Compton suppressed gamma-spectrometry for Comprehensive Nuclear-Test-Ban Treaty samples

The Comprehensive Nuclear-Test-Ban Treaty (CTBT) is supported by a network of certified laboratories that perform high-resolution gamma-spectrometry on global air filter samples for the identification of 85 radionuclides. At the UK CTBT Radionuclide Laboratory (GBL15), the use of advanced Compton suppressed systems has been investigated to reduce the Compton continuum and improve detection sensitivity. Samples collected from the Philippines and during the Fukushima incident have been measured, demonstrating Compton continuum reductions of 28–59 % with suppression factors of 0.1–147.0. Detection sensitivity has been improved with typically 40 % lower MDAs, including ¹⁴⁰Ba to meet CTBT requirements. True coincidence summing effects have been considered, including the application to remove interferences by the elimination of gamma-rays in cascade. This has been demonstrated for the removal of ¹³⁴Cs allowing improved ¹³¹I measurement.     

Development of a cosmic veto gamma-spectrometer

Cosmic radiation contributes significantly towards the background radiation measured by a gamma-spectrometer. A novel cosmic veto gamma-spectrometer has been developed that provides a mean background reduction of 54.5%. The system consists of plastic scintillation plates operated in time-stamp mode to detect coincident muon interactions within an HPGe gamma-spectrometer. The instrument is easily configurable and provides improved sensitivity for radionuclides indicative of nuclear weapons tests and reactor incidents, including ¹⁴⁰Ba, ⁹⁵Zr, ⁹⁹Mo, ¹⁴¹Ce, ¹⁴⁷Nd, ¹³¹I, ¹³⁴Cs and ¹³⁷Cs. This has been demonstrated for Comprehensive Nuclear-Test-Ban Treaty applications to obtain the required ¹⁴⁰Ba MDA of 24 mBq within 2 days counting. Analysis of an air filter sample collected during the Fukushima incident indicates improved sensitivity compared to conventional gamma-spectrometers.     

Innovative concept for a major breakthrough in atmospheric radioactive xenon detection for nuclear explosion monitoring

The verification regime of the comprehensive test ban treaty (CTBT) is based on a network of three different waveform technologies together with global monitoring of aerosols and noble gas in order to detect, locate and identify a nuclear weapon explosion down to 1 kt TNT equivalent. In case of a low intensity underground or underwater nuclear explosion, it appears that only radioactive gases, especially the noble gas which are difficult to contain, will allow identification of weak yield nuclear tests. Four radioactive xenon isotopes, ^131mXe, ^133mXe, ¹³³Xe and ¹³⁵Xe, are sufficiently produced in fission reactions and exhibit suitable half-lives and radiation emissions to be detected in atmosphere at low level far away from the release site. Four different monitoring CTBT systems, ARIX, ARSA, SAUNA, and SPALAX? have been developed in order to sample and to measure them with high sensitivity. The latest developed by the French Atomic Energy Commission (CEA) is likely to be drastically improved in detection sensitivity (especially for the metastable isotopes) through a higher sampling rate, when equipped with a new conversion electron (CE)/X-ray coincidence spectrometer. This new spectrometer is based on two combined detectors, both exhibiting very low radioactive background: a well-type NaI(Tl) detector for photon detection surrounding a gas cell equipped with two large passivated implanted planar silicon chips for electron detection. It is characterized by a low electron energy threshold and a much better energy resolution for the CE than those usually measured with the existing CTBT equipments. Furthermore, the compact geometry of the spectrometer provides high efficiency for X-ray and for CE associated to the decay modes of the four relevant radioxenons. The paper focus on the design of this new spectrometer and presents spectroscopic performances of a prototype based on recent results achieved from both radioactive xenon standards and air sample measurements. Major improvements in detection sensitivity have been reached and quantified, especially for metastable radioactive isotopes ^131mXe and ^133mXe with a gain in minimum detectable activity (about 2 × 10^?3 Bq) relative to current CTBT SPALAX? system (air sampling frequency normalized to 8 h) of about 70 and 30 respectively.     

Beryllium-7 activity at Comprehensive Nuclear-Test-Ban Treaty stations hosted by the United Kingdom

The Comprehensive Nuclear-Test-Ban Treaty (CTBT) is supported by a global network of monitoring stations that perform high-resolution gamma-spectrometry on air filter samples for the identification of radionuclides indicative of nuclear weapons tests and reactor incidents. These daily measurements have created an invaluable resource for understanding variations in natural background radioactivity, including the contribution of ⁷Be. Statistical analysis has been performed on ⁷Be data collected by CTBT stations hosted by the United Kingdom including at British Indian Ocean Territory (RN66), St Helena (RN67) and Tristan da Cunha (RN68) during 2005–2013. The results have been found to follow a lognormal distribution which implies that the ⁷Be activity is the multiplicative product of many small independent factors, such as meteorology, elevation, local station conditions, sample acquisition and analysis. This has the potential to identify discrepant measurements not attributable to the intrinsic variability of the distribution and indicative of station malfunction. Variations in ⁷Be activity have been considered on monthly, weekly and daily timescales and characterised using the geometric mean in accordance with the properties of the lognormal probability density function. Seasonal variations have been identified, with summer maxima and winter minima that are attributable to changes in mixing within the stratosphere and troposphere. Such fluctuations have been examined using the Fast Fourier Transform which may indicate variations associated with the 27 day solar cycle.     

Particulate matter, iron, and zinc in the atmosphere of a large Brazilian town

A Radionuclide Aerosol Sampler/Analyzer (RASA Mark 4) has been developed at PNNL for use in verifying the Comprehensive Nuclear Test Ban Treaty (CTBT). The RASA Mark 4 collects about 20,000 m³ of air per day on a 0.25 m² filter. This filter is automatically decayed for 24 hours, then advanced to a germanium detector for a 24 hour count. This system has been operated in Richland, WA for a limited period of time in a predeployment testing phase. The germanium-detector gamma-ray spectra have been analyzed by automatic spectral analysis codes to determine Minimum Detectable Concentrations (MDC) for a number of isotopes of interest. These MDC's have been compared to other atmospheric measurements in the field and in the laboratory.     

Novel beta-gamma coincidence measurements using phoswich detectors

Summary We have developed an analysis pipeline for air filter gamma-ray spectra, utilizing the software packages UniSampo for peak analysis and Shaman for nuclide identification. In an automated usage mode, spectra that are received via e-mail are processed into a directory tree, analyzed with UniSampo and Shaman, and finally categorized on the basis of the analysis results. Alarms are generated if anything out of the ordinary is observed. Typical applications for an air filter analysis pipeline are national radioactivity surveillance networks and the global radionuclide monitoring network being implemented for verification of the Comprehensive Nuclear-Test-Ban Treaty (CTBT). Our analysis pipeline system has been used by the Finnish national CTBT-authority, the Finnish National Data Center (FiNDC), since July 1999. Evaluation with a randomly selected set of 1518 air filter spectra showed that our pipeline system produces significantly better analysis results than that utilized by the CTBT Organization (CTBTO): our system found 4.2 more peaks per spectrum than the CTBTO system (9 % increase) and identified 5.6 more peaks per spectrum (14 % increase) on the average.     

Performance of HPGe gamma spectrometry system for the measurement of low level radioactivity

Comprehensive quality assurance/quality control procedure is very much necessary to obtain accurate and precise analytical measurement result. This paper discusses the quality control aspects of the High-Purity Germanium (HPGe) based gamma spectrometry system, which has been used for the measurement of low-level radioactivity in environmental samples. The gamma spectrometry system consisting of coaxial n-type HPGe detector having 50% relative efficiency with respect to 7.62 cm x 7.62 cm NaI (Tl), Nuclear Instrumentation Module (NIM) based pulse processing electronic accessories and 8 k MCA. To reduce the background contribution, 7.5 cm thick lead has been placed surrounding the detector. The minimum detectable activities (MDA) with 95% confidence level (for 300 g soil sample and 100,000 s counting time) for important radionuclides such as ²³⁸U, ²²⁶Ra, ²³²Th, ⁴⁰K, and ¹³⁷Cs are 10.4, 4.3, 4.1, 16.9 and 0.1 Bq kg^?1, respectively. The Quality control (X bar R) charts were plotted using ¹³⁷Cs and ⁴⁰K background counts observed periodically, which showed that the fluctuation is well within the confidence limit and confirms the stability of the system. The laboratory has been participating in the proficiency tests (PTs) of the International Atomic Energy Agency (IAEA). In recently concluded PTs, the samples include soil, spiked standard solution, spinach, phosphogypsum and spiked air filter were analysed for the natural, fission and activation products radionuclides. The performance evaluation of the IAEA PTs showed that the laboratory results were in good agreement with the target value, which confirms the reliability and traceability of the gamma spectrometric measurement result of the laboratory.     

Sensitive Analysis of Malondialdehyde in Human Urine by Derivatization with Pentafluorophenylhydrazine then Headspace GC–MS

A sensitive method based on derivatization with pentafluorophenylhydrazine then headspace gas chromatography–mass spectrometry has been used for analysis of malondialdehyde in human urine. Preparation of urine sample by one-step derivatization/evaporation was performed by reaction of malondialdehyde with pentafluorophenylhydrazine in a headspace vial for 10 min; the derivatives were then injected in GC–MS analysis. The reaction was performed at pH 3, and total analysis time was 35 min. The method detection limit was 0.04 μg L^?1. For MDA concentrations of 2.0 and 10.0 μg L^?1 the relative standard deviation was less then 5%. The concentration of MDA in urine was measured to be 0.199 ± 0.252 μmol g^?1 creatinine (0.022 ± 0.028 μmol mmol^?1 creatinine).     

Radon concentration in air, hot spring water, and bottled mineral water in one hot spring area in Thailand

Hot springs are famous as spa resorts throughout the world. However, these areas usually have high natural radioactivity from radon gas. In this study radon concentrations in air, hot spring water, and bottled mineral water produced in a spa area of Suan Phueng district, Ratchaburi province, Thailand were measured. Radon concentrations in air were in the range of 10–17 and 11–147 Bq/m³ for outdoor and indoor, respectively. Committed effective dose from inhale of radon were assessed and found to be in the range of 0.004–0.025, 0.25–0.6, and 1.134 mSv/y for visitor, local people and resort workers, respectively. These doses were in the range of 1.2 mSv/y regulated by UNSCEAR for the general public. Radon in hot spring water ranged from 2–154 Bq/L. Radon in bottled mineral water produced from the hot spring water were in the range of 17–22 and 0.2–0.3 Bq/L for those that stored for 7 and 90 days, respectively, after production. Radon concentration levels were in the range of the US Environmental Protection Agency reference level for radon in air which is 148 Bq/m³ and alternative maximum concentration limit (AMCL) for raw water which is 150 Bq/L. However, when considering the USEPA (Maximum concentration limit), 11 Bq/L, for radon in drinking water, the mineral water should be stored for at least 8–9 days after bottling before selling to the market.     

Analysis of Bile Acids Profile in Human Serum by Ultrafiltration Clean-up and LC-MS/MS

Bile acids (BAs) are useful biomarkers for the diagnosis of many diseases. The pathologies related to bile acid synthesis are often expressed in the first years of life and may lead to serious liver injury. Here we present a sensitive and rapid method for the analysis of the main 14 bile acids in human serum by liquid chromatography-tandem mass spectrometry. The chromatographic separation is performed using a core–shell column which provides improved separation, highly desirable considering the small structural differences among the analytes. All isomeric BAs of interest were resolved in less than 9 min. Sample pretreatment consisted in ultrafiltration of serum after addition of methanol by means of centrifugal filter devices. The calculated LOQs ranged between 2 and 5 ng mL⁻¹ with linearity of the calibration curves in the 5–5,000 ng mL⁻¹ range for all the BAs. The extraction recoveries for all the analytes were higher than 80 %. Intra-day and inter-day coefficients of variation were all below 15 %. The method proposed has been validated and has been applied for the analysis of serum of pediatric patients. This simple procedure allowed minimal consumption of serum sample (about 100 μL) and a rapid assay, easily implementable in routine analysis.

     

Radionuclides from Fukushima accident in Thessaloniki, Greece (40°N) and Milano, Italy (45°)

¹³¹I, ¹³⁷Cs and ¹³⁴Cs were observed in environmental samples in Milano (40°N), Italy and Thessaloniki (45°N), Greece, soon after the nuclear accident in Fukushima, Japan. The radionuclide concentrations were determined and studied as a function of time. In Thessaloniki the ¹³¹I in air was observed for the first time on March 24, 2011. In Milano, the first evidence of Fukushima fallout has been confirmed with ¹³¹I and ¹³⁷Cs measured in wet precipitation collected 2 days later. The maximum ¹³¹I activity concentration in air of 467 ± 25 μBq m^?3, observed in Milano on April 3–4, 2011, was almost similar to the highest value of 497 ± 53 μBq m^?3 observed in Thessaloniki. The ¹³⁴Cs/¹³⁷Cs activity ratio values in air were around 1 in both regions. Soil, grass and milk samples were contaminated with ¹³¹I and ¹³⁷Cs at a low level. Finally, a dose assessment for these two areas showed clearly that the detected activities in all environmental samples were far below levels of concern.     

Diaminobenzene as a Novel Reagent for Nitrite Assay in Environmental Samples: Evidence for Its Mechanistic Aspects

Abstract

o-Phenylenediamine has been used as a reagent to quantify nitrites/nitrates in a variety of sample matrices. The method is based on the cyclization reaction between o-phenylenediamine and nitrite in acid medium. The amine undergoes diazotization with nitrite in the presence of acid to form the diazonium ion, which subsequently cyclizes to yield yellowish orange benzotriazole at room temperature with an absorption maximum at 450 nm. The formed dye has been separated, purified, and characterized by IR, NMR, and spectroscopy techniques. The parameters of the reaction between amine and nitrite have been optimized. The effect of interfering ions on the determination of nitrites/nitrates has been described. The developed method has been applied for the determination of residual NO₂ gas present in the ambient air after fixing it as a nitrite ion using sodium arsenite as a trapping medium. The dye formed has been extracted into organic solvent to improve the detection limit during the measurement of low levels of ambient NO₂ in air. The method obeyed Beer's law in the concentration range 0–250 µg in aqueous medium and 0–50 µg in organic medium with molar absorptivity of 4.09 × 10⁴ L mol^?1 cm^?1 and 4.3 × 10⁴ L mol^?1 cm^?1 respectively. Nitrate is determined by reducing it to nitrite after passing through the copperized cadmium reductor column. The developed method has been applied to determine nitrite/nitrate levels in water, soil, and biological samples.     

Analysis of Pazufloxacin Mesilate in Human Plasma and Urine by LC with Fluorescence and UV Detection,and Its Application to Pharmacokinetic Study

A liquid chromatographic method for analysis of pazufloxacin mesilate in human plasma and urine has been developed and validated for selectivity, sensitivity, accuracy, precision, and stability in pharmacokinetic analysis. The sensitivity of the method was 0.02 μg mL^?1 in plasma and 0.5 μg mL^?1 in urine, with overall intra-day and inter-day precision (RSD < 10%) and accuracy (90–120%) acceptable for clinical pharmacokinetic analysis. Recovery from plasma and urine was 80–110% for both pazufloxacin mesilate and enoxacin, the internal standard. Pazufloxacin was stable in both plasma and urine, with no significant degradation under four different conditions. The method was successfully used in a preliminary study of the bioavailability of pazufloxacin mesilate in healthy human volunteers after intravenous administration of 300 and 500 mg.     

Evaluation of the optimal LNCaP prostate tumour developmental stage to be assessed by 99mTc-HYNIC-βAla-Bombesin(7–14) in an experimental model

The lymph node carcinoma of the prostate (LNCaP) cell line is widely used in prostate cancer diagnostic studies. However, the optimal developmental stage during which to assess LNCaP prostate tumours by in vivo molecular imaging has not been established. This study aimed to assess LNCaP prostate tumours by scintigraphic imaging using technetium-99m (^99mTc)-2-hydrazinonicotinamide (HYNIC)-beta-alanine (βAla)-Bombesin_(7–14) at different stages of tumour development and to compare each developmental stage using histopathological analysis. ^99mTc-HYNIC-βAla-Bombesin_(7–14) (7.4 MBq) was injected into LNCaP prostate tumour-bearing mice after 15, 20 or 25 days of tumour inoculation. Scintigraphic images were obtained 1 and 4 h following radiopeptide injection and tumour tissues were obtained for histopathological analysis. Tumours were not observed by scintigraphic imaging after 15 days of inoculation, but after 20 and 25 days of inoculation, tumours were visualised, with a tumour-to-muscle ratio of 2.14 at 4 h after the radiopeptide injection into mice with 25-day tumours. Histopathological analysis showed that the amount of collagen fibres in the stroma was inversely proportional to the stage of tumour development, whereas the intensity of vascular proliferation was directly proportional to the tumour stage; this explains radiopeptide localisation in LNCaP cells and improved visualisation of the 25-day tumours. In conclusion, the results showed that 25-day tumours presented the most appropriate features for radiopeptide accumulation in LNCaP cells, suggesting that they are in the best stage of tumour development to be assessed by scintigraphic imaging using ^99mTc-HYNIC-βAla-Bombesin_(7–14).     

LC Determination of Malondialdehyde Concentrations in the Human Umbilical Vein Endothelial Cell Culture Medium: Application to the Antioxidant Effect of Vitexin-2″-O-rhamnoside

Vitexin-2″-O-rhamnoside (VOR) presents the leaves of Crataegus pinnatifida Bge. var. major which plays a role in preventing human pathologies related to oxidative stress, but as the principal component in the leaves, little attention has been devoted to its study of antioxidation of VOR. A simple, rapid and sensitive high-performance liquid chromatography method was developed to determine malondialdehyde (MDA) in ECV304 cell culture medium induced by tert-butyl-hydroperoxide (TBHP). The preparation of analyzed samples involved a one-step derivatization with thiobarbituric acid (TBA). The separation was achieved using the Synergi Hydro-RP, a polar endcapped C₁₈ column (250 × 4.6 mm, 4 μm pore size) with a linear gradient elution of acetonitrile and 10 mmol L^?1 of ammonium acetate aqueous solution (pH 6.8). The calibration curve was linear over the ranges 0.0125–1.25 μmol L^?1 MDA (r = 0.9962). The lower limit of quantification of MDA was 0.0125 μmol L^?1. Relative standard deviations of intra-day and inter-day precision were less than 5.2 and 4.4%. The method with high recovery (95.4 ± 1.3%) was successfully applied to the investigation of antioxidation of VOR by determining MDA in ECV304 cell culture medium.     

Carbon Nanotubes/Ionophore Modified Electrode for Anodic Stripping Determination of Lead

Bifunctional combination of carbon nanotubes and ionophore is introduced for anodic stripping analysis of lead (Pb²⁺). Carbon nanotubes are employed to improve the detection sensitivity due to their excellent electrical conductivity and strong adsorption ability. An ionophore is utilized for its excellent selectivity toward Pb²⁺. The proposed carbon nanotubes/ionophore modified electrode shows improved sensitivity and selectivity for Pb²⁺. Low detection limit (1 nM), wide linear range (5 nM–8 µM) and excellent selectivity over other metal ions (Cd²⁺, Cu²⁺, and Hg²⁺) was obtained. The practical application has been carried out for determination of Pb²⁺ in real water samples.     

Flow injection on-line spectrophotometric determination of thorium(IV) after preconcentration on XAD-4 resin impregnated with oxytetracycline

A very sensitive, selective and simple flow injection time-based method was developed for on-line preconcentration and determination of thorium(IV) at micro g L^–1 levels in environmental samples. The system operation was based on thorium(IV) ion retention at pH 4.0 in the minicolumn at a flow rate of 15.2 mL min^–1. The trapped complex was then eluted with 3.6 mol L^–1 HCl at a flow rate of 4.9 mL min^–1. The amount of thorium(IV) in the eluate was measured spectrophotometrically at 651 nm using arsenazo-III solution (0.05 % in 3.6 mol L^–1 HCl stabilized with 1 % triton X-100, 4.9 mL min^–1) as colorimetric reagent. All chemical, and flow injection variables were optimized for the quantitative preconcentration of metal and a study of interference level of various ions was also carried out. The system offered low backpressure and improved sensitivity and selectivity. At a preconcentration time of 60 s and a sample frequency of 40 h^–1, the enhancement factor was 97, the detection limit was 0.25 μg L^–1, and the precision expressed as relative standard deviation was 1.08 % (at 50 μg L^–1), whereas for 300 s of the preconcentration time and a sample frequency of 10 h^–1, the enhancement factor of 357, the detection limit (3σ) of 0.069 μg L^–1 and the precision of 1.32 % (at 10 μg L^–1) was reported. The accuracy of the developed method was sufficient and evaluated by the analysis of certified reference material IAEA-SL-1 (Lake Sediment) and spiked water samples.     

An electrochemical process intensified by bipolar iron particles for nitrate removal from synthetic groundwater

An intensified electrochemical process in an undivided cell using Cu–Zn alloy as cathode and Ti/IrO₂–Pt as anode combined with bipolar iron particles (electro-iron system) has been developed. The performance of nitrate reduction was evaluated using synthetic groundwater. Results showed that the nitrate-N dropped rapidly from 50 to less than 10 mg/L within 100 min in the developed system at current densities in the range of 5–30 mA/cm². Sodium chloride addition was found to have a positive effect on the system performance. No nitrite-N was detected during the electrolysis in the presence of sodium chloride. The concentration of total iron ion in the solutions was found to be less than 0.25 mg/L after 100 min electrolysis. Furthermore, the electrical energy consumption for nitrate reduction in the electro-iron system was saved by approximately 29.4–34.8 % at 5–30 mA/cm². The developed system has been proved to promote electrochemical nitrate reduction and greatly improve the electrical energy efficiency.     

Determination of gross alpha and beta activities in seawater and plankton from the Upper Gulf of Thailand

Gross alpha and beta activities were determined in seawater and plankton samples collected during the wet and dry seasons from 10 different sampling stations in Chonburi, the Upper Gulf of Thailand. Seawater samples were sampling, 1 km from the coastal and 2 m below the water surface, during July 2008 to July 2009. Seawater samples were prepared by coprecipitation technique. Plankton samples were prepared by filtration and dryness on filter paper. Both types of samples were counted using a low background alpha/beta proportional counter with multiple detector type (Berthold LB770). The results showed that gross alpha activities in seawater and plankton sample are in the range of 0.0591 ± 0.0209–0.3914 ± 0.0606 Bq/l and 0.0029 ± 0.0020–0.0294 ± 0.0043 Bq/l, respectively and also showed the lowest and highest activity level in the same sampling time. The activities of gross beta in seawater and plankton sample are in the range of 0.2803 ± 0.0177–1.3064 ± 0.0319 Bq/l and 0.0208 ± 0.0123–0.9151 ± 0.0262 Bq/l, respectively. Minimum detectable activity (MDA) had been observed in the measurements. The MDA of seawater sample were estimated to be 0.0832 Bq/l for alpha and 0.0577 Bq/l for beta at counting time of 100 and 200 min, respectively. In plankton samples, the MDA were estimated to be 0.0053 Bq/l for alpha and 0.0409 Bq/l for beta at the same counting time of 250 min.     

Estimation of free acidity in some hydrolysable metal ions present in reprocessing streams by fiber optic aided spectrophotometry

A fiber optic aided spectrophotometric technique has been developed for the determination of free acidity in nuclear fuel reprocessing streams. In this method, nitric acid forms yellow colour complex with chrome azurol s. The system obeys Lambert–Beer’s law at 542 nm in the range of acidity 4–14 M. The molar absorption coefficient (ε) and Sandell’s sensitivity (S) of complex are 5.23 × 10³ L.mol^?1.cm^?1 and 1.91 × 10^?4 µg/cm² respectively. Relative standard deviation is less than 1 % and correlation coefficient is 0.999. Results of the present method are in good agreement with those obtained by the standard procedure.