Simultaneous Plutonium and Uranium Isotopic Analysis from a Single Resin Bead - A Simplified Chemical Technique for Assaying Spent Reactor Fuels

Abstract

The method uses basic anion resin to adsorb plutonium and uranium from 7–8 M HNO₃ solutions containing dissolved spent reactor fuels. After equilibrating the resin with the solution, a single bead is used to determine the isotopic composition of plutonium and uranium on sample sizes as small as 10^?9 to 10^?10 g of each element per bead. Isotopic measurements are essentially free of isobaric interferences and fission product contamination in the mass spectrometer is eliminated. A very small aliquot of dissolver solution containing 10^?6 g of U and 10^?8 g of Pu is sufficient sample for chemically preparing several resin beads. A single prepared bead is loaded onto a rhenium filament and analyzed in a two-stage mass spectrometer using pulse counting for ion detection to obtain the high sensitivity required. Total quantity of the elements, in addition to isotopic abundances, can be determined by isotope dilution. Other areas where the method may be useful are: in plutonium production, isotope separations, and for trace detection of contamination on reactor parts.     

Isotopic Determination of Silicon by Mass Spectrometry in Plants and Soils Labeled with 30Si

Abstract

A method for isotopic determination of silicon by mass spectrometry in plants and soils labeled with ³⁰Si is reported. The development of this method is for use with studies involving the physiological process of absorption, transport, and redistribution of Si in the soil-plant system by use of the stable isotope ³⁰Si as a tracer. The procedure leads to SiF₄ formation, and the isotopic determination of Si was based on the measurements of the ²⁸SiF₃ ⁺, ²⁹SiF₃ ⁺, and ³⁰SiF₃ ⁺ signals. Relative standard deviation of ³⁰Si abundance measurements (n = 6) were lower than 0.1%, and the detection limit was 0.5 mg Si (dry mass).     

Monitoring Airborne Particulate Mass by Beta Absorption

Abstract

A prototype airborne particulate mass monitor, using the principle of beta radiation absorption, has been fabricated and evaluated on airborne particulate matter. A detection sensitivity of 80 μg/cm² was attained. A series of samples were collected, and a comparison made between the gravimetric and beta absorption results obtained on each sample. This study demonstrated the feasibility of fabricating a fully automated system for the collection and analysis of airborne particulate mass, using the principle of beta absorption attenuation.     

Study of some phenolic-iodine redox polymeric products by thermal analyses and mass spectrometry

Summary This paper describes the use of the mass spectrometry (MS), thermal analyses (TA) and other physico-chemical methods to investigate the structure of two newly synthesized phenolic-iodine derivative polymeric products. These two products are formed as a result of redox-interaction of adrenaline hydrogen tartrate (AHT, I) with iodate (IO^-₃) and periodate (IO^-₄). The characterization of the two products were achieved satisfactorily by using the above tools and their proposed general formulae, were found to be C₅₂H₆₇O₃₆N₄I (AHT- IO^-₃, II) and C₂₆H₃₄O₁₈N₂I₂(AHT- IO^-₄, III). The fragmentation behavior of the main compound (AHT) in MS and TA (TG and DTA) techniques was investigated and compared. The results obtained were used to explain the fragmentation of the products AHT- IO^-₃and AHT- IO^-₄in mass spectrometry and thermal analyses techniques. The stabilities of different fragments were discussed. The results indicate that the two techniques are supporting each other in which the mass spectrometry provides the structural information in gas phase while the thermal analyses provides the quantitative fragmentation in the solid-state.     

Study of the Fragmentation of D-Glucose and Alkylmonoglycosides in the Presence of Sodium Ions in an Ion-Trap Mass Spectrometer

Abstract

Using electrospray ion-trap mass spectrometry, the fragmentation of D-glucose and alkylmonoglycopyranosides (alkyl-GPs) was studied. In the presence of Na⁺, B₁ and ^0,2A fragmentations were observed. The alkyl-GPs also showed a ^2,5Afragmentation. A cluster containing no carbon atoms and adducts of this cluster with neutral molecules were observed. Standards of alkylmonoglycofuranosides (alkyl-GFs) were not available; however, their fragmentation was studied by high-performace liquid chromatography–mass spectrometry (HPLC-MS) and HPLC-MS² using an industrial mixture of alkylpolyglycosides. The cluster and its adducts were more easily formed by the alkyl-GPs than by the alkyl-GFs, but the ^0,2A cross-ring cleavage was more easily produced by the alkyl-GFs.     

Elemental,Isotopic, and Pesticide Analysis of Wild and Cultivated Berries

ABSTRACT

The focus of this study was to investigate differences in isotopic, elemental, and trace pesticide concentrations of wild and cultivated berries from Transylvania. To emphasize differences based on geographical origin, stable isotopic ratios of ²H/¹H, ¹⁸O/¹⁶O, and ¹³C/¹²C were determined by isotopic ratio mass spectrometry. Elemental fingerprinting of berries was performed by inductively coupled plasma mass spectrometry. The determination of trace pesticides in berries was performed by gas chromatography–mass spectrometry. Differences between wild and cultivated berries were evaluated using multivariate statistical analysis. The results suggest that multielemental, isotopic, and trace pesticide fingerprinting is feasible for sample differentiation.     

A Chemical Ionization Mass Spectrometric Study of Fluorescamine and Fluorescamine - Amino Acid Derivatives

Abstract

The chemical ionization mass spectra of fluorescamine and fluorescamine - amino acid derivatives have been studied using methane and ammonia as reagent gases. Major ions in the spectra are protonated molecular ions, adduct ions and ions formed by loss of an oxygen atom.

Fluorescamine, 4-phenyl-spiro[furan-2(3H),1′-phthalan]3,3′-dione, is a powerful new fluorogenic reagent for assaying primary amines.¹ and EI² and EI³ mass spectrometric investigations of fluorescamine and its derivatives were carried out. Our present study reports the CI mass spectral analysis of fluorescamine and some of its amino acid derivatives.     

Analysis of Cyanide in Blood by Headspace-Isotope-Dilution-GC-MS

Abstract

An uncomplicated, rapid, automated procedure for the analysis of low cyanide concentrations in whole blood is reported. The analysis was performed by headspace gas chromatography and mass spectrometry in the (¹H¹²C¹⁴N) and m/z 29 (¹H¹³C¹⁵N). Carryover from cyanide adsorption onto the surface of the needle was prevented by developing a new method that enabled automated flushing of the needle in between each cyanide analysis. Results were compared of ordinary calibrations and those of isotope dilutions. The total time of analysis was 18 min for a single cyanide analysis.     

Ion Implantation Standards as a Spark Source Mass Spectrometric Surface Analysis Calibration Technique: The Analysis of B in Irradiated Zircaloy-2

Abstract

Ion implantation standards were used to calibrate a spark source mass spectrometer (SSMS) near surface region analytical method. Standards were prepared by ion implanting ¹¹B⁺ at 100 keV into Zircaloy-2 at doses in the 3 × 10¹⁵ to 3 × 10^{16 11}B atoms/cm² range. The analytical method was predicated on the idea that both standards and samples could be sparked in a SSMS under essentially identical and reproducible conditions. Calibration plots gave linear log-log results for plots of ¹¹B⁺/¹²²Sn⁺ versus B concentration in the standards. Calibration plots were determined on the basis of 5 to 6 replicate determinations for 3 different implant standard concentration levels. A series of irradiated Zircaloy-2 cladding samples were analyzed and shown to contain not more than 0.06 μg/cm² total B in the near surface region.     

Picogram Detection of Sulfur Hexafluoride by High Pressure Charge Exchange Mass Spectrometry

Abstract

Since air quality in industrial atmospheres is important for personal comfort and safety, tracer experiments using sulfur hexa-fluoride (SF₆) are commonly used to monitor air distributions and flow patterns.

This method involves the determination of SF₆ by high pressure charge exchange mass spectrometry at levels as low as 3 × 10^?12 grams. It employs specific ion detection in combination with gas chromatography to insure a high degree of specificity.     

Development and validation of amitriptyline and its metabolite in human plasma by ultra performance liquid chromatography-tandem mass spectrometry and its application to a bioequivalence study

A method based on ultra performance liquid chromatography tandem mass spectrometry (UPLC–MS/MS) in combination with solid‐phase extraction for sample pretreatment has been developed for the simultaneous analysis of amitriptyline and its main metabolite in human plasma. The extraction of the analytes from plasma samples was carried out by means of a selective SPE procedure using hydrophilic–lipophilic balance cartridges. The assay involves a simple solid‐phase extraction (SPE) procedure of 0.2 mL of human plasma and analysis was performed on a triple‐quadrupole tandem mass spectrometer by multiple reactions monitoring (MRM) mode via electrospray ionization (ESI). The standard calibration curve was linear over the ranges 0.370–95.539 ng/mL for amitriptyline and 0.365–94.374 ng/mL for nortriptyline, expressed by the linear correlation coefficient r², which was better than 0.995 for both. The intra‐ and inter‐day precision and accuracy of the quality control samples were within 10.0%. The recovery was 85.3, 88.4 and 80.7% for amitriptyline, nortriptyline and doxepin respectively. Total run time was 1.2 min only for each sample, which makes it possible to analyze more than 400 samples per day. The method was highly reproducible and gave peaks with excellent chromatography properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Analysis of Tetracycline,Oxytetracycline and Chlortetracycline in Plasma Extracts by Electrospray Tandem Mass-Spectrometry and by Liquid Chromatography

Abstract

Pure standards of tetracyclines (tetracycline, oxytetracycline and chlortetracycline) have been analyzed on a triple quadrupole mass spectrometer with Atmospheric Pressure Chemical Ionization (APCI) and Electrospray Ionization (ESI). ESI appeared to be considerably more sensitive than APCI. Collisional activation of the MH⁺ ions gave fragment ions at m/z values equal to MH⁺ - 35 which corresponds to loss of both H₂O and NH₃. The collisionally induced loss of 35 from MH⁺ was used in developing a mass spectrometric method based on loop injection and selected reaction monitoring (SRM) as the final analytical step. The method was tested on extracts from fortified plasma and the measurements from the MS-MS analysis were compared with results from High Performance Liquid Chromatography (HPLC) analysis of the same samples. The fortified plasma (from pig) samples were purified by chelate affinity chromatography (amberlite XAD columns). After filtration and evaporation of the solvent the redissolved residues were analyzed by HPLC and by MS-MS with ESI. The HPLC eluates (gradient of 0.01 M aqueous oxalic acid and CH₃CN) were monitored at 356 and 369 nm. The signal to noise ratio in the analyses of extracts from plasma fortified to 20 ppb suggests a detection limit for the MS-MS method below 10 ppb of tetracylines in plasma.     

The Measurement of Leucine Enkephalinat the Femtomole Level by Fast Atom Bombardment Mass Spectrometry/Mass Spectrometry Methods

Abstract

FAB-MS/MS methods are used to quantify the neuropeptide leucine enkephalin (LE = YGGFL) in synthetic solutions. Maximum molecular specificity is provided by monitoring two metastable transitions from the LE (M + H)⁺, 556 → 425 and 556 → 336, in a forward geometry (E, B) mass spectrometer using a B/E linked-field selected reaction monitoring technique. Obtained sensitivity is 40 pg LE, which equals 72 fmol. The statistics of the best-fit straight lines are, for m/z 425: y = 34 + 166 (r = 0.999), and for m/z 336: y = 2.5x + 17.2 (r = 0.996).     

Spark-Source Mass Spectrometric Techniques for the Analysis of Lanthanide and Actinide Elements in Microgram and Sub-Microgram Transuranium Samples

Abstract

Lanthanide and actinide impurities in a total sample of 1 to 10 μg of transuranic matrix can be determined by employing the spark-source mass spectrograph and solution technique. A special source glove box permits safe manipulation of transuranium elements with α-emitting radioactivity up to 10¹² dpm. The minimum detection limit is about 10¹² atoms per electrode system and an exposure of 10^?8 coulomb. Relative sensitivity values for the lanthanides and actinides were established with respect to erbium, the internal standard.     

New extractive spectrophotometric methods for the determination of nortriptyline hydrochloride in pure form and pharmaceutical dosages

Two simple, rapid and sensitive extractive spectrophotometric methods have been developed for the assay of nortriptyline hydrochloride (NTPH) in pure and pharmaceutical formulations. These methods are based on the formation of chloroform soluble ion-association complexes of NTPH with bromocresol green (BCG) and with methyl orange (MO) in KCl-HCl buffer of pH 2. The colored species exhibited absorption maxima at 416 and 422 nm for BCG and MO with molar absorptivity values of 2.88 × 10⁴ and 2.29 × 10⁴ L/mol cm, respectively. Reaction conditions were optimized to obtain the maximum color intensity. Various analytical parameters have been evaluated and the results have been validated by statistical data. The methods were successfully applied to the analysis of NTPH in pharmaceutical formulations. The article is published in the original.     

Drug screening in human plasma by cloud-point extraction and HPLC

Cloud-point extraction (CPE) with RP-HPLC/DAD detection was used to develop a screen for six model basic drugs (paracetamol, promazine, amitriptyline, nortriptyline, clomipramine and chlorpromazine) in human plasma. These drugs’ varied hydrophobicities entail different affinities for the micelle-rich phase and CPE extraction efficiencies. Extraction recovery (except paracetamol) was above 80% and reproducibility (RSD%) ranged from 2.88 to 10.26 intraday and from 3.12 to 12.33 interday. The limits of detection were: 0.125 μg mL^?1 (promazine and chlorpromazine), 0.25 μg mL^?1 (amitriptyline and nortriptyline) and 0.5 μg mL^?1 (paracetamol and clomipramine). The method was linear over the ranges: 0.125–1.0 μg mL^?1 (promazine and chlorpromazine), 0.25–1.0 μg mL^?1 (amitriptyline and nortriptyline), 0.5–1.0 μg mL^?1 (clomipramine) and 0.5–10 μg mL^?1 (paracetamol). The procedure is a good alternative to the SPE or LLE sample preparation usually used.     

Electrochemical Oxidation of Nortriptyline and Its Voltammetric Sensing at a Carbon Ionic Liquid Electrode

The electrochemical oxidation of nortriptyline at a carbon ionic liquid electrode (CILE) was investigated. Nortriptyline is electrochemically inactive on conventional electrodes but CILE exhibited excellent electrocatalytic activity toward oxidation of nortriptyline with the well-defined anodic peak at 860 mV. This characteristic was attributed to the outstanding conductivity and electrocatalytic effect of the ionic liquid, 1-octylpyridinum hexaflourophosphate, used as a binder in the construction of the electrode. The influence of experimental parameters such as pH and sweep rate was also studied. The quantitative determination of nortriptyline was performed using differential pulse voltammetry technique. Under selected conditions the anodic peak current was linear to nortriptyline concentration in the ranges of 4.8 × 10^–6 to 2.4 × 10^–5 M and 2.4 × 10^–5 to 6.4 × 10^–5 M, with correlation coefficients of 0.9992 and 09949, respectively. The detection limit was 3 × 10^–7 M.     

The synthesis of metallocene-labelled drugs for biological assays

Several drugs (amphetamine, desipramine, nortriptyline, phenobarbital) have been labelled with metallocenic fragments in order to develop a new immunoassay method. The metallocenic fragments are cymantrenic or benchrotrenic derivatives: the linkage between the organic and organometallic moieties has been achieved by reactions between amino and acidic functional groups. All the products (metallohaptens), purified by different chromatography techniques, have been fully characterized by IR and ¹H NMR spectroscopy and their mass spectra.     

Rearrangement of Ethers: A New Route to Tolterodine

Efficient methods for the syntheses of amines 6b and 9b, the major metabolites of the antidepressant drugs amitriptyline 1a and nortriptyline 1b, are described.     

Ion-Molecule Reaction Products Found in the Mass Spectra of Trimethylsilyl Derivatives

Abstract

Mass spectrometric studies of trimethylsilyl derivatives of glycerophosphates revealed the presence of several ions of mass greater than M⁺. It is suggested that these ions are formed by the reaction of abundant fragment ions containing positively charged silicon with neutral molecular species.