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.     

Developments in radioanalytics: from Geiger counters to single atom counting

Progress in radioanalytical science, mainly in radiometrics and mass spectrometry technologies for ultra-sensitive analyses of radionuclides applied in natural sciences is shortly reviewed. While in the radiometrics sector the greatest developments have been made in underground Ge gamma-spectrometry, in the mass spectrometry sector the accelerator mass spectrometry had dominant position reaching the status of single atom counting and compound specific analysis for some long-lived radionuclides.     

Recent developments in radioanaytical technologies for environmental investigations

Radiometric techniques, specifically underground gamma-ray spectrometry, have been recently widely applied in the analysis of short and medium-lived radionuclides in the environment. Long-lived radionuclides have been mostly analysed by Accelerator Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. These developments have considerably improved the detection limits for analysis of radionuclides in the terrestrial and marine environments. They have also decreased required sample volumes so applications, which have not been possible before either because of sample size or required sensitivity, have become feasible. The recent developments are illustrated by applications of radiometric and mass spectrometry techniques in isotope hydrology and oceanography.     

Recent developments in radiometric and mass spectrometry methods for marine radioactivity measurements

The most important recent developments in radiometric techniques have been the operation of high efficiency HPGe detectors with anticosmic or antiCompton shielding often placed underground, ship-board measurements of ²³⁴Th using gamma-spectrometry or beta-counting and underwater gamma-spectrometry. In mass spectrometry techniques, the availability of high resolution ICP-MS and applications of AMS for the analysis of long-lived radionuclides have opened doors for investigations which previously required too large samples, or were not possible because of lack of sensitivity. These developments are illustrated by several examples of marine radioactivity studies, which include contaminated sites (e.g., Fangataufa Atoll) and open ocean studies (e.g., the Atlantic Ocean) as well as analyses of IAEA reference materials. A comparison of Pu results obtained by alpha-spectrometry, ICP-MS and AMS has shown that a reasonably good agreement has been obtained between all three methods.     

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.     

Nanomaterials in mass spectrometry ionization and prospects for biological application

The rapid development of nanotechnology has revolutionized scientific developments in recent decades. Mass spectrometry (MS) measurements are no exception and have benefited greatly from integration of nanomaterials in every step of analysis. This brief review summarizes recent developments in the field with the focus on the use of nanomaterials as alternative media to facilitate analyte ionization in laser-desorption ionization–mass spectrometry (LDI–MS) and secondary ion mass spectrometry (SIMS). The biological applications of both techniques are also detailed. The use of nanomaterials in other aspects of MS analysis, for example in sample clean-up and indirect analyte quantification, is briefly discussed.     

Determination of long-lived radionuclides in concrete matrix by laser ablation inductively coupled plasma mass spectrometry

A laser ablation system using a Nd:YAG laser was coupled both to a quadrupole inductively coupled plasma (ICP) mass spectrometer and to a double-focusing sector field ICP mass spectrometer. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was applied for the determination of long-lived radionuclides in a concrete matrix. The investigated samples were two laboratory standards with a concrete matrix, which we doped with different long-lived radionuclides (e.g. ⁹⁹Tc, ²³²Th, ²³³U, ²³⁷Np) from the ng g⁻¹ to μ g⁻¹ concentration range and an undoped concrete material (blank). Detection limits for long-lived radionuclides in the 10 ng g⁻¹ range are reached for LA-ICP-MS using the quadrupole mass spectrometer. With double-focusing sector field ICP-MS, the limits of detection are in general one order of magnitude lower and reach the sub ng g⁻¹ range for ²³³U and ²³⁷Np. A comparison of mass spectrometric results with those of neutron activation analysis on undoped concrete sample indicates that a semiquantitative determination of the concentrations of the minor and trace elements in the concrete matrix is possible with LA-ICP-MS without using a standard reference material.     

Laser ionization mass spectrometry in inorganic trace analysis

Summary Among the different spectrometric techniques for trace analysis Laser Ionization Mass Spectrometry (LIMS) is well established as a trace analytical method. With the LIMS technique the sample material is evaporated and ionized by means of a focused pulsed laser in a laser microplasma, which is formed in the spot area of the irradiated sample. All chemical elements in the sample materials are evaporated and ionized in the laser plasma. The ions formed are separated according to their mass and energy by a time-of-flight, quadrupole or double focusing mass spectrometer. In this review the characteristics and analytical features, some recent developments and applications of laser ionization mass spectrometry in inorganic trace analysis are described.     

Radionuclide determination in environmental samples by inductively coupled plasma mass spectrometry

The determination of naturally occurring and anthropogenic radionuclides in the environment by inductively coupled plasma mass spectrometry has gained recognition over the last fifteen years, relative to radiometric techniques, as the result of improvement in instrumental performance, sample introduction equipment, and sample preparation. With the increase in instrumental sensitivity, it is now possible to measure ultratrace levels (fg range) of many radioisotopes, including those with half-lives between 1 and 1000 years, without requiring very complex sample pre-concentration schemes. However, the identification and quantification of radioisotopes in environmental matrices is still hampered by a variety of analytical issues such as spectral (both atomic and molecular ions) and non-spectral (matrix effect) interferences and instrumental limitations (e.g., abundance sensitivity).The scope of this review is to highlight recent analytical progress and issues associated with the determination of radionuclides by inductively coupled plasma mass spectrometry. The impact of interferences, instrumental limitations (e.g., degree of ionization, abundance sensitivity, detection limits) and low sample-to-plasma transfer efficiency on the measurement of radionuclides by inductively coupled plasma mass spectrometry will be described. Solutions that overcome these issues will be discussed, highlighting their pros and cons and assessing their impact on the measurement of environmental radioactivity. Among the solutions proposed, mass and chemical resolution through the use of sector-field instruments and chemical reactions/collisions in a pressurized cell, respectively, will be described. Other methods, such as unique sample introduction equipment (e.g., laser ablation, electrothermal vaporisation, high efficiency nebulization) and instrumental modifications/optimizations (e.g., instrumental vacuum, radiofrequency power, guard electrode) that improve sensitivity and performance will also be examined.     

Accelerator mass spectrometry: ultra-sensitive analysis for global science

Accelerator mass spectrometry (AMS) is the analytical technique of choice for the detection of long-lived radionuclides that cannot be practically analysed with decay counting or conventional mass spectrometry. AMS has been used for the analysis of ¹⁴C, ¹⁰Be, ³⁶Cl and other cosmogenic radionuclides in archaeology, geology and environmental science. In addition, the ultrasensitivity of AMS is being applied in biomedicine to study the exposure of human tissues to chemicals and biomolecules at attomole levels. AMS is also being considered for the detection of anthropogenic radionuclides, such as ¹²⁹I and ²³⁶U, in environmental samples for the verification of the nuclear non-proliferation agreements. The state of the art of AMS is reviewed with examples from some recent applications.     

Mass spectrometry with plasma sources at atmospheric pressure--state-of-the-art and some developmental trends

The state-of-the art and trends of development in ICP-MS are presented. Special reference is made to progress in plasma sources, which can be used as ion sources and, especially, the inductively coupled plasma and new microwave plasma sources. Further, progress in sample introduction for plasma mass spectrometry is discussed with special reference to new pneumatic nebulizers, enabling, e.g., work with microflows of solutions at high efficiency, new developments in ultrasonic nebulization, in electrothermal evaporation, laser ablation and hydride generation. Innovation in the types of mass spectrometers used is discussed with special reference to the use of reaction and collision cells, sector field mass spectrometry, time-of-flight mass spectrometry and multicollector mass spectrometers. Challenging applications in the field of speciation, especially in environmental samples with the example of the chromium speciation, and in materials analysis, with special reference to the analysis of ceramic powders with and without on-line matrix removal, are also discussed.     

Increasing specificity of tandem mass spectrometry by laser‐induced dissociation

Mass spectrometry offers an arsenal of tools for diverse proteomic investigations. This perspective article reviews some of the recent developments in the field of coupling laser‐induced dissociation with mass spectrometry (LID‐MS). Strategies involving labelling with a chromophore to induce specific photo‐absorption properties are considered, with a focus on specific amino acid derivatization. Some of the opportunities and challenges of LID‐MS after targeted labelling for increasing specificity in complex sample analysis are discussed.     

Capillary electrophoresis inductively coupled plasma mass spectrometry

Chemical speciation (extraction of elemental information and identification of molecular environment for an analyte in a complex sample) has been a long sought after goal for analytical chemists. Recently, because of successful developments in more sensitive element-specific detectors and gentle separation schemes, which preserve the true chemical information in a real sample, routine speciation experiments are becoming a common occurrence in the scientific literature. For many reasons, the combination of capillary electrophoresis (for separation of different chemical species) with inductively coupled plasma mass spectrometry (for element and isotope specific detection) has emerged as the method of choice for these analyses. In this article the basic principles of capillary electrophoresis inductively coupled plasma mass spectrometry are discussed. Design consideration for instrument interface, anticipated difficulties with speciation experiments and applications for specific matrices and analytes are also presented in this article.     

Low-level gamma-ray spectrometry for environmental samples

Low-level gamma-ray spectrometry with large volume HPGe detectors has been widely used in analysis of environmental radionuclides. The reasons are excellent energy resolution and high efficiency that permits selective and non-destructive analyses of several radionuclides in composite samples. Although the most effective way of increasing the sensitivity of a gamma-ray spectrometer is to increase counting efficiency and the amount of the sample, very often the only possible way is to decrease the detector’s background. The typical background components of a low-level HPGe detector, not situated deep underground, are cosmic radiation (cosmic muons, neutrons and activation products), radioactivity of construction materials, radon and its progenies. A review of Monte Carlo simulations of background components of HPGe detectors, and their characteristics in coincidence and anti-Compton mode of operation are presented and discussed.     

Determination of isotope ratios of metals (and metalloids) by means of inductively coupled plasma-mass spectrometry for provenancing purposes — A review

Since considerable time, isotopic analysis of different elements present in a sample, material or object (such as the ‘light’ elements H, C, N, O and S and ‘heavy’ elements, such as Sr and Pb), has been used in provenancing studies, as several factors — defined by “the environment” or origin of the sample — can lead to measurable differences in their isotopic composition. For the light elements, traditionally, (gas source) isotope ratio mass spectrometry (IR-MS) is used, while for a long period of time, thermal ionization mass spectrometry (TIMS) was considered as the only technique capable of detecting subtle variations in the isotopic composition of the ‘heavier’ elements. However, since the introduction of the first inductively coupled plasma mass spectrometers (ICP-MS), considerable attention has been devoted to the development of methodologies and strategies to perform isotopic analysis by means of ICP-MS. While the relatively modest isotope ratio precision offered by single-collector ICP-MS may already be fit-for-purpose under some circumstances, especially the introduction of multi-collector ICP-MS instruments, equipped with an array of Faraday detectors instead of a single electron multiplier, has lead to tremendous improvements in the field of isotopic analysis. As a result, MC-ICP-MS can be seen as a very strong competitor of TIMS nowadays, while it even provides information on the small isotopic variations shown by some elements, that are not or hardly accessible by means of TIMS (e.g., elements with a high ionization energy). Owing to these new instrumental developments, the application field of isotopic analysis by means of ICP-MS is continuously growing, also in the field of provenance determination. This paper is intended as a review of the developments in and the recent applications of isotopic analysis by means of ICP-MS in this specific research field.     

A concise review of mass spectrometry imaging

Mass spectrometric imaging allows the investigation of the spatial distribution of molecules at complex surfaces. The combination of molecular speciation with local analysis renders a chemical microscope that can be used for the direct biomolecular characterization of histological tissue surfaces. MS based imaging advantageously allows label-free detection and mapping of a wide-range of biological compounds whose presence or absence can be the direct result of disease pathology. Successful detection of the analytes of interest at the desired spatial resolution requires careful attention to several steps in the mass spectrometry imaging protocol. This review will describe and discuss a selected number of crucial developments in ionization, instrumentation, and application of this innovative technology. The focus of this review is on the latest developments in imaging MS. Selected biological applications are employed to illustrate some of the novel features discussed. Two commonly used MS imaging techniques, secondary ion mass spectrometric (SIMS) imaging and matrix-assisted laser desorption ionization (MALDI) mass spectrometric imaging, center this review. New instrumental developments are discussed that extend spatial resolution, mass resolving power, mass accuracy, tandem-MS capabilities, and offer new gas-phase separation capabilities for both imaging techniques. It will be shown how the success of MS imaging is crucially dependent on sample preparation protocols as they dictate the nature and mass range of detected biomolecules that can be imaged. Finally, developments in data analysis strategies for large imaging datasets will be briefly discussed.     

Recent developments in DNA adduct analysis using liquid chromatography coupled with mass spectrometry

The formation of DNA adducts by genotoxic agents is an early event in cancer development, and it may lead to gene mutations, thereby initiating tumor development. The measurement of DNA adducts can provide critical information about the genotoxic potential of a chemical and its mechanism of carcinogenesis. In recent decades, liquid chromatography coupled with mass spectrometry has become the most important technique for analyzing DNA adducts. The improvements in resolution achievable with new chromatographic separation techniques coupled with the high specificity and sensitivity and wide dynamic range of new mass spectrometry systems have been used for both qualitative and quantitative analyses of DNA adducts. This review discusses the challenges in qualitative and quantitative analyses of DNA adducts by liquid chromatography coupled with mass spectrometry and highlights recent developments towards overcoming the limitations of liquid chromatography coupled with mass spectrometry methods. The key steps and new solutions, such as sample preparation, mass spectrometry fragmentation, and method validation, are summarized. In addition, the fundamental principles and latest advances in DNA adductomic approaches are reviewed.     

Mass spectrometry of long-lived radionuclides

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic elements in the nuclear industry, for quality assurance and determination of the burn-up of fuel material in a nuclear power plant, for reprocessing plants, nuclear material accounting and radioactive waste control. Inorganic mass spectrometry, especially inductively coupled plasma mass spectrometry (ICP-MS) as the most important inorganic mass spectrometric technique today, possesses excellent sensitivity, precision and good accuracy for isotope ratio measurements and practically no restriction with respect to the ionization potential of the element investigated—therefore, thermal ionization mass spectrometry (TIMS), which has been used as the dominant analytical technique for precise isotope ratio measurements of long-lived radionuclides for many decades, is being replaced increasingly by ICP-MS. In the last few years instrumental progress in improving figures of merit for the determination of isotope ratio measurements of long-lived radionuclides in ICP-MS has been achieved by the application of a multiple ion collector device (MC-ICP-MS) and the introduction of the collision cell interface in order to dissociate disturbing argon-based molecular ions, to reduce the kinetic energy of ions and neutralize the disturbing noble gas ions (e.g. of ¹²⁹Xe⁺ for the determination of ¹²⁹I). The review describes the state of the art and the progress of different inorganic mass spectrometric techniques such as ICP-MS, laser ablation ICP-MS vs. TIMS, glow discharge mass spectrometry, secondary ion mass spectrometry, resonance ionization mass spectrometry and accelerator mass spectrometry for the determination of long-lived radionuclides in quite different materials.     

Capillary electrophoresis/mass spectrometry relevant to pharmaceutical and biotechnological applications

Advanced analytical techniques play a crucial role in the pharmaceutical and biotechnological field. In this context, capillary electrophoresis/mass spectrometry (CE/MS) has attracted attention due to efficient and selective separation in combination with powerful detection allowing identification and detailed characterization. Method developments and applications of CE/MS have been focused on questions not easily accessible by liquid chromatography/mass spectrometry (LC/MS) as the analysis of intact proteins, carbohydrates, and various small molecules, including peptides. Here, recent approaches and applications of CE/MS relevant to (bio)pharmaceuticals are reviewed and discussed to show actual developments and future prospects. Based on other reviews on related subjects covering large parts of previous works, the paper is focused on general ideas and contributions of the last 2 years; for the analysis of glycans, the period is extended back to 2006.     

Mass spectrometry of natural organic phosphorus

This article provides a review of the use of modern mass spectrometry (MS) for quantitative and qualitative measurements of organic phosphorus compounds in nature. Included is a brief discussion of recent developments in large molecule mass spectrometry, focusing on time-of-flight (TOF) and ion cyclotron resonance (ICR) mass analysis techniques, as well as electrospray (ESI) and inductively coupled plasma (ICP) ionization. The use of ICP with high-resolution mass spectrometry for quantitative measurements of total phosphorus and as a detector coupled to HPLC and CE for defining organic phosphorus speciation is demonstrated using results from a study of phosphorus cycling in a treatment wetland. Qualitative identifications of individual phosphorus compounds by ultrahigh resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is demonstrated using dissolved organic phosphorus isolated from this same wetland.