Critical comparison of radiometric and mass spectrometric methods for the determination of radionuclides in environmental, biological and nuclear waste samples

The radiometric methods, alpha (α)-, beta (β)-, gamma (γ)-spectrometry, and mass spectrometric methods, inductively coupled plasma mass spectrometry, accelerator mass spectrometry, thermal ionization mass spectrometry, resonance ionization mass spectrometry, secondary ion mass spectrometry, and glow discharge mass spectrometry are reviewed for the determination of radionuclides. These methods are critically compared for the determination of long-lived radionuclides important for radiation protection, decommissioning of nuclear facilities, repository of nuclear waste, tracer application in the environmental and biological researches, these radionuclides include ³H, ¹⁴C, ³⁶Cl, ⁴¹Ca, ^59,63Ni, ^89,90Sr, ⁹⁹Tc, ¹²⁹I, ^135,137Cs, ²¹⁰Pb, ^226,228Ra, ²³⁷Np, ²⁴¹Am, and isotopes of thorium, uranium and plutonium. The application of on-line methods (flow injection/sequential injection) for separation of radionuclides and automated determination of radionuclides is also discussed.     

Billionfold data increase from mass spectrometry instrumentation

The mass spectrometers of 1910–1950 gave 10–100 separately measurable mass values (resolution increments) in a single spectrum; the few other analytical methods then with this capability, such as emission spectroscopy, were not suitable for molecular characterization. The introduction of high-resolution mass spectra 40 years ago gave a 10² increase in resolution increments, while tandem mass spectrometry (MS²) 30 years ago promised a similar exponential gain. A key to the present realization of this was the discovery of Fourier-transform mass spectrometry 20 years ago, while electrospray ionization of large molecules 10 years ago greatly extended the upper mass limit of spectra. These improvements can now give 10⁵–10⁶ resolution increments in the mass spectrum of a large molecule. Extending this with MS² ions in any of > 10⁴ mass regions can be dissociated to produce a mass spectrum with these > 10⁵ resolution increments. With the several steps of MS ⁿ now achievable, this represents a > 10⁹ data gain since 1950. However, utilization of this amazing capability is in its infancy, presenting a tremendous challenge for our field.     

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life

Stable isotope ratio measurements have been used as a measure of a wide variety of processes, including solar system evolution, geological formational temperatures, tracking of atmospheric gas and aerosol chemical transformation, and is the only means by which past global temperatures may be determined over long time scales. Conventionally, isotope effects derive from differences of isotopically substituted molecules in isotope vibrational energy, bond strength, velocity, gravity, and evaporation/condensation. The variations in isotope ratio, such as ¹⁸O/¹⁶O (δ¹⁸O) and ¹⁷O/¹⁶O (δ¹⁷O) are dependent upon mass differences with δ¹⁷O/δ¹⁸O=0.5, due to the relative mass differences (1 amu vs. 2 amu). Relations that do not follow this are termed mass independent and are the focus of this Minireview. In chemical reactions such as ozone formation, a δ¹⁷O/δ¹⁸O=1 is observed. Physical chemical models capture most parameters but differ in basic approach and are reviewed. The mass independent effect is observed in atmospheric species and used to track their chemistry at the modern and ancient Earth, Mars, and the early solar system (meteorites).     

Analysis and elimination of systematic errors originating from coulomb mutual interaction and image charge in Fourier transform ion cyclotron resonance precise mass difference measurements

The effect of mutual Coulomb-mediated interactions between ions of two different mass-to-charge ratios (but equal ion cyclotron orbital radii) on their Fourier transform ion cyclotron resonance (FT/ICR) mass spectral frequency difference is derived analytically and measured experimentally. For a cylindrical ion trap, ion packets are modeled theoretically as infinitely extended lines of charge, and contributions to cyclotron frequency difference due to direct Coulomb repulsion between the lime charges as well as the forces arising from image charge induced on the trap electrodes by each line charge are calculated. A striking theoretical prediction is that the effect on ICR frequency difference of mutual Coulomb repulsion between ions in a mass doublet may be compensated by the image-charge effect. As a result, there is an optimal (calculable) ion cyclotron orbital radius at which the measured cyclotron orbital frequency difference between ions of two different mass-to-charge ratios is independent of mutual Coulomb-mediated interactions between the two components of the mass doublet! Moreover, if the two mass-doublet component ions are present in equal numbers, then the measured ion cyclotron orbital frequency difference is also independent of all Coulomb-mediated interactions between the two types of ions! Thus, the single largest systematic error in measurement of mass difference in a mass doublet by FT/ICR mass spectrometry may be virtually eliminated by appropriate control of ICR orbital radius and/or by performing measurements at various relative abundance ratios and extrapolating to equal relative abundance of the two mass-doublet components. We report experimental tests and verification of these predictions for two different mass doublets: ³He⁺/³H⁺ (cylindrical trap at 4.7 Tesla) and ¹²C¹H ₂ ⁺ /¹⁴ N⁺ (cubic trap at 7.0 Tesla). From the latter measurement, we determine the mass of atomic nitrogen as m(¹⁴N)=14.003 074 014(19) u.     

Development of quadrupole mass spectrometers using rapid prototyping technology

In this report, we present a prototype design of a quadrupole mass filter (QMF) with hyperbolic electrodes, fabricated at the University of Liverpool using digital light processing (DLP), a low-cost and lightweight 3D rapid prototyping (RP) technique. Experimental mass spectra are shown for H₂⁺, D₂⁺, and He⁺ ions to provide proof of principle that the DLP mass filter is working as a mass analyzer in the low-mass range (1 to 10 amu). The performance of the DLP QMF has also been investigated for individual spectral peaks. Numerical simulations of the instrument were performed by coupling CPO and Liverpool QMS-2 programs to model both the ion source and mass filter, respectively, and the instrument is shown to perform as predicted by theory. DLP thus allows miniaturization of mass spectrometers at low cost, using hyperbolic (or other) geometries of mass analyzer electrodes that provide optimal ion manipulation and resolution for a given application. The potential of using RP fabrication techniques for developing miniature and microscale mass analyzers is also discussed.     

Accuracy and long-term reproducibility of lead isotopic measurements by multiple-collector inductively coupled plasma mass spectrometry using an external method for correction of mass discrimination

The precision of isotopic measurements of Pb by thermal ionization mass spectrometry (TIMS) is limited by the fact that this element does not possess an invariant isotope ratio that can be used for the correction of mass fractionation by internal normalization. Multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) can overcome this limitation, because with plasma ionization, elements with overlapping mass ranges are thought to display identical mass discrimination. With respect to Pb, this can be exploited by the addition of Tl to the sample solutions; the mass discrimination factor obtained for Tl can then be used for the correction of the measured Pb isotope ratios. In this article we present the results of a detailed study that investigates the accuracy and precision of such an external correction technique for mass discrimination based upon the results of multiple analyses of a mixed standard solution of NIST SRM-981 Pb and SRM-997 Tl. Our data indicate that normalization of the Pb isotope ratios to the certified isotopic composition of SRM-997 Tl produces Pb isotopic results that are significantly lower than recently published reference values by TIMS. This systematic offset can be eliminated by renormalization of the Pb data to a different Tl isotopic composition to obtain an empirically determined mass discrimination factor for Pb that generates accurate results. It is furthermore shown that a linear law is least suited for the correction of mass discrimination, whereas a power or exponential law function provide significantly more accurate and precise results. In detail, it appears that a power law may provide the most appropriate correction procedure, because the corrected Pb isotope ratios display less residual correlations with mass discrimination compared to the exponentially corrected data. Using an exponential or power law correction our results, obtained over a period of over seven months, display a precision (2σ) of better than 60 parts per million (ppm) for ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁷Pb/²⁰⁶Pb and of better than 350 ppm for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb. This represents a significant improvement compared to conventional TIMS techniques and demonstrates the potential of MC-ICPMS for routine, high-precision measurements of Pb isotopic compositions.     

Fast visualization of the mass transfer processes at the electrode/electrolyte interface with a Mach-Zehnder interferometer

A Mach-Zehnder interfeometer is employed to visualize the mass transfer processes at the electrode/electrolyte interface during the potentiodynamic sweep of the Pt electrode in 0.1 mol dm^?3 K₄Fe(CN)₆ with 0.5 mol dm^?3 KCl solution at 20 mV s^?1. The changes of solution??s refractive index, brought about by the mass transfer during the reaction, can be recorded in situ in interferograms. The distributions of the optical path difference are obtained by numerical reconstruction of interferograms to reflect changes of solution??s refractive index and the mass transfer processes. The mass transfer of [Fe(CN)₆]^4? and [Fe(CN)₆]^3? is presented visually. This method provides a new approach to detect the mass transfer processes at the electrode/electrolyte interface in real-time.     

The observation of broad metastable ion peaks in the surface-induced dissociation mass spectra of protonated and cationated peptides

The product ion mass spectra of protonated and cationated peptides of relative molecular mass (RMM) 555–574 Da have been obtained by surface-induced dissociation of MH⁺ and [M + Cat]⁻ ions in a four-sector tandem mass spectrometer equipped with a specially designed collision cell. A linked scan of the electric and magnetic sector field strengths of the second mass spectrometer was used to transmit the fragment ions arising from collisions with a stainless steel surface. The resulting mass spectra contained broad metastable ion peaks produced by the dissociation of MH⁺ and [M + Cat]⁺ ions before the second magnetic sector, in the fourth field-free region of the instrument.     

Cu(II) removal enhancement from aqueous solutions using ion-imprinted membrane technique

In this study, Cu(II)-ion-imprinted membrane adsorbents were prepared via cross-linking of blended chitosan/poly(vinyl alcohol) using glutaraldehyde as cross-linker and copper ions as template. The ability of IIMs to adsorb copper ions from aqueous solutions was assessed using a batch of experiments under different conditions by changing cross-linking density (0.05 mass %, 0.1 mass %, and 0.2 mass %), template content (0.2 mass %, 0.5 mass %, and 0.9 mass %), initial analyte concentration (50 mg L^?1, 100 mg L^?1, and 150 mg L^?1), and adsorbent concentration (0.5 g L^?1, 1.0 g L^?1, and 2.0 g L^?1). The Taguchi method was used to plan a minimum number of experiments. The following optimal levels were thus determined for the four factors: cross-linking density: 0.1 mass %; template content: 0.5 mass %; initial analyte concentration: 150 mg L^?1; and adsorbent concentration: 0.3 g L^?1.     

The negative ion mass spectra of mixtures of sulphur and organic compounds. I—The formation of [M+Sn]− from the mixture of sulphur and dinitriles

The negative ion mass spectra of sulphur, dinitriles and their mixtures were studied. The abundance of negative ions of sulphur was almost comparable to that of positive ions. In the negative ion mass spectrum of a mixture of sulphur and dinitrile, intense and characteristic peaks of [M + S_n]^? (n = 2, 3, 4, etc.) were observed resulting from ion–molecule association of dinitrile with the S_n^? anions. As a standard sample of a negative ion mass spectrum, sulphur itself has proved useful in the lower mass region (below m/e 256: S₈^?).     

Investigation of some pentasubstituted 1,4-dihydropyridines by means of fast ion bombardment,chemical ionization and electron impact mass spectrometry

Positive fast ion bombardment, positive chemical ionization (CI⁺) and positive electron impact (EI) ionization mass spectrometry were used to investigate a number of relatively large and structurally related organic molecules. Some of the major dissociation pathways observed in the CH₄-CI⁺ mass spectra are not present under NH₃-CI⁺ conditions, but are obtained in the collision-induced dissociation (CID) spectrum of the 50 eV MH⁺ molecular ion, formed in the latter reaction. The resemblance between the EI mass spectra and their fast ion bombardment counterparts, the effect of changing the energy of the bombarding Cs⁺ ion beam over the range 2–16 keV and the different degrees of internal excitation of ions formed in different CI reagent gases are discussed.     

Mass selective separation applied to radioisotopes of cesium

A technique that uses the intrinsic mass‐based separation capability of a quadrupole mass spectrometer has been used to resolve spectral radiometric interference of two isotopes of the same element. In this work the starting sample was a mixture of ¹³⁷Cs and ¹³⁴Cs and was (activity) dominated by ¹³⁷Cs. This methodology separated and ‘implanted’ ¹³⁴Cs that was later quantified for spectral features and activity with traditional radiometric techniques. This work demonstrated a ¹³⁴Cs/¹³⁷Cs activity ratio enhancement of >4 orders of magnitude and complete removal of ¹³⁷Cs spectral features from the implanted target mass (i.e. 134). Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of fluorine on stabilization/solidification of radioactive fluoride liquid waste in magnesium potassium phosphate cement

This paper investigated the effect of fluorine mass fraction on magnesium potassium phosphate cement (MKPC) stabilization/solidification (S/S). The solidified object was a simulated fluid containing Co²⁺, Sr²⁺, Cs⁺ and F⁻. The results showed when the fluorine mass fraction increased, the setting time of the MKPC slurry extended. Under the same conditions, the 28-day compressive strength of the MKPC solidified forms reduced, and the freeze–thaw resistance enhanced. When the fluorine mass fraction was more than 6 wt%, a new product (MgF₂) appeared and caused the structure to become evacuated. Meanwhile, leaching concentration of the researched ions increased, especially Cs²⁺ and F⁻. When the fluorine mass fraction of the MKPC solidified forms was 12 wt%, a very small amount of wagnerite was observed.

     

Mass spectra of π-cyclopentadienyl-diene cobalt complexes

Many reports on the mass spectra of organotransition-metal complexes have appeared in recent years,¹ whilst there have only been a few reports on the mass spectra of transition metal olefin complexes, some metal carbonyl olefin complexes²³⁴ and π-cyclooctenyl-π-cyclooctadienyl cobalt.⁵ Recently fragmentation paths of π-cyclopentadienyl-cyclooctadiene rhodium were elucidated by King.⁶ The present authors found metastable ions in the mass spectra of π-cyclopentadienyl-diene cobalt complexes as well as in the mass spectra of π-cyclopentadienyl-diene rhodium complexes.⁷. In the present paper the authors wish to report the mass spectra of several π-cyclopentadienyl diene cobalt complexes.     

High resolution studies of the origins of polyatomic ions in inductively coupled plasma-mass spectrometry,Part I. Identification methods and effects of neutral gas density assumptions,extraction voltage,and cone material

Common polyatomic ions (ArO⁺, NO⁺, H₂O⁺, H₃O⁺, Ar₂⁺, ArN⁺, OH⁺, ArH⁺, O₂⁺) in inductively coupled plasma-mass spectrometry (ICP-MS) are identified using high mass resolution and studied using kinetic gas temperatures (T_gas) determined from a dissociation reaction approach. Methods for making accurate mass measurements, confirming ion identifications, and correcting for mass bias are discussed. The effects of sampler and skimmer cone composition and extraction voltage on polyatomic ion formation are also explored. Neutral species densities at several locations in the extraction interface are estimated and the corresponding effects of the T_gas value are calculated. The results provide information about the origins of background ions and indicate possible locations for their formation or removal.     

Imaging mass spectrometry of gold nanoparticles in a tissue section as an immunohistochemical staining mass probe

For analysis of low abundance peptides in a tissue section, immunohistochemical staining through antibody‐antigen interaction is a usual technique. The antibody is conjugated with a probe moiety that aids in highly sensitive detection. Gold nanoparticles, which show excellent chemical stability and variation of surface modifications, are expected to act as a sensitive mass probe to desorb gold ions (Au⁺, Au₂⁺, Au₃⁺) that are distinguishable from fragment ions from organic molecules. Here, green fluorescent proteins (GFP) in a tissue section of a transgenic zebrafish were detected by the gold mass probe conjugated with antibodies. Due to the efficient ionization and desorption of gold ions, imaging mass spectrometry of Au₂⁺ ions indicated the distribution of gold nanoparticles stained in a tissue section, and the mass signal distribution was consistent with the area where the GFP‐expressing cells were distributed. Conventional immunofluorescence techniques showed intense autofluorescence that come from intrinsic fluorophores in the tissue section. In contrast, the gold nanoparticles acted as an immunostaining mass probe that displayed significantly lower background signals.     

Cyclization of peptide b9 ions

The product ion mass spectra obtained by CID of the b₉ ions derived by loss of neutral alanine from the MH⁺ ion of the peptides Tyr(Ala)₉, (Ala)₄Tyr(Ala)₅, and (Ala)₈TyrAla are essentially identical, indicative of full cyclization reaction to a common intermediate before fragmentation. This leads to abundant nondirect sequence ions in the product ion mass spectra of the b₉ ions. The product ion mass spectra of the b₈ ions from the first two peptides also are essentially identical. The fragmentation of the MH⁺ ions also leads to low intensity nondirect sequence ions in the product ion mass spectra. N-terminal acetylation blocks the cyclization and eliminates nondirect sequence fragment ions in the product ion mass spectra.     

Detection mass bias in atmospheric pressure ionization mass spectrometry

A previously uncharacterized source of detection mass bias is shown to be associated with atmospheric pressure ionization mass spectrometry (APIMS), and is attributed to a mass dependence in the sampling of ions from the supersonic free jet expansion of gas emerging from the ion source. The halide ions Cl ^?, Br^?, and I^? are shown to be transported from the ion source aperture to a quadrupole mass filter with efficiencies that increase linearly with increasing mass of the ion. While the polyatomic anions SF ₆ ^- and C₇F ₁₄ ^- are detected with even greater efficiencies than would be expected for monatomic anions of the same mass, this additional sensitivity to the polyatomic anions is thought to be related to ion loss processes occurring within the ion source. The experimental conditions under which these mass bias effects can be minimized or enhanced in APIMS are described.     

Enhancement of the effective resolution of mass spectra of high-mass biomolecules by maximum entropy-based deconvolution to eliminate the isotopic natural abundance distribution

Although high-resolution Fourier transform ion cyclotron resonance mass spectrometry can resolve individual isotopic masses for biomolecules of more than 100 ku, its effective mass accuracy is limited by the distribution of naturally occurring rare isotopes (¹³C, ¹⁵N, ¹⁸O, ³⁴S, etc.). In this article, we compare least-squares and maximum entropy methods for deconvolution of the isotopic natural abundance distribution to narrow the mass spectral isotopic abundance envelope for greatly enhanced effective mass resolution. We apply both methods to yield deconvolved high-resolution deuterium distributions for peptides and proteins subjected to H/D exchange prior to electrospray Fourier transform ion cyclotron resonance mass analysis. In addition, we show that even unresolved isotopic envelopes from a quadrupole mass spectrometer can be narrowed for considerably improved resolution there as well.     

Determination of arsenic compounds in marine mammals with high-performance liquid chromatography and an inductively coupled plasma mass spectrometer as element-specific detector

Total arsenic concentrations and the concentrations of individual arsenic compounds were determined in liver samples of pinnipeds [nine ringed seals (Phoca hispida), one bearded seal (Erginathus barbatus)] and cetaceans [two pilot whales (Globicephalus melas), one beluga whale (Deliphinapterus leucus)]. Total arsenic concentrations ranged from 0.167 to 2.40 mg As kg⁻¹ wet mass. The arsenic compounds extracted from the liver samples with a methanol/water mixture (9:1, v/v) were identified and quantified by anion- and cation-exchange chromatography. An ICP–MS equipped with a hydraulic high-pressure nebulizer served as the arsenic-specific detector. Arsenobetaine (0.052–1.67 mg As kg⁻¹ wet mass) was the predominant arsenic compound in all the liver samples. Arsenocholine was present in all livers (0.005–0.044 mg As kg⁻¹ wet mass). The tetramethylarsonium cation was detected in all pinnipeds ( < 0.009 to 0.043 mg As kg⁻¹) but not in any of the cetaceans. The concentration of dimethylarsinic acid ranged from < 0.001 to 0.109 mg As kg⁻¹ wet mass. Most of the concentrations for methylarsonic acid ( < 0.001 to 0.025 mg As kg⁻¹ wet mass) were below the detection limit. Arsenous acid and arsenic acid concentrations were below the detection limit of the method (0.001 mg As kg⁻¹). An unknown arsenic compound was present in all liver samples at concentrations from 0.002–0.027 mg As kg⁻¹. © 1998 John Wiley & Sons, Ltd.