 keV) strong differences in corresponding CID spectra for the same analyte are observed, causing problems with library searches in databases as e.g., abundant peptide side-chain fragmentations mainly occurring in the 8 to 20 keV collision regime are not considered. In contrast, differences in CID spectra of carbohydrates among different TOF/RTOF instruments are less clear-cut, because the required collision energy is spread across a wide range. Especially, carbohydrate cross-ring cleavages require less collision energy in the keV-range than the corresponding peptide side-chain fragmentations. Some of these carbohydrate cross-ring fragmentations are even observed by very low energy CID (< 1 eV fragmentation amplitude). Similar observations can also be made for glycoconjugates (e.g., the drug tylosin A). The lipid class triacylglycerol needs rather high collision energies for dissociating carbon-carbon bonds based upon classical charge-remote fragmentation mechanisms. Comparison of high-energy CID-data of ESI generated triacylglycerol precursors with CID spectra from MALDI generated precursors shows different mechanisms for charge-remote fragmentations. MALDI-TOF/RTOF-instruments operated in the elevated high-energy CID mode exhibit a strong potential in structural analysis of natural and synthetic biomolecules with information often not obtainable by low energy CID.

Low Uncertainty Reverse Isotope Dilution ICP-MS Applied to Certifying an Isotopically Enriched Cd Candidate Reference Material: A Case Study

An analytical method is presented based on reverse isotope dilution single detector inductively coupled plasma magnetic sector mass spectrometry (ID-ICP-SMS) and applied to the specific case of the certification of a (111)Cd enriched candidate Cd spike calibration material (nominal mass fraction 10 mg kg(-1) in 5% HNO3 solution). Uncertainty propagation was used as a tool for both determining the analytical approach and validating it. The robustness of close to "exact matching" reverse IDMS to correction of measured isotope intensities for multiplicative (mass discrimination) and (semi)additive effects (dead time, instrumental background, and isobaric interference) is discussed. The very low experimental relative standard deviation of the mean (0.08%) of eight replicate determinations indicated that all significant sources of uncertainty had probably been taken into account for the estimation of the final combined uncertainty statement (U(c) = 0.17%, k = 1). IRMM-621 was used as comparator. Uncertainties on IUPAC isotopic abundances of 111Cd and 112Cd, for the natural Cd solution involved between the two enriched materials, formed nearly 60% of U(c). The repeatability of the isotope ratio measurements contributed less than 10%. Correction for procedural blank necessitated somewhat unusual calculations (potential contamination of an enriched material with natural Cd). The procedure also involved a quadrupole based ICP-MS judged to be appropriate for the characterization of the isotopic composition. For comparison purposes, direct IDMS results are simulated using identical experimental input data. Finally, a significant background signal in the 106-116 mass region, observed only with the magnetic sector instrument, was attributed to argon based isobaric interferences.