Estimation of trace levels of plutonium in urine samples by fission track technique

Individual monitoring of radiation workers handling Pu in various nuclear installations requires the detection of trace levels of plutonium in bioassay samples. It is necessary to develop methods that can detect urinary excretion of Pu in fraction of mBq range. Therefore, a sensitive method such as fission track analysis has been developed for the measurement of trace levels of Pu in bioassay samples. In this technique, chemically separated plutonium from the sample and a Pu standard were electrodeposited on planchettes and covered with Lexan solid state nuclear track detector (SSNTD) and irradiated with thermal neutrons in APSARA reactor of Bhabha Atomic Research Centre, India. The fission track densities in the Lexan films of the sample and the standard were used to calculate the amount of Pu in the sample. The minimum amount of Pu that can be analyzed by this method using doubly distilled electronic grade (E. G.) reagents is about 12 μBq/L.     

Determination of track registration efficiency and radiation chemical yield for loss of ester bonds due to gamma rays in Cellulose Acetate Butyrate (CAB) nuclear track detector

The fission track registration efficiency of an indigenously prepared Cellulose Acetate Butyrate (CAB) solid state nuclear track detector (SSNTD) has been determined and is found to be (0.89 ± 0.04). Radiation chemical yield, G-value for loss of ester bonds in this detector exposed to gamma rays from a Co-60 source has also been determined by FT-IR spectrometry. The amount of ester bonds lost due to the exposure was estimated from the change in absorbance of C=O and C–O–C bonds with the gamma dose. The G-value for breaking of ester bonds in CAB detector is found to be about 37/100 eV.     

Estimation of track registration efficiency in solution medium and study of gamma irradiation effects on the bulk-etch rate and the activation energy for bulk etching of CR-39 (DOP) solid state nuclear track detector

The fission track registration efficiency of diethylene glycol bis allyl carbonate (dioctyl phthalate doped) [CR-39 (DOP)] solid state nuclear track detector (SSNTD) in solution medium (K _wet) has been experimentally determined and is found to be (9.7 ± 0.5) × 10⁻⁴ cm. This is in good agreement with the values of other SSNTDs. The gamma irradiation effects in the dose range of 50.0–220.0 kGy on the bulk etch rate, V _b and the activation energy for bulk etching, E of this solid state nuclear track detector (SSNTD) have also been studied. It is observed that the bulk etch rates increase and the activation energies for bulk etching decrease with the increase in gamma dose. These results have been explained on the basis of scission of the detector due to gamma irradiation.     

Some investigations of sea sands from the Black Sea coastline

Alpha to spontaneous fission branching ratios of heavy actinides such as²³⁸Pu and²⁴⁰Pu in solution have been determined by solid state nuclear track detectors (SSNTDs). The detectors used in the present studies are LR-115, CR-39 (DOP), Lexan polycarbonate and Tuffak polycarbonate. Before using Tuffak polycarbonate, a detailed and systematic study on the registration and chemical etching characteristics of fission fragment tracks in this detector was also carried out. The experimentally measured values of alpha to spontaneous fission ratios by this method are found to agree well with the expected values.     

Modification of etching properties of a newly developed nuclear track detector called allyl bis-(2-nitroxy-ethyl) carbomate (ABNEC)–allyl diglycol carbonate (ADC) copolymer [ABNEC:ADC (1:9)] by gamma irradiation

The gamma irradiation effects on the bulk etch rate, V _b of an indigenously prepared new nuclear track detector which is a copolymer of allyl bis-(2-nitroxy-ethyl) carbomate (ABNEC) and allyl diglycol carbonate (ADC) [ABNEC:ADC (1:9)] were studied in the dose range of 25.0–250.0 kGy and etching temperature range of 60–80 °C. The bulk etch rates increase and the activation energy values for bulk etching of gamma-irradiated detectors decrease with the increase in gamma dose indicating the scission of the detector. UV–visible spectra of the unirradiated and the irradiated films were also taken to explore the possibility of using this new detector for gamma dose measurements.     

Effect of gamma irradiation on the etching properties of Lexan and Makrofol-DE polycarbonate plastics

It is observed that for Lexan and Makrofol-DE polycarbonate plastic detectors the mean diameters of fission fragments from a ²⁵²Cf source increases as a result of gamma-ray exposure. We have studied the bulk etching rate and track etching rate before and after gamma-ray irradiation on Lexan and Makrofol-DE polycarbonate plastics. The mechanism of Lexan and Makrofol-DE polycarbonate plastic detectors can be understood with the help of this exposures. It is also noted that degree of ordering of Lexan and Makrofol-DE polycarbonate is dependent on the gamma ray dose due to degradation and cross-linking processes. The results show that bulk and track etch rate increases with gamma dose while activation energy associated with bulk and track etch rates at a particular temperature and sensitivity decreases with gamma dose.     

Determination of guaiphenesin and sodium benzoate in Liqufruta garlic cough medicine by high performance liquid chromatography

A new and simple isocratic high-performance liquid chromatographic method with ultraviolet detection is described for simultaneous determination of active guaiphenesin and preservative sodium benzoate in Liqufruta garlic cough medicine formulation. The chromatographic separation was achieved using a Zorbax CN; 150 mm × 4.6 mm and 5 μm particle size column employing acetonitrile and water (20: 80, v/v) containing 0.1% formic acid (pH 3.5 ± 0.05) as the mobile phase. The method was validated with respect to linearity, range, precision, accuracy, specificity, limit of detection and limit of quantitation. The both analytes were detected by UV-Vis detector at 245 nm. The method was linear over the concentration range of 0.2–0.8 mg/mL and 0.02–0.06 mg/mL for guaiphenesin and sodium benzoate, respectively. The limit of detection was found to be 0.14 μg/mL for GP and 0.06 μg/mL for SB and the quantification limit was 0.54 μg/mL for GP and 0.22 for SB. Accuracy, evaluated as recovery, was in the range of 97.8–100.0%. Intra-day precision and intermediate precision showed relative standard deviation <1% in each case.     

The use of solid-state nuclear track detection for the study of boron and fissile nuclide distributions in steel samples

The technique of boron autoradiography using cellulose acetobutyrate (CAB) film for measuring the distribution of boron in stainless steels, is described. The method involves the irradiation of the specimen and detector with thermal neutrons, and the development of the α-particle tracks arising from the nuclear reaction¹⁰B(n, α)⁷Li. A related technique for the measurement of fissile nuclides in steel hulls, is also described. In this case, a polycarbonate detector, Lexan, is used to detect the fission-particles from the thermal neutron fission of²³⁵U or²³⁹Pu, present in the surfaces of the specimens. The principles of the methods are described, and an outline of the techniques presented. The quantitative aspect of the method is considered and the results on various specimens discussed.     

"Dilute-and-shoot" triple parallel mass spectrometry method for analysis of vitamin D and triacylglycerols in dietary supplements

A method is demonstrated for analysis of vitamin D fortified dietary supplements that eliminates virtually all chemical pretreatment prior to analysis, which is referred to as a “dilute-and-shoot” method. Three mass spectrometers, in parallel, plus a UV detector, an evaporative light-scattering detector (ELSD), and a corona charged aerosol detector (CAD) were used to allow a comparison of six detectors simultaneously. Ultraviolet data were analyzed using internal standard, external standard, and response factor approaches. The contents of gelcaps that contained 2,000 IU (50 μg) vitamin D₃ in rice bran oil, diluted to 100 mL, were analyzed without the need for lengthy saponification and extraction. Vitamin D₃ was analyzed using UV detection, extracted ion chromatograms, selected ion monitoring (SIM) atmospheric pressure chemical ionization mass spectrometry (APCI-MS), and two transitions of multiple reaction monitoring (MRM) APCI-MS. The internal standard, external standard, and response factor methods gave values of 0.5870 ± 0.0045, 0.5893 ± 0.0041, and 0.5889 ± 0.0045 μg/mL, respectively, by UV detection. The values obtained by MS were 0.6117 ± 0.0140, 0.6018 ± 0.0244, and 0.5848 ± 0.0146 μg/mL by SIM and two transitions of MRM, respectively. The triacylglycerols in the oils were analyzed using full-scan APCI-MS, electrospray ionization (ESI) MS, up to MS⁴, an ELSD, and a CAD. The method proved to be very sensitive for vitamin D₃, as well as triacylglycerols (TAGs), allowing identification of intact TAGs containing fatty acids up to 28 carbons in length. LC-ESI-MS of glycerin polymers is also demonstrated.     

Capillary gas chromatography of metal chelates of diethyl dithiocarbamates

Summary Capillary GC of metal chelates of diethyl dithiocarbamate (DDTC) was examined on a methylsilicone DB-1 column, (25 meter, 0.2 mm. i.d) with a film thickness of 0.25 μm. Elution was carried out at the initial column temperature of 180°C and programmed at 5°C min⁻¹ to 260°C. Detection was by FID or ECD. Symmetrical peaks with base line separation were obtained with the metal chelates of copper(II), nickel(II), cobalt(III), manganese(II) and chromium(III). The ECD gave better sensitivity than the FID with a linear calibration range of 5–50 μg mL⁻¹ and detection limits 2.0–6.0 μg mL⁻¹, corresponding to 111–333 pg of metal ion reaching the detector. The method was applied to the determination of metal ions in water and pharmaceutical preparations with a coefficient of variation (CV) within 4.0%. When compared with a standard flame AAS method the results revealed no significant difference.     

Physicochemical Studies of the Sea-Surface Microlayer

In physicochemical studies on the sea-surface microlayer (SML) in seawater, the main researches conducted were as follows: (1) It was found that there is an objective layer of sudden change in physical and chemical properties between the SML and the subsurface layer in seawater. (2) The SML thickness was determined and should be about 50±10 μm. (3) The Gibbs model of the SML was extended, and the multilayer model of the SML was advanced. (4) The original-location method, which corresponds with the traditional removal-location method, was founded and used to determine the SML thickness. The results obtained from the two methods were almost identical. (5) An abnormal phenomenon was found when the Gibbs solution adsorption was applied to the seawater system, the reason for which was discussed preliminarily.     

The etching,optical and thermal response of a newly developed nuclear track detector called NADAC-ADC copolymer to gamma-irradiation

The bulk-etch rates of a newly developed track detector which is a copolymer of N-allyloxycarbonyl diethanolamine-bis allylcarbonate (NADAC) and allyl diglycol carbonate (ADC) [NADAC-ADC (1:1, w/w)] have been determined at different temperatures to deduce its activation energy. The energy of activation is found to be (0.93 ± 0.07) eV. This compares very well with the values of activation energy reported in the literature for the most commonly used nuclear track detectors. The effects of gamma irradiation on this new detector in the dose range of 47.0–145.0 kGy have also been studied using bulk etch, UV–visible spectroscopic, and thermogravimetric analysis (TGA) techniques. The activation energy for bulk etching calculated from bulk etch rates measurements at different temperatures, optical band gaps determined from the UV–visible spectra, and the values of onset temperature of decomposition (T₀) calculated from TGA curves were found to decrease with the increase in gamma dose. These results have been explained on the basis of scission of the detector due to gamma irradiation.     

Optimization of a high-performance liquid chromatography method to quantify bilirubin and separate it from its photoproducts

A rapid reversed-phase (RP) high-performance liquid chromatography method for the isolation of bilirubin from its photoproducts (e.g., biliverdin) is reported. The method is based on isocratic elution using methanol:water as the mobile phase. A 2⁴ full-factorial experimental design approach was adopted. For the optimization, the best separation was obtained using a flow rate of 1.50 mL/min, a mobile phase of 99∶1 methanol:water (v/v) at pH 3.60, and a 150×4.6 mm id RP (C₁₈) column containing 5-μm particles. These conditions produced the fastest total retention time of 3.38±0.055 min, and other chromatographic parameters were acceptable. Under the optimum conditions, a linear calibration curve for bilirubin was obtained over the 1.0–40.0 μg/L concentration range studied. The limit of quantification was 0.79 g/L and the limit of detection was 0.24 μg/L. Bilirubin in solution was monitored by ultraviolet detection at 450 nm.     

Instrumental neutron activation analysis of gunpowder residues

A procedure has been developed for the detection of gunpowder residues deposited on the hand of a person firing a gun. The method is based on neutron activation analysis of the antimony level on the surface of the hand. The surface materials are removed by a film made by spraying a 4% solution of cellulose acetate in acetone, which sets to form a thin film that can readily be stripped off. This technique was found to be preferable to the paraffin-lift technique which is in common use. Following neutron activation of the film in a nuclear reactor, antimony is assayed by high-resolution Ge(Li) spectrometry without prior chemical processing. The sensitivity of the method is about 5·10⁻⁹ g Sb, with a precision of about ±10% at a neutron flux of 5·10¹³ n·cm⁻²·sec⁻¹. Analysis of twenty samples taken from the hands of persons who had fired a pistol gave Sb levels of 0.4±0.2 μg, compared with 0.024±0.013 μg found on the hands of persons who had not fired a revolver. The possible extension of the present technique to include the determination of additional elements is discussed. Project carried out with the support of the Office of the Chief Scientist to the Ministry of Defense and with the collaboration of the Israel Police.     

Absolute fission yields in the fast neutron induced fission of 233U by track etch combined with gamma-ray spectrometry

The absolute fission yields of twenty seven fission products were determined in the fast neutron induced fission of ²³³U, employing track etch in combination with gamma-ray spectrometry. The total number of fissions was measured by registering the fission tracks on a small strip of lexan, a solid state track detector. The fission products were analysed by gamma-ray spectrometry. The measured yield values were compared to the ENDF/B-VI compilation and show a good agreement.     

Characterization of a capacitance-coupled contactless conductivity detection system with sidewall electrodes on a low-voltage-driven electrophoresis microchip

A new type of capacitance-coupled contactless conductivity detection (C⁴D) system with sidewall electrodes was proposed for integration on a silicon-on-isolator–poly(dimethylsiloxane) (SOI-PDMS) hybrid low-voltage-driven electrophoresis microchip. By a microelectromechanical system process, the sidewall electrodes were fabricated precisely at either side of the separation channel. The area of the capacitor electrodes was the maximum value to improve the detection sensitivity with an enhanced capacitance effect. According to the simulation results, the structural parameters of the sidewall electrodes were determined as 550-μm length, 15-μm width, 80-μm separation distance, and 1-μm isolator thickness. The integrated microdevice with the SOI-PDMS hybrid electrophoresis microchip was very compact and the size was only 15 cm × 15 cm × 10 cm (width × length × height), which permitted miniaturization and portability. The detector performance was evaluated by K⁺ testing. The detection limit of the conductivity detector was determined to be 10^-9 and 10^-6 M for K⁺ in the static and electric-driven modes, respectively. Finally, the C⁴D was applied to low-voltage-driven electrophoresis on a microchip to carry out real-time measurement of the separation of amino acids. The separations of 10^-4 M lysine and phenylalanine in the low-voltage-driven electrophoresis mode were performed with an electric field of 300 V/cm and were completed in less than 15 min with a resolution of 1.3. The separation efficiency was found to be 1.3 × 10³ and 2.8 × 10³ plates for lysine and phenylalanine, respectively, with a migration time reproducibility of 2.7 and 3.2%. The conductivity detection limit of amino acids achieved was 10^-6 M. The proposed method for the construction of a novel C⁴D integrated on an SOI-PDMS hybrid low-voltage-driven electrophoresis microchip showed the most extensive integration and miniaturization of a microdevice, which is a further crucial step toward the realization of the “lab-on-a-chip” concept.     

Metal-coated fused silica fibers as a support for immobilized compounds yielding a volatile analyte (C<Subscript>2</Subscript>H<Subscript>4</Subscript>)

This paper presents the results of investigations of chemically modified fibers comprising an immobilized compound that yields ethene as the analyte in generated standard gaseous mixtures. Prior to chemical modification, the fibers were coated with a thin aluminum layer to improve their mechanical strength. Commercially available Al-coated fibers were used in this work. During thermal decomposition of the immobilized compound, reproducible quantities of the analyte per unit fiber length were obtained for all the investigated fibers (fiber diameter (μm)/outside diameter (μm) of the Al-coated fiber = 110/146, 220/300, and 660/830), amounting to 0.685 ± 0.032, 0.8300 ± 0.0081, and 1.092 ± 0.010 ng cm⁻¹, respectively. The proposed procedure can be used successfully for the generation of measured component of matrix-free reference materials.     

Development and validation of rapid HPLC method for determination of doxofylline in bulk drug and pharmaceutical dosage forms

A simple, selective, rapid, and economical reversed phase high performance liquid chromatography(RP-HPLC) method for the determination of doxofylline in the commercial dosage form has been developed and validated. The separation and quantification were achieved on an HiQ Sil C 18 W column using a mobile phase of acetonitrile: buffer (50: 50), pH 3, at a flow rate of 1 mL/min with detection of analyte at 272 nm. The separation was achieved within 3.1 ± 0.3 min for doxofylline sample. The method showed good linearity in the range of 10–80 μg/mL. The intra and inter day RSD ranged from 0.37–0.53%. The recovery (mean ± S.D.) of low, middle and high concentrations were 100.04 ± 0.80, 100.01 ± 0.20, 100.07 ± 0.30 respectively. Limit of detection and limit of quantification were 0.03 and 0.1 μg/mL, respectively.     

Nuclear analytical techniques for quantification of uranium for its recovery from seawater

Nuclear analytical techniques namely fission track technique using solid state nuclear track detector (SSNTD) and instrumental neutron activation analysis (INAA) have been standardized and applied for quantification of low uranium concentrations in liquid samples such as feed, elute and brine and solid sorbent samples respectively. The quantification of uranium is required for its recovery study from seawater, which is one of the potential sources of uranium. The uranium concentration of a liquid sample obtained by SSNTD method was compared with the other well established conventional techniques like ICP-MS, ICP-AES, adsorptive stripping voltametry and alpha spectrometry. INAA was applied for uranium concentration determination in the radiation grafted polyamidoxime sorbent samples.     

Analysis of trace uranium in Indian tobacco samples

The trace uranium concentrations have been determined in tobacco obtained from different brands of commercially available cigarette, beedi, chewing tobacco and also in pan masala, using fission track registration technique. Consumption of tobacco orally or by smoking may result in the intake of radioactive elements into the human body causing hazardous effects. External detector method was employed for the determination of uranium using Makrofol-KG as the fission track detector. The range of uranium was found to vary between 0.066–0.106 ppm, 0.042–0.079 ppm and 0.043–0.092 ppm, in tobacco from samples of cigarette, beedi and chewing tobacco, respectively, and between 0.073–0.203 ppm in pan masala samples.